JPS605613B2 - thermoplastic composite material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention comprises a rubber-modified impact-resistant resin, a powdered inorganic filler,
The present invention relates to a thermoplastic composite material made of animal oil and/or vegetable oil and having excellent impact resistance, moldability, and molding shrinkage.

Conventionally, it has been well known that inorganic fillers are blended into thermoplastic resins, and glass fiber reinforced resins are the most typical example thereof.

This glass fiber reinforced resin is a composite material that has high tensile strength and bending strength, and has improved creep strength, heat distortion temperature, molding shrinkage, etc., and has characteristics that cannot be obtained from thermoplastic resin or glass fiber alone. Extreme emphasis is placed on giving certain products. In addition, since the inorganic fillers used in resin materials blended with inorganic fillers are generally inexpensive, they are useful for those involved in resin products because they can provide composite materials with new substances at low cost. It is attractive and is being actively developed as a multifunctional resin that can save resources for the first time since the oil crisis. however,
When an inorganic filler is added to a resin, the impact resistance and moldability of the resin usually decrease, making it difficult to create a composite material that takes advantage of the respective characteristics of the thermoplastic resin and the inorganic filler. Since this is extremely difficult, generally a specific combination of a thermoplastic resin and an inorganic filler with affinity is selected, or a third component is added that blends the interface between the thermoplastic resin and the inorganic filler. The current situation is to add them to obtain properties as a composite material.

On the other hand, rubber-modified impact-resistant resins such as ABS resin and HI polystyrene, which have been given impact resistance by rubber, are also used for glass fibers and powdered calcium carbonate (Special Publications Publication No. 44-17).
It is known to incorporate various fillers such as (Japanese Patent Publication No. 532), but when glass fiber is incorporated, although the rigidity of the resin is improved, the impact resistance is inevitably reduced, and powdered calcium carbonate In this case, the impact resistance of the resin deteriorates even more significantly, and the original characteristics as an impact resistant resin are completely lost, making it difficult to put it into practical use.

Therefore, regarding the combination of rubber-modified impact-resistant resin and inorganic filler, only glass woven ABS resin has been put into practical use, and powdered inorganic filler, which is more economical than glass fiber, has been put into practical use. It has been considered almost impossible to obtain rubber-modified impact-resistant resin composites that maintain their original impact resistance. Therefore, the present inventors have attempted to minimize the decrease in impact resistance when compounding rubber-modified impact-resistant resins with powdered inorganic fillers such as calcium carbonate and clay, and to improve moldability, dimensional stability, and rigidity. As a result of intensive studies to obtain an excellent composite material with balanced properties, the above objective was achieved by further blending a specific oil and fat into a composition consisting of a rubber-modified impact-resistant resin and a powdered inorganic filler. We have discovered what can be achieved and arrived at the present invention.

That is, in the present invention, animal oil and/or vegetable oil is added in an amount of 10 to 3 parts by weight to 10 parts by weight of a composition consisting of 50 to 9% by weight of a rubber-modified impact-resistant resin and 2 to 5% by weight of a powdered inorganic filler. The present invention provides a thermoplastic composite material in which the following components are blended in parts by weight.

The rubber-modified impact-resistant resin used in the present invention is a thermoplastic resin imparted with impact resistance by rubber.
BS resin and HI polystyrene are representative.

The rubber materials mentioned here include polyurethane, butadiene-styrene copolymer rubber, butadiene-acrylonitrile copolymer rubber, polychloroprene, ethylene-propylene copolymer rubber, acrylic rubber, etc., and resins modified with these rubber materials. The phase is mainly composed of aromatic vinyl monomers such as styrene and Q-tatylstyrene, vinyl cyanide monomers such as acrylonitrile, and acrylic acid or methacrylic acid ester monomers such as methyl methacrylate. Polymers containing other copolymerizable vinyl monomers, such as polystyrene, styrene-acrylonitrile copolymers, styrene/acrylonitrile/methyl methacrylate copolymers, and blends thereof with other polymers such as polyvinyl chloride. Things, etc. As a modification method using a rubbery substance, a method is mainly adopted in which vinyl monomers forming a resin phase are graft-polymerized in the presence of a rubbery substance by emulsion polymerization, emulsion-suspension polymerization, bulk polymerization, etc. It is also possible to modify the thus obtained graft polymer or rubber by blending it with a thermoplastic resin. The rubber content of these rubber-modified impact-resistant resins is usually 8 to 5% by weight, and may also contain small amounts of additives such as antioxidants and metal soaps. The powdered inorganic filler used in the present invention is at least one selected from calcium carbonate, clay, talc, gypsum, poppy seed, sotsuji, white carbon, calcium metasilicate, glass powder, carbon black, asbestos, shirasu balloon, etc. Among them, calcium carbonate is preferred because it provides the best impact resistance.

The average particle diameter of these powdered inorganic fillers is not particularly limited as long as they are available, but those of 0.01 to 20 F are usually preferred, and whisker-like fillers can also be used in some cases. The blending amount of the powdered inorganic filler varies somewhat depending on the rubber content of the rubber-modified impact-resistant resin and the type of filler, but generally it is 2% for the rubber-modified impact-resistant resin.
The content is 5 to 5% by weight, preferably 5 to 35% by weight, and if it is blended in more than 5% by weight, the drop in impact resistance becomes even more severe, which is not preferable. These compositions consisting of rubber-modified impact-resistant resin and powdered inorganic filler have significantly reduced impact resistance of the rubber-modified impact-resistant resin itself, but by adding animal oil and/or vegetable oil to the composition. It is possible to restore the impact resistance of objects to a practical range. The animal oil used in the present invention is at least one type of oil (fat, oil) collected from animals, such as aquatic animal oils such as fish oil, fresh oil, liver oil, beef tallow, pork fat,
Examples include land animals such as mutton fat.

In addition, vegetable oil is oil (fat, oil) extracted from plants.
For example, drying oils such as linseed oil, tung oil, and eno oil; semi-drying oils such as sesame oil, rapeseed oil, cottonseed oil, and soybean oil; non-drying oils such as camellia oil, olive oil, and castor oil; Examples include coconut oil, palm kernel oil, and wood wax.

The optimum amount of these oils and fats to be used differs depending on the type of rubber-modified impact-resistant resin and powdered inorganic filler, especially the number of oil absorption systems of the filler, but in general, rubber-modified impact-resistant resin and powdered inorganic filler are used. The filler is added in an amount of 10 to 3 parts by weight based on 10 parts by weight of the filler composition. If the amount of oil and fat added is 1 part by weight, no impact resistance recovery effect can be obtained, and if the amount is more than 3 parts by weight, the moldability of the composite material decreases, making it impractical, which is not preferable. Examples of methods for blending the rubber-modified impact-resistant resin, powdered inorganic filler, and fats and oils include blending the fats and oils into a composition consisting of the resin and the filler;
A method of simultaneously mixing resin, filler, and oil and fat;
Examples include a method of blending fillers and/or fats and oils during polymerization of the resin, and a common roll, Banbury mixer, beletizer, etc. can be used for beletizing the mixed bran.

When compounding, various additives such as lubricants such as fatty acid amides, fatty acids, metal soaps, and alcohols, and plasticizers such as phosphate esters, phthalate esters, fatty acid esters, and glycol esters can be added.In particular, oleic acid ( (unsaturated fatty acids), the impact resistance of the composite material can be further improved. The composite material of the present invention can be molded with good moldability by ordinary injection molding, extrusion molding, etc., and the molded product obtained has good moldability from low temperature to room temperature, and has practical value. big.

The effects of the present invention will be explained in further detail with reference to Examples below.
Example 1 5 parts by weight of distilled water, 50% solids polybutadiene latex (average particle size 0.25, gel content 92%) 1
0 parts by weight and 0.0 parts by weight of ferrous sulfate as a polymerization initiation aid.
1 part by weight, 10 parts by weight of dextrin, and 0.5 part of sodium pyrophosphate were initially charged into a small polymerization vessel equipped with a sieve.

Furthermore, a mixed solution consisting of 35 parts by weight of styrene monomer to which 0.25 parts by weight of t-dodenyl mercaptan was added and 15 parts by weight of acrylonitrile monomer was prepared, and then 0.24 parts by weight of the polymerization initiator Cumen Hydro Panawood Sid was prepared. 24 parts by weight of sodium laurate and emulsifier were emulsified in 25 parts by weight of distilled water.

These two solutions were added dropwise to the initially charged polybrazine latex mixture at a uniform charging speed, and emulsion polymerization was carried out at 60° C. for 4 hours including 3 maturation times.

The polymerized latex was coagulated with 1.5% sulfuric acid, then neutralized with alkali, and centrifuged to achieve a grafting rate of 40%.
ABS resin powder was obtained. The grafting rate of this polymer is maintained at 40±5%. Separately, 10 parts by weight of water and 0.0 parts polyvinyl alcohol as a suspending agent were added.
3 parts by weight of the polymerization initiator azobisisobutyronitrile, 0.2 parts by weight of the chain transfer agent n-octylmecaptan, 2 parts by weight of the dissolved styrene monomer, and the weight of the acrylonitrile monomer la. Add 8 parts
Styrene-acrylonitrile copolymer beads ■ obtained by suspension polymerization for 0:04 hours were blended with o■ and 'B} so that the rubber content was 17%, and carbonic acid having various average particles was added to the ABS resin obtained. Calcium and 20 qo of beef tallow, which is a brown viscous liquid, are blended according to the blending method shown in Table 1.
The powder was mixed for 5 to 1 minutes using a powder mixer with a rotation speed of 100 pm.

Next, the screw diameter is 4, and the screw L/D is 2.
2. The pellets were pelletized from an extruder under the conditions of a rotational speed of 80 pm, a cylinder temperature of 23,000, and a die temperature of 210° C., and the impact resistance of each pellet was evaluated. The Izod impact strength is a value measured by molding a 1/2 x 1'2 inch test piece from each pellet and making a 1/10 inch notch in accordance with ASTM-D-256-56.

The results are shown in Table 1. 1st *The increase in impact strength before and after adding beef tallow is shown as an improvement rate.

As shown in Table 1, impact strength is 22.4 kg・cm'
When adding io%~30% calcium carbonate to arc (notched) Amo resin, the impact value is 2.8~4.5k90 skin'
It deteriorates with the skin (notched), and decreases almost regardless of the particle size distribution of calcium carbonate, causing the main pot to lose almost all of its properties as an impact resin.

When beef tallow is added to the resin whose impact strength has decreased, the impact strength increases again and becomes suitable for practical use.
The impact improvement effect of the present invention is remarkable.

As shown in the impact strength improvement rate, adding beef tallow to ABS resin only improves it by 10.7%, but adding beef tallow to ABS/calcium carbonate composition improves it by 111-235%.
% also improves impact strength. Example 2 The ABS resin produced in Example 1 was coated with calcium carbonate having an average particle size of 0.08 mm and Nisseki CCR (manufactured by Nisseki Calcium) and an average particle size of 6.

3. Blend French calcium carbonate SS #30 (manufactured by Nitto Funka) as shown in Table 2, add castor oil, a yellow transparent liquid, at 2000 pm and mix with a powder mixer rotating at 200 pm.
Stir mixed for ~10 minutes.

Next is the screw diameter 40 side? "Screw L/D=22
The materials were pelletized from an extruder under the following conditions: rotation speed 80 pm, cylinder temperature 230° C., and die temperature 210 oo, and the Izod impact strength of each material was evaluated using the same machine as in Example 1. The results are shown in Table 2.

Table 2 also shows the impact strength improvement rate (rate of change in impact value before and after adding castor oil) when castor oil is added to A-mo resin and when added to ABS/calcium carbonate composition. 3
It was shown to.

As is clear from Tables 2 and 3 of Table 3, the effect of improving impact resistance by adding castor oil is significant.

Example 3 Polybutadiene latex 6 with a solid content of 50%
20 parts by weight of distilled water, 0.0 parts by weight of ferrous sulfate as a polymerization initiation aid, and 2.0 parts by weight of dextrin. parts by weight,
Add 1 part of sodium pyrophosphate, then add 100 parts by weight of styrene monomer, 6 parts by weight of acrylonitrile monomer and 0.5 parts by weight of n-octylmethylcaptan as a chain transfer agent. It was placed in a small polymerization apparatus equipped with a frame machine.

Furthermore, 5 parts by weight of potassium oleate as an emulsifier and 0.5 parts by weight of cumene hydrovanoxide as a polymerization initiator were emulsified in 5 parts by weight of distilled water, and this emulsion was added to the above polybutadiene latex monomer mixed solution. Add 7
Emulsion polymerization was carried out at 0q04 hours.

After the polymerization, the latex was coagulated with 1.5% sulfuric acid, neutralized with a sodium hydroxide solution, centrifuged, and dried to obtain an ABS resin powder. This ABS resin/Guber has an average particle size of 0.08, and is a precipitated calcium carbonate with a glossy appearance C.
Blend CR (manufactured by Shiraishi Calcium) with whale oil, a brown liquid at 2,000 pm, and coconut oil, a smooth transparent liquid at 20 pm, according to the formulation shown in Table 4, and mix it with a rotary powder mixer at 200 pm. It was pelletized using an extruder with a rear screw diameter of 3Q and a sail of 0, and the Izod impact strength was measured in the same manner as in Example 1. The results are shown in Table 4. Table 4 Example 4 Inorganic fillers such as Talc MS (manufactured by Nippon Talc), gypsum (manufactured by Toray Industries) and Union Kushi (manufactured by Takehara Chemical) and soybean oil are added to the ABS resin produced in Example 1 as shown in Table 5. The impact strength was measured using the following formulation.

Table 5 As is clear from Table 5, impact strength is improved when soybean oil is added to a composition consisting of clay, gypsum, turk, and ABS resin.

Example 5 Commercially available polystyrene resin (manufactured by Asahi Dow) was blended with inorganic fillers such as Kei Minato Simgon (manufactured by Nippon Talc) and clay, and castor oil as shown in Table 6, and kneaded, beletized, and molded. Then, the Wizodt impact strength was measured.

Table 6 HI Polystyrene resin-inorganic filler system also recovers impact strength by adding castor oil.

Claims (1)

[Claims] 1. Thermoplastic composite made by blending 10 to 30 parts by weight of animal oil and/or vegetable oil to 100 parts by weight of a composition consisting of 50 to 98% by weight of rubber-modified impact-resistant resin and 2 to 50% by weight of powdered inorganic filler. material.