JPS5918419B2 - resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a filler for thermoplastic resins, and more particularly to a filler for thermoplastic resins with improved mechanical strength and workability, and in particular to a filler material for thermoplastic resins with improved mechanical strength and workability. Desirable results can be obtained when used with vinyl resins.

Blending inorganic fillers with thermoplastic resins such as vinyl chloride resins is expected to improve the physical properties of the resins, such as hardness, rigidity, heat resistance, and flame retardance, but simply blending them will not improve processability. In addition to a significant drop in impact strength, there are other drawbacks such as discoloration of the resin composition blended with an inorganic filler.

It is already known to mix and disperse rubber particles such as ABS and MBS in order to improve the impact resistance of molded products made of hard vinyl chloride resin.

However, when blending an inorganic filler with vinyl chloride resin, a dramatic improvement in impact strength cannot be expected by simply blending rubbers such as ABS and MBS.
The improvement required a large amount of expensive rubber, which was not economically viable.

Furthermore, the silane coupling agent used when filling thermosetting resin with glass fiber has a large effect on impact strength and processability in systems where vinyl chloride resin is filled with an inorganic filler. There was one thing that was obvious.

In addition, methods have been proposed to improve the interfacial condition with vinyl chloride resin, such as coating with stearic acid, resin acid, etc., or polymerizing a vinyl monomer with a carboxy group on an inorganic material, but the impact resistance However, no significant improvement was observed in terms of workability, and the results were not satisfactory.

As a result of intensive study on ways to improve the drawbacks that occur when filling thermoplastic resins with inorganic fillers, we found that
A low molecular weight substance A having a hydrolyzable silicon functional group, which is synthesized by reacting a low molecular weight substance B of ~30,000 with a hydrosilicon compound of 15% by weight or less, is coated with Si-OH, Al on the surface. We have found an interesting fact that this can be improved by bonding to an inorganic filler having a hydroxyl group such as -OH.

It is not clear why mechanical strength and workability are improved when a thermoplastic resin is filled with a filler coated through such chemical bonding, but according to the method of the present invention, thermoplastic resin It is possible to bond low-molecular-weight substances that are compatible with the inorganic filler to the surface of the inorganic filler, improving processability, and it is thought that these low-molecular-weight substances also play the role of impact mitigation.

The low molecular weight material of the present invention refers to a low molecular weight material B having a molecular weight of 300 to 30,000 (one of which has at least one or more unsaturated bonds) in the general formula (R. is 1
represents a group selected from a valent hydrocarbon group and a halogenated monovalent hydrocarbon group, a is an integer of 0, 1, or 2, and X is a functional group selected from a halogen, an alkoxy group, an acyloxy group, and a ketoximate group. Indicates a group or an atom.

) is a low molecular weight compound having at least one silicon atom with a hydrolyzable functional group synthesized by reacting with a hydrosilicon compound of (2), and has a structure as exemplified by formula (2).

Of course, it is also possible to convert the hydrolyzable group X of the low molecular weight substance A produced as above into another hydrolyzable group Y by a general operation.

Here, Y is an alkoxy group, an acyloxy group, an amide group,
This group is selected from hydrolyzable groups such as acid amide groups, aminooxy groups, and ketoximate groups. In the step of reacting the hydrosilicon compound with this low molecular weight substance B, a transition metal complex catalyst is usually used.

As a transition metal complex catalyst, it has already been published in the Journal of the Society of Organic Synthetic Chemistry, Vol.
As reported in Vol. 8, p. 919 (1970),
Group transition metal complex compounds selected from platinum, rhodium, cobalt, palladium and nickel are advantageously used. In particular, platinum catalysts such as chloroplatinic acid, platinum metal, platinized activated carbon, platinum chloride, and platinum olefin complexes are excellent. This hydrosilylation reaction is carried out from -3'C to 150°C.
Although this can be achieved at any temperature, it is more preferable to carry out the reaction at a temperature in the range of 60°C to 120°C from the viewpoint of suppressing side reactions. A reaction time of 2 hours or less is sufficient, and solvents may or may not be used, but if used, solvents such as ethers, aliphatic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons may be used. Active solvents are suitable. The low molecular weight substance B of the present invention has at least one unsaturated bond in the molecule and has a molecular weight of 300% between that of a monomer and a polymer.
For example, unsaturated diene polymers such as polybutadiene, polyisoprene, and chloroprene can be mentioned.

In addition, even if the material is originally saturated, such as polyoxyalkyne or polyester, it may be used as long as it has an unsaturated group introduced therein by some means. Regarding these low molecular weight substances, copolymers and modified ones can also be used, and it is of course possible to use some of these low molecular weight substances in combination.

More detailed examples of polybutadiene that can be used include polybutadiene with a fine structure with a different ratio of 1,4 bonds to 1,2 bonds, copolymers of butadiene and styrene or acrylonitrile, etc. -0H1-COOHl- as a terminal functional group
These include low molecular weight substances such as SHL-Br, and those modified by methods such as epoxidation, maleation, half-esterification, and hydrogenation.

Furthermore, as a method of converting a saturated type into an unsaturated type, there is a method described in JP-A No. 47-21486, that is, reacting a terminal agent having an unsaturated bond at the end of the polymer. For example, a low molecular weight product of formula (3) in which propylene oxide is polymerized at low temperature and its terminal end is terminated with allyl chloride or the like can be mentioned. Inorganic fillers to which the method of the present invention can be applied include silica gel, kaolin, glass, zonotrite, asbestos alumina, etc.
It has a hydroxyl group such as H. The method for treating these inorganic fillers with the low molecular weight substance A is not particularly limited, but the following method can be used. That is, the dried inorganic filler is placed in a flask, and a dehydrated organic solvent is added thereto and stirred to disperse the inorganic filler. The low molecular weight substance A is added thereto and stirred under dry conditions to react with the hydroxyl groups on the surface of the inorganic filler. The organic solvent used here may be any solvent used in the hydrosilylation reaction. The reaction is carried out at a temperature between room temperature and the reflux temperature of the solvent, and amines can be added to neutralize the released hydrochloric acid and accelerate the reaction, as in the case of using a chloro functional group. You can also take it. After the solvent is removed by a general procedure after the reaction, it is preferable to heat the product at a temperature of about 100° C. for several hours in order to complete the condensation reaction between the hydroxyl groups on the surface of the inorganic material and the low molecular weight substance A. Regarding the amount of coating, the low molecular weight substance A used for coating
The optimum amount varies depending on the type and structure of the inorganic filler, but it is generally less than 100 parts, generally 5 to 3 parts.
Even a small amount, such as 0 parts, can sufficiently exhibit its effect.

Since most of the low molecular weight substance A is liquid, the method of the present invention is easy to process, and a large effect can be obtained with a smaller amount than when using a high molecular weight rubber such as MBS. Very cheap and highly reactive halogenated silane compounds such as methyldichlorosilane and trichlorosilane can be used, and commercially available silane couplings 11.11. Furthermore, it is possible to coat the surface of an inorganic material with a low molecular weight material through chemical bonding, which is very advantageous in terms of cost.

Furthermore, along with this treated filler, ABS. M
One of the effective points of this treatment is that by using an impact-strengthening agent such as BS, the impact strength of the composition can be improved without interfering with the impact-strengthening effect of these high molecular weight rubbers. It is.

Thermoplastic resins applicable to the present invention include polyvinyl chloride resins, polyethylene, polypropylene, polystyrene, and the like.

Furthermore, the method of blending the coated filler of the present invention with a thermoplastic resin can be carried out by mixing the thermoplastic resin and the filler of the present invention using a pen shell mixer, etc., and performing normal processing. It is also possible to blend vinyl monomers, such as vinyl chloride, styrene, acrylic monomers such as MMA, by polymerizing in the presence of a filler by polymerization methods such as bulk, suspension, and emulsification.

It is also possible to produce a foam using the resin composition thus produced as a raw material.

The filler of the present invention can be used alone or as described above, in ABS.
．． Although it can be used in combination with MBS, it is of course possible to use other fillers in combination as necessary.

Next, the method of the present invention will be illustrated in Examples.

The fluidity of the example (comparative example) of the present invention was determined by the Koka type flow (
Temperature 200℃, load 1001<g/d1 nozzle 1φXl
L) The impact strength was measured using a test piece prepared under the same conditions as the processing method shown in Example 1 using an Izot (u-notch) impact tester.

Example 1 Hydrosilylation reaction: polybutadiene homopolymer (
Manufactured by Zeon Huels, trade name Polyoil 130, M
W3, OOO) 109, 0.69 ml methyldichlorosilane and 0.70 ml chloroplatinic acid solution (9.5 x 10
-4mu/MO is added and reacted at 100°C for 1 hour with stirring.

After the reaction was completed, unreacted methyldichlorosilane was removed under reduced pressure. 2 Coating treatment: The acicular crystalline silicate zonotrite obtained by hydrothermal synthesis is dried and then crushed.
09 was dispersed in 500 ml of tetrahydrofuran.

The low molecular weight compound A synthesized in step 1 was added thereto, and stirring was continued for 60 minutes. Tetrahydrofuran was then removed using a rotary evaporator, air-dried, and further heated at 80°C for 1 hour to complete the condensation reaction, yielding a coated filler. 30 parts of this filler, 100 parts of polyvinyl chloride resin (P=1,000), 2.0 parts of tribasic lead sulfate, 1.0 part of basic stearate, 0.5 part of lead stearate, calcium stearate. A hard vinyl chloride resin molding material was obtained by kneading 0.5 parts of a processability improver and 2.0 parts of a processability improver with a roll for 5 minutes at 1800e-X.The Koka formula flow value of this molding material was 5.6X10-2? /Sec.

In addition, the Izot impact strength of a test piece made by press-molding this molding material at 190°C x 15 minutes x 50 kg/morning was 12.
．． It was 5 kg/d. Comparative Examples 1 and 2 The results of a hard vinyl chloride resin molding material prepared by kneading 30 parts of untreated Zonotlite and 10 parts of a silane coupling agent (A-1100 manufactured by Nippon Unika Ichi) treated Zonotlite according to the formulation of Example 1 are as follows. It is as follows.

The flow values and Izot impact strengths when using low molecular weight rylonitrile copolymer polybuta) and CS-15 (styrene copolymer polybuta) were as follows.

The flow value and Izod impact strength when using rice polymers (MW6, OOO and 12,000) were as follows.

*The results when adding (Kanebuchi Chemical B-22) were as follows.

*The flow value and Izot impact strength when using trite were as follows.

Asbestos (JOhns paddle Anville company 7M-0
5), the results were as follows.

Claims (1)

[Claims] 1. At least 1
Molecular weight 300-30,00 with 3 or more unsaturated bonds
A resin composition containing a thermoplastic resin and a filler formed by bonding a low molecular weight substance having a hydrolyzable silicone functional group synthesized by reacting a low molecular weight substance of 0 with 15% by weight or less of a hydrosilicon compound. .