JPS584046B2 - Method for producing thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a thermoplastic resin composition, and more particularly to a method for producing a thermoplastic resin composition with excellent dyeability, paintability, adhesiveness, etc.

Conventionally, it has been known that dyeability, paintability, adhesiveness, and compatibility with other polymers can be improved by adding unsaturated acids to thermoplastic resins such as polypropylene using peroxides.

However, in the conventional method, sufficient effects could not be obtained because the amount of unsaturated acid added was very small.

An object of the present invention is to provide a method for producing a thermoplastic resin to which a large amount of unsaturated acids is added.

The present inventors have conducted extensive research to develop a method for adding a large amount of unsaturated acids to thermoplastic resins, particularly polystyrene, ethylene-vinyl acetate copolymer, polyethylene terephthalate, etc., and have found that by adding rubber. It was discovered that a thermoplastic resin to which a large amount of unsaturated acids were added could be obtained by the reaction, and the present invention was completed.

0.1 to 20 parts by weight of rubber and 0.1 to 80 parts by weight of unsaturated acids per 100 parts by weight of one type of thermoplastic resin selected from the group consisting of polystyrene, ethylene-vinyl acetate copolymer, polyethylene terephthalate, and polycarbonate.
The present invention provides a method for producing a thermoplastic resin composition, characterized in that the thermoplastic resin composition is added and reacted in the proportion of parts by weight.

Thermoplastic resins that can be used in the method of the present invention exclude polyolefin resins such as polyethylene and polypropylene, which have already been studied, and specifically include the above four types of thermoplastic resins.

Next, the unsaturated acids used in the method of the present invention are acids having unsaturated bonds, their anhydrides, metal salts, amides, imides,
Acids with unsaturated bonds include maleic acid, citraconic acid, crotonic acid, itaconic acid,
Acrylic acid, sorbic acid, mesaconic acid, angelic acid,
Examples include methacrylic acid.

Furthermore, rubber, which is one of the raw materials in the method of the present invention, is
Based on their properties, rubber can be divided into liquid rubber and solid rubber.

Here, the liquid rubber is a polymer having a number average molecular weight of 500 to 10,000 and having a diene monomer as a main component, and preferably exhibits fluidity at room temperature.

Examples of such liquid rubber include carboxyl groups, hydroxyl groups, mercapto groups, halogen atoms, amino groups,
1,2 with functional groups such as aziridino group and epoxy group
- Liquid rubbers such as polybutadiene, 1,4-polybutadiene, polyisoprene, polychloroprene, styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, butadiene-isoprene copolymers, phtadiene-pentadiene copolymers, and terminal hydroxylated 1,2 - Unsaturated dicarboxylic acid half esters such as polybutadiene, 1,4-polybutadiene, or 1 with a number average molecular weight of 500 to 10,000 without functional groups
, 2-polybutadiene, 1,4-polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, thermally decomposed rubber, ozone decomposed rubber, and mixtures of the liquid rubbers listed above.

On the other hand, the solid rubber is not particularly limited, but is usually 1,2-polybutadiene, 1,4-po,butadiene, polyisoprene, polychloroprene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, or a mixture thereof. Suitably used.

Furthermore, these rubbers contain carboxyl groups, hydroxyl groups, mercap. group, amine group, aziridine group, epoxy group,
It may have a functional group such as a halogen atom.

The reaction conditions when carrying out the method of the present invention may be selected appropriately taking into consideration the properties of the above-mentioned raw materials used, but generally the reaction temperature is 60 to 300°C, and the reaction time is determined by using a solvent or If a medium is not used, each raw material may be kneaded using a Banbury mixer, screw extruder, continuous kneader, etc. for 2 to 30 minutes; if a solvent or medium is used, each raw material is mixed and kneaded for 30 minutes. Do this for ~15 hours.

Regarding the blending amount of each raw material, thermoplastic resin 100
0.1 to 20 parts by weight of rubber, preferably 1 part by weight
~10 parts by weight, and unsaturated acids are 0.1 to 80 parts by weight,
Preferably it is 1 to 50 parts by weight.

Rubber contributes to the introduction of a large amount of unsaturated acids into the thermoplastic resin, and adding less than 0.1 part by weight will not provide a sufficient effect, and adding more than 20 parts by weight will result in poor thermoplasticity. The heat resistance of the resin composition decreases, and the appearance also deteriorates.

If the amount of unsaturated acids added is less than 0.1 part by weight, the amount added is too small to sufficiently modify the thermoplastic resin.

Further, even if more than 80 parts by weight is added, the properties of the composition will not improve in proportion to the amount used.

In carrying out the method of the present invention, a radical generator may be added in addition to the above-mentioned raw materials, or the process may be carried out in the presence of a suitable solvent or medium.

In addition, ultraviolet absorbers, antioxidants, inorganic fillers, etc. can be added as necessary.

The radical generator is not particularly limited as long as it promotes the reaction with thermoplastic resins, rubbers, and unsaturated acids, but examples include penzoyl peroxide, lauroyl peroxide, dicumyl peroxide, α, α′- Bis(t-butylperoxydiisopropyl)benzene, 2
,5-dimethyl-2,5-di(1-butylperoxy)
Examples include organic peroxides such as hexane, di-t-butyl peroxide, cumene hydroperoxide, and t-butyl hydroperoxide, azobis compounds such as azobisisobutyronitrile, and thiuram disulfide.

The radical generator is 2 parts per 100 parts by weight of the thermoplastic resin.
It is added in an amount of 0 parts by weight or less, usually 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight.

The solvent may be any solvent that has the effect of swelling and dissolving the thermoplastic resin, such as xylene, toluene,
Hydrocarbons such as tetralin, decalin, and heptane, and halogenated hydrocarbons such as monochlorobenzene and dichlorobenzene can be used.

Further, the medium is preferably one that does not dissolve the thermoplastic resin but merely disperses it.

The amount of solvent or medium is 5000 parts by weight per 100 parts by weight of thermoplastic resin.
It can be used within a range of up to parts by weight considering operational convenience.

Further, as for the ultraviolet absorber, any known substance can be used, such as 2(2'-hydroxy-5'-methylphenyl)pensotriazole, 2(2'-hydroxy-3',5'-di-t-butylphenyl) ) Penzotriazole UV absorbers such as benzotriazole, 2-
Penzophenone ultraviolet absorbers such as hydroxy-4-methoxypenzophenone and 2-hydroxy-4-octoxybenzophenone, phenyl salicylate, 4-t
Examples include phenyl salicylate ultraviolet absorbers such as butylphenyl salicylate.

The antioxidant is used to impart heat resistance, and examples thereof include aromatic amines such as phenyl-β-naphthylamine, hydroquinone, and aldehyde amine condensates.

These ultraviolet absorbers and antioxidants are used in an amount of 100 parts by weight or less per 100 parts by weight of rubber.

Furthermore, as inorganic fillers, calcium carbonate, talc,
Examples include clay, alumina, zinc white, magnesium oxide, diatomite, mica, calcium sulfite, calcium sulfate, calcium silicate, glass powder, glass fiber, asbestos, gypsum fiber, and mixtures thereof.

The inorganic filler has an average particle size of 10 μm or less, and is used in an amount of 500 parts by weight or less per 100 parts by weight of the thermoplastic resin. Especially when a solvent or medium is not used, it may be used as appropriate in consideration of moldability, etc. It is preferable to add.

According to the method of the present invention, it is possible to add 1 to 80% by weight of unsaturated acids to the thermoplastic resin excluding polyolefin resins, and it is possible to produce a thermoplastic resin composition with a high amount of acid addition. can.

However, in normal applications, the amount of acid added may be about 1 to 20% by weight, which not only improves properties such as paintability and adhesion, but also provides a resin composition with high compatibility with other polymers. It will be done.

Examples of the present invention will be shown next, but the present invention is not limited thereto.

Example 1 Terminal hydroxylation 1,4 for thermoplastic resin 45f
-Polybutadiene (number average molecular weight 3000, trade name:
Poly Bd R 4 5 HT , ARCO
Chem. Div), 9 g of unsaturated acid, and 300 d of xylene as a solvent were dissolved by heating and stirring in a 500 ml reactor, and 0.0 g of dicumyl peroxide was added.
9 g was added and refluxed for 2 hours.

After the reaction is completed, it is cooled and reprecipitated in a large excess of methanol.
The unreacted unsaturated acid was removed by washing to obtain a white powdery resin composition.

The results of determining the amount of acid added to the resin composition by the titration method were
Shown in the table.

Comparative Example 1 No terminal hydroxylated 1,4-polybutadiene was added,
Table 1 shows the results of the same operations as in Example 1.

Example 2 15 g of polycarbonate (molecular weight 30,000, manufactured by Idemitsu Petrochemical Co., Ltd.), terminal hydroxylated 1,4-polybutadiene (number average molecular weight 3000, trade name: Pol)
y Bd R 4 5 HT , ARCO Chem
Div) 0.75 g, maleic anhydride 3 g and chlorobenzene 300 ml were heated and dissolved in a 500 ml reactor, and 0.3 L of dicumyl peroxide was dissolved. After adding and reacting for 2 hours, the same operations as in Example 1 were carried out to obtain 16 g of a white powdery resin composition.

The amount of acid addition between this resin composition and a resin obtained by performing the same operation as above without adding polybutadiene was measured using an IR absorption spectrum (characteristic peak of maleic anhydride 1 8 6 0
When compared in terms of cm, the amount of acid added to the resin composition obtained by the method of the present invention was about twice as much.

Example 3 In the GPPS and maleic anhydride system of Example 1, S was used instead of terminal hydroxylated 1,4-polybutadiene.
BS (MI = 6.0, Product name: Cauliflex Tg1
102 (manufactured by Shell Chemical Co., Ltd.)), the resulting resin composition had an acid value of 37. 8 mg・
KOH/g, acid addition amount was 3.3 wt%.

In addition, if SBS was not added, the acid value was 9.9■K.
OH/g and acid addition amount was 0.9 wt%.

Example 4 45 g of HIPS from Example 1, terminal hydroxylation 1,4
- 2.25 g of polybutadiene and 9 g of maleic anhydride
were kneaded at 180°C for 15 minutes to obtain a resin composition.

The acid value of this resin composition was 41.4 mg·KOH/g, and the amount of acid added was 3.6 wt%.

As a result of performing the same operation as above without using terminal hydroxylated 1,4-polybutadiene, the acid value of the resulting resin composition was 8.7 ■KOH/g, and the amount of acid added was 0.8 wt.
%Met.

Claims (1)

[Scope of Claims] 1. 0.1 to 20 parts by weight of rubber and 100 parts by weight of one thermoplastic resin selected from the group consisting of polystyrene, ethylene-vinyl acetate copolymer, polyethylene terephthalenite, and polycarbonate. Saturated acids 0.1~
A method for producing a thermoplastic resin composition, which comprises adding 80 parts by weight and reacting the composition. 2. The manufacturing method according to claim 1, wherein the reaction temperature is 60 to 300°C.