JP2563033B2 - Manufacturing method of composite resin - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a composite resin. More specifically, it relates to a polyolefin-based composite resin having excellent mechanical properties (restoration ability, impact resistance, etc.), paintability, and adhesiveness.

[0002]

2. Description of the Related Art Polyolefin resins have excellent workability,
Since it is inexpensive, it is used as an industrial raw material for various molded products. However, they often have drawbacks such as impact resistance, paintability, and inferior adhesiveness as seen in polypropylene, for example. As a method for producing a composite resin for improving this, a method of mixing a polypropylene resin and a resin obtained by polymerizing an aromatic vinyl compound or the like in the presence of rubber (for example, JP-A-64-11147) and A method of reacting an isocyanate group-containing compound with a hydroxyl group-containing compound in the presence of a thermoplastic resin such as a polyolefin resin (for example, Japanese Patent Application No. 3-180396) is known.

[0003]

However, the method of mixing a polypropylene resin and a resin obtained by polymerizing an aromatic vinyl compound in the presence of rubber is not stable because the dispersion system is unstable. The restoration ability and impact resistance are not sufficiently satisfied. In terms of production, both the polymerization of the monomer in the presence of rubber and the mixing of the obtained resin and the polypropylene resin must be performed, which is complicated. Further, a composite resin obtained by polymerizing a polyurethane resin in the presence of a polyolefin resin has a problem that a sufficient dispersion is not obtained although a good dispersion system is obtained.

[0004]

The inventor of the present invention has reached the present invention as a result of extensive studies to solve these problems. That is, the present invention relates to polyolefin resin (1) 1
20 to 1000 parts by weight of a rubbery copolymer (2) containing 00 parts by weight and a styrene compound as a copolymerization component, and 1 selected from the group consisting of a styrene compound, (meth) acrylonitrile and vinyl group-containing carboxylic acids.
Polymerization of (3) in a mixture with 50 to 1000 parts by weight of one or more radically polymerizable monomers (3) in a state where (1) and (2) are melted or dissolved or dispersed in (3). , A non-reacted (3) is removed by continuously sending the polymerization product to a demonomer tank equipped with an exhaust device and / or a vacuum device, in a strong mixing zone of a mixer. It is a manufacturing method.

Specific examples of the polyolefin resin (1) used in the production method of the present invention include polyethylene resins [high density polyethylene, medium density polyethylene, low density polyethylene, ethylene and one or more other vinyl compounds (for example, α-olefin, vinyl acetate, methacrylic acid, acrylic acid, etc.), polypropylene resin [polypropylene, copolymer of propylene and one or more other vinyl compounds, etc.], polybutene, poly -4
-Polyolefins such as methylpentene-1, oligomers or elastomers thereof, and blends of two or more of these. Of these, preferred are polyethylene resins and polypropylene resins. The number average molecular weight is usually 700 to 500000, preferably 1000.
~ 200,000.

A rubbery copolymer containing a styrene compound used as a copolymerization component in the production method of the present invention (2)
Examples thereof include a copolymer composed of a styrene compound and a conjugated diene and / or a partially hydrogenated product thereof, and the like.

Styrene compounds include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, ethylstyrene and divinyl. Benzene, N,
Examples thereof include N-diethylaminostyrene, and of these, preferred are styrene and α-methylstyrene.

As the conjugated diene, butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene,
Examples include 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene, and the like, and among these, butadiene and isoprene are preferable.

The content of the styrene compound in the rubbery copolymer (2) used in the production method of the present invention is usually 5 to 90% by weight, preferably 10 to 85% by weight. If it is less than 5% by weight, the compatibility with the polymer of the radically polymerizable monomer (3) will decrease, and if it exceeds 90% by weight, the compatibility with the polyolefin resin (1) will decrease and sufficient physical properties will be obtained. Can't get

As the copolymer structure of the rubbery copolymer (2) used in the production method of the present invention, a block copolymer, a random copolymer or a mixture thereof can be mentioned. Among these, a block copolymer is preferable.

Among the radically polymerizable monomers (3) used in the production method of the present invention, examples of the styrene compound include the styrene compounds described above in the section of the rubbery polymer. Examples of vinyl group-containing carboxylic acids include vinyl group-containing carboxylic acids [(meth) acrylic acid, maleic anhydride, fumaric acid, itaconic acid, etc.], (meth) acrylic acid esters [C1-18 aliphatic hydrocarbons (for example, methyl). , Ethyl, propyl, hydroxyethyl, glycidyl, etc.), C6-12 alicyclic hydrocarbons (eg cyclohexyl, dicyclohexyl etc.), C6-20 aromatic hydrocarbons (eg phenyl, naphthyl, p-methylphenyl),
(Meth) acrylic acid esters such as C7-21 araliphatic hydrocarbons (such as benzyl), and imidized products of vinyl group-containing dicarboxylic acids [maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide] Etc.] etc. can be mentioned. Of these, the preferred one is
It is a styrene compound. The content of the styrene compound in the radical-polymerizable monomer is usually 30% by weight or more, preferably 50% by weight or more in order to further improve the compatibility with (2).

Used in the production method of the present invention (1), (2),
The weight ratio of (3) is usually (1) :( 2) :( 3) = 100: (20 to 1000) :( 20
~ 1000), preferably 100: (50-200) :( 50-500).
If (2) or (3) is less than 20 or more than 1000, a sufficient modifying effect cannot be obtained, resulting in deterioration of physical properties.

When polymerizing the radical polymerizable monomer, a known radical polymerization initiator or an organic solvent may be used if necessary.

The polymerization temperature is not particularly limited as long as it is a temperature at which the radically polymerizable monomer is substantially polymerized, but is usually 80 to 260 ° C.

The polymerization time can be controlled by the residence time of the radically polymerizable monomer in the intensive mixing zone, and is usually 10 seconds to 60 minutes.

In the production method of the present invention, (1), (2) and (3) are supplied to the intensive mixing zone in such a manner that (1) and (2) are melted or (3)
There is no particular limitation as long as it can be maintained in a dissolved or dispersed state. To melt or dissolve or disperse (1) and (2) in (3), a known melter, dissolver or disperser can be used, and heat treatment is performed to accelerate melting and dissolution. It doesn't matter.

In the process of the present invention, the polymerization is carried out in a strong mixing zone, but the type and shape of the mixing zone are not limited as long as the resin has the ability to mix the molten resin. For example, a highly compressible screw having a reverse thread portion, a mixing zone having a ribbon-shaped stirring blade, or the like can be used.

The method of removing the unreacted (3) in the production method of the present invention is to carry out polymerization in a strong mixing zone, and then send it to a weak mixing zone as compared with this strong mixing zone, under normal pressure or reduced pressure conditions. Can be done by
The weak mixing zone can be set by the screw, the shape of the stirring blade, and the increase of the volume of the mixing zone. Unreacted
The removal of (3) can be performed by attaching an exhaust device and / or a vacuum device to the weak mixing zone.

In the production method of the present invention, the mixer is a mixer having an area having an intense mixing section and a mixer having a mixing area which is continuously weak compared to the intense mixing section and which can remove unreacted radically polymerizable monomers. If so, there is no particular limitation.
Specific examples include a kneader, a Banbury mixer or a high-viscosity reaction tank directly connected to a demonomerization tank provided with an exhaust device and / or a vacuum device, and a single-screw or twin-screw extruder. Among these, a single-screw or twin-screw screw type extruder is preferable in terms of economy and mixing ability.

In the production method of the present invention, it is possible to add a reinforcing agent such as calcium carbonate, silica, clay or glass fiber to the extent that the properties of the composite resin are not impaired. As other additives, for example, an antioxidant, a heat stabilizer, an ultraviolet absorber, a coloring agent, a lubricant, a flame retardant, a pigment and the like can be added.

[0021]

The present invention will be further described with reference to the following examples, but the present invention is not limited thereto. In the following description, part means part by weight. Examples 1 to 7 and Comparative Examples 1 and 2 Barrel temperatures of 145-2
A composite resin was obtained by feeding the mixture at 50 ° C. to a twin-screw extruder having a reverse screw type screw in front of a vacuum vent while keeping the residence time at least 2 minutes.

[0022]

[Table 1]

Note: DCP; dicumyl peroxide SBS; styrene butadiene block copolymer (TR2000 made by Japan Synthetic Rubber) SEBS; hydrogenated SBS (H1051 made by Asahi Kasei) PP-1; polypropylene (J609H made by Ube Industries) PP-2 Polypropylene (RJ385 manufactured by Ube Industries) Resin A; polystyrene resin with a number average molecular weight of 8000 Resin B; 40 parts of styrene, 20 parts of SBS (TR2000) and 0.8 part of DCP were polymerized by a twin-screw extruder to obtain a resin. The physical properties of the composite resin are shown in Table 2 below.

[0024]

[Table 2]

* 1: Breaking during bending Tensile strength and tensile elongation at break; Conforms to JIS-K6301 Restoring force: A flat plate with a thickness of 3 mm, a width of 150 mm and a length of 90 mm is bent 180 degrees at the center in the horizontal direction and held for 10 seconds. The angle from the horizontal plane after 10 minutes is shown after restoration. (0 degree indicates a completely restored state) Paintability: Urethane for PP (two-component) type After coating, a cross-cut test is performed to show the number of 100 pieces that did not come off.

[0026]

The composite resin obtained by the production method of the present invention has a stable dispersion system due to the grafting effect of polyolefin as compared with the conventional resin composition and the simply mixed composite resin, and has excellent mechanical strength. Since it shows recovery ability, paintability, etc., it can be applied to various molded products and can be used in various applications such as polyolefin and styrene thermoplastic resin.

Claims (5)

(57) [Claims] 1. Polyolefin resin (1) 100 weight
20 to 1000 parts by weight of a rubbery copolymer (2) containing 1 part and a styrene compound as a copolymerization component, and one selected from the group consisting of styrene compounds, (meth) acrylonitrile and vinyl group-containing carboxylic acids. In a mixture with 50 to 1000 parts by weight of the above radical-polymerizable monomer (3), the polymerization of (3) is carried out in a state where (1) and (2) are melted or dissolved or dispersed in (3), Perform in the intensive mixing zone of the mixer, then continuously vent the polymerization products.
A process for producing a composite resin, characterized in that the unreacted (3) is removed by sending it to a demonomerization tank equipped with a storage and / or vacuum device . 2. A polyolefin resin (1) and a stylus.
Rubbery Copolymer Containing Ren Compound as Copolymerization Component
Body (2), styrene compound, (meth) acrylonite
Selected from the group consisting of carboxylic acids containing ryl and vinyl groups
One or more kinds of radically polymerizable monomers (3) parts by weight
The mixture of (1) and (2) is melted or dissolved in (3).
Reverse-screw type before decompression vent, in solution or dispersed state
Installed on a single-screw or twin-screw extruder with a screw section
Then, while performing strong mixing with the reverse screw type screw part,
To remove unreacted (3) continuously in the vent part
Characteristic composite resin manufacturing method. 3. (1) is a polypropylene resin and /
Alternatively, the method according to claim 1 or 2, which is a polyethylene resin. 4. The (2) is one or more copolymers selected from the group consisting of a copolymer with butadiene, a copolymer with isoprene and a partial hydrogenated product thereof, and a copolymerization component. The method according to any one of claims 1 to 3, which is a rubbery copolymer containing 5 to 90% by weight of a styrene compound. 5. The method according to claim 1, wherein (3) is a radical-polymerizable monomer containing 30% by weight or more of styrene.