JPS58217531A - Production of glass-fiber reinforced polyolefin - Google Patents

Abstract

PURPOSE:To obtain the titled polyolefin capable of providing moldings excellent in strength, heat resistance, etc., by melt-blending glass fiber, which has been pretreated with a specified treating agent to improve its adhesion to polyolefins, with a polyolefin. CONSTITUTION:A treating agent is prepared by mixing a polyolefin film-forming agent (e.g., polypropylene or polybutadiene) with an organosilane compound of formula I or II (wherein R1 is a 1-10C alkoxy, acyloxy or a halogen, R2 is H or methyl and n is 0-5), e.g., vinyltriethoxysilane, and a radical reaction initiator (e.g., benzoyl peroxide or t-butyl peroxyacetate). The purpose glass fiber- reinforced polyolefin is prepared by treating glass fiber with this treating agent, and melt-blending the treated glass fiber with a polyolefin (e.g., polypropylene).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a glass fiber reinforced polyolefin, and more specifically, a method for producing a glass fiber reinforced polyolefin by melt-kneading glass fibers treated with a specific treatment agent and molten polyolefin. It is about the method.

Polyolefins have excellent physical and chemical properties that make them useful as plastics, films, fibers, and other molding materials, but their relatively flexible properties make them difficult to use as structural parts. When used in the manufacture of products that require strength, such as glass fibers, it is widely used to strengthen them with various types of fillers, such as inorganic fillers such as glass fibers, or organic fillers.

However, since polyolenoin is structurally a non-polar polymer, its adhesive strength with glass fibers is weak.

For this reason, a sufficient reinforcing effect cannot be obtained simply by mixing and melting polyolefin and glass fiber. In order to improve these defects, we synthesized a modified polyolefin in which a polar compound such as an unsaturated carboxylic acid was introduced into the polyolefin.
It is widely practiced in the art to produce glass fiber-reinforced polyolefins by mixing and melting this modified polyolefin or a mixture of modified polyolefins and unmodified polyolefins with glass fibers.

Examples of methods for producing such glass fiber-reinforced polyolefin include a graft copolymer of olefin and α,β-monoethylenically unsaturated carboxylic acid, a copolymer made of glass fiber (Japanese Patent Publication No. 15467/1983), epoxy A polyolefin obtained by graft polymerization of a vinyl compound and/or a vinylidene compound having a group and a glass fiber treated with a specific silane compound (Japanese Patent Publication No. 49
-10983), but all of the above methods require that modified polyolefin be produced in advance and then melt-mixed with glass fiber.

However, K, which modifies unmodified polyolefin, requires a separate manufacturing process, which increases the manufacturing cost of modified polyolefin. This is the current situation.

Therefore, proposals have been made to omit the manufacturing process of such modified polyolefins. For example, a method in which glass fibers treated with an aminoalkylsilane compound, an epoxy compound, and unmodified polyolefin are mixed and then injection molded (Japanese Patent Publication No. 7332/1983), a mixture of glass fibers and unmodified polyolefin is mixed with aliphatic monocarbon A method in which additives such as acids are mixed and then injection molded (Japanese Patent Publication No. 49-49029), or a method in which glass fibers having a bismaleamide acid-containing treated coating and unmodified polyolefin are injection molded (Japanese Patent Publication No. 56-14)
No. 0049) and the like have been proposed, but the reinforcing effect of glass fibers is not sufficient by any of the manufacturing methods.

Therefore, there is a strong desire in the industry to develop a method for producing glass fiber-reinforced polyolefins with excellent physical properties using unmodified polyolefins as starting materials and using simple production processes without the need to use modified polyolefins. It is rare.

In view of this situation, the inventors of the present invention have conducted extensive research and have developed glass fibers that have been subjected to specific treatments.

The inventors have discovered that when kneaded with a molten polyolefin, a glass fiber reinforced polyolefin having excellent properties can be produced even when an unmodified polyolefin is used, and the present invention has been achieved.

That is, 9 the present invention provides a method for producing glass fiber reinforced polyolefin by melt-kneading polyolefin and glass fiber, which comprises: (a) a polyolefin film forming agent; (b) the following general formula (1):
Or a method for producing a glass fiber-reinforced polyolefin, which comprises mixing and melt-kneading the organosilane compound represented by (1) and (c) glass fibers treated with a treatment agent consisting of a radical reaction initiator. .

CH2= CH-St (R1)3
(1) 2 CH2= C-C-0'-(CH2)n-5l(R1)
3 (II) 1 (In the formula, R1 represents an alkoxy/group having 1 to 10 carbon atoms, an acyloxy group, or a ).rogen atom, R2 represents a hydrogen atom or a methyl group, and n represents an integer of 0 to 5. ) Polyolefins preferably used in the present invention include ethylene, propylene, 1-butene, 3-methyl-1-butene,
Examples include homopolymers such as 3-methyl-1-pentene and 4-methyl-1-pentene, and copolymers thereof.

What is the shape and length of the glass fiber used in the present invention?

Although not particularly limited, for example, chopped strands or rovings cut into 3 wM to 6 diagonals can be used.

In the present invention, the glass fiber is the component (a).

Those treated with a processing agent consisting of component (b) and component (c) are used.

The polyolefin film forming agent used in the treatment of glass fibers in the present invention must have a polarity similar to that of the polyolefin used in the present invention. Such film-forming agents include, for example, polypropylene.

polyethylene or its copolymer, polybutadiene,
Examples include copolymers of polybutadiene and polypropylene, polyethylene, etc.

However, if necessary, the polyolefin film-forming agent may be partially introduced with carboxyl groups or the like.

The general formula (
Specific examples of the organic silane compound represented by 1) or (II) include vinyltriethoxysilane and vinyltri(methoxyethoxy)7rane.

vinyl acetoxysilane, vinyltrimethoxysilane,
Vinyltrichlorosilane, methacryloxytrimethoxysilane, γ-methacryloxyglobiltrimethoxysilane, γ-methacryloxypropyltriacetoxysilane, methacryloxytriethoxysilane, γ-methacryloxyglobiltriethoxysilane etc. can be mentioned.

Examples of the radical reaction initiator used in the treatment of glass fibers in the present invention include various organic peroxides, diazo compounds, and disulfide compounds. Most preferred. Examples of the organic peroxide include benzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5
-di(1-butylperoxy)hexane, α,α'-bis(t-butylperoxy)diisopropylbenzene.

p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-cybidroba-oxide.

Examples include t-butylperoxybenzony), t-butylperoxyacetate, t-butylperoxybenzonylate, and the like.

Further, the glass fiber treatment agent used in the present invention may contain other additives such as lubricants that are usually mixed into the treatment agent during the glass fiber spinning step. Examples of such lubricants include:

Uses surface-active compounds with normal lubrication performance
□Can. As a specific example, carbon number 12
・-18 higher fatty acid amide, polyol and carbon number 12
-18 higher fatty acid esters to which ethylene oxide has been added, polyolefin dispersions, and the like.

In order to treat glass fibers using a treatment agent consisting of the above-mentioned components, for example, a mixed aqueous dispersion of the above-mentioned components is prepared, and then the surface of the glass fibers is coated with an applicator in one spinning step according to a known method. It should be applied to. A more desirable method is first.

An aqueous dispersion containing a film-forming agent, an organosilane compound, and optionally a lubricant is prepared, used to treat glass fibers in the spinning process, and then dried at high temperature to remove water, followed by a radical reaction. The action of the radical reaction initiator can be made more effective by treating with a low boiling point organic solvent solution containing an initiator and then removing the organic solvent at a low temperature of 20 to 50°C.

As a method for making the organic peroxide aqueous, for example, after dissolving the organic peroxide in an organic solvent.

Methods include mixing water with vigorous stirring in the presence of an ionic or nonionic surfactant, or heating an organic peroxide above its melting point and then mixing water in the presence of a surfactant. can be given.

The amount of the treatment agent attached to the glass fiber is preferably 05 to 20% by weight based on the glass fiber as a solid content.

The above-mentioned (a) constituting the treatment agent for treating glass fibers
) to (c) component blending ratio is 100wt of processing agent aqueous liquid
As active ingredients per %, the polyolefin film forming agent is 1 to 20 wt%, especially 2 to 10 wt%, and the organic silane compound is 0.05 to 5 wt%, especially 01 to 2 wt%.
, the radical reaction initiator is 0.01 to 3 wt%, especially 0
．． 05-2. Preferably, it is Owt%. still.

The lubricant is 0.01 to 3 wt%, especially 005 to 1. Ow
It is desirable that it be within the range of t. Furthermore, when the treatment with the organic heptadranyl compound and the radical reaction initiator is performed in an organic solvent solution, the concentration may be within the same range as the concentration of each component in the aqueous solution of the treatment agent.

In order to produce a glass fiber reinforced polyolefin according to the present invention, it is necessary to mix the glass fibers treated with a treatment agent as described above with a molten polyolefin and melt-knead the mixture. The melt-kneading method is not particularly limited, and various known devices can be selected and used as appropriate, but a particularly preferred method is a method of melt-kneading using an extruder. The type of extruder used for this purpose is not particularly limited, but it is necessary to have a supply port in the middle of the extruder in addition to the hopper. Extrusion temperature is normal.

The temperature may be within the range of 180 to 300°C, and the residence time in the extruder is not particularly strictly limited, but is usually 9°C.

It can be carried out for a period of 0.5 to 10 minutes. Further, the residence time from the hopper to the glass supply port is not particularly limited, but it is necessary that the polyolefin is melted at the glass supply port.

After blending polyolefin and glass fiber.

In the extrusion method in which this blend is fed into a hopper, the reinforcing effect is extremely small, and it is not possible to obtain a glass fiber reinforced polyolefin with excellent physical properties.

The amount of glass fiber treated with a treatment agent is usually 5 to 60 wt based on the total weight of the glass fiber reinforced polyolefin.
% is appropriate, but as an injection molding material it is 10-40%.
wt% is appropriate.

According to the present invention, a glass fiber reinforced polyolefin with excellent mechanical properties and heat resistance is produced using a low-cost unmodified polyolefin resin without using a pre-modified modified polyolefin through a simple manufacturing process. Because it becomes possible to do so.

It is extremely valuable as an industrial manufacturing method.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Examples 1-5. Comparative examples 1 to 3 Various processing agents shown in Table 1 were taken in the proportions shown in Table 1.

An aqueous dispersion of a glass fiber treatment agent was prepared. Incidentally, various organic silane compounds shown in Table 1 and Table 2 were used as the organic silane compounds.

Table 1 Glass fibers with a fiber diameter of 13 μm were spun using the above treatment agent, and 800 glass fiber strands were wound into a cake and dried at 130° C. for 10 hours.

Separately, an acetone solution of 1.0 wt % benzoyl peroxide was prepared, filled in a container equipped with a rotating vine roller, and covered with a top lid to prevent the acetone from scattering as much as possible.

Next, the strands are continuously pulled out from inside the dried glass fiber cake and introduced into the acetone solution.
After passing the strand while it is in even contact with the top of the rotating roller.

The glass fiber strand was wound up into a paper tube, and the inside of the glass fiber strand was sufficiently impregnated with benzoyl peroxide. After drying the strands after the above treatment at 40C for 16 hours, use a cutter to
The strands were cut into two lengths to obtain chopped strands.

Using this chopped strut, a glass fiber reinforced polyolefin was produced using an extruder shown in FIG. That is, unmodified polypropylene (Ube Industries J-109
G) 7 is fed from the hopper 1 of a vent-type extruder with a scree diameter of 30 mm and a vent 3, and the chopped strands 8 are separately fed from the glass fiber feed port 2 provided in the middle of the extruder. It was continuously supplied using the supply feeder 4, extruded, and chipped. Extrusion conditions were as follows: The cylinder temperature was 40°C, the screw 5 was rotating at 1100 rpm, the residence time from hopper 1 to nozzle 6 was approximately 1 minute, and the residence time from glass fiber supply port 2 to nozzle 6 was 45 seconds. there were. The glass fiber content is based on the total amount.
The rotation speed of the supply feeder 4 was adjusted so that it was 20wj%.

Using the obtained chips, test pieces were molded using a 35-ounce screw injection molding machine, and various physical properties were measured.

The measurement results are shown in Table 2.

/ / / / Examples 6-10 Various processing agents shown in Table 3 were used in the proportions shown in Table 3.

An aqueous dispersion of a glass fiber treatment agent was prepared.

Glass fibers having a fiber diameter of 13 μm were spun using the above treatment agent, and 800 glass fiber strands were wound into a cake and dried at 130° C. for 10 hours.

Separately, 1 wt % acetone solutions of each of the various organic silane compounds shown in Table 4 and dicumyl peroxide were prepared.

After processing into strands as in Example 1 and drying.

It was cut into a length of 3.2 WM to obtain chopped strands.

This chopped strand was extruded under the same conditions as in Example 1 to form chips. A test piece was formed using this chip, and various physical properties were measured.

The results are shown in Table 2.

In the case where the organosilane compound having a specific structure used in the treatment of glass fibers in the present invention is coated by post-treatment (although it can be coated with Glass fiber reinforced polypropylene with good physical properties could be produced.

/ 7・・'7・7' 7/ / / / Comparative Examples 4 to 6 Except for using a polyvinyl acetate aqueous dispersion, a polyurethane aqueous dispersion, and an acrylic ester aqueous dispersion instead of a polypropylene aqueous dispersion. An aqueous dispersion having the same composition as in Example 3 was prepared and used for spinning to produce glass fiber strands.

This strand was treated with benzoyl peroxide in the same manner as in Example 3, dried, and then cut to obtain chopped strands. This was kneaded with polypropylene under the same extrusion conditions as in Example 1 to form chips.

Table 5 shows the physical properties of a test piece molded using this chip.

When an aqueous polyvinyl acetate dispersion, an aqueous polyurethane dispersion, and an aqueous acrylic ester dispersion were used as the film forming agent, the physical property values were much lower than those of Example 3.

Comparative Examples 7-11 Various chopped strands 2 made in Examples 1-5
0 wt% mixed with 80 wt% polypropylene.

Evenly dispersed. Next, this mixture was put into the hopper of the same extruder as in Examples 1 to 5, the glass supply port in the middle of the extruder was sealed, and the cylinder temperature was 240°C.

It was extruded and chipped at a screw rotation speed of 1100 rpm.

Table 6 shows the physical properties of a test piece molded using this chip.

As shown in Table 6, even if chopped strands treated with the special treatment agent used in the present invention are used, the mixture of chopped strands and polypropylene is simultaneously fed into the hopper of the extruder.

The physical properties of the glass fiber reinforced polypropylene were extremely low compared to Example 1'.

Example 11 Chopped strands treated in the same manner as in Example 8 were kneaded with high-density polyethylene (melt index 7.5) under the same extrusion conditions as in Example 8 to form chips.

Table 7 shows the physical properties of a test piece molded using this chip.

As shown in Table 7, the physical properties of the 1-reinforced polyethylene were also significantly improved compared to Comparative Example 12.13 (described later).

Comparative Example 12 Chopped strands subjected to the same treatment as in Example 8 except for using an aqueous polyvinyl acetate dispersion as a film forming agent were kneaded with high-density polyethylene under the same extrusion conditions as in Example 8, Made into chips.

Table 7 shows the physical properties of a test piece molded using this chip.

When polyvinyl acetate was used as the film-forming agent, physical property values were also lower than in Example 11 in the case of reinforced polyethylene.

Comparative Example 13 Polyethylene and glass fiber were extruded and chipped under the same conditions as Example 8, except that instead of feeding polyethylene and glass fiber into the extruder separately, they were fed simultaneously from the rear hopper of the extruder. went.

A test piece was molded using the obtained chip, and its physical properties were measured.

The results are shown in Table 7.

In the case of polyethylene, the mixture with glass fiber is simultaneously fed into the hopper of the extruder.

The physical properties of the glass fiber reinforced polyethylene were extremely low compared to Example 11.

Table 7

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a sectional view of an extruder used for producing the glass fiber reinforced polyolefin of the present invention. 1 is hopper, 2 is glass fiber supply port, 3 is ventro,
4 is a feeder, 5 is a screw, 6 is a nozzle, 7 is a polyolefin, and 8 is a glass fiber. Patent applicant Unitika Co., Ltd.

Claims (1)

[Claims] (]) A method for producing a glass fiber reinforced polyolefin by melt-kneading a polyolefin and glass fibers, comprising: a molten polyolefin; (a) a polyolefin film forming agent; (b) the following general formula (υ): or (11) and (c) the production of a glass fiber-reinforced polyolefin, which is characterized by mixing and melt-kneading glass fibers treated with a treatment agent consisting of a radical reaction initiator. Method. CH2= CH-Si (R1)3
(1)2 CH2= C-C-0-(CH2)n-5t(Rh)3
(1) (In the formula, R1 is an alkoxy group having 1 to 1 o carbon atoms. An acyloxy group or a halogen atom, R2 is a hydrogen atom or a methyl group, and n is an integer of 0 to 5.)