JP2563828B2 - Reinforcing glass fiber bundle and method for producing resin body - Google Patents

Description

TECHNICAL FIELD The present invention relates to a reinforcing gasra fiber bundle and a method for producing a resin body.

[Prior Art] A glass fiber bundle is manufactured by adding and bundling a sizing agent to a large number of glass fibers pulled out from a bushing, and is widely used for reinforcing a resin.

The sizing agent is determined according to the type of resin to be reinforced.

As a sizing agent for glass fibers (strands) used to reinforce acrylonitrile-styrene resin (AS resin) and acrylonitrile-butadiene-styrene resin (ABS resin), AS resin emulsion, ABS resin emulsion or A sizing agent containing a urethane resin emulsion (hereinafter referred to as AS-based, ABS-based, urethane-based sizing agent, respectively) is known.

[Problems to be solved by the invention] A strand obtained by using an AS-based or ABS-based sizing agent is
It can be used to reinforce S-based resins and ABS-based resins, and fiber-reinforced resin bodies (FTP) with high strength can be obtained.
-Based and ABS-based sizing agents have poor sizing properties and are prone to problems such as fluffing.

Strands obtained using the urethane sizing agent,
The sizing property is good, and the above-mentioned trouble does not occur, but when this strand is used for reinforcing AS-based and ABS-based resins, there is a drawback that FTP having sufficient strength cannot be obtained.

The present inventor provides a sizing agent which, when used for reinforcement of an AS-based resin or an ABS-based resin, provides a strong FTP and has good sizing property and does not cause trouble during handling of strands. To make acrylonitrile
Styrene copolymer emulsion or acrylonitrile
Butadiene / styrene copolymer emulsion 1-10 wt%
It has been found that suitable results can be obtained by using a sizing agent for glass fibers containing 0.5 to 7 wt% of urethane emulsion and a patent application has been filed.

The present invention aims to further enhance the effects of the above-mentioned prior application.

[Means for Solving the Problems] In order to achieve the above object, in the present invention, a sizing agent containing a urethane emulsion is attached to glass fibers to form a fiber bundle, and then acrylonitrile is formed on the surface of the fiber bundle. -Production of reinforcing glass fiber bundles by adding a post-treatment liquid containing styrene copolymer emulsion (AS emulsion) or acrylonitrile-butadiene-styrene copolymer emulsion (ABS emulsion), and urethane emulsion on glass fibers A sizing agent containing is bundled to form a fiber bundle, and then a post-treatment liquid containing an acrylonitrile-styrene copolymer emulsion or an acrylonitrile-butadiene-styrene copolymer emulsion is attached to the surface of the fiber bundle, followed by cutting. , Chopped strands and ax obtained by drying Producing the resin body by kneading under heating and Ronitoriru-styrene resin or acrylonitrile-butadiene-styrene resin.

 Next, the present invention will be described more specifically.

In the present invention, as the urethane resin emulsion, those obtained by a known method of copolymerizing a polyol and a polyisocyanate can be preferably used.

In the present invention, a sizing agent containing a urethane resin emulsion (hereinafter referred to as the present sizing agent) is attached to the glass fibers pulled out from the bushing in accordance with a conventional method to form a glass fiber bundle. The content of the urethane resin emulsion in this sizing agent is suitably 0.5 to 7 wt% as a solid content.

In the present sizing agent, in addition to the above emulsion, it is preferable to further contain an epoxy resin emulsion, a coupling agent such as a silane coupling agent, and a lubricant such as a polyoxyethylene alkyl ether.

The content of the epoxy resin emulsion, the coupling agent and the lubricant in the sizing agent is 0 to 5w as a solid component.
Appropriately t%, 0.2-5 wt%, 0-1 wt% wt%.

The amount of sizing agent added is the solid content for glass fiber.
0.2 to 2 wt%, preferably 0.3 to 1.5 wt% is suitable.

A post-treatment liquid containing an AS emulsion or an ABS emulsion, preferably an AS emulsion, is added to the strand.

Appropriately, the addition is carried out in a dry state so that the water content of the strand is preferably 12 wt% or less.

In the present invention, as the AS resin emulsion, it is suitable to use the one obtained by copolymerizing acrylonitrile and styrene by a suspension polymerization method or an emulsion polymerization method, preferably an emulsion polymerization method. The weight ratio of acrylonitrile and styrene is preferably 20 to 60:80 to 40.

Further, as the ABS resin emulsion, a suspension polymerization method or emulsion polymerization method of acrylonitrile, butadiene, and styrene,
It is suitable to use those obtained by copolymerization by the emulsion polymerization method. The weight ratio of acrylonitrile and styrene is preferably 20 to 60:80 to 40.

The concentration in the post-treatment liquid is 1 to 10 wt% of the total amount of AS resin emulsion and ABS resin emulsion, preferably 3 to 8 w.
t% is appropriate.

The post-treatment liquid can be applied by using a spray or a roll coater.

The amount of post-treatment liquid added to the glass fiber as solid content
It is suitable to set it to 0.2 to 2 wt%, preferably 0.3 to 1.5 wt%.

The strand thus obtained is dried and cut into chopped strands (main CS), which is kneaded with AS resin and ABS resin under heating to obtain FTP.

The strands may be dried after the cutting step,
Alternatively, the strands may be dried and then cut.

As the AS-based resin, those obtained by polymerizing acrylonitrile and styrene by a suspension polymerization method or an emulsion polymerization method can be preferably used.

As the ABS resin, those obtained by copolymerizing acrylonitrile, butadiene and styrene by a suspension polymerization method or an emulsion polymerization method, or those obtained by melt-mixing an AS resin and a butadiene resin can be preferably used.

There is no particular limitation on the method for producing FTP using the present CS and AS resin or ABS resin, and known methods can be used.

For example, the present CS and AS-based resin or ABS-based resin are kneaded with an extruder to form pellets, and these pellets are used as a raw material and FT by injection molding method.
You can get P.

The amount of CS in FTP is 10-40wt%, preferably 20-3
It is suitable to set it to 0 wt%.

[Operation] The urethane resin emulsion contained in this sizing agent
While closely adhering to the glass fiber to cover its surface to improve the bundling property, when this CS is kneaded with the AS resin or the ABS resin under heating, it acts as a friction reducing agent, and the glass fiber at the time of kneading To prevent the shredding of FTP and contribute to the increase of FTP strength.
S resin emulsion or ABS resin emulsion covers the surface of urethane resin emulsion and serves as matrix resin.
It is considered that it strongly binds to AS-based resin or ABS-based resin and increases the strength of FTP.

[Example] A sizing agent having the following composition was added to a glass fiber having a diameter of 13 µ as a solid component in an amount of 0.3 wt% and 1,000 strands were bundled into a strand.

Sizing agent composition Urethane resin emulsion 1.5wt% Silane coupling agent 0.6wt% A post-treatment liquid containing 5.5wt% AS resin emulsion is added to this strand as a solid component at 0.7wt%, dried and cut to length. It was 3 mm CS.

20 parts by weight of this CS and 80 parts by weight of AS resin were kneaded at 250 ° C. to form pellets, and FTP test pieces by injection molding method were obtained.

The results of measuring the tensile strength of this test piece by the method of ASTM D638 and the Izod impact strength by the method of ASTM D256 are shown in the attached table.

This strand also had a good bundling property, and fluff did not occur during handling.

[Comparative Example] A sizing agent having the following composition was added to a glass fiber having a diameter of 13μ as a solid component in an amount of 1.0% by weight, 1,000 strands were bundled into a strand, dried, and cut into a length of 3 mm to obtain CS. did.

Sizing Agent Composition Urethane Resin Emulsion 1.5 wt% AS Resin Emulsion 5.5 wt% Silane Coupling Agent 0.6 wt% Using this CS, a test piece manufactured by the same method as in Example 1 was measured in the same manner as in Example. The results are shown in the attached table.

[Effects of the Invention] The strand obtained by the method of the present invention has good sizing properties, and by using this strand for reinforcement of AS-based resin and ABS-based resin, it is possible to obtain FTP with high strength.

Claims (14)

(57) [Claims] 1. A sizing agent containing a urethane emulsion is applied to glass fibers to form a fiber bundle, and the surface of the fiber bundle is then subjected to an acrylonitrile / styrene copolymer emulsion or an acrylonitrile / butadiene / styrene copolymer emulsion. A method for producing a reinforcing glass fiber bundle, which comprises adding a post-treatment liquid containing: 2. The sizing agent is, in addition to the urethane emulsion, an epoxy resin emulsion, a silane coupling agent,
The manufacturing method according to claim 1, further comprising at least one lubricant. 3. The sizing agent comprises 0.5 to 7 wt% of urethane emulsion and 0 to 5 w of epoxy resin emulsion as solid components.
t%, silane coupling agent 0.2 to 5 wt%, lubricant 0
3. The manufacturing method according to claim 2, wherein the content is 1 wt%. 4. The method according to claim 1, 2 or 3, wherein the amount of the sizing agent added is 0.2 to 2 wt% of the glass fiber as a solid content. 5. The method according to claim 1, wherein the post-treatment liquid contains 1 to 10 wt% of acrylonitrile / styrene copolymer emulsion or acrylonitrile / butadiene / styrene copolymer emulsion. 6. The production method according to claim 1, 2, 3, 4, or 5, wherein the amount of the post-treatment liquid added is 0.2 to 2 wt% of the glass fiber as a solid content. 7. The production method according to claim 1, wherein the weight ratio of acrylonitrile and styrene in the copolymer is 20 to 60:80 to 40. 8. A glass fiber is applied with a sizing agent containing a urethane emulsion to form a fiber bundle, and an acrylonitrile-styrene copolymer emulsion or an acrylonitrile-butadiene-styrene copolymer emulsion is then formed on the surface of the fiber bundle. The chopped strands obtained by adding a post-treatment liquid containing, cutting and drying the acrylonitrile-styrene resin or acrylonitrile-
A method for producing a resin body, which comprises kneading with a butadiene / styrene resin under heating. 9. The method according to claim 7, wherein the sizing agent further contains at least one of an epoxy resin emulsion, a silane coupling agent and a lubricant in addition to the urethane emulsion. 10. A sizing agent, as a solid material, comprises 0.5 to 7 wt% of urethane emulsion and 0 of epoxy resin emulsion.
10. The manufacturing method according to claim 9, wherein the silane coupling agent is contained in an amount of .about.5 wt%, the silane coupling agent is included in an amount of 0.2 to 5 wt%, and the lubricant is included in an amount of 0 to 1 wt%. 11. The production method according to claim 8, 9 or 10, wherein the amount of the sizing agent added is 0.2 to 2 wt% of the glass fiber as a solid content. 12. The production method according to claim 8, 9, 10 or 11, wherein the post-treatment liquid contains 1 to 10 wt% of an acrylonitrile-styrene copolymer emulsion or an acrylonitrile-butadiene-styrene copolymer emulsion. 13. The production method according to claim 8, 9, 10, 11 or 12, wherein the amount of the post-treatment liquid added is 0.2 to 2 wt% of the glass fiber as a solid content. 14. The weight ratio of acrylonitrile and styrene in the copolymer is from 20 to 60:80 to 40, and the weight ratio is 8,9,10,11,1.
The manufacturing method according to 2 or 13.