JP2000072492A - Glass fiber and glass fiber reinforced thermoplastic resin using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To increase the adhesiveness of a glass fiber to a matrix resin and to improve the mechanical strength and the hot water resistance of a glass fiber reinforced thermoplastic resin by sticking a specific quantity of a sizing agent containing a toluene sulfonate to the glass fiber. SOLUTION: A sizing agent containing toluene sulfonate is applied on glass fiber. The coating weight of the toluene sulfonate is controlled to 0.01-0.5 wt.%. As the toluene sulfonate, p-toluene sulfonate is preferably used. As a coating film forming agent for the sizing agent, an urethane resin or a combination of the urethane resin and an epoxy resin can be used and if necessary, a silane based or a titanate based coupling agent, a lubricant, an anti-static agent and the like can be added. The ratio of the glass fiber to the matrix resin is suitably 2-80% and the glass fiber is desirably in a state of dried chopped strand.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a glass fiber and a glass fiber reinforced thermoplastic resin (FR) using the same as a reinforcing material.
TP).

[0002]

2. Description of the Related Art Generally, glass fibers are formed by drawing molten glass from a number of nozzles provided at the bottom of a platinum bushing, and a sizing agent is applied to the surface of each glass fiber (glass filament). Later, hundreds ~
Thousands are bundled into one strand and then wound.

[0003] In addition, the FRTP is obtained by cutting the strand obtained as described above into a predetermined length to form a chopped strand, and kneading the resulting strand with a thermoplastic resin while heating the strand.
Then, it is manufactured by molding into a predetermined shape by various molding methods.

[0004] The sizing agent comprises a film forming agent, a coupling agent, a lubricant, an antistatic agent and the like.
In the case of the glass fiber used for P, a resin molding having high strength is obtained by selecting a film-forming agent or a coupling agent that provides good adhesion to the matrix resin as a component of the sizing agent. .

[0005]

However, RRTP is
It is used in various applications, and among them, there are varieties used under high temperature and high humidity environments.
RTP is required to have excellent heat resistance and hot water resistance. That is, if the heat resistance and the hot water resistance of FRTP are poor, the strength deteriorates during long-term use under high temperature or high humidity even if the initial strength is high.

It has been known that an epoxy resin may be used as a film forming agent for a glass fiber sizing agent in order to improve the heat resistance of FRTP. In addition, since the epoxy resin contains an epoxy group (glycidyl group) having high reactivity with other groups in its molecular chain, adhesion to many matrix resins is improved, and FRTP having high mechanical strength is obtained. Is obtained.

[0007] The heat resistance of FRTP is improved as the thermal decomposition resistance of the film-forming agent is higher. However, since epoxy resin is also excellent in thermal decomposition resistance, using this as a film-forming agent increases the heat resistance. FRTP is obtained.

However, glass fibers using an epoxy resin as a film-forming agent have poor convergence. When a chopped strand is prepared from such a glass fiber and kneaded with the resin, the fiber is defibrated into fluffy balls. Easy,
There is a problem that glass fibers are clogged during the process of sending the chopped strands to the molding machine or in the molding machine, and the workability is deteriorated.

In addition to the epoxy resin, a urethane resin is used as a film forming agent, and the glass fiber using the urethane resin is excellent in convergence. The heat resistance of FRTP improves as the amount of the sizing agent attached decreases, and the urethane resin has the effect of increasing the sizing ability of the glass fiber. FRTP with good convergence and high heat resistance
There is an advantage that it becomes possible to obtain

However, glass fibers using a urethane resin are inferior in adhesiveness to a matrix resin as compared with glass fibers using an epoxy resin, so that the mechanical strength of FRTP tends to decrease and the hot water resistance also decreases. It has the problem of being easy.

The present invention has been made in view of the above circumstances. Even when a urethane resin is used as a film-forming agent, FRTP having excellent mechanical strength and hot water resistance can be obtained.
Further, even if the amount of the sizing agent is reduced, good sizing properties can be maintained, so that a glass fiber capable of obtaining FRTP having excellent heat resistance and FRTP using the same as a reinforcing material are provided. It is intended to do so.

[0012]

The present inventor has conducted various experiments to achieve the above object. As a result, the present inventors have applied a sizing agent containing a toluenesulfonate salt to glass fibers, When the salt is attached to the glass fiber,
Adhesion between glass fiber and matrix resin improves,
It has been found that when FRTP is produced using this glass fiber, the mechanical strength is improved and the hot water resistance is also improved.

Therefore, when a toluene sulfonate is contained in the sizing agent, even if a urethane resin is used as a film-forming agent, the decrease in the mechanical strength and the hot water resistance of FRTP can be suppressed and the sizing agent can be used. The present inventors have found that even if the amount of adhesion is reduced, a glass fiber having good convergence can be obtained, and thus FRTP having excellent heat resistance can be obtained, and the present invention has been proposed.

That is, the glass fiber of the present invention is characterized by being coated with a sizing agent containing a toluenesulfonate, and having an adhesion amount of the toluenesulfonate of 0.01 to 0.5% by weight.

Further, the glass fiber reinforced thermoplastic resin of the present invention is coated with a sizing agent containing a toluene sulfonate, and has an adhesion amount of the toluene sulfonate of 0.01 to 0.5.
It is characterized by using glass fiber which is% by weight as a reinforcing material.

[0016]

The glass fiber of the present invention is coated with a sizing agent containing a specific amount of toluenesulfonate, so that it has excellent adhesiveness to a matrix resin, and FRTP using this as a reinforcing material has a high mechanical strength. And hot water resistance is also improved.

Examples of the toluenesulfonate include sodium o-toluenesulfonate, sodium m-toluenesulfonate, sodium p-toluenesulfonate, lithium o-toluenesulfonate, lithium m-toluenesulfonate, p-toluenesulfonic acid. Lithium, potassium o-sulfonate, potassium m-sulfonate, and lithium p-sulfonate can be mentioned, but in view of widespread use and low cost, it is most preferable to use sodium p-toluenesulfonate.

The amount of the toluene sulfonate attached to the glass fiber is 0.01 to 0.5% by weight, preferably 0.1 to 0.5% by weight.
05 to 0.4% by weight. That is, if the content is less than 0.01% by weight, the above-mentioned effects cannot be sufficiently obtained, while the content of 0.1% by weight is insufficient.
If the content is more than 5% by weight, the effect cannot be expected to increase so much.
Not economical and not preferred.

As the film-forming agent of the sizing agent in the present invention, a urethane resin or a combination of a urethane resin and an epoxy resin can be used. If necessary, a coupling agent such as a silane or titanate compound, a lubricant , An antistatic agent and the like are added.

The matrix resin of FRTP of the present invention is not particularly limited, and may be, for example, PET resin or PBT.
Resin or other polyester resin, polyamide resin, olefin resin such as polyethylene or polypropylene, styrene resin such as AS resin or ABS resin, polycarbonate resin, thermoplastic resin such as polyacetal resin or polyphenylene sulfide (PPS) resin or polymer alloy thereof However, when a PPS resin is used, a remarkable effect can be obtained, which is preferable.

The ratio of the glass fiber to the matrix resin is suitably from 2 to 80% by weight, and the glass fiber is desirably used after the chopped strand is dried.

[0022]

The glass fiber and the glass fiber reinforced thermoplastic resin of the present invention will be described below in detail with reference to Examples and Comparative Examples.

(Example) First, 5.0% by weight of a non-yellowing urethane emulsion (solid content: 40%), 0.6% by weight of γ-aminopropyltriethoxysilane, 1.0% by weight of sodium P-toluenesulfonate And a sizing agent consisting of 93.4% by weight of deionized water.

Then, after applying this sizing agent to the surface of glass fiber having a diameter of 10 μm (organic substance adhesion amount: 0.3% by weight), 4000 glass fibers are bundled, cut into strands, and cut into 3 mm lengths to be chopped. The strands were dried. The amount of sodium p-toluenesulfonate attached to the glass fibers of the chopped strand thus obtained was 0.1% by weight.

This chopped strand 40% by weight and P
PS resin (KPS No. 21 manufactured by Kureha Chemical Industry Co., Ltd.)
4) 60% by weight was kneaded while being heated to 320 ° C., pelletized according to a conventional method, and the pellets were injection molded to produce FRTP.

Comparative Example 1 A sizing agent consisting of 5.0% by weight of a non-yellowing urethane emulsion (solid content: 40%), 0.6% by weight of γ-aminopropyltriethoxysilane, and 94.4% by weight of deionized water Was applied (0.3% by weight of organic matter attached), and FRTP was produced under the same conditions as in the example.

(Comparative Example 2) Novolak type epoxy emulsion (solid content 50%) 4.0% by weight, γ-aminopropyltriethoxysilane 0.6% by weight, deionized water 9
A sizing agent consisting of 5.4% by weight is applied (the amount of organic matter attached is 0.
3% by weight), except that FRT was performed under the same conditions as in Examples.
P was produced.

With respect to each of the thus obtained FRTPs, the tensile strength, bending strength, and heat resistance after normal and after immersion in hot water were examined, and the convergence of each chopped strand used as a reinforcing material was examined. 1 is shown.

[0029]

[Table 1]

As is clear from Table 1, when the example and the comparative example 1 were compared, both exhibited good convergence of the chopped strands and good heat resistance of the FRTP. The examples were superior in tensile strength and bending strength after immersion in hot water.

In addition, comparing Example and Comparative Example 2, both showed good values for the tensile strength, flexural strength, and heat resistance of FRTP under normal conditions and after immersion in hot water, but showed that the convergence of chopped strands was good. Was better in the examples.

The tensile strength in the table is as per ASTM D-6.
38, the flexural strength was measured based on ASTM D-790, and the tensile strength after immersion in hot water was:
After performing an autoclave treatment in which FRTP is maintained at 140 ° C. for 100 hours, the tensile strength was determined. The larger this value, the better the hot water resistance.

The heat resistance is determined by chopped strand and P
After drying the glass fiber reinforced pellets obtained by kneading with the PS resin at 130 ° C. for 10 hours to remove moisture,
It is determined by measuring the weight loss rate of the pellet after heating at 300 ° C. for 4 hours (the ratio of the weight after heating to the weight before heating). That is, the smaller the value is, the smaller the gas generation amount is, and the more excellent the heat resistance is.

Further, the convergence was evaluated by putting 3 kg of PPS resin and 2 kg of glass fiber into a tumbler, rotating them for 5 minutes, taking out fluff balls generated using a sieve, and calculating the weight of the fluff balls. And
Those with a weight of less than 10 g were regarded as good, and those with a weight of 100 g or more were regarded as poor.

[0035]

As described above, the glass fiber of the present invention can obtain FRTP excellent in mechanical strength and hot water resistance even when a urethane resin is used as a film forming agent.

Since the amount of sizing agent attached can be reduced, the heat resistance of FRTP can be improved while maintaining good sizing properties.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C08J 5/08 C08J 5/08 B29K 105: 06

Claims (2)

[Claims] 1. A sizing agent containing a toluenesulfonate is applied, and the adhesion amount of the toluenesulfonate is 0.1.
Glass fiber characterized in that the content is from 0.01 to 0.5% by weight. 2. A sizing agent containing a toluenesulfonic acid salt is applied, and the amount of the attached toluenesulfonic acid salt is 0.02.
A glass fiber reinforced thermoplastic resin comprising 1 to 0.5% by weight of glass fiber as a reinforcing material.