JPS6217048A - Sizing agent - Google Patents

Abstract

PURPOSE:To produce a plastic laminate without carrying out desizing and the secondary surface treatment by using a monofilament treated with a sizing agent contg. a film-forming agent and a lubricant such as polyethyleneimine and epoxy resin-modified silicone. CONSTITUTION:The sizing agent contains a film-forming agent and at least on kind of lubricant among polyethyleneimine, epoxy resin-modified silicone and an imidazoline surfactant. In this case, 10-40pts.wt. lubricant is preferably added to 100pts.wt. film-forming agent. At least one kind between a urethane- modified polyester resin and polyurethane resine is used as the film-forming agent. The polyethyleneimine shown by formula I and having >=1,000 polymerization degree is preferably used. The epoxy resin-modified silicone represented by formula II (x is 1-500, y is 1-500 and R is a 1-5C alkylene group) is preferably used. The imidazoline surfactant expressed by formula III (R' or R'' is alkyl or alkenyl) is preferably used.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a sizing agent for glass strands.

(Conventional technology) Glass cloth, glass thread, glass roving.

Glass fiber products such as glass chopped strand mats are generally manufactured by the following method.

A monofilament is made by melting and spinning raw materials such as clay, and a sizing agent is applied to the monofilament to satisfy ease of spinning and processability such as heating, warping, weaving, aligning, cutting, and mat forming. The required number of monofilaments coated with the agent are bundled to form a glass strand.

These strands are heated into glass threads, and the glass threads are woven into glass cloth.

Alternatively, several to dozens of water strands may be bundled together to form a glass roving. Alternatively, multiple strands are cut and formed into a sheet with a binder to form a glass chopped strand mat.

Sizing agents are essential in the production of these glass fiber products. The performance required of a sizing agent is not only excellent workability of glass strands, for example, excellent weavability in the case of glass thread, but also good heat resistance and electrical properties of synthetic resin laminates using glass fiber base materials. It is necessary to do so.

(Problems to be Solved by the Invention) However, with conventional sizing agents, it has been difficult to achieve both strand workability and properties of synthetic resin laminates, such as solder heat resistance in the case of glass threads. Therefore, this problem has been dealt with by removing the strand sizing agent by firing etc. after fiber manufacturing, and then re-treating the cloth surface with a synthetic resin and a more adhesive secondary treatment agent. There were problems such as deterioration of the glass thread due to the process, and high cost due to the need for an Ising process and a secondary treatment process.

The present invention provides a sizing agent that can solve this problem.

(Means for solving problems) The sizing agent of the present invention is a film forming agent.

Polyethyleneimine, epoxy resin modified silicone.

It contains at least one type of lubricant such as an imidazoline surfactant.

Figure 1 shows a method for producing glass strands, in which molten glass 2 flows out from multiple nozzles with platinum electrodes called bushings 3 in a trough-shaped furnace 1 (cross section) made of fireproof bricks. This results in a large number of monofilaments 4. A large number of these monofilaments coated with the sizing agent are focused by a focusing guide 8 to form a glass strand, which passes through a traversing device 9 and is wound into a winder 10.

As the film forming agent of the sizing agent of the present invention, at least one of urethane-modified polyester resin and urethane resin is used.

The urethane-modified polyester resin is a reaction product of a polyester resin having, for example, an isocyanate group at the end and a polyhydric alcohol compound having two or more hydroxyl groups, and is particularly desirable.

It is a reaction product of polyester having isocyanate end groups and polyethylene glycol (molecule 1=4000-10000>).

Preferred urethane resins are aliphatic polyurethane resins and aliphatic polyesters.

It is a reaction product of aliphatic polyether and aliphatic incyanate. Examples of aliphatic polyesters include esters of adipic acid, sepatic acid, and ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, 1.3-butanediol, trimethylolpropane, and the like. Examples of aliphatic polyethers include polypropylene glycol and polyethylene glycol. Examples of aliphatic isocyanates include hexamethylene diisocyanate. These may be used alone or in combination.

Lubricants include polyethyleneimine, epoxy-modified silicone, and imidazoline surfactants.

At least one of these is used.

The polyethyleneimine is represented by the general formula (1) and preferably has a degree of polymerization n=1000 or more.

(CH2-CH2-Nl-f) n(1) The epoxy-modified silicone is represented by the general formula (2), and includes terminal glycidoxypropyl-polydimethylsiloxane, terminal glycidoxypropyl-polymethylphenylsiloxane,
terminal glycidoxypropyl-polyphenylsiloxane,
Examples include polyglycidoxypropylmethyl-dimethylsiloxane copolymer, polyglycidoxypropylmethyl-methylphenylsiloxane copolymer, and polyglycidoxypropylmethylsiloxane.

Here x=1~500. y=1 to 500 is preferable, and R
is preferably an alkylene group having 1 to 5 carbon atoms.

The imidazoline surfactant is represented by the general formula (3) and 1
For example, 2-lauryl-hydroxyethylimidazoline,
2-Cetyl-hydroxyethylimidazoline, 2-stear 1 true hydroxyethylimidazoline, 2-oleyl-hydroxyethylimidazoline, 2-hebutadecenyl-hydroxyethylimidazoline, 2-myristyl-hydroki ) ye Diethylimidazoline, 2-oleyl-hydroxypropylimidazoline, etc. are used. R'.

R'' is preferably an alkyl group or an alkenyl group.

These may be used alone or in mixtures.

The blending amount is based on 100 parts by weight of the film forming agent.

10 to 40 parts by weight of lubricant is preferred.

In addition, coupling ml (at least one type of silane coupling agent, chromium coupling agent, titanium coupling agent, zircon coupling agent, etc.) is added in an amount of 1 to 100 parts by weight of the film forming agent. (20 parts by weight), antistatic agents (ammonium chloride, lithium chloride, etc.), and other film forming agents (epoxy resin, polyester resin, polyvinyl acetate resin, silicone resin, etc.) are added.

When sizing glass monofilaments, it is applied in an amount of 0.1 to 5% by weight based on the glass monofilaments. The monofilament treated in this way was
Approximately 1,000 strands are bundled together to form a glass strand. This glass strand.

For example, it is heated to form a glass thread, and this glass thread is woven into a glass cloth, which is used for manufacturing laminates, etc., without desizing or secondary surface treatment.

The present invention will be specifically explained below using Examples and Comparative Examples.

<Example> The sizing agents of Examples 1 to 5 listed in Appendix Table 1 were prepared, and immediately after the molten glass was pulled out as a monofilament from a bushing with 400 nozzles, each sizing agent was applied using an applicator. The glass strand was then wound into a bundle using a focusing guide to prepare a glass strand roll. Using this finger body, heat the strand with a twisting machine (number of twists: 1 twist/25mm) L thickness: 67.5t
A glass thread of eX was prepared. Next, using this glass thread, the warp density was 44 threads/25 mm, and the weft density was 33 threads/25 mm.
A glass cloth was obtained by weaving under the condition of 25 mm. Table 1 shows the results of measuring the number of surface fuzz per 177 f of glass cloth. These glass cloths were coated with epoxy resin varnish by a known method to obtain prepregs. Thereafter, eight sheets of prepreg were stacked and press-molded under conditions of a temperature of 168° C., a press pressure of 80 kg, a mold clamping time of 80 seconds, and a synthetic resin laminate having a thickness of 155 mm was produced.

A 5Qmm square specimen was cut out from this synthetic resin laminate.
The sample was placed in a steam autoclave at 21° C. for 1 hour to absorb moisture. This sample was immersed in a 260° C. solder bath for 3 minutes and changes in appearance were observed. The results are shown in Appendix 1 as solder heat resistance after moisture absorption. From the results shown in Appendix Table 1, the glass strands obtained by the manufacturing method according to the present invention have excellent workability.

It can also be seen that the synthetic resin laminate has excellent solder heat resistance after moisture absorption.

Comparative Examples> The sizing agents of Comparative Examples 1 to 4 listed in Appendix Table 1 were prepared and evaluated in the same manner as in the Examples.

Attached Table 1 shows the results of the number of surface fluff of the glass cloth and the results of the soldering heat resistance after moisture absorption treatment. It can be seen that the glass strand of the comparative example is inferior in glass cloth workability and soldering heat resistance after moisture absorption.

(Effects of the Invention) The film forming agent of the sizing agent used in the glass strand of the present invention has a high film strength.

In addition, since it is flexible, it has excellent processability of glass threads, such as weaving properties. Since the lubricant has excellent reactivity with the 2 synthetic resin, the soldering heat resistance of the laminate after moisture absorption is improved.

[Brief explanation of the drawing]

FIG. 1 is a simplified cross-sectional view showing a method of manufacturing a glass strand. Explanation of symbols 1, furnace 2, molten glass 3, bushing 4, monofilament 5, applicator 6, roller 7, sizing agent 8, focusing guide 9, traversing device 10, winder

Claims (1)

[Claims] 1. A sizing agent containing a film forming agent and at least one lubricant selected from polyethyleneimine, epoxy resin-modified silicone, and imidazoline surfactant.