JP3440428B2 - Glass cloth and manufacturing method thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fray-preventing glass cloth for use in printed wiring boards and a method for manufacturing the glass cloth. More specifically, the present invention uses a novel specific polyamide resin anti-fray agent to prevent fraying of the cut end of a glass cloth woven by various types of looms, in particular, a fragmented loom such as an air jet loom (prevention of ear fraying). The present invention relates to a glass cloth and a method for producing a glass cloth using a solvent solution in which the anti-fray agent is adjusted to a specific viscosity. Furthermore, the novel anti-fraying agent for glass cloth of the present invention is characterized in that it is a specific water-soluble or water-dispersible polyamide resin.

[0002]

2. Description of the Related Art In recent years, for weaving glass cloth, a fragment loom such as an air jet loom has become mainstream instead of a cored loom such as a fly shuttle loom. In the glass cloth woven by the fragment loom, the wefts are individually driven with a constant length and cut into a little longer than the width of the cloth,
It has the characteristic that "the ears" remain in both ears. When the glass cloth having such tufts is used as it is in the step of impregnating the varnish such as epoxy resin, the tufts excessively impregnate the varnish or the cut glass fibers adhere to the surface of the prepreg. However, this will cause problems in terms of quality.

On the other hand, in the case of removing such tufts or in the case of dividing into two pieces or three pieces in order to obtain an arbitrary width not only in the fragment weaving machine but also in the glass cloth woven by the corrugated weaving machine, the anti-raveling treatment is performed. If you use it for the varnish impregnation process by simply mechanically cutting it without applying the glass varnish, the warp of the glass cloth will be easily frayed and it will wind around the roll, which will cause a great loss such as the need to stop the production line or take measures. Occurs. Therefore, in order to prevent the above-mentioned fraying,
The following methods have been studied.

That is, an attempt was made to cut the glass yarn while melting and adhering the glass yarn with the laser beam at the tufted portion or the ground portion of the glass cloth. However, its adhesive strength is weak, and there are drawbacks such as easy peeling of the adhesive part even with a slight squeezing, and minute molten balls at the end of the glass yarn that are formed during melting and dropping into the varnish. Has not reached.

Attempts have also been made to use thermosetting resins such as epoxy-based or phenol-based resins (JP-A-4-19110, JP-A-6-2277).
JP-A-5-222676, JP-A-6-19296
No. 5, etc.). However, even though glass cloth has a relatively high resistance to solvents such as methyl ethyl ketone, methyl cellosolve, toluene, hexane, acetone, and dimethylformamide contained in varnishes such as epoxy resin, it does not harden until it is cured after being applied to the glass cloth. It takes a considerable amount of time, and there are problems in terms of equipment and productivity.

Attempts have been made to use thermoplastic resins such as polyethylene terephthalate, polybutylene terephthalate, polyphenylene ether, and ethylene-vinyl acetate copolymer. Among them, conventionally used ethylene-vinyl acetate copolymers and the like have insufficient solvent resistance and are not preferable for use in printed wiring board applications.

Attempts have also been made to use a solution of polyethylene terephthalate or the like in a halogenated lower hydrocarbon solvent such as methylene chloride or chloroform (Japanese Patent Laid-Open Nos. 59-15563 and 60). -194182, JP-A-63-31567
4, JP-A-63-85158, JP-A-2-
No. 216277, JP-A-5-321153,
JP-A-6-57665 and JP-A-6-200480.
No. This method can almost solve the problems in prepreg production, but as is well known, solvents such as methylene chloride are unfavorable solvents in the working environment.
The biggest issue is environmental measures.

That is, it is necessary to make a closed system for all steps of solution preparation, storage, coating, and drying, which results in a large capital investment and an increase in the manufacturing cost of glass cloth.
There are still problems to be solved. Moreover, the use of such an organic solvent is not preferable in terms of environmental protection.

[0009]

DISCLOSURE OF THE INVENTION The present invention solves the problems of the prior art as described above and, in addition, it is preferable in terms of environmental hygiene and is a specific fray which is useful for producing a high quality prepreg. An object of the present invention is to provide a glass cloth which has been subjected to anti-raveling with an inhibitor and a method for producing a glass cloth which is carried out using a solvent solution in which the anti-raveling agent is adjusted to a specific viscosity.

[0010]

Means for Solving the Problems The present inventors have
As a result of diligent research to solve the problem,
Especially as an anti-fraying agent for stumpsspecificWater soluble or water
We found that dispersible polyamide resins are effective
The invention was completed. That is, the present invention is:
As an inhibitorPoly (obtained by ring-opening polymerization of lactam)
Graft polymerization of hydrophilic monomer on amide resinWater soluble
Of water-dispersible or polyamide resin with glass cloth ears
Of the anti-fray agent applied to a certain width
Width lefthandProviding glass cloth characterized by being cut
To do. Also,   Both ears of glass cloth or inside
As an anti-raveling agentObtained by ring-opening polymerization of lactam
Polymerization of Hydrophilic Monomer on Polyamide Resin
Let300c of water-soluble or water-dispersible polyamide resin
After diluting with a solvent to a viscosity of ps or less and applying and drying
The anti-fray agent on both ears, leaving a certain width
Manufacture of glass cloth characterized by cutting the cloth
Provide a way. Also,   Characterized in that the solvent is water
Have A method for manufacturing the described glass cloth is provided. Since
Hereinafter, the present invention will be described in detail.

[I] Anti-raveling agent: The present invention is a novel raveling-preventing agent for preventing raveling of the cut end of a glass cloth woven by various types of looms, particularly a fragment loom such as an air jet loom (prevention of ear raveling). As an agent, especially polyamido obtained by ring-opening polymerization of lactam
It is characterized in that a water-soluble or water-dispersible type polyamide resin obtained by graft-polymerizing a hydrophilic monomer into a resin is used. Specifically, La as fraying prevention agent of the present invention
The polyamide resin obtained by the ring-opening polymerization of
A glass cloth in which a water-soluble or water-dispersible polyamide resin obtained by graft-polymerizing an aqueous monomer is applied to a certain width of the edge portion of the glass cloth, dried, and the applied anti-fray agent is cut to leave a certain width. Is. By ring-opening polymerization of the lactam used in the glass cloth of the present invention
Grafting hydrophilic monomer on the obtained polyamide resin
The combined water-soluble or water-dispersible polyamide resin preferably uses water as a solvent, particularly from the viewpoint of environmental hygiene.

By ring-opening polymerization of lactam according to the present invention
Grafting hydrophilic monomer on the obtained polyamide resin
The polymerized water-soluble or water-dispersible polyamide resin is generally obtained by water-solubilizing an insoluble polyamide resin, for example, a polyamide resin obtained by ring-opening polymerization of lactam (for example, N-methoxymethylated nylon). N-alkoxymethylated nylon such as N-ethoxymethylated nylon and N-butoxymethylated nylon) and hydrophilic monomers (acrylic acid, methacrylic acid, hydroxyethyl acrylate, polyethylene glycol monomethacrylate, itaconic acid, acrylamide, N).
-Methylol acrylamide etc.) (1: 0.3
Graft-polymerized (by weight ratio) (Japanese Patent Publication No. 7-258
54 JP) and the like.

The lactam thus obtained is
Polyamide resin obtained by ring-opening polymerization is
A water-soluble or water-dispersible polyamide resin obtained by graft-polymerizing a mer generally exhibits rubber elasticity and is flexible, and its heat resistance and solvent resistance are remarkably improved as the crosslinking reaction proceeds. Such a polyamide resin is applied to a portion of the glass cloth to be cut with a constant width. Upon coating, the polyamide resin should be 300 cps or less, preferably 100 cps
Below, it is necessary to dilute with a solvent to more preferably have a viscosity of 5 to 30 cps. The viscosity of polyamide resin is 3
A liquid thicker than 00 cps is not preferable because it does not sufficiently impregnate the single yarn of the glass cloth.

Solvents for reducing the viscosity of the polyamide resin include methylene chloride, carbon tetrachloride, chloroform,
Halogenated lower hydrocarbon solvents such as trichloroethylene and alcohols, ethers, ketones and the like are used, but water is most preferable from the viewpoint of preventing human body or environmental pollution. On the other hand, the resin may be used in combination with other resins such as melamine resin, epoxy resin, urethane resin, or mixed with a curing agent such as citric acid or lactic acid or a curing accelerator thereof.

[II] Method for Producing Anti-Fray Glass Cloth As a method for applying the anti-fray agent to the glass cloth, a die coater, a spray coater, a roll coater and the like can be mentioned. The coating width should be as narrow as the adhesive strength allows, but in industrial production, considering the variation, it is 10
mm or less, preferably 4 to 8 mm. It is important to adjust the coating amount so that the resin solid content is 2 to 10% by weight, preferably 2 to 6% by weight, based on the coated portion of the glass cloth. At this time, if it is less than 2% by weight, a sufficient anti-raveling effect cannot be obtained, and if it exceeds 10% by weight, the applied portion becomes thicker than the other portions, causing abnormalities such as ear height.

The method of the present invention comprises ring-opening polymerization of a lactam as an anti-raveling agent on both ears of a glass cloth or on the inside thereof.
Hydrophilic monomer is added to the polyamide resin obtained by
A raft-polymerized water-soluble or water-dispersible polyamide resin is diluted with a solvent to a viscosity of 300 cps or less, applied and dried, and then the glass cloth is cut while leaving a certain width of the anti-raveling agent on both ears. The present invention relates to a method for producing a glass cloth. In the method of the present invention, the glass cloth coated with the anti-raveling agent is further dried in a dryer under the condition that the moisture contained in the anti-raveling agent scatters without being overheated within a predetermined time. Although not particularly limited, for example, 100 to 200 ° C. and 5 to 30 seconds are suitable.

Any of the heating methods may be used to dry the anti-fray agent applied to the glass cloth, and examples thereof include a hot air drying method, an infrared drying method, a microwave drying method and a cylindrical drying method. The infrared drying method and the microwave drying method are preferable because it is desirable to avoid heating of a portion other than the anti-raveling agent application portion. After drying
It does not matter if a melting step at 200 to 300 ° C. is added.
After passing through the drying and melting steps, the glass cloth is cut with a slitter at approximately the center of the applied anti-fray agent.
As the cutting position, it is desirable to cut the center of the coating width, but in industrial manufacturing, it is desirable to take the variation into account and the coating width center line ± 20% of the coating width. Therefore, the glass cloth after cutting is in a state in which the anti-fray agent having a width of 7 mm or less is applied to both ears, and the ears including the tufts are removed from the glass cloth.

In the glass cloth used in the present invention, the number of warp yarns and weft yarns per unit length, the thickness, and the weight per unit area correspond to Japanese Industrial Standard R-3414 and US military standard (MIL standard). However, the present invention is not limited to this, and any one can be used.
For example, this glass fiber may have not only E glass and C glass but also various glass components such as S glass, H glass, and D glass. Further, any of the glass cloth at the stage where the sizing agent necessary for weaving is attached, the glass cloth at the stage where the sizing agent is removed, or the glass cloth which has been already treated with a silane coupling agent or the like by a known surface treatment method. But good.

[0019]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, which do not limit the scope of the present invention. (Example 1 ) A water-soluble polyamide resin [Toresin FS-350, manufactured by Teikoku Chemical Industry Co., Ltd.] was diluted with water to prepare a 10% by weight anti-raveling agent. Anti-fray agent for roll coater
10m width along the warp inside both ears of the glass cloth
m and then dried at 120 ° C. for 30 seconds. this
At this time, the adhesion amount of the anti-raveling agent is glass cloth [762
8, Asahi Schwabel Co., Ltd.]
The amount was%. In addition, the glass cloth can be
The central part of the inhibitor was cut with a slitter. After cutting
When one warp at the end is pulled off perpendicularly to the warp
The strength of the tensile tester [Autograph AGS-500D,
Shimadzu Corp.] to obtain dry ear strength
It was Also, after soaking in dimethylformamide for 5 minutes, air dry
The measured glass cloth was measured in the same manner to obtain the wet ear strength.
It was On the other hand, apply anti-fray agent to the center of the glass cloth
Measure the thickness of each part and calculate according to the following formula to obtain the thickness ratio.
It was Thickness ratio = thickness of anti-fraying agent applied part + glass black
Center thickness

Comparative Example 1 A polyester resin [HARDIC A-1300, manufactured by Asahi Kasei Kogyo Co., Ltd.] was dissolved in trichlorethylene to obtain 10
The same procedure as in Example 1 was carried out except that the anti-raveling agent was adjusted to a weight percentage. The results are shown in Table 1 below.

[0021]

[Table 1]

[0022]

INDUSTRIAL APPLICABILITY The glass cloth in which fraying has been prevented according to the present invention is obtained by ring-opening polymerization of lactam as a fraying preventing agent.
Grafting hydrophilic monomer on the obtained polyamide resin
Since the polymerized water-soluble or water-dispersible polyamide resin is used, the adhesive strength is high and the ear frayability is excellent. Further, since the coating has flexibility, the glass cloth of the present invention may be wound, disentangled, or cracked or broken at the coated portion even when passing through a roll in the process, or wavy ears. There is no occurrence. Polyamylene obtained by ring-opening polymerization of lactams used as fray preventing agent in the present invention
Water-soluble or water-dispersible polyamide resin obtained by graft-polymerizing a hydrophilic monomer onto the resin is excellent in resistance to the solvent used for the varnish, and therefore the ears may be frayed during the process of impregnating and drying the varnish. There is no.

Further, ring-opening polymerization of lactam used in the present invention
Hydrophilic monomer is added to the polyamide resin obtained by
RAFT polymerization was water-soluble or water-dispersible polyamide resins fraying inhibitor are the water-soluble or water-dispersible, applied from the <br/> tone made, throughout the entire process of drying, there is no working environment pollution, It is also effective for environmental conservation. The glass cloth obtained by the method of the present invention has almost no difference in thickness between the ears and the other portions, so a prepreg is produced using the glass cloth, and when cut and stacked to a certain size, the center is There is almost no difference in height between the part and the end part. As described above, the glass cloth according to the present invention can be effectively used for printed wiring board applications.

─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-59-15563 (JP, A) JP-A-48-90312 (JP, A) JP-A-6-192965 (JP, A) JP-A-6- 25975 (JP, A) JP 6-341065 (JP, A) JP 6-240578 (JP, A) JP 60-221346 (JP, A) JP 60-219281 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) D06C 25/00 C09J 177/00-201/10

Claims (3)

(57) [Claims] 1. Ring-opening polymerization of lactam as an anti-raveling agent
Hydrophilic monomer is added to the polyamide resin obtained by
A glass cloth, wherein a raft-polymerized water-soluble or water-dispersible polyamide resin is applied to a certain width of an edge portion of the glass cloth, and the applied anti-fray agent is cut while leaving a certain width. 2. Both ears of the glass cloth or the inside thereof,
Obtained by ring-opening polymerization of lactam as anti-fray agent
Graft-polymerized hydrophilic monomer to polyamide resin
300cps soluble or water-dispersible polyamide resin
A method for producing a glass cloth, which comprises diluting with a solvent to the following viscosity, applying the solution, and drying, and then cutting the glass cloth with leaving a certain width of the anti-raveling agent in both ears. 3. The solvent is water.
2. The method for producing a glass cloth according to 2 .