WO2013149400A1

WO2013149400A1 - Treatment process for flattening electronic-grade glass fiber cloth and electronic-grade glass fiber cloth produced by using same

Info

Publication number: WO2013149400A1
Application number: PCT/CN2012/073598
Authority: WO
Inventors: 杜甫; 孙小虎; 邹新娥
Original assignee: 上海宏和电子材料有限公司
Priority date: 2012-04-06
Filing date: 2012-04-06
Publication date: 2013-10-10
Also published as: KR20150001797A; CN104246049A; CN104246049B

Abstract

The present invention relates to a treatment process for flattening electronic-grade glass fiber cloth and the electronic-grade glass fiber cloth produced by using same. First, the yarns are wound on the warp beam while sizing the yarn monofilament to take the sizing finishing process, and then the obtained warps are combined and woven to get fatty glass fiber cloth. Subsequently, the obtained fatty glass fiber cloth is set in a steaming oven for fumigating and swelling. With the effect of the ejection and fumigation of the saturated steam under the high temperature and high humidity environment, the highly expansive starch among the yarns swells rapidly under the heat and humidity, and the spaces among yarn bundles increase when the yarn bundles are kept under the high temperature and high humidity environment for some time to form secondary structural reorganization. And subsequently, the obtained swollen glass fiber cloth is heated continuously and stewed to degrease under the high temperature. Finally, the obtained degreased glass fiber cloth is opened by high-pressure injection, extruded to eliminate excess water, and impregnated with a silane coupling agent through a surface processing machine.

Description

Electronic grade glass fiber cloth flat processing process and electronic grade glass fiber cloth thereof

The invention relates to an electronic grade glass fiber cloth flattening process and an electronic grade glass fiber cloth produced thereby. Background technique

Electronic grade glass fiber base fabric is the upstream substrate for the printed circuit industry. With the booming development of the electronics industry in recent years, the thin and light, laminated, high-frequency, multi-functional integration of electronic products continues to develop. The performance requirements of the upstream electronic material substrate are becoming more and more demanding. The wettability, dimensional stability, high temperature resistance (interlayer peel strength) and low surface roughness of the glass fiber base fabric will be the continuous concern and requirements of downstream customers. the key of.

Nowadays, new lead-free resins, environmentally friendly halogen-free resins and high-Tg resins, which are widely used by downstream enterprises, are mainly chemically modified polyfunctional epoxy resins, and a large proportion of fillers are added, and the adjustment properties of downstream high-performance resins are changed. The electronic glass fiber cloth substrate manufactured by the conventional existing process is unsuitable or mismatched, resulting in a decrease in wettability, difficulty in discharging the gas inside the prepreg, and easy voiding inside the substrate.

At present, the treatment of glass fiber base fabrics in the domestic industry is mostly maintained at the traditional level of pulping, weaving, desizing, and coupling agent treatment. The degree of fiber opening and the wettability are limited, and it is impossible to match and satisfy the high performance resin. Requirements.

Summary of the invention

The invention aims to overcome the deficiencies of the traditional process, and provides an electronic grade glass fiber cloth flat processing process and an electronic grade glass fiber cloth produced thereby, which is a perfection and excavation of the existing glass cloth production process, and is treated by fumigation swelling. A more complete degree of opening and flatness is obtained, whereby the electronic grade glass fiber cloth has good wettability, high impregnation, small permeability, smooth surface, flat flatness of the glass cloth, and improved adhesion to the resin interface, and enhanced Adaptability to downstream high performance resins.

The present invention is implemented by the following technical solutions, which in turn include the following steps:

Firstly, the yarn is sizing while winding the yarn on the warp beam. The slurry is made of high-swelling starch. The temperature of the monofilament sizing is controlled at 3 (T70 ° C, drying temperature 120 TT 18 (TC, operation). At a speed of 5 (Tl50 m/min, a pulverization treatment was carried out, and the obtained warp beam was woven by an air jet loom to obtain a non-defatted glass fiber cloth.

The vacancy of the cavity is 0. 0f0. 3 MPa, lasting, the undeployed glass cloth is placed in a steaming furnace for fumigation and swelling. time 0. 5h^24h, saturated steam pressure 0. ri. 2Mpa, non-greased cloth sprayed and fumigated by saturated steam gas in high temperature and high humidity environment, so that the high-swelling starch inside the yarn is hot and wet. Rapid expansion, the yarn bundle stays in a high temperature and high humidity environment for a certain period of time will widen the gap between the fiber bundles to form a secondary structure reorganization.

The glass fiber cloth having an organic content of 0. 0 Γ 0.1% or less is obtained after the squeezing treatment is carried out at a high temperature for continuous heating and degreasing treatment.

Finally, the degreased glass cloth is subjected to a high-pressure jet for opening treatment, and the excess water is removed by extrusion, and the silicon germanium coupling agent is impregnated by a surface treatment machine to obtain uniform fiber opening, reduced thickness, loose structure, and flatness. A high degree of fiberglass cloth.

The invention is an innovative improvement of the prior art, increases the fumigation and swelling process, improves the fiber opening effect of the glass cloth, thereby improving the flatness of the glass cloth, reducing the surface roughness of the glass cloth, and improving the combination of the resin and the glass cloth interface. Force to adapt to the changing requirements of the new downstream environment. After the glass fiber cloth treated by the process of the present invention, the fiber yarn bundle is loose, the warp and weft interlacing points are smooth, the warp yarn width is increased, the glass cloth thickness is decreased, and the internal stress is lowered.

DRAWINGS

The technical solutions of the present invention are further described below in conjunction with the accompanying drawings and embodiments.

Fig. 1 is a schematic view of a steam furnace body for high-pressure fumigation treatment of an electronic grade glass fiber cloth.

detailed description

Example 1

The 1080# specification was trial-produced, and it was flattened by the production process of the present invention.

According to IPC regulations, D450 yarn (11.2tex yarn) is used, and 60 (end/inch) is used to prepare the warp beam. The slurry is preferably high-swelling starch slurry, slurry temperature 60 ° C, drying temperature. At 140 ° C, the running speed was 100 m/min, and the whole pulp processing was carried out, and the obtained warp beam was subjected to a warp and weaving process to obtain a non-defatted glass fiber cloth.

The above-mentioned defatted glass fiber cloth is placed in a steaming steaming furnace for fumigation and swelling treatment: first, the steaming furnace is vacuum-treated, and the vacuum degree of the steaming furnace is controlled at -0. IMPa I, and 0.88 Pa of saturated steam is sprayed in the furnace body. The steam steamer body was kept at a constant pressure of 0.1 IMpa and 140 ° C for a period of 8 hrs and then taken out for cooling.

3% I的玻璃纤维布。 After the above-mentioned swelled glass cloth was placed at 320 ° C, after 64 hrs for continuous, batch degreasing treatment, after degreasing treatment to obtain a glass fiber cloth with an organic content of 0.3% I.

The degreased glass is placed at a pressure of 10KG/cm2, a pore size of 0. 10, a water temperature of 35 ° C, a vibration frequency of 40 Hz, and a high-pressure jet is used for the opening treatment, and the excess pressure is removed by a pressure roller having a pressure of 15 KG/cm 2 . And after impregnating the silicon germanium coupling agent with a surface treatment machine, the glass fiber with uniform fiber opening, reduced thickness, loose structure and high flatness is obtained. Vib.

Comparative Example 1 (1080# specification glass fiber cloth)

According to the conventional production process, the finished fabric obtained by impregnating the silicon germanium coupling agent through a surface treatment machine with a 1080 cloth produced by Shanghai Honghe Electronic Materials Co., Ltd. is compared.

The glass fiber yarn is woven by an air jet loom to obtain a non-defatted glass fiber cloth, and after two direct desizing of about 40 CTC, the organic content of the glass fiber cloth reaches 0.3% I, and is obtained by impregnating the silicon germanium coupling agent with a processor. Electronic grade glass fiber cloth compared with Example 1, see Appendix 1

Example 2:

The 1078# specification was prototyped, and it was flattened by the production process of the present invention.

According to IPC regulations, D450 yarn (11.2tex yarn) is used, and 54 (end/inch) is used to prepare the warp beam. The slurry is preferably high-swelling starch slurry, slurry temperature 60 ° C, drying temperature. At 140 ° C, the running speed was 100 m/min, and the whole pulp processing was carried out, and the obtained warp beam was subjected to a warp and weaving process to obtain a non-defatted glass fiber cloth.

The above-mentioned non-defatted glass fiber cloth is placed in a steaming steaming furnace for fumigation and swelling treatment: first, the steaming furnace is vacuum-treated, and the vacuum degree of the steaming furnace is controlled at -O.lMPa, and O. SMpa saturated steam is sprayed in the furnace body to maintain The steaming furnace body was cooled at a constant pressure of 0.1% isostatic pressure at 140 ° C for 8 hrs.

The swelled glass cloth was subjected to continuous and batch degreasing treatment at 320 ° C for 64 hrs. After the degreasing treatment, a glass fiber cloth having an organic content of 0.3% I was obtained.

Then, the degreased glass is placed in a high pressure jet with a pressure of 12 KG/cm 2 , a pore diameter of 0.10, a water temperature of 35 ° C, and a vibration frequency of 45 Hz. The excess pressure is removed by a pressure roller having a pressure of 15 KG/cm 2 . And after impregnating the silicon germanium coupling agent with a surface treatment machine, a glass fiber cloth having uniform fiber opening, reduced thickness, loose structure and high flatness is obtained, see Table 1

Comparative Example 2 (1078 cloth)

According to the traditional production process, the 1078 cloth produced by Shanghai Honghe Electronic Materials Co., Ltd. is compared with the finished product obtained by impregnating the silicon germanium coupling agent through a surface treatment machine.

The glass fiber yarn is woven by air jet loom to obtain non-defatted glass fiber cloth. After two direct desizing of about 38 CTC, the organic content of the glass fiber cloth reaches 0.3%, and the silicon germanium coupling agent is impregnated by the processor for comparison. Electronic grade fiberglass cloth, see Schedule 1

Example 3:

Trial production (3) 106# specification, which is flattened by the production process of the present invention. According to IPC regulations, D900 specification yarn (5.5tex yarn) is used, and 56 (end/inch) is used to prepare the warp beam. The slurry is preferably high-swelling starch slurry, slurry temperature 60 ° C, drying temperature. At 140 ° C, the running speed of SOm / min was subjected to a slurry processing, and the obtained warp beam was subjected to a warp and weaving process to obtain a non-defatted glass fiber cloth.

The above-mentioned non-defatted glass fiber cloth is placed in a steaming steaming furnace for fumigation and swelling treatment: first, the steaming furnace is vacuum-treated, and the steaming degree of the steaming furnace is controlled at -O. lMPa, and the steaming furnace body is sprayed with O. SMpa saturated. Steam, keep the steam steamer body at 0. IMpa pressure, 140 ° C constant temperature and constant pressure, continue to cool for 6 hrs.

The above-mentioned swelled glass cloth was subjected to continuous and batch degreasing treatment at 320 ° C for 64 hrs. After the degreasing treatment, a glass fiber cloth having an organic content of 0.3% I was obtained.

The degreased glass is placed in a high pressure jet with a pressure of 8 KG/cm 2 , a pore diameter of 0.10 mm, a water temperature of 35 ° C, and a vibration frequency of 35 Hz. The excess pressure is removed by a pressure roller having a pressure of 15 KG/cm 2 . After being impregnated with a silicon germanium coupling agent by a surface treatment machine, a glass fiber cloth having uniform fiber opening, reduced thickness, loose structure and high flatness is obtained, as shown in Table 1.

Comparative Example 3 (106 cloth)

According to the conventional production process, the 106 cloth produced by Shanghai Honghe Electronic Materials Co., Ltd. is compared with the finished product obtained by impregnating the silicon germanium coupling agent through a surface treatment machine.

After the glass fiber yarn is woven by the air jet loom, the non-defatted glass fiber cloth is obtained, and after two direct desizing of about 36 CTC, the organic content of the glass fiber cloth reaches 0.3%, and the silicon germanium coupling agent is impregnated by the treating machine for comparison. Electronic grade fiberglass cloth, see Schedule 1.

Schedule 1

Tour process

Water absorption rate (PCT-2h * ) 1.06 1.13 0.45 1.45 1.51 0.78 Performance

Note:

Test method for warp and weft width: Under the microscope, take three pictures of the left, middle and right collection points of the full width of the electronic grade glass fiber cloth, measure the width of the warp and weft at each collection point, and finally take the average value.

Thickness measurement: Using a digital display, measuring accuracy of 0. 001mm micrometer (thickness gauge) instrument, taking three collection points in the left, middle and right of the full range of electronic grade fiberglass cloth, measuring the thickness of the cloth, and finally measuring Take the mean.

Air permeability measurement: Use the imported TEXtest air permeability meter to measure the air permeability of the cloth surface at the left, middle and right sides of the electronic grade fiberglass cloth bundle, and finally take the average value.

Impregnation measurement: Three samples of 10cm*10cm size were sampled at the left, middle and right positions of the electronic grade fiberglass cloth. The sample was placed in an organic solvent, and the side of the lamp was used to observe the sample surface infiltration in a closed dark room. Status, record time, and finally take the mean.

Heat resistance test: After impregnating the resin with an electronic grade glass fiber cloth, the laminate is laminated with six sheets, and the pressed sheet is cut into a size of 5 cm*5 cm, and then cooked at 120 ° C and 1. lbar. The thermal shock was carried out in a tin furnace at 283 ° C, and the delamination of the plate surface was completed, and the average value was taken.

Moisture content test: After impregnating the resin with electronic grade glass fiber cloth, the laminate is laminated with six sheets, and the pressed sheet is cut into 5cm*5cm size, 105°C, dried for 30min, and weighed to obtain the weight. Si, and then after 120 ° C, 1. lbar cooking to obtain s2, (s2-sl) / sl to obtain the water absorption resin of the board, and finally take the average value.

Compared with the prior art, the glass cloth treated by the invention is shown in the attached table 1. The warp and weft yarn width is large, the cross section of the warp and weft yarn becomes flatter, and the thickness is obviously decreased. It is known from the common sense that one piece of paper and ten sheets of paper respectively The difference in the speed of wetting into the water, and the faster infiltration speed is very meaningful for industrial production, which can increase the productivity of a company and make the company more competitive. The improvement of the infiltration property is crucial for adapting to the emerging high-performance resins such as halogen-free and high heat resistance which are difficult to be impregnated in the downstream industry. The glass fiber yarn bundle of the invention has looseness, smoothness of warp and weft interlacing point, low surface roughness, reduction of internal stress, dimensional stability, heat resistance, water absorption rate, high temperature resistance (interlayer peeling strength) and the like. It is better to meet the needs of matching the adjustment and adjustment of resin in the downstream industry, and it can adapt to the trend of the downstream of the upstream electronic material substrate due to the development of the industry.

Claims

Rights request

1. An electronic grade glass fiber cloth flattening process, characterized in that the steps are as follows: First, the yarn is sizing while winding the yarn on the warp beam, and the slurry is selected to have high swelling property. The temperature of the starch, monofilament sizing is controlled at 3 (T70 ° C, drying temperature 120TTl8 (TC, running speed 5 (Tl50m / min, for the whole pulp processing, the obtained warp beam and warp, weaving with air jet loom) Then, the non-defatted glass fiber cloth is obtained; then, the non-defatted glass fiber cloth is placed in a steam steaming furnace to be fumigated and swelled, so that the non-defatted cloth is sprayed and fumigated by saturated steam gas in a high temperature and high humidity environment. The high-swelling starch inside the yarn is heated and wet, and the yarn bundle stays in a high temperature and high humidity environment for a certain period of time, which will widen the gap between the fiber bundles to form a secondary structure reorganization;

The glass fiber cloth having an organic content of 0. 0 Γ0. 1% or less is obtained after the degreasing treatment is carried out at a high temperature;

2. The process for flattening an electronic grade glass fiber cloth according to claim 1, wherein the fumigation treatment is performed by: placing a non-defatted cloth in a sealed cavity, the cavity The vacuum degree is 0. 0Γ0. 3~MPa, the duration is 0. 5h~24h, the saturated steam pressure is 0. Γΐ. 2Mpa.

An electronic grade glass fiber cloth, which is produced by the flattening process of claim 1 or 2.