TWI352559B - Cyclic olefin copolymer fiber with low dielectric - Google Patents

Description

t. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a cyclic smoky copolymer fiber. More specifically, the present invention relates to a ring-contacted (four) fiber having an age constant, a method for producing the same, and a resin substrate for a printed circuit board. Eight [Prior Art] Recently, as electronic communication devices continue to move toward high-speed transmission, the demand for high-frequency components for printed circuit board (PCB) towels has also increased. In high-frequency circuits, the speed of transmission depends on the dielectric constant (ddectric = r, ant) (Dk) and dieleetrie 1gss of the insulating material. The high dielectric constant of the material = s' will cause the transmission speed to drop, the signal interference 'signal age electrical loss increase ‘large: 1 problem; the consumption represents the electric field loss of energy in the insulating material, the secret value of the value loss. Shame, the development of materials that can generally be 1 in the industry and dielectric loss, has become the choice of insulating materials in the printed circuit board, the choice of glass weave ==, the method of clothing through the suspension of the glass fiber into the fabric form of the fabric reinforcement Then, 'Add 2 to remove water t to open / to adhere the copper fl to the t substrate ' of the resin substrate by hot pressing, and then laminate. ^ Side or both sides of the surface to form a copper-clad glass fiber, although it has the advantages of high mechanical strength and dimensional stability, but the enthalpy is limited by the dielectric constant of the glass fiber main component Si 〇 2 is 39, the common break = The dielectric constant of the dimension can only be reduced to about 4.6. In addition, the process of making glass fiber ^ uses a temperature of more than 1500 C for melting: spinning, and the glass fiber in the process of depolymerization must use high temperature to burn off the material, so that the glass fiber strength is reduced by about 1/3 ' A glass fiber fabric is formed. The use of a high-temperature process requires relatively high temperature resistance due to the relatively high temperature resistance of the equipment, and the high-temperature process must consume a large amount of energy at the manufacturing cost. Seven: It is unfavorable. ~ Therefore, there is a need in the industry for a material that can reduce the dielectric constant and achieve comparable mechanical strength and size to the glass fiber. For example, CN1854173A 'eydic olefin copolymer (eydic: copolymer) can achieve the above-mentioned properties of lowering the dielectric constant and achieving good characterization. For example, the structural formula of Topas®. [Formula 1]

5 1352559 Qualitative dielectric constant, low water absorption, good insulation ^ Its molecular structure, the flexibility of the polymer is not ill%, and the county should be 51 fresh, touching _ she is complicated. The still/i of the polymer ii is prepared in a simple process for a ring having a low dielectric constant. [Invention] It is an object of the present invention to solve the above problems with the prior art. In order to solve the problems as described above, one of the objects of the present invention is to compound the polyolefin, and to delay the cold-known technical touch miscellaneous reading point of the cyclic olefin copolymer via the 9-mer. To improve the glass fiber dielectric constant of 4.6. The electric tenth pass is lower than one aspect of the invention according to the invention, a low dielectric constant is the base, accounting for 1 to 7.5 wt%; wherein the person is cut and quasi-cooled late, the series _, the The hydrocarbon filaments process is extended into crystals to obtain a fiber that has a lower than that of the glass fiber. *Dielectric Constant of 4.6% In some preferred embodiments of the invention, the polyolefin is 2 to 5% by weight. The polyolefin-based mixing standard, wherein the molecular chain of the cycloolefin copolymer is entangled, but the content of the non-olefin copolymer is low, and there is a disadvantage of not having a crystal; therefore, May cause the dielectric constant of the fiber to be undesirably high. 1♦ The content of olefin is over 25. In some preferred embodiments of the invention, the polyolefin is divided into 100,000 JL, 300,000 Mw; weight averaged molecular

Weig) ° & Saki touch annihilation secrets mixed with mixed ages in one whole? The molecular weight of the alkene can control its compatibility. In addition, the south of the y knife of the polythene hydrocarbon may cause the dielectric constant of the fiber to be unfavorably high. Polyhydrocarbon refers to all polymers composed of C and hydrazine. In one embodiment of the present invention, the polyolefin is selected from the group consisting of: polyene, poly, polyamine, and in some preferred embodiments of the present invention, the poly is agglomerated * preferably implemented For example, the delay quench is used to smelt, carry the process temperature, and record the temperature. c to 3 耽, tempering two to 3 ° ° C 'and cooling temperature of 10 (rC to 16 (fC. delay ΐΐ, can avoid the formation of crystallization of cyclomethine copolymer in the process of forming fibers) a method of breaking. The method of "a low-dielectric constant cycloolefin copolymer fiber pile" comprises the following steps: (a) adding a ring-smoke copolymer and a polyolefin from a feed tank, Juicy smoke accounts for 1 to 7.5 wt%; (b) 炫融_ The ring is a total of (4) and hydrocarbons, with a shaft-solution, the melting temperature is 300. 〇 to 320. 〇; (0 = the body passes Spinning holes having a specific pore diameter are ejected to form a squirrel, (d) = filaments are passed through a tempering device, and the tempering temperature is · c to (6) = filament passing-cooling device The cooling temperature is as follows: 0 to MOC; and ω = the feed passes through the light material device and the cyclic olefin copolymer fiber. n ^ based on the weight of the weaving dimension, the molecular weight of the far polyolefin is in some of the present invention In the preferred embodiment, the polyolefin is 2 to 5% by weight. In some preferred embodiments of the invention, 200,000 to 250, 〇〇〇 MW. In some preferred embodiments, the poly-dimer, poly-, poly-, money, and mixtures thereof. In the preferred embodiment, the polyolefin is polypropylene or polyethylene. According to still another aspect of the invention, a slab for a printed circuit board comprises an insulating resin and a woven fabric, and the woven fabric is reinforced by a low dielectric constant cycloolefin copolymer fiber. In some preferred embodiments of the present invention, the insulating resin is a triterpene resin, a bismaleimine triazine resin, a polytetrafluoroethylene resin, and a mj compound. Embodiments of the present invention The functions, features, and advantages of the present invention will be further understood from the following description of the preferred embodiments of the present invention. First, the melt spinning of the cyclic olefin copolymer fibers of the present invention will be described by way of FIG. Silk Process '1 is a spur spinning device for producing the low dielectric constant ring-diffuse copolymer fiber of the present invention. Referring to Figure 1, the melt spinning device (100) comprises: a spinning pump (1, n), Feeding Cao (3, 13), extruder (5, 15), melting device (17), tempering device (19) Cooling device (21), wire feeding wheel (23, 25, 27), and coiler (29). The raw material of the raw material of the cyclic olefin copolymer and the raw material of the polyolefin are respectively added to the feeding tank (3, In 13), after being pressed by the extruder (5, 15), the supply amount is controlled by the spinning pump (1, 11), and the amount of the two raw materials used is supplied to the melting device in an appropriate ratio (17). The raw material masterbatch of the cyclic olefin copolymer 8 is selected from the trans-hydrocarbon (4) sold by Ti_ Company under the trade name of TOPAS®, and its molecular weight is about 8 〇 to 150,000 Mw (weight average molecular weight; ―café averaged) M〇iecuiar is called. The olefinic raw material masterbatch is selected from the group consisting of polyene, polyester, polyamide, nylon, and mixtures thereof. More polypropylene wire is thinner. For example, the merchandise sold by Taihua Company can be selected to have a molecular weight of about 100,000 to 300,000 Mw. In the marshaling device (17), the lysine copolymer is subjected to polymerization at a high temperature, and the polyolefin is mixed into the cyclic olefin copolymer during the polymerization to form a copolymer of the copolymer and the hydrocarbon. Body (composition). The temperature of the hiding device (Π) is controlled above the melting point of the two raw materials, preferably from 兕^^ to 32〇. -= below the smelting device (17), with a plurality of spinnerettes (not shown) 'W# hydrocarbon copolymer and polyolefin melt (composition) after being passed through the spinning hole, extruded Molding to form a filament of a cyclic olefin copolymer. Among them, depending on the thickness of the final fiber, the _ hole may have a plurality of different pore sizes, for example, 〇·2 mm to 0.25 mm. The filament of the w-cycloolefin copolymer then enters the tempering device (19), and by the tempering = control, the filament of the cycloolefin filament can be gradually returned from the high temperature heterogeneous state, k to the solid state. The tempering temperature is preferably controlled from 280 ° C to 300 ° C. The cycloolefin-touched filaments are then placed in a cooling device (9), cooled by the control of 'straight two! The filament of the cyclic olefin copolymer is cooled at an appropriate rate, and because the sudden temperature change is too rapid, the filament breakage is preferably '1'. . To 160. . . Furthermore, depending on the needs of the 'cooling' we (21) can provide fans or steam to adjust the cooling rate and efficiency. Then, the filaments are passed through appropriate guiding means (23, 25, 27) and coiled (to obtain the low dielectric constant ring-diffuse copolymer fiber of the present invention. ^ 敕 fiber' such as a godet ( 23, 25, 27), the role of the main fine force, etc. In the refining spinning device (100) 'depending on the needs, can be ° and the number of guiding devices, these guiding devices can be warmed or Room temperature, in order to adjust the tension of the fiber to the desired state [low dielectric constant cycloolefin copolymer fiber] (10)) Preparation of low dielectric constant ring Example 1 with ΗΞΗΗ == (four), the secret; The pump (1, u) is supplied in the amount. Yu Xuan 5 Insects '7^1 吏 is supplied to the melting device at a ratio of 98:2 (17) 'Saki-pressed the cyclic olefin copolymer and polyolefin, 15 holes ^ spinning ί ί Ϊ temperature is 32 (rc. The glaze is ejected by having a η·2 η ο Γ, I4 hole to form a filament. The filament is passed through a tempering device to a degree of WC. The filament is passed through a cooling device (21), Cooling the filaments through a suitable 5 丨 device (23, 25, W g 4 (29) ' to obtain a cyclic olefin copolymer fiber. To observe the spinning: Example 2 20 Repeat the steps of Example 1. And conditions, but using different = degree, the tempering temperature is complete. c, the cooling temperature is 1 眺. The copolymer fiber is obtained, and the spinning result is observed with the naked eye. Second example 3, the steps and conditions of the example 1 are repeated, but the use Different tempering temperature households have temperature, tempering temperature is 3 〇〇., cooling temperature is just... get ^: copolymer fiber, observe the spinning result with the naked eye. , " Example 4 10 25 Μ,% , the steps and conditions of the example i, but using different tempering temperatures and cold tempering temperature of 3 (KrC, cooling temperature is obtained. The fiber is observed by the naked eye. The raw material of the raw material of the raw material masterbatch (trade name: TOPAS®) of the yttrium olefin copolymer is added to the feed tank. 3, 13), after fH/5, 15) extrusion, 'supply amount 1、 by spinning system (1, U). (4) 使用 raw material usage amount is supplied to the smelting device in a ratio of 98: 2 (17) Since the (17) Zhongxuan Ronglong the cyclic olefin copolymer and polyolefin, if, the county temperature is 320t. The solution is passed through the 〇.2 surface (four) out to the shaft material. The device is warm, and the device is passed through the cooling device (21) to cool the C. The wire is passed through appropriate guiding devices (23, 25, silk results i if face 29), The hydrocarbon copolymer fibers were obtained. The process conditions of the spinning examples 1 to 4 and the comparative examples and the spinning results were visually observed in the table] Table 1:

—1 亮融温度(°c) tempering temperature (°c) Cooling temperature (°c) will end, result example 1 320 280 100 Λ Example 2 320 280 120 Δλ Λ Example 3 320 300 ------ -- 140 L -Λ D Example 4 320 300 一----- 160 〇Comparative Example 320 200 —------ 1 ——25 -------- X v ,,叫,七研', X: Can't be spun. ^Examples i to 4 and the experimental results of the comparative examples show that the __ _ cold part (delay qUench) can make the cyclic olefins in a solution state, gradually return to the solid state, and appropriate materials [printed circuit Resin substrate for board] ':=====Printing tA5 Raw material masterbatch of virgin cycloolefin copolymer (trade name T0PAS<8>) 10 11 The raw material of the polyolefin of 77 is added to the raw material. In the trough (3, 13), the 'squeezing of the crushing machine (5, 15) is forced by the soft wire, and the hammer is supplied by the spinning pump (1, U). ί. The amount of the material used is supplied to the melting device (17) in a ratio of 98:2 to open the crucible and the polystyrene in the opening 7), and the melting temperature is 32. (rc. The waste is ejected through a spinning hole having a diameter of 15 , to form a filament. The filament is passed through a tempering device at a temperature of WC. The filament is passed through a cooling device (21), Cooling ί ^ 壮 C. The filaments are passed through appropriate guiding means (23, 25, 27) and coiled flat (29) to obtain a cyclic olefin copolymer fiber. 20 Cycloolefin after spinning into a filament The copolymer fiber, followed by sizing and de-feeding, to form a fabric reinforcement in the form of a fabric, adding an epoxy resin, a layer of insulating material, to form a resin matrix by bonding a plurality of layers of insulating material. Thereafter, the copper foil is attached to one side surface of the resin substrate by hot pressing to form a copper clad laminate for measuring a dielectric constant (Dk) value. The standard test method specified in IPC 2.5.5.9 is used for measurement and measurement. The electrical value is 1 and the measured dielectric constant (Dk) is 2.5 (@1 GHz). t #(Dk) Example 6 The procedure of Example 5 and the spinning conditions were repeated, but using different proportions of the ring-diffusing copolymer and polyolefin. Cyclic olefin copolymer: polyolefin = 95: 5. According to the example 12 25 ^ job method, the dielectric constant (four) is called GHz) 〇 3.6 (@1

The tM hydrocarbon is a total of 5 ϊ: ΐ: ‘but _ _ 实 实 实 实 聚烯烃 婶 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃. According to GHz). The test method for the test method of the test 5 has a dielectric constant (Dk) value of 4.8 qing tM8 10 furnace 5 and spinning conditions' but using different proportions of ring slag and polyolefin. Ring copolymer: polyolefin = 9G: 1G. Tested according to the same test method as real GHz, the measured f-constant value (Dk) value is 8.4 (@1 ΜΜΜ 15 glass fiber substrate, tested according to the same test method as in Example 5, measured dielectric The constant (Dk) value is 46 to 4 8 (@1 GHz). The process conditions and dielectric constant (Dk) values of the fruit and the control are measured. Table 2: The weight of the cycloolefin copolymer in the fiber The weight of the polyolefin in the weight of the glass fiber Dk value (@1 GHz)

13 1352559 The results of Table 2 'dielectric constant (10)) increased slightly with the increase of 曰, a slight increase trend. Therefore, although the instance of ^ f can be used for money. Such equal changes are obvious to those skilled in the art. …'to this end

Again, the factor affecting the dielectric constant (Dk) value of the resin substrate, in addition to the addition amount of the polyhydrocarbon, when other is applied, for example, the dielectric constant (Dk) value of the resin of the added person is the county hydrocarbon itself. The dielectric constant (Dk) value, etc., in the actual application of the f-face 'can select the dielectric resin with a lower dielectric constant (Dk) value, or adjust the molecular weight of the polyolefin, and close the final lion hydrocarbon copolymer to form a resin. The dielectric constant (Dk) value of the substrate 15. Such equal variations are readily apparent to those skilled in the art. In addition to the dielectric constant (Dk) value, after the cyclic olefin copolymer fiber of Example 5 of the present invention was formed into a resin substrate, the water absorption, dimensional stability, insulation, glass transition temperature, and the like were also measured, and the results were compared. The specifications of the printed circuit board are summarized in Table 3.

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table 3 :

〇. Better than specifications; △: equivalent to specifications. It is known from the county that compared to the conventional printed electricity made of glass fiber 5

% hangs; |wear, water absorption, thermal stress, and glass iii. As a result of printed circuit board specifications, the dielectric loss and linear ΐ expansion coefficient are equivalent to the results of printed circuit wire specifications. ·, ,,, at 80 ° C to 18 〇.匚 Put the fiber in the hot water for a short length. In addition, the COC fiber of Example 5'6, 8 was tested for hot water shrinkage. The hot water shrinkage rate refers to the percentage of the fiber shrinkage length after heating for 30 minutes and after drying. The results are summarized in Table 4. 10 Table 4: 140°C hot water shrinkage 8〇°C hot water shrinkage rate (%) 1〇〇〇c hot water shrinkage £ (%) 160°C hot water shrinkage rate (%) 180°C hot water shrinkage rate (%)

The results of I ft show that the hot water shrinkage rate of the C) fiber of Example 5 and 6 is 120 〇 C. The hot water shrinkage rate is still 'transfer temperature mTg) 178 ° C, the hot water shrinkage ffl indicates the spinning forming process. In the middle, the stress is not affected by the large drawing, and the test is provided. The amount of the substrate is ϋΐ Γ Γ Γ Γ 实例 实例 实例 实例 实例 实例 实例 实例 实例 实例 实例 实例 实例 实例 实例 实例 实例 实例 实例 实例 实例 实例 实例 实例 实例 实例 实例 实例 实例 实例 实例 实例 实例The fiber cloth and the glass fiber produced in Example 5 of the fiber and the diameter of 0.2 mm of the glass fiber were about 34 V / 3 two-fold. The result of the test is not obvious. The denseness of the fiberglass cloth Γ :5=::2 (Ϊ2 r base; for the following,: Q: The use of the words is not _ sex and _ _. The detailed description of the preferred embodiments of the present invention is not intended to be limited to the scope of the invention, and the scope of the invention is as follows: 16 1352559 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a melt spinning apparatus for producing a low dielectric constant cyclic olefin copolymer fiber of the present invention.

15 1 ' 11 3,13 5 ' 15 17 19 21 23 ' 29 100 25,27 Spinning pump feed trough extruder Melting device tempering device Cooling device Feeding wheel, guiding device coiler, take-up device Melt spinning device

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Claims (1)

1352559 VII. Patent application scope: 1. The low dielectric constant cycloolefin polymer rib, its nuclear olefin copolymer; and hydrocarbon j based on the weight of the fiber, accounting for 1 to 7.5% by weight; i it^ Delayed cooling of the silk process, the polyolefin entangles the ring olefin chain 'but does not form a crystal' to obtain a fiber having a dielectric constant lower than that of the glass, I, and 4. 2 Hi is the lowest dielectric constant of the ring-like copolymer fiber in the first item, based on the weight of the fiber, the polyolefin system accounts for 2 to 5 f % 〇3· ^申ίίί range 1 The low dielectric constant of the cyclic olefin copolymer fiber is difficult to have the molecular weight of the polythene hydrocarbon to be fine, (8) paradox. 4. The base of the low dielectric constant of the hydrocarbon copolymer fiber of the first item is selected from the group consisting of polyene, polyester, poly, nylon, and mixtures. 5' The lower number of cyclic olefin copolymer fibers of item 4, wherein the s-heteropolyene is polypropylene or polyethylene. 6. The low dielectric constant of the ring-diffuse copolymer fiber i The temperature of the lion-spun spinning process is 300C to 320C, the tempering temperature is 280〇c to 3, and the temperature is 100°C to 160°. (: A method for producing a constant cyclic olefin copolymer fiber, wherein the package (8) is added to a cyclic olefin copolymer and a poly-hydrocarbon by a tank, and the poly-smoke accounts for i 18 1352559 to 7.5% by weight; (b) smelting Extruding the cyclic olefin copolymer and polyolefin to form a melt having a smelting temperature of 300 ° C to 320 ° C; (c) ejecting the glare through a spinning hole having a specific pore diameter to form a filament (d) passing the filament through a tempering device at a tempering temperature of 280 〇 to 30 〇t; (e) passing the filament through a cooling device at a cooling temperature of i〇〇〇c And (f) passing the filament through a suitable guiding device and a winding device to obtain a cyclic olefin copolymer fiber. 8. The manufacturing method according to claim 7, wherein the fiber is made of fiber The poly-hydrocarbon system is 2 to 5% by weight based on the weight of the polymer. The method of claim 7, wherein the polyolefin has a molecular weight of 20 〇, 〇〇〇 to 25 〇, 〇〇 The manufacturing method of claim 7, wherein the polyolefin is selected from the group consisting of polyenes and polyhydrocarbons. The polyester, polyamine, nylon, and a mixture thereof. The method of claim 10, wherein the polyene is a polypropylene or polyethylene. U. A resin substrate for a printed circuit board. 'Equipped with an insulating resin and a fabric reinforcement made of a low dielectric constant cycloolefin copolymer fiber according to any one of claims 5 to 5. Item 12: The substrate for a printed circuit board, wherein the insulating resin is selected from the group consisting of epoxy resin, polyphenylene oxide resin, double Malayan 19 13 1352559 amine triazine resin, polytetrafluoroethylene resin, and Its mixture. 20