KR900008333B1 - Film or sheet having a rough surface and manufacturing method thereof - Google Patents

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Description

Film or sheet having a rough surface and manufacturing method thereof

1 is a schematic view of the manufacturing process of the film or sheet of the present invention.

2 is a schematic view of another manufacturing process of the film or sheet of the present invention.

3 is another system diagram of the process of the present invention.

4 and 5 are process charts for producing a single-side metal-clad laminate obtained by roughening the resin side surface using a film having a rough surface of the present bearing.

6 is a manufacturing diagram of the test laminate.

7 is a general process diagram for manufacturing a multi-layer printed circuit period.

The present invention relates to a film and a sheet having a novel rough surface composed of a polymer of 4-ethyl-1-pentene and a method for producing the same.

Films and sheets having a non-oriented rough surface of the present invention are particularly useful for the production of multiple layers of printed circuit boards whose use is increasing in various types of electrical devices.

In general, in the manufacturing method of a plurality of layers of printed circuit boards, one-sided metal-clad laminates or double-sided metal-clad laminates are manufactured, an electric circuit is printed on the laminates, and the printed circuit boards are then prepregd. The resin surface of the metal-clad laminate on one side should be rough to enhance the adhesion between the resin side of the metal-clad laminates and the prepregs.

The one-sided or double-sided metal-clad laminate described above is produced by overlapping the metal foil (foi1) and the prepreg and then compressing them by heating them to cure the prepreg. A rough film or sheet is placed on the surface of the prepreg during the curing process.

The film and sheet having a rough surface according to the present invention are useful as a film having a roughened surface described above so as to roughen the resin-side surface of a single-faced metal-clad laminate.

Japanese Patent Publication No. 52-34664 describes a method for producing a biaxially oriented film having a matte surface composed of methyl-pentene polymer, which biaxially oriented a film composed of metalpentene polymer, high density polyethylene and polystyrene. And heat curing the final film to become a matte film. However, there is no description of using a film having matte surfaces to roughen the resin-side surface of the laminate.

Japanese Laid-Open Patent Publication No. 52-49823 discloses a laminate prepared by a further process characterized by placing a releasing film having a surface roughness of 0.5 to 5 mu on a pregreg containing a thermosetting resin, followed by heating. However, the publication describes only triacetate films for release films.

Japanese Patent Application Laid-Open Nos. 57-70653, 58-163648, and 57-70654 describe that 4-methylpentene-1 sheet is used as a release film when producing a laminate from prepreg and metal foil. But. These publications do not describe the use of roughened films as release films.

A film that provides roughness to the multilayer circuit board described above, a two-sided oriented film of polyvinyl fluoride containing a significant amount of low molecular weight fillers and 5% calcium carbonate, namely Tedlar (manufactured by DuPont, USA) TEDLAR (trade name) can be purchased commercially. However, since this film is produced by two-side orientation, low molecular weight materials and calcium carbonate are deposited on its surface. Therefore, when this film is used to produce single-sided metal clad laminates by alternately overlapping copper foil and prepreg, overlapping a tedlar film between the copper foil and prepreg layers, and then heat compressing them to cure the prepreg layer, Since the present materials and calcium carbonate move to the surface of the laminated copper foil, the adhesion between the copper surface and the resist layer becomes unsatisfactory and also the etching is not satisfactory while continuing to process the multilayer circuit boards.

To date, triacetyl cellulose films with rough surfaces by sandblasting have been used, but in this case fine sand and cellulose cause the same problems as mentioned above for Tedlar.

The present invention provides a film or sheet having essentially unoriented surface roughness composed of a homopolymer or copolymer of 4-methyl-1-pentene having a surface roughness of 0.5-10 micrometers.

Also provided is a method of making a film floating sheet having a rough surface as described above. The manufacturing step is as follows.

(1) Preparation of a melt composition made of homopolymer or copolymer of 4-methyl-1-pentene.

(2) Extrusion of the melt composition to form a film or sheet.

(3) at least one roller passes the film or sheet between a pair of rollers having a rough surface, or the film or sheet is placed in contact with the roller having a rough surface, wherein the surface roughness of the roller is 0.5-10 microns. Meter, this rolling is carried out at a pressure and temperature sufficient to replicate the roughness of the surface of the roller onto the surface of the film or sheet.

Also provided is a method of producing a film or sheet having a rough surface as described above.

(1) Preparation of a melt composition made of homopolymer or copolymer of 4-ethyl-1-pentene.

(2) extruding the melt composition and (3) pressurizing the melt composition as a roller having a rough surface to form a film or sheet having a rough surface, or through a pair of rollers in which at least one roller has a rough surface; Passing the molten composition, wherein the surface roughness of the rough roller is 0.5-10 micrometers, and the rolling is performed at a temperature and pressure at which the surface roughness of the roller can be replicated on the surface of the film or laminate.

Another object of the present invention is to superimpose a film or sheet having a rough surface on the stacking pile consisting of the prepreg and the metal foil so that the rough surface of the rough film or the sheet is in contact with the surface of the prepreg on the opposite side of the metal foil. One or more stacks of chucks are placed between heat compression plates and compressed with heating to cure the prepreg to cure the prepreg so that the roughness of the film or sheet with the rough surface is replicated on the surface of the cured prepregs. It relates to the use of a film or sheet having essentially unoriented surface roughness for producing a laminate.

The film or sheet of the present invention consists of a homopolymer crystal of 4-methyl-1-pentene or a copolymer crystal of one or more olefins and 4-methyl-1-pentene. The polymer has a sufficient durability at the temperature at which the prepreg is cured. It should have a high softening point so that it is also easily coarse at temperatures below the softening temperature. The olefins are α-olefins having 2 to 20 carbon elements, for example ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-dicene, 1-detradisene, 1-hexadycene and 1-octadicene. The polymers are at least 85 mole%, preferably 90-98 mole% 4-methyl-1-pentene Contains units. The melt flow rate of the 4-methyl-1-pentene homopolymer or copolymer is preferably 0.5-250 g / 10 minutes, particularly preferably 5-120 g / 10 minutes, when gauging at a temperature of 260 ° C. and a load of 5 kg. Polymers having a melt flow rate of 0.5 g / 10 min or less have poor molding properties because the melt viscosity is too high. Polymers having a melt flow rate of 200 g / 10 min or more have too low melt viscosity, so that the mechanical strength is too low and the molding properties are poor.

The film and sheet may contain additives or fillers. One such additive is silicone oil, which improves the peeling properties of the film from the cured predrag. The silicone oil has, for example, the following general formula.

Here, R is the same or different and represents a saturated or unsaturated aliphatic group optionally containing a hydrogen atom, an aromatic hydrocarbon group or a hetero atom, and n represents a positive integer.

Aromatic hydrocarbon groups are lower alkyl groups having 1-3 carbon atoms and substituted or unsubstituted aromatic hydrocarbon groups having 6-12 carbon atoms, for example, phenyl, tril, ethylphenyl. Isopropyl phenyl, naphthyl, and biphenyl.

Unsaturated or saturated aliphatic groups are, for example, alkyl groups having 1-16 carbon atoms such as betyl, ethyl, propyl, butyl, pentyl and hexyl, vinyl, 2-propenyl, propargyl, 3-butenyl, 4-phene Alkynyl or alkenyl having 2-6 carbon atoms such as tenyl and 5-hexenyl, and cyclones having 5-6 carbon atoms such as cyclopentyl, cyclohexyl, cyclopentenyl and cyclohexenyl Include aliphatic groups.

The viscosity of the silicone oil is measured by a rotary viscometer at 25 ° C., and 5 × 10 −8 × 10 ⁶ cps is better, and 5 × 10 ² -5 × 10 ⁶ cps is better.

The film or sheet preferably contains 0.01-6% by weight of silicone oil relative to the 4-ethyl-1-pentene polymer, and more preferably 0.5-5% by weight. The amount of silicone oil is such that the silicone oil cures from the film or sheet. It should be limited as described above so as not to be moved to the surface of the resin so as not to lower the adhesive strength between the metallized laminate on one side and the cured resin substrate of the prepreg when they are assembled.

Moreover, the films and sheets of the present invention may contain fillers such as calcium carbonate, silica, mica, barium sulfate, talc and the like in amounts that do not lower the tensile strength. Such fillers are usually used in an amount of not more than 43 parts by weight, preferably in an amount of not more than 20 parts by weight, with respect to the weight of the 4-methyl-1-pentene polymer. The fillers provide improved strength to the film surface. It may be.

Finally, the films and sheets of the present invention may contain thermal stabilizers, weathering agents, rust inhibitors, copper inhibitors, antistatic agents and the like, depending on the end use of the film or sheet.

The film and sheet of the present invention have rough surfaces on one or both sides thereof. Roughness is transmitted and replicated, for example, on the resin side surface of the metal clad laminate.

The average surface roughness is 0.5-10 micrometers. Average surface roughness below 0.5 micrometers may not provide sufficient surface area to improve adhesion between the cured resin and the prepreg. On the other hand, average surface roughness of 10 micrometers or more may provide too strong adhesion between the film of the present invention and the cured resin, which may eventually cause some of the film to adhere or break upon the cured resin. The maximum surface roughness is preferably 20% or less of the film or sheet thickness.

According to the present invention, the average surface roughness is represented by the centerline average roughness Ra determined by JISBO601-1970, and is also measured by, for example, a surface composition measurement window (SE-3A type) provided by KKKosaka Kenkyusho in Japan. .

The thickness of the film or sheet in the present invention is usually 5-1000 micrometers, preferably 15-200 micrometers.

Films and sheets of the invention are prepared from a composition containing 4-methyl-1-pentene alone or a copolymer and optionally additives and / or fillers.

The composition is melted, for example, at 270 ° C.-320 ° C. and extruded from the die

The roughened film or sheet is then produced by one of two methods.

One method allows the molten composition to form a film or sheet by a roller having a rough surface and at the same time have a rough surface. The method is shown schematically in FIGS. 1 and 2.

Another method is to extrude the composition to form a film or sheet and then roughen the surface of the film or sheet. This method is schematically shown in FIG.

Referring to FIG. 1, the apparatus used by the manufacture of the film or sheet of the present invention consists of a T-die and a pair of rollers 2a and 2b adjacent the extruder outlet of the T-die, at least one of which is 0.5 It has a rough surface 4a with an average surface roughness of -10 micrometers.

The molten composition is extruded through a conventional T-die and also passed between rollers having a temperature of 40-100 ° C. at a pressure of 3-40 kg / cm ² to form a film or sheet with a rough surface. Or sheet 5 is wound on a roll of roll (not shown). If both rollers have a rough surface, the film or sheet will have rough surfaces on both sides.

Referring to FIG. 2, the apparatus consists of a roller 2c and a roller 6, to which a T-die, 1, a rough film 4b is adhered to the surface. Rough film 4b is made of a material having a surface roughness of 0.5 to 10 micrometers and also having a higher softening temperature than that of the film or sheet 5 of the present invention. The materials of the coarse film 4b are, for example, fluororesins such as edylenetetra fluoride resin, polyvinylidene fluoride, and the like, polysulfone and polyvinyl ether ketone.

Referring to FIG. 3, a combination of haul-off device 3 and surface treatment device 7 is used. As shown in FIG. 3, the molten composition is extruded through T-die 1, the formed film or chop is cooled in the howl-off device 3 and the film or sheet is then transferred from the howl-off device 3 to the surface treatment device 7 Is sent. The surface treatment apparatus 7 includes heating rollers 8 and rollers 2d and 2e for roughening the pair of surfaces, at least one of which has a rough surface having roughness of 0.5-10 micrometers. The cooling film or sheet provided from the howl off device 3 is heated again by the heating roller 8 to a constant temperature, at which temperature the roughness of the rollers 2d and 2e roughening the surface is replicated on the heated film or sheet. Where the heating temperature is higher than the softening temperature of the film or sheet, for example 140 to 220 ° C. Finally, the heated film or sheet is rolled in pairs at a pressure of 40-100 kg / cm ² rollers 2d and 2e. Passing between provides surface roughness to the film or sheet. If only one of the rough rollers 2d and 2e has a roughening surface, only one side of the film or sheet is roughened, and if both rollers 2d and 2e have a roughening surface, both sides of the film or sheet Roughen it. Alternatively, the surface treatment apparatus 7 may include only one roughening roller, as shown in FIG. 2, rather than a pair of roughening rollers.

The roughening roller itself may have a rough surface as shown in FIG. 1, or may alternatively be constituted by a roller in which a rough film is adhered to the surface of the roller having no rough surface as shown in FIG.

In the latter case, the method of the present invention can be economically implemented by adhering a rough film to a roller of a device for producing a conventional film or sheet.

The films and sheets of the present invention are particularly useful for the production of multilayer printed circuit boards. 7 illustrates a general manufacturing method of a multilayer printed circuit board.

One or more inner circuit boards 23 or 33, prepregs 22 or 32, a pair of one- or double-sided metal clad laminates 21a and 21b or 31a and 31b and the external devices 24 or 34 7 (a) or 7 (b Stack as shown in Fig. 2) and place the stacked pile between the two heated compression plates 26 or 36 through cushioning 25 or 35. The pile is compressed while being heated to cure prepregs to form a tightly integrated laminate, then drilled through holes, plating through-holes and etching the surface to complete the multilayer printed circuit board.

The adhesion between the resin shaft surfaces of the single-side metal clad laminates or inner layer circuit boards 21a, 21b and 23 and the prepreg 22 described above is improved by providing roughness on the surface of the resin substrate.

The above-described one-sided or double-sided metal laminates 21a, 21b, 31a, and 31b and inner circuit boards 23 and 33 stack the copper foil and the prepreg, and then compress the overlapping pile by heating the prepreg to harden, thereby compressing the overlapping pile. Between the resin substrates of the prepregs thus prepared are bonded to each other.

In such a method, by laminating a roughened film or sheet on the surface of the prepreg opposite to the copper foil, a one-sided copper clad laminate having a roughened surface can be obtained. The film or sheet of the present invention is very preferred as a rough surface film used in the present invention.

In most cases, one or more of the above-mentioned piles consisting of copper foil and prepreg are stacked and then heat-compressed to simultaneously produce one or more metallized laminates. In such a case, the roughened film also acts as a release material.

Example 1

3, copolymer crystals of 4-beta-l-pentene, 1-hexadecene and 1-octadecene having 95 mol% of 4-methyl-1-pentene units and a melt flow rate of 26 g / 10 min. It melts at 280 ° C. with a small amount of phenol crab antioxidant in an extruder 9 having a diameter of 65 mm.

The molten polymer was extruded through the multi-substrate T-die 1, and the extruded polymer was cooled to 60 ° C with a chill roller to form a film having a thickness of 50 micrometers.

The final film was then heated to 200 ° C. with heating rollers 8 and then the heated film was passed between a pair of roughening rollers 2d and 2e to roughen the surface of the film.

As can be seen in FIG. 4, the final fabricated glass-reinforced epoxy resin prepregs 12a and 12b with a rough film 13a, 500 micrometers thick, and copper foils 11a and 11b with a thickness of 40 micrometers Was laminated. Instrument 15 was placed on both sides of the stacked pile, and the pile was placed between two heated compression plates 17 through cushioning 6. By pre-heating the pile in 180 ℃ and compressed at a pressure of 3Okg / cm ² for 3 minutes, and then re-compressed to a pressure of 5kg / cm ² for 3 minutes to cure the epoxy prepreg to prepare a double-sided metal clad laminate.

Then, as shown in FIG. 5, one side metallized laminates 11a / 12a and 11b / 12b were peeled from the roughened film 13a. As shown in FIG. 6, the one-side metal-clad laminate was laminated 11a / 12a and 11b / 12b through prepreg 12c. The stacked pile was placed between the hot compressive plates through the instrument 15 and cushions 16 and the prepreg was cured as described above to form a multi-layer period.

Although the embodiments described above represent a model for the manufacture of a multilayer substrate, in practice, as shown in Figs. 7A and 7B, one or more inner layer circuit boards are laminated on one side in the manufacture of the multilayer printed circuit board. It can be stacked between the sieves.

One side of the metal-clad laminate and the multilayer board as described above were evaluated as follows.

The peel strength (kg / 15mm) between the one-side metal-clad laminate and the roughened film (kg / 15mm) between the cured epoxy resin 12a of the one-side metal-clad laminate and the cured resin 12c converted from the epoxy prepreg was examined. It was measured by peeling at a peel rate of 200 mm / bone using an instrument (Instron type universal tester manufactured by Instron Company, USA).

Physical properties were measured as follows.

(1) Gloss: ASTM-D2457 (angle 60 °)

(2) Surface roughness surface structure measuring device: (K.K.Kosaka Kenkyusho)

(3) Tear strength: ASTM-D1922

The results are shown in the table.

Example 2

The method of Example 1 was repeated except that a roller having a surface roughness of 2 micrometers was used.

The results are shown in the table.

Example 3

The method of Example 1 was repeated except that a roller having a surface roughness of 7 micrometers was used.

The results are shown in the table.

Example 4

As shown in FIG. 2, the method of Example 1 was repeated except that a roller was prepared by adhering the film having a rough surface to the roller.

The results are shown in the table.

Example 5

The method of Example 1 was repeated except that 5.3 parts by weight of calcium carbonate was mixed with 100 parts by weight of 4methyl-1-pentene copolymer.

The results are shown in the table.

Example 6

A film that had been extruded from the T-die under the conditions described in Example 1 but had a rough surface was used to produce the multilayer printed circuit board.

The results are shown in the table.

Example 7

The method of Example 1 was repeated except that a surface with an average roughness of 20 micrometers was used instead of a roller to roughen the rough film.

The results are shown in the table.

8 to implementation

The method of Example 1 was repeated except that 66.7 parts by weight of calcium carbonate was mixed with 100 parts by weight of 4-ethyl-pentene copolymer.

The results are shown in the table.

Peel strength (1): between one side metal clad filler (copper foil / hardening epoxy resin) and rough film

Peel strength (2): between the cured epoxy resin layer and the prepreg of one side metal clad filler

As can be seen from the table, the peel strength between the cured epoxy resin layer and the rough surface film in Examples 1 to 5 was about 0.03-0.1 kg / 15 mm, indicating that the peeling property was improved and the rough surface epoxy resin layer. The peel strength between the cured and prepreg was about 2.8-4.0 kg / 15mm, indicating improved adhesion.

On the other hand, films with smooth surfaces show better peeling properties but do not improve the adhesion between the cured resinosis and the prepreg.

Furthermore, as can be seen in Example 7, films with surface roughness as high as 25 micrometers provide poor peeling properties such as exhibiting high peel strength of 1.1 kg / 15 mm, as can be seen from Example 8 . Films containing too much filler provide poor peeling properties such as high peel strength of 1.2 kg / 15 cm and low tear strength of 3-5 kg / cm.

Since the film and sheet of the present invention are homopolymer or copolymer crystals of 4-methyl-pentane, they exhibit good properties inherent in the polymer containing 4-ethyl-1-pentene, that is, excellent curability, impact resistance and heat resistance. . Moreover, since the films or sheets of the present invention do not contain a large amount of inorganic fillers, they are not easily torn or destroyed and no impurities are deposited on their surfaces.

Therefore, when used for the production of single-sided metal clad laminates as coarse films or sheets, they also do not soften and break during the prepreg curing and also easily peel off from the cured resin. Since they do not deposit impurities thereon, the surface of the copper foil contains no impurities that interfere with the etching process.

Furthermore, since the film and the felt of the present invention have at least one rough surface having a surface roughness of 0.5-10 micrometers, improved peeling properties are cured to provide between the roughened resin and the film or sheet, and also to improve The adhesive is cured and provided between the cured resin total body and the cured prepreg.

Therefore, the present films and sheets are particularly useful for the production of metal-coated laminates, and are therefore useful for the production of multilayer printed circuit boards.

Claims (7)

Homopolymer crystals of 4-methyl-1-pentene with surface roughness of 0.5-10 micrometers or 4-methyl-1-pentene and ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene A film or sheet having a rough surface composed of copolymer crystals of α-olefins selected from the group consisting of 1-decadedecene and 1-octadecene. The film or sheet of claim 1, wherein the film or sheet has a rough surface with at least 85 mol% of 4-methyl-1-pentene in the copolymer. The film or sheet of claim 1, wherein the film or sheet has a rough surface further containing 0.5-5% by weight of silicone oil relative to the weight of the polymer or copolymer of 4-methyl-1-pentene. (1) homopolymers of 4-methyl-1-pentene or 4-methyl-1-pentene and ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-nesene, 1-decracene and 1- Preparing a melt composition of a copolymer of α-olefin selected from the group consisting of octadecene. (2) extruding the melt composition to form a film or sheet; (3) surface roughness of the film or sheet under a temperature and pressure at which the surface roughness of the roller can be replicated on the surface of the film or sheet. A method of making a film or sheet having a rough surface consisting of passing a roller having a rough surface of micrometers between at least one pair of rollers or contacting a roller having a rough surface. The method of producing a film or sheet having a rough surface as claimed in claim 4, wherein the roller having a rough surface is made of a film or sheet having a rough surface adhered to the roller and the roller. (1) homopolymers of 4-methyl-1-pentene or 4-methyl-1-pentene with ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-tetracene and 1-octa Preparing a melt melt composition with a copolymer of α-olefin selected from the group consisting of decene, (2) extruding the melt composition, and (3) the surface roughness of the roller is replicated on the surface of the film or sheet Having a rough surface configured to pass a molten composition or contact with a roller having a rough surface between at least one roller pair having a rough surface having a surface roughness of 0.5-10 micrometers under a temperature and pressure that can be achieved. Method of making a film or sheet. The method for producing a film or sheet having a rough surface according to claim 6, wherein the roller having a rough surface is a roller and a surface adhered to the surface of the roller is a rough film or sheet.

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