KR20180126013A - Release film suitable for the manufacture of multilayer printed circuit boards - Google Patents

Abstract

It is possible to easily and sufficiently peel off a metal surface having a high roughness such as a blackening treated copper foil even after a step in a severe condition such as a hot press under a condition where the temperature, Lt; RTI ID = 0.0 > releasing < / RTI > film. The problem is solved by a release film for a process comprising a thermoplastic resin, the at least one side of which has the following characteristics:
(1) The film stability property R measured by the nanoindentation method at a test temperature of 180 占 폚,
R ≥ 70 (%)
to be.

Description

Release film suitable for the manufacture of multilayer printed circuit boards

The present invention relates to a releasing film for a process having excellent mold release characteristics on a metal surface having a high surface roughness such as a so-called blackened copper foil, and more specifically, a release film for process used suitably for the production of a metal / resin laminate such as a multilayer printed wiring board having a roughened copper foil layer, and a method for producing a metal / resin laminate such as a multilayer printed wiring board using the same will be.

Recently, with the rapid development of electronic devices and the integration degree of ICs, the printed wiring boards are widely used in order to meet the demands of higher precision, higher density, and higher reliability.

Examples of such a printed wiring board include a single-sided printed wiring board, a double-sided printed wiring board, a multilayer printed wiring board, and a flexible printed wiring board. (Hereinafter also referred to as " MLB ") in that an insulating layer is interposed between conductors of three or more layers in particular so that tangential lines between arbitrary conductors and an electronic component to be implemented and an arbitrary conductor layer can be formed. Has been expanding.

Such an MLB may be formed by, for example, a pair of copper clad laminated boards or a pair of double-sided copper clad laminate boards with a double-sided jacket to form prepregs (epoxy resin or the like) And they are inserted into a jig, and at the same time, they are hot-pressed through a cushioning material in a press hot plate to cure the prepreg to form a laminated body which is firmly integrated, and holes, through hole plating And then etching the surface.

In the process of manufacturing such MLB, a release film is used between a normal copper-clad laminate (outer plate) and a jig. Examples of the release film for this process include 4-methyl-1-pentene copolymer, polytetrafluoroethylene, polyester, syndiotactic polystyrene, and the like. A film made of a high heat-resistant resin that does not melt in the heating and pressing process at the time of hot pressing, and has excellent rigidity and surface smoothness (see, for example, Patent Documents 1 to 4).

The copper foil of the copper-clad laminate is often subjected to surface roughening such as so-called blackened copper foil which is roughened by oxidizing the surface or by etching with acid to improve adhesion with epoxy resin . In this case, in the above-mentioned release films for each process, the copper foil surface may penetrate the surface of the film at a degree of heating and pressing at the time of hot pressing, resulting in a problem that the release film can not be peeled off.

On the contrary, a polypropylene and / or polyethylene layer (B) is provided on at least one outermost layer of a layer (A) composed of a 4-methyl-1-pentene (co) polymer and substantially not containing wax or silicon And the polypropylene and / or polyethylene layer (B) on at least one of the outermost layers of the sheet is peeled off, and the heat shrinkage ratio in the stretching direction is 20% or more. It has been proposed to use a film (see, for example, Patent Document 5).

However, with the development of the related art, the demand for release films for process such as release films for multilayer printed wiring boards has been increasing year by year, so that it is easy to be applied to metal surfaces having high roughness even under the poor process conditions such as high- There is a strong demand for a releasing film for process which can be sufficiently peeled off. Simply by increasing the rigidity and surface smoothness of the release film, it could not meet such a demand.

[Patent Document 1] Japanese Patent Application Laid-Open No. 2004-082717 [Patent Document 2] Japanese Unexamined Patent Application Publication No. 10-67027 [Patent Document 3] JP-A-2014-8720 [Patent Document 4] JP-A-2001-246635 [Patent Document 5] Japanese Patent No. 4489699 Specification

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a method of manufacturing a metal article having high roughness such as a blackened copper foil after a step in a severe condition such as a hot press under a condition where temperature, It is an object of the present invention to provide a releasing film for a process which can easily and sufficiently peel off from the surface.

As a result of intensive investigations to solve the above problems, the inventors of the present invention have found that when the film stability property R measured by a nanoindentation method at a test temperature of 180 캜 is measured, And found that the problems can be solved effectively, and the present invention has been accomplished.

That is, the present invention and the respective embodiments thereof are as described in the following [1] to [10].

[One]

A release film for a process comprising a thermoplastic resin, the at least one side of the release film having the following characteristics:

(1) The film stability property R measured by the nanoindentation method at a test temperature of 180 占 폚,

R? 70 (%).

[2]

A release film for a process comprising a thermoplastic resin, the release film for a process according to [1], wherein at least one surface thereof has the following characteristics:

(2) The hardness H measured by the nanoindentation method at a test temperature of 180 占 폚,

H ≥ 40 (MPa)

to be.

[3]

The release film for a process according to [2], wherein at least one surface having the characteristics of (1) and at least one surface having the characteristics of (2) are the same surface.

[4]

The release film for a process according to any one of [1] to [3], which comprises a polyester resin and / or a polyamide resin.

[5]

The release film for a process according to any one of the above [1] to [4], which has a stretched or non-stretched polyester film layer or a stretched or non-stretched polyamide film layer.

[6]

The release film for a process according to any one of [1] to [5], which is used for peeling from a roughened metal surface.

[7]

The release film for a process according to any one of the above [1] to [6], which is used for peeling from a metal surface having a surface roughness Rz of 1.0 to 6.5 μm.

[8]

A step of hot-pressing the release film according to any one of [1] to [7] above in contact with the roughened metal foil layer on at least one surface having the characteristics of (1)

A step of peeling the process release film from the metal foil layer,

≪ / RTI > characterized in that the metal / resin laminate comprises a metal.

[9]

The production method according to the above [8], wherein the metal / resin laminate is a multilayer printed wiring board.

[10]

An electrical and electronic apparatus having a multilayer printed circuit board manufactured by the manufacturing method according to the above-mentioned [9].

The release film for a process of the present invention can be applied to a metal surface having a high degree of roughness such as a blackened copper foil after a step under a severe condition such as a thermal press at a higher temperature, , A technical effect with a high practical value that can not be realized in the prior art, which can be easily and satisfactorily peeled off without requiring the use of a high-melting-point engineering plastic which does not use a mold release agent, .

The production method using the process release film of the present invention can produce an electric / electronic part having a metal / resin laminated structure such as a multilayer printed wiring board with high productivity in a high degree of freedom.

1 is a schematic cross-sectional view of a cured double-sided copper-clad laminate in which a copper foil layer is laminated on both sides of a glass fiber-epoxy resin composite insulator.
Fig. 2 is a schematic cross-sectional view showing a state in which an adhesive prepreg and a copper foil layer are laminated on the double-sided copper clad laminate of Fig. 1 and a release film is laminated on both surfaces.
3 is a schematic cross-sectional view of a multilayer laminate obtained by pressure-molding the multilayer laminate of FIG. 2;
4 is a schematic cross-sectional view showing a state in which an adhesive prepreg and a double-sided copper clad laminate are laminated on the multilayer laminate of Fig. 3, and a release film is laminated on both surfaces. Fig.
5 is a schematic cross-sectional view of a multilayer laminate obtained by pressure-molding the multilayer laminate of FIG. 4;

(Release film for process)

The release film for a process according to the present invention is a film comprising a thermoplastic resin, and at least one of its faces has a film stability value R measured by a nanoindentation method with a maximum indenting load of 2 mN at a test temperature of 180 캜 (Characteristic (1)) of not less than 70 (%).

When the film stability value R is in the above range, peeling from a metal surface having high roughness such as a blackening-treated copper foil or the like can be facilitated, particularly after adhesion to a metal surface having a relatively high temperature, high pressure and / or long- Therefore, the release film for processing of the present invention can be suitably used for the production of a metal / resin laminate having a metal layer having a high-roughness surface, particularly for the production of a multilayer printed wiring board having a copper foil layer subjected to blackening treatment and roughening treatment have.

The film stability property R was measured by unloading a triangular diamond indenter (Berkovich indenter) with a line angle of 115 ° at a measurement temperature of 180 ° C by using a nanoindenter at the maximum indentation load of 2 mN on the film measurement surface, , And the ratio of the indentation depth at the maximum indentation load (2 mN) to the indentation depth after the removal (0 mN), which is measured by the following formula.

Film stability property R (%) = (indentation depth after removal / indentation depth at maximum indentation load) x 100

Since the film stability property R is in the above range, the mechanism by which peeling from the surface of the metal having high roughness such as the blackening treated copper foil surface is easy is not necessarily clear, nor is it intended to be bound to a particular theory, , The film surface deformed in accordance with the concavo-convex pattern of the high-roughness metal surface is restored to a smoother form when it is hot-pressed against the metal surface having high pressure and / or long- It is presumed that there is some relation with the partial disappearance of the adhesion.

The film stability property R is more preferably 73% or more, particularly preferably 75% or more.

In view of workability and handling, the film stability is preferably 90% or less, and particularly preferably 85% or less, although the film stability property R is preferably high in terms of peelability, and is not particularly limited in the present invention.

The type of resin to be used in order to set the film stability property R of the release film of the present invention to the above range is not particularly limited, and polyester resin, polyamide resin, polytetrafluoroethylene containing a constituent unit derived from tetrafluoroethylene A fluorine resin such as fluoroethylene and ethylene-tetrafluoroethylene copolymer, a urethane resin, and a polystyrene resin. They may also be used in combination.

The resin to be used may be a thermoplastic resin, and a thermosetting resin or an active energy ray-curable resin for crosslinking by adding an active energy ray such as ultraviolet ray or electron beam may be used.

Setting the film stability property R of the release film of the present invention within the above range can be achieved by a method of increasing the molecular weight of the resin, a method of containing a crosslinking agent including a reactive group such as an epoxy group in a resin film, The method of preparing the resin film, the method of performing the heat treatment on the resin film, and the like. Another method for achieving such film stability value R of the release film of the present invention includes, for example, rubbing the surface of the film. When the above-described surface hardness is to be achieved by rubbing the surface of the release film, the rubbing method is not particularly limited, but a conventional rubbing apparatus can be used, for example.

In the release film for a process according to the present invention, at least one surface thereof has a hardness H of 40 (MPa) or more as measured by a nanoindentation method with a maximum indentation load of 2 mN at a test temperature of 180 캜, ).

When the hardness H is in the above range, peeling from a metal surface having a high roughness such as a roughened surface of a copper foil, and peeling after adhesion with a metal surface having a relatively high temperature, high pressure and / or long- Therefore, with the release film for process according to the present invention, the embodiment having the characteristic (2) can be more suitably used for producing a multilayer printed wiring board or the like having a metal surface with high illuminance such as a blackened copper foil layer.

The hardness H was calculated by dividing the maximum indentation load (F) by the maximum indentation load (Berkovich indenter) at a measuring temperature of 180 ° C by using a nanoindenter after pushing the triangular diamond indenter (Berkovich indenter) _max ) and the indentation depth (h _c ).

Hardness H = F _{max / (} 23.96 x h _c ² )

The mechanism by which the hardness H is in the above range makes it easier to peel off the surface of a metal having a high roughness such as a blackened copper foil surface is not necessarily clear and is not intended to be bound to a particular theory, Even in the case of hot pressing with a metal surface having a high pressure and / or a long time of high roughness, the degree of deformation of the film surface having a high hardness following the concavo-convex pattern of the metal surface with high roughness is small and the degree of close contact with the metal surface is small It is presumed that there is some relation with.

The hardness H is more preferably 45 MPa or higher, and particularly preferably 55 MPa or higher.

From the viewpoints of workability and handling, it is preferable that the hardness H of the film is not more than 130 MPa, and particularly preferably not more than 115 MPa, although the hardness H of the film is preferably high in terms of peelability.

The setting of the hardness H of the release film of the present invention within the above range can be carried out by a method of increasing the molecular weight of the resin, a method of containing a crosslinking agent including a reactor such as an epoxy group in a resin film, a method of orienting resin molecules , A method of performing heat treatment on the resin film, and the like.

In the above-mentioned aspect of the process release film of the present invention, it is preferable that at least one surface having the characteristic (1) and the at least one surface having the characteristic (2) are the same surface. That is, in the above aspect of the present invention, it is preferable that at least one surface has both of the characteristics (1) and (2).

Since the at least one surface has the characteristics of (1) and the characteristic of (2) at the same time, the peeling from the surface of the metal having a high degree of roughness becomes easier, so that such a surface is subjected to so- It is particularly suitable for use in contact with a metal surface having a high surface roughness such as a copper foil.

It is preferable that the process release film of the present invention has a contact angle with respect to water of at least one surface thereof, preferably at least one surface having the above-mentioned characteristic (1), of 90 to 130 degrees. By having such a contact angle, the release film for processing of this embodiment has a low wettability and is excellent in peelability from a metal surface having a high roughness, in particular, a blackened copper foil surface, and a mold release after hot pressing, It can be made even easier.

The contact angle of the at least one surface with respect to water is preferably 95 ° to 120 °, more preferably 98 ° to 115 °, and still more preferably 100 ° to 110 °.

It is also preferable that the releasing film for processing of the present invention has a tensile elastic modulus at 120 ° C of 75 MPa to 500 MPa or a tensile elastic modulus at 170 ° C of 75 MPa to 500 MPa. It is also preferable that the release film for processing of the present invention has a tensile elastic modulus at 120 ° C of 75 MPa to 500 MPa and a tensile elastic modulus at 170 ° C of 75 MPa to 500 MPa.

Since the tensile elastic modulus at 120 占 폚 is 75 MPa to 500 MPa or the tensile elastic modulus at 170 占 폚 is 75 MPa to 500 MPa, the generation of wrinkles in the hot press process and the like can be effectively suppressed.

The release film for processing of the present embodiment preferably has a tensile elastic modulus at 120 ° C of 80 MPa to 400 MPa, more preferably 85 MPa to 350 MPa, further preferably 88 MPa to 300 MPa, Particularly preferably from 90 MPa to 280 MPa.

The release film for processing of the present embodiment preferably has a tensile elastic modulus at 170 캜 of 80 MPa to 400 MPa, more preferably 85 MPa to 350 MPa, even more preferably 88 MPa to 300 MPa, MPa to 280 MPa, more preferably 95 MPa to 200 MPa, and particularly preferably 105 MPa to 170 MPa.

The releasing film for processing of this embodiment is particularly preferable because both the tensile elastic modulus at 120 ° C and the tensile elastic modulus at 170 ° C are both within the above preferable range because the degree of freedom and use diffuse during processing.

The release film for a process of the present invention has a thermal dimensional change ratio of 23 to 120 캜 in the TD direction (transverse direction) of 3% or less, or a thermal dimension of 23 to 170 캜 in the TD direction (transverse direction) It is preferable that the rate of change is 4% or less. Further, it is more preferable that the thermal dimensional change ratio at 23 占 폚 to 120 占 폚 in the TD direction (transverse direction) is 3% or less and the thermal dimensional change rate at 23 占 폚 to 170 占 폚 in the TD direction (transverse direction) is 4%

The thermal dimensional change ratio in the TD direction (transverse direction) of 23 ° C to 120 ° C is 3% or less, or the thermal dimensional change rate in the TD direction (transverse direction) of 23 ° C to 170 ° C is 4% It is possible to more effectively suppress the occurrence of wrinkles on the surface. In this embodiment, the mechanism in which the generation of wrinkles is more effectively suppressed from the fact that the rate of thermal dimensional change in the transverse direction (TD) uses the specific value is not necessarily clear. However, by using a film having relatively small thermal expansion / contraction, It is presumed that the thermal expansion / contraction of the release film for the process by heating / cooling is suppressed.

In the process for producing a release film for a process according to the present embodiment, the thermal dimensional change rate in the TD direction (transverse direction) of 23 ° C to 120 ° C is preferably 2.5% or less, more preferably 2.0% or less, and further preferably 1.5% or less. On the other hand, it is preferable that the thermal dimensional change rate in the TD direction (transverse direction) at 23 캜 to 120 캜 is -5.0% or more.

In the release film for a process according to the present embodiment, the thermal dimensional change rate in the TD direction (transverse direction) of 23 ° C to 170 ° C is preferably 3.5% or less, more preferably 3.0% or less, and further preferably 2.0% or less. On the other hand, it is preferable that the thermal dimensional change ratio in the TD direction (transverse direction) at 23 캜 to 170 캜 is -5.0% or more.

In the release film for a process of the present invention, the sum of the thermal dimensional change rate in the TD direction (transverse direction) and the thermal dimensional change rate in the MD direction (long direction in manufacturing the film, hereinafter also referred to as "longitudinal direction" desirable.

That is, the sum of the thermal dimensional change ratio in the transverse direction (TD) direction of the process release film at 23 ° C to 120 ° C and the thermal dimensional change rate at 23 ° C to 120 ° C in the longitudinal (MD) direction is preferably 6% The sum of the thermal dimensional change rate in the TD direction (transverse direction) of 23 DEG C to 120 DEG C and the thermal dimensional change rate in the MD direction of 23 DEG C to 120 DEG C is preferably 5.0% or more.

The release film for a process according to the present embodiment has a thermal dimensional change rate in a range of 23 占 폚 to 120 占 폚 in a transverse direction (TD) and a thermal dimensional change rate in a longitudinal direction (MD) of 23 占 폚 to 120 占 폚 of 6% It is possible to more effectively suppress the occurrence of wrinkles in the process and the like.

The sum of the thermal dimensional change rate in the transverse direction (TD) of 23 DEG C to 170 DEG C and the thermal dimensional change rate of 23 DEG C to 170 DEG C in the longitudinal direction (MD) of the process release film of the present invention is preferably 7% , And the sum of the thermal dimensional change rate in the TD direction (transverse direction) of 23 ° C to 170 ° C and the thermal dimensional change rate in the MD direction of 23 ° C to 170 ° C is -5.0% or more.

The release film for a process according to the present embodiment has a thermal dimensional change rate in the transverse direction (TD) of 23 ° C to 170 ° C and a thermal dimensional change rate in the MD direction of 23 ° C to 170 ° C of 7% It is possible to more effectively suppress the occurrence of wrinkles in the process and the like.

The thickness of the process release film of the present invention is not particularly limited as long as the film can be used as a film and can be used as a release film. The thickness is usually 5 to 150 占 퐉, preferably 15 to 100 占 퐉, 25 to 80 μm.

The at least one surface of the release film for process of the present invention may satisfy the following characteristics: (1) the film stability property R measured by the nanoindentation method at a test temperature of 180 占 폚 is R? 70 (%); But it is preferable to include a polyester resin and / or a polyamide resin because a suitable film stability value R can be realized relatively easily and inexpensively.

(Polyester resin)

The polyester resin preferably used in the present invention may be homopolyester or copolymerized polyester. When a homopolyester is used, it is preferably obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic glycol. Examples of the aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalene dicarboxylic acid. Examples of the aliphatic glycol include ethylene glycol, diethylene glycol, 1,4-cyclohexane di Methanol and the like. Representative polyesters include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and the like. On the other hand, as the dicarboxylic acid component using the copolymer polyester, isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalene dicarboxylic acid, adipic acid, sebacic acid, (E.g., p-oxybenzoic acid), and the like. Examples of the glycol component include ethylene glycol, diethylene glycol, propylene glycol, butanediol, 1,4-cyclohexane dimethanol, neopentylglycol, and the like.

The polyester preferably used in the present invention may be one obtained by a melt polymerization reaction. However, when a raw material obtained by solid phase polymerization of a polyester obtained by polymerizing a melt after polymerization is used, the amount of oligomers contained in the raw material may decrease desirable.

The amount of the oligomer contained in the polyester is preferably 0.7% by weight or less, more preferably 0.5% by weight or less. When the amount of the polyester oligomer is small, the amount of the oligomer contained in the process release film of the present invention is reduced, and the effect of preventing oligomer deposition on the film surface is particularly high.

In embodiments where the process release film comprises a polyester resin, the layer comprising the polyester resin may contain particles for the primary purpose of imparting slippery. The type of particles contained therein is not particularly limited as long as it is a particle capable of imparting lubricity, and specific examples thereof include silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, , Titanium oxide, and the like. Further, heat-resistant organic particles described in JP-A 59-5216 and JP-59-217755 can be used. Examples of other heat-resistant organic particles include thermosetting urea resins, thermosetting phenol resins, thermosetting epoxy resins, and benzoguanamine resins. It is also possible to use precipitation particles in which a part of metal compounds such as catalysts are precipitated and finely dispersed in the polyester production process

On the other hand, the shape of particles to be used is not particularly limited, and any of spherical, massive, rod-shaped, and flat-shaped particles may be used. There are no particular restrictions on hardness, specific gravity, color, etc. These series of particles may be used in combination of two or more kinds, if necessary.

The average particle diameter of the particles used is generally in the range of 0.01 to 3 占 퐉, preferably 0.01 to 1 占 퐉. When the average particle size is 0.01 m or more, the aggregation of the particles is suppressed and the sufficient dispersibility is facilitated. On the other hand, when the average particle size is 3 m or less, the surface roughness of the film is suppressed within a desirable preferable range.

The content of particles in the polyester layer is generally in the range of 0.001 to 5% by weight, preferably 0.005 to 3% by weight. When the content of the particles is 0.001% by weight or more, the film is sufficiently lubricated, and if it is 5% by weight or less, sufficient transparency of the film is secured.

The method of adding particles to the polyester layer is not particularly limited, and conventionally known methods are employed. For example, the polyester constituting each layer may be added at every stage of production, but preferably the polycondensation reaction can proceed after the esterification step or the transesterification reaction.

A method of mixing a polyester raw material with a slurry of a particle dispersed in ethylene glycol or water using a vent type kneading extruder or a method of mixing a polyester raw material with a dried particle using a kneading extruder .

(Polyamide resin)

The polyamide resin preferably used in the present invention may be an aliphatic polyamide resin or an aromatic polyamide resin, but an aliphatic polyamide resin is more preferable.

The aliphatic polyamide resin can be prepared by ring opening-polymerization of lactam; Polycondensation reaction of an aliphatic diamine component and an aliphatic dicarboxylic acid component; Polycondensation of an aliphatic aminocarboxylic acid, and the like.

Examples of the aliphatic polyamide obtained by ring opening polymerization of lactam include polyamide 6, polyamide 11, polyamide 12 and polyamide 612 and the like. Examples of the aliphatic polyamide obtained by the polycondensation of the aliphatic diamine component and the aliphatic dicarboxylic acid component include polyamide 66, polyamide 610, polyamide 46, polyamide MXD6, polyamide 6T, polyamide 6I and polyamide 9T .

Among them, polyamide 6 or polyamide 66 is preferable; Polyamide 66 is more preferable. Such a polyamide can realize the above-mentioned characteristic (1) comparatively easily, and has not only a high melting point but also a high elastic modulus, and excellent heat resistance and mechanical properties. In addition, it is advantageous also in the case of forming a laminated film because the adhesiveness to other layers is relatively good.

A film using a polyamide having not only a high melting point but also a high elastic modulus and excellent heat resistance and mechanical properties is effectively suppressed from wrinkling and tearing, and is thus also suitable from the standpoint of keeping a molded article and press equipment clean.

The melting point of the aliphatic polyamide as measured by the DSC method is preferably at least 190 캜. Since it has a melting point of 190 占 폚 or higher, wrinkles can be effectively suppressed even when a process such as hot pressing at a relatively high temperature is performed.

(Other resin)

And may further comprise a resin other than the polyester resin or the polyamide resin, the polyester resin or the polyamide resin. Preferable examples of other resins include heat-resistant elastomers (elastomers) having excellent creep resistance against tensile stress and compressive stress at high temperatures, and heat-resistant elastomers having high elastic recovery properties, which are difficult to relieve stresses do.

As such heat-resistant elastomer, thermoplastic polyamide-based elastomer, thermoplastic polyester-based elastomer and the like are preferable in consideration of affinity with polyester resin or polyamide resin.

Examples of the thermoplastic polyamide-based elastomer include a block copolymer having a polyamide as a hard segment and a polyester or a polyether as a soft segment. Examples of the polyamide constituting the hard segment include polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 11, and the like. Examples of the polyethers constituting the soft segment include polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene glycol (PTMG), and the like.

Examples of the thermoplastic polyester elastomer include a block copolymer having a crystalline polymer composed of a crystalline aromatic polyester unit as a hard segment and a non-crystalline polymer composed of a polyether unit or an aliphatic polyester unit as a soft segment do. Examples of the crystalline polymer composed of the crystalline aromatic polyester unit constituting the hard segment include polybutylene terephthalate (PBT), polybutylene naphthalate (PBN) and the like. Examples of the amorphous polymer composed of polyether units constituting the soft segment include poly (tetramethylene ether) glycol (PTMG) and the like. Examples of the amorphous polymer composed of aliphatic polyester units constituting the soft segment include aliphatic polyesters such as polycaprolactone (PCL).

Specific examples of the thermoplastic polyester elastomer include block copolymers of polybutylene terephthalate (PBT) and polytetramethylene ether glycol (PTMG); Block copolymers of polybutylene terephthalate (PBT) and polycaprolactone (PCL); Block copolymers of polybutylene naphthalate (PBN) and aliphatic polyester, and the like.

The melting point of the thermoplastic polyamide-based elastomer and the thermoplastic polyester-based elastomer measured by the DSC method is preferably 190 ° C or higher. Further, even if the melting point of the thermoplastic elastomer is less than 190 캜, the thermoplastic elastomer is crosslinked chemically by preparing a crosslinking agent with the crosslinking agent, or physically crosslinked with ultraviolet rays, electron beams, gamma rays, etc., The elastic restoration property can be improved.

The polyester resin or the polyamide resin may further include known additives to the extent that the object of the present invention is not impaired. The additive may be, for example, an antistatic agent, an antioxidant, a heat-resistant stabilizer including, for example, a copper compound system, a known additive such as a lubricant such as calcium stearate and aluminum stearate, a heat stabilizer, a lubricant, Or a combination thereof.

(Polyester film layer and polyamide film layer)

The polyester resin or polyamide resin preferably used in the present invention is generally used in a stretched or unstretched film form. That is, the process release film of the present invention preferably has a stretched or non-stretched polyester film layer or a stretched or non-stretched polyamide film layer.

The thickness of the polyester film layer suitable for constituting all or a part of the release film for processing of the present invention is not particularly limited as long as the film can be produced as a film, but is generally 12 to 250 탆, preferably 25 to 188 μm, and more preferably in the range of 38 to 125 μm. In the case of a stretched polyester film, the thickness is preferably 3 to 50 μm, more preferably 5 to 35 μm, and even more preferably 7 to 20 μm. Further, in the case of a non-oriented polyester film, it is preferably 5 to 80 μm, more preferably 8 to 50 μm, and particularly preferably 10 to 35 μm.

The production method of the polyester film is not particularly limited and can be suitably produced by conventionally known methods. In the case of a stretched polyester film, it is preferable to produce the polyester film according to the following guidelines, for example.

First, a method of obtaining an unstretched sheet by cooling and solidifying a molten sheet extruded from a die using the above-mentioned polyester resin in a cooling roll is preferable. In this case, in order to improve the planarity of the sheet, it is necessary to increase the adhesion between the sheet and the rotary cooling drum, and it is preferable to select the electrostatic adhesion method and / or the liquid application adhesion method. Next, the obtained unstretched sheet preferably extends in the biaxial direction. In the case of net shear stretching, the unstretched sheet is first stretched in one direction by a roll or tenter stretching machine. The stretching temperature is generally 70 to 120 占 폚, preferably 80 to 110 占 폚, and the stretching ratio is usually 2.5 to 7 times, preferably 3.0 to 6 times. And then extend in a direction perpendicular to the stretching direction of the first step. The stretching temperature is usually 70 to 170 ° C, and the stretching ratio is usually 3.0 to 7 times, preferably 3.5 to 6 times. Subsequently, the film is heat-treated under tension at a temperature of 180 to 270 ° C or under relaxation of 30% or less to obtain a biaxially oriented film. In the above stretching, a method of performing stretching in one direction in two or more steps can be selected. In this case, it is preferable that the stretching magnifications in the two directions finally become the above ranges.

In the present embodiment, simultaneous casting can be selected for the production of the polyester film. The simultaneous ply-folding method is a method in which the above-mentioned unstretched sheet is subjected to simultaneous stretching orientation in the machine direction and the width direction at a temperature controlled to 70 to 120 ° C, preferably 80 to 110 ° C, Is generally 4 to 50 times, preferably 7 to 35 times, more preferably 10 to 25 times as large as the area ratio. Subsequently, the stretched oriented film is subjected to heat treatment under tension at a temperature of 170 to 250 ° C or under relaxation of 30% or less. As for the simultaneous axial stretching apparatus for selecting the stretching method, a conventionally known stretching method such as a screw method, a pantograph method, and a linear driving method can be appropriately selected.

When the polyester film layer has a coating layer formed on its surface, a so-called coating stretching method (in-line coating) in which the film surface is treated during the stretching process of the polyester film described above can be carried out. When the coating layer is formed on the polyester film by the coating stretching method, coating can be performed simultaneously with the stretching, and the thickness of the coating layer can be made thinner depending on the stretching magnification, and the polyester film layer having the desired coating layer It can be efficiently produced.

The thickness of the polyamide film suitable for constituting all or a part of the release film for the process of the present invention is not particularly limited as long as the film can be formed into a film, but is generally 12 to 250 탆, preferably 25 to 188 탆 , More preferably in the range of 38 to 125 占 퐉. In the case of a drawn polyamide film, the thickness is preferably 3 to 50 μm, more preferably 5 to 35 μm, and even more preferably 7 to 20 μm. Further, in the case of a non-oriented polyamide film, it is preferably 5 to 80 μm, more preferably 8 to 50 μm, and particularly preferably 10 to 35 μm.

The method for producing the polyamide film is not particularly limited and can be suitably produced by a conventionally known method. In the case of a drawn polyamide film, it is preferable to produce it according to the following description, for example.

The oriented polyamide film can be obtained, for example, by extruding a polyamide resin, molding it into a film (original film), and then stretching it. When the polyamide resin is extruded, the polyamide resin can be extruded alone, and can be used by dry blending with a polyamide resin and other resins such as a thermoplastic polyamide elastomer. Or melt-kneaded using a twin-screw extruder.

In the case of producing a biaxially stretched polyamide film, it is preferable to subsequently stretch the obtained unstretched film in the biaxial direction. In the case of net shear stretching, the unstretched sheet is first stretched in one direction by a roll or tenter stretching machine. The stretching temperature is usually 30 to 220 ° C, preferably 50 to 210 ° C, and the stretching magnification is usually 1.5 to 4.5 times, preferably 2.5 to 4.0 times. And then extend in a direction perpendicular to the stretching direction of the first step. The stretching temperature is usually 30 to 220 占 폚, and the stretching magnification is usually 1.5 to 4.5 times, preferably 2.5 to 4.0 times.

And then heat-treated at 190 to 210 캜 to obtain a biaxially stretched polyamide film. In the above stretching, a method of performing stretching in one direction in two or more steps can be selected. In this case, it is preferable that the stretching magnifications in the two directions finally become the above ranges.

As for the production of the polyamide film of this embodiment, the simultaneous casting method can be selected. The simultaneous ply-folding method is a method in which the above-mentioned unstretched polyamide film is simultaneously oriented in the machine direction and the width direction under the temperature control at 30 to 220 ° C, preferably 50 to 210 ° C, It is generally 1.5 to 20 times, preferably 5 to 15 times, more preferably 8 to 12 times as large as the magnification. Subsequently, heat treatment is performed at a temperature of 190 to 210 DEG C to obtain a stretched polyamide film. Conventionally known stretching methods such as a screw method, a pantograph method, and a linear driving method can be suitably selected for the simultaneous axial stretching device for selecting the stretching method.

(Multilayer film)

The process of the present invention may be a single layer or a multilayer film of two or more layers, as long as it is against the object of the present invention.

At least one surface of at least one layer positioned on the outermost layer has (1) a film stability property R, measured by the nanoindentation method at a test temperature of 180 DEG C, of R? 70 (%), .

The material of each of the films constituting the multilayer film of two or more layers is not particularly limited, but it is preferable that the film has the following properties: (1) the film stability property R measured by the nanoindentation method at a test temperature of 180 deg. C is R? 70 At least one layer containing a polyester resin and / or a polyamide resin is preferable.

The layer other than at least one layer having the above-mentioned characteristic (1) may be a layer containing a polyester resin and / or a polyamide resin, and the other layer may be a resin, for example, a layer containing another thermoplastic resin. More specifically, it is possible to use, for example, poly (phenylene sulfide) resin (PPS resin), polysulfone resin (PSF resin), polyether sulfone resin (PES resin), polyether ether ketone resin PEEK resin), polyimide resin (PI resin), polyamideimide resin (PAI resin), polyetherimide resin (PEI resin), polyethylene naphthalate resin (PEN resin), polyacetal resin A resin such as a polycarbonate resin (PC resin), a polyphenylene ether resin (PPE resin), a polybutylene terephthalate (PBT resin), a polyethylene terephthalate resin (PET resin), a cyclic polyolefin resin ), Syndiotactic polystyrene resin (SPS resin), polymethylpentene resin (PMP resin), polymethylmethacrylate resin (PMMA resin), polyethylene resin (PE resin), polypropylene (PP resin), polystyrene resin (PS resin), polyvinyl acetate resin (PVAc resin), acrylonitrile butadiene styrene resin (ABS resin) or acrylonitrile styrene resin (AS resin) .

The method of laminating two or more resin layers in the above embodiment is not particularly limited and conventionally known methods can be suitably used. For example, a layer containing a polyester resin and / or a polyamide resin and a resin other than When laminated layers are formed, a multilayer film (original film) can be obtained by co-extruding a polyester resin and / or a polyamide resin and another resin to extend it. Alternatively, a stretched film comprising a separately obtained polyester resin and / or a polyamide resin and a stretched film composed of another resin may be laminated by thermocompression bonding, an adhesive, an adhesive layer, or the like. In order to obtain an original film by co-extruding a polyester resin and / or a polyamide resin and another resin, a film production method such as a T-die method or a cylindrical die method (inflation method) can be generally used.

The adhesive used for the lamination by the adhesive layer, and the resin used for the adhesive layer may be a resin capable of improving the adhesion between the both layers, and there is no particular limitation, and epoxy compounds, isocyanate compounds, acrylic compounds and urethane compounds Can be appropriately selected and used. It is also possible to use a polyester resin, a polyamide resin or other resin to be adhered, a resin which is the same as or similar to the resin, an unsaturated carboxylic acid and / or an acid anhydride thereof.

Examples of the unsaturated carboxylic acid and / or acid anhydride used as the graft monomer include an unsaturated compound having at least one carboxylic acid group having 3 to 20 carbon atoms and an unsaturated compound having at least one carboxylic anhydride group. Examples of the unsaturated group include a vinyl group, a vinylene group, and an unsaturated cyclic hydrocarbon group. Specifically, unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid; Maleic acid, fumaric acid, itaconic acid, citraconic acid, allylsuccinic acid, mesaconic acid, glutaconate, Unsaturated dicarboxylic acids such as nadic acid, methyl nadic acid, tetrahydrophthalic acid and methyl hexahydrophthalic acid; Unsaturated dicarboxylic acids such as maleic anhydride, itaconic anhydride, citraconic anhydride, arylsuccinic anhydride, glutaconic anhydride, anhydrous nadic acid TM, anhydrous methylnadic acid, anhydrous tetrahydrophthalic acid and anhydrous methyl tetrahydrophthalic acid And carboxylic acid anhydrides. These may be used alone or in combination of two or more. In particular, maleic acid, maleic anhydride, nadic acid and anhydric nadic acid are preferable.

The graft rate is usually less than 20% by weight, preferably 0.1 to 5% by weight, more preferably 0.5 to 2% by weight. Since the amount of the graft is in the above range, the graft-modified resin can realize sufficient adhesiveness without impairing mechanical properties, stability, etc. as a resin. The graft-modified resin can be produced by a known graft polymerization method such as a solution method, a melt-kneading method, etc. Among them, a solution method obtained in the form of a solution is preferable.

The release film for a process of the present invention can be easily and sufficiently peeled off from a metal surface such as copper having a high degree of roughness even under severe conditions such as a hot press at a higher temperature, Therefore, it can be suitably used in a process involving peeling of a metal surface having a large surface roughness or a roughened metal surface, for example, in a process of manufacturing a metal / resin laminate including a multilayer printed wiring board.

When the release film for a process according to the present invention is used in a process for producing a metal / resin laminate, the release film for process according to the present invention is preferably subjected to (1) a film resistance value R measured by a nanoindentation method at a test temperature of 180 ° C Is subjected to a hot press process in contact with the roughened metal foil layer on at least one surface having the characteristics of R? 70 (%), and then the process separable film is peeled from the metal foil layer.

The surface roughness of the copper foil layers such as the cross-section copper-clad laminate and the double-side copper-clad laminate, which are the materials of the multilayer printed wiring board, is generally Rz 1.0 to 6.5 μm and generally 1.5 to 4.0 μm. And is particularly suitable for peeling from a metal surface such as a copper foil layer having the same surface roughness.

Hereinafter, the use of the process release film of the present invention in the production of a multilayer printed circuit board will be described by taking the production of a five-layer printed wiring board as an example.

A printed circuit pattern is formed on the copper foil layer 2 and the copper foil layer 3 of the double-sided copper clad laminate composed of the copper foil layer 2 and the copper foil layer 3 and the reinforced glass fiber-epoxy resin composite insulator 1, And an etching treatment using an organic acid-based etching agent. The etching treatment such as the blackening treatment is a treatment of roughening the surface of the copper foil, and it is possible to improve the adhesion with the adhesive prepreg.

Next, the first multi-layer lamination is performed between the substrate and the copper foil layer 7 using the adhesive prepreg 6. At this time, the process release film 4 according to the present invention is placed on the outside of the copper foil layer 2, and the process release film 5 corresponding to the present invention is similarly placed on the outside of the copper foil layer 7, (Fig. 2). Conditions of heat and pressure, for example, is preferably set to 190 ℃, pressure 30 kg / cm ^2, time 40 minutes.

After heating and pressing, the process release films 4 and 5 of the present invention can be easily peeled off, and the occurrence of surface scratches of the copper foil layers 2 and 7 can be effectively suppressed (FIG. 3).

As shown in Fig. 4, a three-layer substrate composed of a laminate composed of the copper foil layer 11, the copper foil layer 9 and the reinforced glass fiber-epoxy resin composite insulator 10 and the copper foil layer 2, the copper foil layer 3, 8 is used to perform a second multi-layer lamination. The release film 5 and the release film 4 are placed on the outer sides of the copper foil layer 11 and the copper foil layer 2, and are laminated and integrated by heating and pressing. Heating and pressing conditions, for example, is preferably set to 190 ℃, pressure 30 kg / cm ^2, time 40 minutes.

After heating and pressing, the process release films 4 and 5 of the present invention can be easily peeled off, and the occurrence of surface scratches of the copper foil layers 2 and 11 can be effectively suppressed (FIG. 5).

As described above, the use of the process release film of the present invention in the production of a multilayer printed circuit board has been described as an example of the production of a five-layer printed circuit board. However, the process release film of the present invention is not limited to the manufacture of multilayered printed circuit boards Can also be used suitably. In addition, not only a multilayer printed wiring board but also a member having a metal surface with a high degree of illuminance such as the production of a metal / resin laminate can be preferably used because of its excellent peelability from a rough surface even in a manufacturing process for heating and pressing.

By using the process release film of the present invention, a multilayer printed wiring board can be manufactured with high quality, low cost, and high production efficiency. Such a multilayer printed wiring board can be suitably used for mounting electronic components, and is suitably mounted on electrical and electronic devices used in information processing apparatuses, displays, communication apparatuses, transportation apparatuses, and the like.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

In the following EXAMPLES / COMPARATIVE EXAMPLES, properties / characteristics were evaluated in the following manner.

(Film stability value R by the nanoindentation method at 180 DEG C)

(Berkovich indenter) of 115 ° angle with a nanoindenter using a nanoindenter at a measurement temperature of 180 ° C, and then depressurized to the film measurement surface at a maximum indentation load of 2 mN to determine the indentation depth at the maximum indentation load (2 mN) The depth of indentation after removal (0 mN) was measured. The ratio of the indentation depth at the maximum indentation load (2 mN) obtained after calculation according to the following formula and the indentation depth after removal (0 mN) was defined as the film stability value R.

Film stability value R = indentation depth after unloading / indentation depth at maximum indentation load

(Hardness H by nanoindentation at 180 DEG C)

The maximum indentation load ( _Fmax ) and the indentation depth (Bmax) of the triangular diamond indenter (Berkovich indenter) of 115 ° angles with a nanoindenter at a measuring temperature of 180 ° C were measured at the maximum indentation load of 2 mN (hc) according to the following formula.

Hardness H = F _{max / (} 23.96 x h _c ² )

(Dissimilarity)

After releasing the press and cooling, the releasing film for the process was peeled off by applying a tensile force by hand to the release film for the production of the copper clad laminate in the hot press, and the peelability was evaluated based on the following criteria.

?: When the tensile force was applied after releasing the press, the release film for the process was simply peeled off from the surface of the copper foil layer.

X: The release film for processing is in close contact with the surface of the copper foil layer and can not be peeled off by hand.

As the release film for the process, a biaxially stretched PET (polyethylene terephthalate) film (UNITIKA, product name: EMBLET PET12) having a thickness of 12 μm was used.

The film stability property R of the biaxially stretched PET film measured by the nanoindentation method at a test temperature of 180 占 폚 was 70.8% and the hardness H measured by the nanoindentation method at the same test temperature of 180 占 폚 was 111.0 MPa.

The copper-clad laminate was prepared by using FR4 (glass epoxy / copper foil 18 μm on both sides, 250 × 200 mm × 0.2 mmt) and using an organic acid-based etching agent (MEC Co., Ltd., product name: MEC V-Bond. BO-7790V) And a roughened copper clad laminate having an etching degree Ra of 2 μm was used. The adhesive layer was laminated between the copper-clad laminate and the copper-clad laminate through a resin layer (adhesive prepreg). Further, a release film for processing was further placed on the uppermost surface and the lowermost surface of the copper clad laminate and hot- And the peelability of the film from the copper foil was confirmed.

As a result of applying the tensile force by hand after release of the press and cooling, the release film for the process was easily peeled from the copper foil layer.

As the release film for the process, a biaxially stretched nylon film (KOHJIN Film & Chemicals Co., Ltd., product name: BONYL RX) having a thickness of 15 μm was used.

The biaxially oriented nylon film had a film stability value R of 77.7% as measured by the nanoindentation method at a test temperature of 180 ° C and a hardness H of 58.7 MPa as measured by the nanoindentation method at the same test temperature of 180 ° C.

The manufacturing process of the laminate was used under the same conditions as in Example 1. [

As a result of applying a tensile force after release of the press and cooling, the release film easily peeled off from the copper foil layer.

In a 40 mm extruder screw extruder T-die film molding machine using commercially available PBT (polybutylene terephthalate) resin (Tm = 224 占 폚, IV = 1.2 (Mitsubishi Engineering-Plastics, trade name: Novaduran 5020) A 20 mu m non-oriented PBT film was produced under the conditions of a resin temperature of 250 DEG C, a chilled roll temperature of 80 DEG C and an air chamber constant pressure of 440 mmHG, and used as a release film for the process.

The film stability property R measured by the nanoindentation method at a test temperature of 180 占 폚 of the non-extensible PBT film was 78.3%, and the hardness H measured by the nanoindentation method at the same test temperature of 180 占 폚 was 68.0 MPa.

The manufacturing process of the laminate was used under the same conditions as in Example 1. [

As a result of applying a tensile force after release of the press and cooling, the release film easily peeled off from the copper foil layer.

As the release film for the process, a non-oriented nylon film (TORAY ADVANCED FILM Co., Ltd., product name: rayfanno NO.1401) having a thickness of 20 μm was used.

The film stability property R measured by the nanoindentation method at a test temperature of 180 占 폚 of the non-oriented nylon film was 76.6%, and the hardness H measured by the nanoindentation method at the same test temperature of 180 占 폚 was 81.9 MPa.

The manufacturing process of the laminate was used under the same conditions as in Example 1. [

As a result of applying a tensile force after releasing the press, the releasing film was easily peeled from the copper foil layer.

[Comparative Example 1]

As the release film for the process, a biaxially stretched polyethylene terephthalate (PET) film (TORAY ADVANCED FILM Co., Ltd., product name: lumirror F865) having a thickness of 16 μm was used.

The film stability property R of the biaxially stretched PET film measured by the nanoindentation method at a test temperature of 180 캜 was 68.5% and the hardness H measured by the nanoindentation method at the same test temperature of 180 캜 was 34.7 MPa.

The manufacturing process of the laminate was used under the same conditions as in Example 1. [

Although the tensile force was applied after release of the press, the release film was in close contact with the surface of the copper foil layer and could not be removed by hand.

The results are summarized in Table 1.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Release film Stretched PET Stretched nylon Lead-free PBT Non-renewable nylon Stretched PET EMBLET
PET12 BONYL RX Unleaded film
Forming rayfanno NO.1401 lumirror
F865 Film thickness μm 12 15 20 20 16 Film stability property R (180 DEG C) % 70.8 77.7 78.3 76.6 68.5 Film Hardness H (180 ° C) Mpa 111.0 58.7 68.0 81.9 34.7 Peelability ○ ○ ○ ○ X

The release film for a process of the present invention can be easily peeled off from a metal surface having a high degree of roughness even after a process under severe conditions and exhibits high availability in the fields of industry, .

1: Glass fiber-epoxy resin composite insulator
2: Copper foil layer
3: Copper foil layer
4: release film
5: release film
6: Adhesive prepreg
7: Copper foil layer
8: Adhesive prepreg
9: Copper foil layer
10: Glass fiber-epoxy resin composite insulator
11: Copper foil layer

Claims (10)

A releasing film for a process comprising a thermoplastic resin, wherein at least one side of the releasing film has the following characteristics:
(1) The film stability property R measured by the nanoindentation method at a test temperature of 180 占 폚,
R ≥ 70 (%).
The process according to claim 1, wherein the release film for process comprises a thermoplastic resin, wherein at least one side thereof has the following characteristics:
(2) The hardness H measured by the nanoindentation method at a test temperature of 180 占 폚,
H ≥ 40 (MPa).
The release film for a process according to claim 2, wherein at least one surface having the characteristics of (1) and at least one surface having the characteristics of (2) are the same surface.
4. The release film according to any one of claims 1 to 3, comprising a polyester resin and / or a polyamide resin.
5. The release film according to any one of claims 1 to 4, having a stretched or non-stretched polyester film layer or a stretched or non-stretched polyamide film layer.
6. The release film according to any one of claims 1 to 5, used for peeling from a roughened metal surface.
7. The release film for a process according to any one of claims 1 to 6, which is used for peeling from a metal surface having a surface roughness Rz of 1.0 to 6.5 占 퐉.
A process for hot-pressing a release film for process according to any one of claims 1 to 7 in contact with a roughened metal foil layer on at least one surface having the characteristics of (1)
A step of peeling the process release film from the metal foil layer,
≪ / RTI > characterized in that the metal / resin laminate comprises a metal.
The manufacturing method according to claim 8, wherein the metal / resin laminate is a multilayer printed wiring board.
An electrical and electronic apparatus having a multilayer printed circuit board manufactured by the manufacturing method according to claim 9.

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