TW201008770A - Release film - Google Patents

Abstract

To provide a release film applicable to a wide variety of thermoplastic liquid crystal polymer films. The release film comprises an ultrahigh molecular weight polyolefin film layer and a reinforcement layer which is laminated to the polyolefin film layer. The polyolefin film layer has a molecular orientation ratio (SOR) of not less than 0.95 and less than 1.05 in the longitudinal direction, and a negative value of coefficient of the average thermal expansion in the planar direction; and the reinforcement layer has a positive value of coefficient of the average thermal expansion in the planar direction. Such a release film is used in a hot pressing step of a process for producing a circuit board comprising a thermoplastic liquid crystal polymer film as (i) a base, (ii) a coverlay film, or (iii) both.

Description

201008770 VI. INSTRUCTIONS: RELATED PARTY This patent claims the priority of Japanese Patent Application No. 2008-1630, filed on Jun. 23, 2008, which is incorporated herein by reference in its entirety. [Technical Field] The present invention relates to a release film which is used in hot press forming of a printed circuit board and which is excellent in heat resistance, release property, non-contamination property, and easy to be discarded, and is used. A method of manufacturing a printed circuit board of a release film. [Prior Art] In the manufacturing process of a printed circuit board such as a printed wiring board, an elastic wiring board, or a multilayer printed circuit board, a film formed of a thermoplastic liquid crystal polymer having an optically anisotropic molten phase is present (hereinafter A copper-clad laminate such as a TLCP film is used as a release film when it is used for hot-press copper foil. In the manufacturing process of a flexible printed circuit board, a coated thin film formed of a TLCP film is heat-pressed to a flexible printed circuit board body in which a circuit has been formed, and is thermally bonded by a thermosetting adhesive to prevent a coating film. Bonding to the hot platen, and the release film is also widely used. This release film is used for heat resistance at the high temperature during hot melt forming of the TLCP film. -4-201008770 For example, Patent Document 1 discloses a release film which is excellent in heat resistance, release property, non-contamination property, and which is easy to dispose of. This document describes a combination of a metal layer and a thermoplastic film having a specific shear modulus as a release film. Since the thermoplastic film of the release film has a specific shear modulus, the cushioning property due to thermal deformation of the thermoplastic film can be prevented during hot press forming, and the unevenness on the substrate is excellent. Motivation. However, when using this release film, depending on the type of the TLCP film, β may be deformed to make it impossible to use it as a printed circuit board. PRIOR ART DOCUMENT PATENT DOCUMENT Patent Document 1: International Publication No. 2008/012940 A SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION An object of the present invention is to provide a substrate or a coating film which is a printed circuit board even if a TLCP film g is used. It can also be applied to a wide range of release films of TLCP films. Another object of the present invention is to provide a release film which can extremely prevent the deformation of a circuit occurring on a printed circuit board without pre-adjusting the thermal expansion coefficient of the TLCP film. Further, another object of the present invention is to provide a printed circuit board capable of preventing circuit deformation extremely high even when a printed circuit board using a TLCP film is hot-pressed at a high temperature by using such a release film. . 201008770 The means for solving the problem The inventors of the present invention have been able to use a printed circuit board because some TLCP films are deformed by hot pressing, and the release film is further examined. First, the previous observation is that when the TLCP film has a positive thermal expansion coefficient during hot pressing, the thermoplastic film forming the release film moving with the TLCP film must also have a positive thermal expansion coefficient.

However, further consideration of this point of view, in fact, a release film composed of a plurality of layers, a thermoplastic film having a positive thermal expansion coefficient combined with a metal layer having a positive thermal expansion coefficient will increase the thermal expansion coefficient of the TLCP film. Depending on the type of TLCP film, the stress of thermal expansion from the thermoplastic film will be transferred to the TLCP film, resulting in deformation of the TLCP film. Secondly, in order to explore an effective means for preventing the deformation of such a TLCP film, it was found that the release film was obtained by combining an ultrahigh molecular weight polyolefin film having a negative thermal expansion coefficient with a reinforcing layer having a positive thermal expansion coefficient. Not only the release property and the thickness direction are excellent, but even in the temperature range in which hot pressing is performed, the stress derived from thermal expansion can be effectively prevented from being transmitted to the TLCP film, and as a result, it is found to be applicable to a wide variety of types. The release film of the TLCP film completes the present invention. That is, the present invention is a film obtained by using a thermoplastic liquid crystal polymer which forms an optically anisotropic molten phase as (i) a substrate, a (Π) coating film or a (ruthenium substrate and a coating film 2) In the manufacturing process of the printed circuit board, a release film of 201008770 is used for hot press forming, and the release film is provided by superposing an ultrahigh molecular weight polyolefin film layer and a reinforcing layer, the ultrahigh molecular weight polyolefin film. In the layer, the molecular orientation SOR in the longitudinal direction of the film is in the range of 0.95 or more and less than 1.05, and the average thermal expansion coefficient of the film in the plane direction is negative 値, and the average thermal expansion coefficient of the reinforcing layer in the planar direction of the reinforcing layer is The release film of the above-mentioned ultrafine molecular weight polyolefin film layer, the average coefficient of thermal expansion coefficient (MUP) in the plane direction may be -1x10_cmcm/cm/°C or less, and the thermal expansion coefficient of the above-mentioned reinforcing layer in the planar direction The average (MRE) can be lxl (T6 to 30xl (T6cm/cm/°C). Further, the ultrahigh molecular weight polyolefin constituting the ultrahigh molecular weight polyolefin film layer The viscosity average molecular weight is mostly more than 10,000. In the release film, the average thermal expansion coefficient (MUP) of the ultrahigh molecular weight polyolefin film layer in the planar direction and the average thermal expansion coefficient (MRE) of the reinforcing layer in the planar direction. The average (Μτ) may also be negative 値. The thickness of each layer may be appropriately set, for example, the thickness (A) of the ultrahigh molecular weight polyolefin film layer may be about 30 to 200/zm, and the thickness of the reinforcing layer (B) , may be about 10 to 100 #m, and the thickness of the reinforcing layer (B) to the thickness (A) of the ultrahigh molecular weight polyolefin film layer (B) / (A) may be 60/40 to 10/90 The present invention further includes a method of manufacturing a printed circuit board by using a film formed of a thermoplastic liquid crystal polymer forming an optically anisotropic molten phase by (2010) a substrate, (ii) a coating film. Or (iii) a method of manufacturing a printed circuit board by hot pressing and forming a substrate and a coating film, wherein the thermosetting layer is joined to the hot plate at the time of hot press forming, as in the first to the patent application scope Release film of any of the seven items. For example, hot pressing The shape temperature may be selected from a temperature lower than a melting point of the thermoplastic liquid crystal polymer by 15 ° C or higher, and a temperature higher than the melting point by 15 ° C (for example, about 250 to 320 ° C). Also included is a printed circuit board produced by the manufacturing method. The present invention also includes an invention relating to a material for lamination, which is formed by forming a printed circuit board, a coating film, or a substrate and a coating film. a film formed by the optically anisotropic melt phase of the thermoplastic liquid crystal polymer, and placed on the circuit board and the coating film, so that the printed circuit board and the coating film are sandwiched, and the reinforcing layer is The average thermal expansion coefficient in the planar direction is a positive reinforcing layer combination 'the ultrahigh molecular weight polyolefin film constituting the release film, and is composed of a laminate material sandwiched between the hot plates for hot press forming. In the laminated material, the molecular orientation S OR of the ultrahigh molecular weight polyolefin film layer in the long direction of the film is 0.9 5 or more, and is less than 1.05, and the plane of the film The average expansion of the thermal expansion coefficient is negative Zhi. 201008770 In the present specification, the average of the thermal expansion coefficients in the planar direction is the thermal expansion coefficient in the direction of the machine axis in the plane direction of the film or the like (hereinafter simply referred to as the MD direction) and the direction orthogonal to the mechanical axis direction (hereinafter referred to as The sum of the coefficients of thermal expansion in the TD direction is divided by the average 値 of 2. Advantageous Effects of Invention According to the present invention, a super-high molecular weight polyolefin film layer having a thermal expansion coefficient of negative enthalpy and a reinforcing layer having a positive thermal expansion coefficient are combined to form a release film, so that it can be applied to a wide variety of TLCP films, and can also be reduced in printing. The board is deformed by hot press forming. By adjusting the thermal expansion coefficient of the ultrahigh molecular weight polyolefin film layer and the reinforcing layer to a specific level, the circuit deformation of the printed circuit board can be extremely prevented without pre-adjusting the thermal expansion coefficient of the TLCP film. [Embodiment] Form for carrying out the invention [release film] The release film of the present invention is a TLCP film (that is, a film formed of a thermoplastic liquid crystal polymer forming an optically anisotropic molten phase) as (i) In the manufacturing step of a printed circuit board of a substrate, a (U) coating film, or (iii) a substrate and a coating film, the film is used for hot press forming, and the release film is an ultrahigh molecular weight polyolefin film layer. And at least one type of reinforcing layer is equipped in a laminated state. .201008770 (Ultra High Molecular Weight Polyolefin Film) The ultrahigh molecular weight polyolefin film has a molecular orientation SOR of 0.95 or more and less than 1.05 in the long direction of the film, and the average thermal expansion coefficient of the film in the plane direction is negative. . When the molecular orientation SOR of the film of the ultrahigh molecular weight polyolefin film in the long direction is in the range of 0.95 or more and less than 1.05, the alignment state of the molecules can be maintained to be the same, and the cooling can be prevented during or after the hot pressing. Printed circuit boards are unevenly tilted or deformed due to the anisotropy of the film. For high-density wiring or thin boards, the SOR should be in the range of 0.98 to 1.03. In order to prevent the deformation of the circuit of the printed circuit board or the inclination of the whole circuit board, the average (MUP) of the coefficient of thermal expansion of the ultrahigh molecular weight polyolefin film in the plane direction must be negative 値, preferably 1 lx (T 6 cm / cm / ° C Hereinafter, it is more preferably a 500xl (T6~ - 10x10-6cm/cm/°C or so, especially about 400xl0_6~-30xlO_6cm/cm/°C. Since the thermal expansion coefficient of the printed circuit board is positive (for example, 18xl (T6cm) ❹ / cm / °C or so), the thermal expansion side is easily deformed due to the stress in the plane direction during hot pressing. However, the thermal expansion coefficient of the ultra-molecular weight polyolefin film constituting the release film is negative, by causing The force of deformation in the plane direction and the deformation on the heat-shrinking side can relax the thermal expansion of the entire laminated body which occurs during hot pressing. The thickness of the ultrahigh molecular weight polyolefin film is preferably in the range of 30 to 20 0 m. Especially in the range of 30 to 180 ym. If the film is too thick, the thermal contraction force of the thermal expansion coefficient of the negative enthalpy of the film will increase by -10-08708770, and the printed circuit board may be inclined in the contraction direction. If the film is too thin, it will be connected. In the thickness of the circuit provided on the printed circuit board, the cushioning property of the release film is insufficient and the fluidity is insufficient, and the adhesion to the liquid crystal polymer film is lowered. The method for producing the ultrahigh molecular weight polyolefin film The method has a predetermined s OR and a coefficient of thermal expansion, and is not particularly limited and can be produced by various methods. For example, such an ultrahigh molecular weight polyolefin film can be obtained by an ultrahigh molecular weight having a prescribed intrinsic viscosity. Polyolefin® is produced by blow molding. When performing blow molding, it is preferable to use a characteristic viscosity [7?] measured at 135 °C in a decalin solvent to be 5 dl / g or more, preferably 7 dl / g ' or more. Ultra-high molecular weight polyolefin of 8~25dl/g, especially if the intrinsic viscosity is less than 5dl / g, the mechanical strength such as tensile strength and impact strength is insufficient, and because of the low melt viscosity, it is easy to occur in the spiral mold. Due to the bending caused by the co-circumference of the melt and the core of the ultrahigh molecular weight polyolefin, or the deviation caused by the bending of the mold core, it is difficult to produce a uniform film, and the formability is poor. The intrinsic viscosity [7?] Upper limit There is no particular limitation, but if it exceeds 25 dl / g, the melt viscosity is too high, and the extrusion formability is poor. The viscosity average molecular weight of the ultrahigh molecular weight polyolefin is 1,000,000 or more, preferably about 2 million to 7 million, especially 300. 10,000 to 6 million. The method for determining the intrinsic viscosity required to calculate the viscosity average molecular weight is determined according to nS K7367-3: 1999. Shear elasticity of ultrahigh molecular weight polyolefin at hot press forming temperature-11-

201008770 rate, can be selected from a wide range of 5xl04~lxl07Pa, preferably j xl06Pa, more preferably lxl05~5xl05Pa (for example, above, and below 5xl05Pa), especially lxl〇5~3xl05Pai elastic rate based on dynamic viscoelasticity It can be measured by measurement and can be measured by an ammeter. Ultrahigh molecular weight polyolefins such as ultrahigh molecular weight poly ultrahigh molecular weight polypropylenes and the like, among which ultrahigh olefins are preferably used. The ultrahigh molecular weight polyethylene may contain ethylene as a repeating monoolefin, and may also contain other copolymerization components. Other copolypropylene, 1-butene, 1-hexene, 1-octene, 4-methylene, etc., carbon 2 to 20, etc.; methyl acrylate, ester, butyl acrylate, 2-ethylhexyl acrylate Ester, propyl ester, methyl methacrylate, ethyl methacrylate, methyl butyl acrylate, 2-ethylhexyl methacrylate, methacrylic acid, etc. - unsaturated carboxylic acid ester; acrylonitrile, methyl propyl aldehyde , methacrolein, vinyl ethyl ether, styrene, ester, and the like. Such copolymerized components can be used singly or in combination. Among such copolymer components, α-olefin is preferred. The amount of polyethylene contained 99.5 mol% of the above repeating unit and 99.8 mol% or more. In the ultrahigh molecular weight polyolefin, it can be blended with no materials, fibers, nucleating agents, release agents, antioxidants (anti-heat stabilizers, etc.) according to requirements, and can be used alone or in combination of two or more kinds of inorganic chelating agents. Special restrictions, such as Lu Yin 1x105~5 1 X 1 05 to Ξ right. Shearing by viscoelastic ethene, or sub-quantity, in addition to B: Ingredients such as keic-penta-acrylic acid cyclohexyl acrylate Acid cyclohexyl ester from nitrile, propylene vinyl acetate • more than two kinds of ultra-high molecular weight, should be included; machine aging agent), : use. Calcium citrate, oxygen -12- 201008770 Titanium, mica, talc, barium sulfate, alumina, cerium oxide, water white mineralization and other layered complexes. The fibers are not particularly limited, and are, for example, inorganic fibers such as glass fibers, carbon fibers, boron fibers, strontium carbide fibers, and alumina fibers; and organic fibers such as aromatic polyamines. The above antioxidant is not particularly limited, and is, for example, 1,3,5-trimethyl-2,4,6-parade (3,5-di-t-butyl- 4-hydroxybenzyl)benzene, 3,9-double {2-(3-(3-t-butyl-4-hydroxy-5-methylphenyl))-propionyloxy]-1,1-dimethylethyl}-2,4,8,10 - A hindered phenolic antioxidant such as tetraoxaspiro[5,5]undecane. The above thermal stabilizer is not particularly limited, and is, for example, phosphoric acid (2,4-di-t-butylphenyl ester), trilauryl phosphate, 2-tert-butyl-phosphate-α-(3-t-butyl-phosphate- 4-hydroxyphenyl)-p-isopropylphenyl ester, bis(p-decylphenyl ester), 3,3'-dithiodipropionate dimyristyl ester, 3,3'-thiodipropionate distearyl Ester, pentaerythritol tetrakis(3-laurylthiopropionate), ditridecyl 3,3'-dithiodipropionate, and the like. Using such an ultrahigh molecular weight polyolefin, blow molding is carried out by a known or customary method, and an ultrahigh molecular weight polyolefin film having the specified SOR and thermal expansion coefficient used in the present invention can be obtained. Further, the obtained film may have a predetermined S OR and a coefficient of thermal expansion, and may also introduce a three-dimensional cross-linking degree to enhance the degree of polymerization of the polymer during polymerization, or may be subjected to post-treatment such as electron beam crosslinking after polymerization. The ultrahigh molecular weight polyolefin film can be used in a single layer or in a plurality of layers, and a plurality of layers formed of different materials can be used as needed to carry out a plurality of layers -13-201008770. (Reinforcing layer) The average coefficient of thermal expansion of the reinforcing layer in the plane direction of the reinforcing layer must be positive, for example, preferably lxl (in the range of T6 to 30x10-6 cm/cm/°C. If the coefficient of thermal expansion is negative, The combination of the thermal expansion coefficient of the negative enthalpy of the ultrahigh molecular weight polyolefin film increases the degree of thermal shrinkage and tilts the printed circuit board in the contraction direction. On the other hand, if the coefficient of thermal expansion is too high, the printed circuit board is reversed. The ground layer is inclined in the direction of expansion. The reinforcing layer preferably has heat resistance. When the coating film made of the liquid crystal polymer is bonded to the printed circuit board by heat fusion, the build-up temperature must be high, generally 26 (TC or more. Therefore, it is suitable for The material of the reinforcing plate is a metal foil which is less oxidatively degraded, for example, an aluminum foil or a stainless steel foil is used, and other materials are preferably a polyimide film of a thermosetting resin, etc. These materials may be used alone or in combination. Two or more. ® In addition, the reinforcing layer can be used in a single layer, or in a multiple layer structure, and can be multi-layered by a film formed of different materials according to requirements. The thickness of the layer should be in the range of 1 〇~1 〇〇Mm, especially in the range of 20~50//m. If the reinforcing layer is too thick, the coefficient of thermal expansion in the plane direction is increased by the effect of positive enthalpy. The influence of the thermal expansion coefficient of the negative enthalpy of the ultrahigh molecular weight polyolefin film causes the printed circuit board to be inclined. If the reinforcing layer is too thin, the influence of the thermal expansion coefficient of the negative enthalpy of the ultrahigh molecular weight polyolefin film is increased, so that the printed circuit board Tilt. -14-

201008770 The release film of the present invention is characterized in that the above-mentioned ultrahigh molecular weight poly-fired and reinforcing layer overlaps in a laminated state. Not only in the form of coincidence, it is integrated. The ultrahigh molecular weight polyolefin film and the reinforcing layer are composed of one piece, but may be used in a super high molecular weight polyolefin film layer when a plurality of overlapping films are used, for example, in a release film, considering the heat number of the entire release film. The average 値(MT) of the average of the plane expansion coefficient (MUP) and the coefficient of the plane direction of the reinforcing layer (MRE) may also be negative as a lxl0_6~-200xl0_6cm/cm/°C, particularly suitable. — —150xl0_6cm / cm / °C or so. In the release film, the ratio of the thickness (B) of the reinforcing layer to the thickness (A) of the ultrahigh polyolefin film layer (B) / (A) should be appropriately set to form the thermal expansion coefficient of each layer, but the coefficient of thermal expansion is drawn. Positive and negative, showing release and adhesion 13 points, for example, (B) / (A) is preferably 60/40~10/90 5 5 / 45 - 1 5 / 85 ° used in the release film of the present invention The surface of the ultra-high molecular weight film should have smoothness, but it can also have two-acting operation and anti-adhesion. In order to remove the air-moulding, the embossing pattern is designed at least on one side. Further, a release agent such as a release agent may be applied to the surface of the ultra-high molecular weight polyolefin film layer on the side of the f-reinforcing layer to have a male form. [Manufacturing method of printed circuit board] The hydrocarbon film can also be made into a general system. f Thermal expansion 値 of the expansion system I, preferably 5x10-6~ The molecular weight can be offset by i; the view is particularly suitable for the olefin thin, the need to slide I, or the side of the I side to improve -15- 201008770 In the method of manufacturing a printed circuit board according to the present invention, a TLCP film is used as the (i) substrate, (ii) a coating film, or a (Hi) substrate and a coating film, and is formed by hot press forming to produce a printed circuit board. When the release film is disposed, the reinforcing layer is connected to the hot plate. (TLCP film)

In the present invention, the raw material of the thermoplastic liquid crystal polymer film which is the substrate of the printed circuit board or the film of the coating layer is not particularly limited, and specific examples thereof are the compounds classified in the following (1) to (4), and Known thermotropic liquid crystal polyesters derived from derivatives thereof and thermally conductive liquid crystal polyester decylamines. However, in order to produce a polymer obtained by forming an optically anisotropic molten phase, a combination of each raw material compound has an appropriate range. (1) Aromatic or aliphatic dihydroxy compounds (refer to the representative example of Table 1) (Table 1) Chemical structural formula of a representative example of an aromatic hydrazine or a fatty dihydroxy compound (X-based hydrogen atom or halogen atom, low-grade Alkyl, phenyl, etc.)

X

H0~〇~^〇~0H (γ-〇---ch2---s-etc)

HO ((3⁄4) nOH (n is an integer of 2 to 12) -16- 201008770 (2) Aromatic or aliphatic dicarboxylic acid (refer to the representative example of Table 2) (Table 2)

Chemical structural formula of a representative example of an aromatic or aliphatic dicarboxylic acid HOOC-^^-COOH

H00C Chat-Η00ί:~Ο"£^Ο~α)0Η

HOOC(CH2)nCOOH (η is an integer of 2 to 12) (3) Aromatic or aliphatic hydroxycarboxylic acid (refer to the representative example of Table 3) (Table 3) Representative examples of aromatic or aliphatic hydroxycarboxylic acid Chemical structure

ϊ〇-〇〇-ε〇〇Η Η0.

\\ />-c〇〇H (4) Aromatic diamine, aromatic hydroxylamine or aromatic aminocarboxylic acid (refer to the representative example of Table 4) (Table 4) Aromatic diamine 'aromatic Chemical structural formula of a representative example of a hydroxylamine or an aromatic aminocarboxylic acid

I^N-^-COOH -17- 201008770 A representative example of the liquid crystal sensitizing molecule obtained by such a raw material compound is a copolymer containing a structural unit shown in Table 5. (Table 5) Representative examples of thermoplastic liquid crystal polymers Copolymers Copolymers ❹

.Copolymer)~0~c Copolymer ~o~〇-〇-°~0~γ_〇-〇- Copolymer ginseng (Υ, _〇---ch2---s — etc.) The thermoplastic liquid crystal polymer of the present invention preferably has a heat resistance and processability expected from the film, and preferably has a melting point in the range of about 200 to about 400 ° C, particularly preferably in the range of about 25 0 to about 350 ° C. However, from the viewpoint of film manufacturing, it has a lower melting point and is easy to manufacture. In the present invention, the liquid crystal polymer film is obtained by extrusion molding a thermoplastic liquid crystal polymer. It can be carried out by any one of the extrusion molding methods -18 · .201008770, but it is known that the T-die film stretching method and the blow molding method are industrially helpful. A film obtained by stretching a film formed film and a laminated plastic body carrying the film may also be used. In particular, the laminated plastic body stretching method or the blow molding method is applied not only to the mechanical axis direction of the film (hereinafter referred to as the MD direction) but also to the direction orthogonal thereto (hereinafter referred to as the TD direction), so that it can be obtained. A film that balances the mechanical properties and thermal properties in the MD and TD directions. When the release film of the present invention is used, various TLCP films can be used as the substrate or the coated film regardless of the change in the thermal expansion coefficient of the TLCP film. That is, the thermal expansion coefficient of the TLCP film may be almost the same or may vary before and after the hot press forming. In particular, the release film of the present invention is used, and the thermal expansion coefficient of the TLCP film is greatly changed before and after the hot press forming (for example, the coefficient of thermal expansion (Ha) after hot press forming and the coefficient of thermal expansion before hot press forming ( The difference between Hb) is l〇~50xl (about T6cm/cm/°C, preferably 20~40 xl (T6cm/cm/°C, which can prevent deformation of the circuit substrate. 9) Thermoplastic liquid crystal polymer used in the present invention. The film may be of any thickness, including a plate shape or a sheet shape of 2 mm or less. However, when a copper plated laminate having a thermoplastic liquid crystal polymer film as an electrically insulating layer is used as a printed circuit board, the film thickness of the film is used. It should be in the range of 20 to 150, especially in the range of 20 to 50; am. If the thickness of the film is too thin, the rigidity or strength of the film becomes small. When the electronic component is mounted on the printed circuit board. It is deformed by pressurization, and the positional accuracy of the wiring is deteriorated, which is an adverse effect. -19- 201008770. The electrical insulating layer of the main circuit board such as a personal computer can use the above thermoplastic liquid crystal polymer film and other electrical insulation. Material, for example A composite of a glass cloth substrate. Further, in the thermoplastic liquid crystal polymer film, an additive such as a lubricant or an antioxidant may be blended. For example, a printed circuit board may be a substrate of the above TLCP film, and is known as a TLCP film. Or a conventional method for forming a circuit layer formed of a conductor such as copper. Such a printed circuit board such as a flexible printed circuit board, a multilayer printed circuit board, etc. When a TLCP film is used as a coating film, The coating film and the printed circuit board can be bonded by hot press forming. In this case, a thermosetting resin such as an epoxy resin can be used between the coating film and the printed circuit board, and then hot pressing can be performed between the coating film and the printed circuit board. In the present invention, the press forming temperature may be selected according to the kind of the thermoplastic liquid crystal polymer constituting the TLCP film, and the forming temperature may be selected from a temperature lower than the melting point of the thermoplastic liquid crystal polymer by 15 ° C. The above range is lower than the melting point by a temperature of 15 ° C. For example, the forming temperature of such a type may be selected from the range of 25 0 to 30 ° C (preferably 260 to 310 ° C). In the hot press forming, the reinforcing layer side constituting the release film of the present invention is brought into contact with the hot plate, and the ultrahigh molecular weight polyolefin film layer side is brought into contact with the circuit surface or the coated film surface of the printed circuit board. [Printed circuit board] The printed circuit board obtained by using the release film of the present invention can be extremely highly prevented from deformation of the circuit due to hot press forming, and has a high density wiring, or The thin circuit board can be effectively utilized without being affected by the tilt caused by the deformation of the circuit. For example, the deformation rate of the circuit substrate for measuring the distance between the circuits on the circuit board before and after the hot pressing is about 0.01-0.06%, preferably Less than 0.05%. [Material for lamination] In the present invention, a material for lamination which is composed of the above TLCP film and the above-mentioned super ® high molecular weight polyolefin film may be passed. In this case, the TLCP film is used to form a printed circuit board, a coating film, or a substrate and a coating film, and the ultrahigh molecular weight polyolefin film is placed on the circuit board and the coating film. The printed circuit board and the reinforcing layer sandwiched by the coating film are used in combination. EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited by the examples. The various physical properties in the examples were determined by the following methods. (Molecular Orientation SOR) SOR (Segment Orientation Ratio) is an index indicating the degree of molecular alignment. Unlike the previous MOR (Molecular Orientation Ratio), it considers the thickness of an object. This molecular orientation SOR is calculated as follows. First, in the known microwave molecular aligning machine, the liquid-21-201008770 crystalline polymer film is inserted into the microwave resonant waveguide, so that the film surface is perpendicular to the direction of the microwave, and the electric field strength of the microwave passing through the film is measured. (Microwave transmission intensity). Next, based on this measurement, m値 (referred to as a refractive index) was calculated from the following formula. m = ( Ζο / Δ z ) x C 1— v max / vo ) However, Zo is the device constant, Λζ is the average thickness, and v max is the β vibration with the largest microwave transmission intensity when the vibration number of the microwave is changed. The number, νο is the number of vibrations with the maximum microwave transmission intensity when the average thickness is zero (that is, when there is no object). Secondly, when the rotation angle of the object with respect to the vibration direction of the microwave is 0°, that is, the direction in which the vibration direction of the microwave is optimally aligned with the molecules of the object, and the direction with the minimum microwave transmission intensity is m値Is m. When the rotation angle is 90°, m値 is m9. The molecular orientation SOR is composed of me / mo. And calculate. (coefficient of thermal expansion cm/cm/°C) Ο The coefficient of thermal expansion α refers to the coefficient of expansion divided by the temperature difference when heated at a constant temperature rise rate from room temperature to the vicinity of the heat distortion temperature of the film, as follows. Calculated. First, one of the ends of the cut-away film was fixed by using a known thermomechanical analysis device, and the tensile load was applied to the other end, and the amount of expansion at a certain temperature increase rate was measured. The length of the tensile direction of the film is mm), the length of the film when heated is L! (mm), the temperature is T2 (°C), the room temperature is Ti (°C), and the thermal expansion -22- 201008770 coefficient α It can be calculated by the following formula. « = C( Li- L〇) / ( T2- TO) / L〇 (xl0_6cm/cm / °C) Further, in the present invention, L〇 = 20mm, T2 = 150T:, 1 = 25°C, stretching The load is 1 g. (Shear modulus Pa) A viscoelastic galvanometer (AR2000, manufactured by TA Instruments Japan) was used to measure at a temperature increase rate of 4 ° C /min, a number of cycles of 1 Hz, a tilt of 1.1 ® %, and a normal stress of 5 N. (Deformability of coating film) The appearance of the coating film on the printed circuit board after lamination was evaluated based on the following criteria. 〇: The coating film has no defects such as deformation, cracking and wrinkles. △: There is no problem such as deformation or cracking on the coating film, and only slight wrinkles are observed. Ο X: There are defects such as deformation, cracking, and wrinkles on the coating film. (Releasability) The ease of peeling off the release film from the printed circuit board after lamination was evaluated based on the following criteria. Good: After hot press forming, the release film can be simply peeled off from the printed circuit board, and the printed circuit board after peeling is not deformed. Poor: After hot press forming, it is difficult to peel off the release film from the printed circuit board, and the printed circuit board after peeling will be deformed. -23- 201008770 The heat rate is divided into two parts: the distance between the distances and the distance between the boards and the distance between the boards. The percentage of the roads. After the rate of electricity, the pressure is changed before the pressure is changed. After the electric test of the road test (calculated by pressure. (The melting point of the TLCP film °C), the thermal change of the film is observed using a differential scanning calorimeter. That is, the TLCP film is heated at a rate of 10 ° C / min to make it completely After melting, the melt was rapidly cooled to 50 ° C at a rate of 10 ° C /min, and when the temperature was increased at a rate of 10 ° C /min, the position of the endothermic peak appeared as a melting point. Example 1) The molecular orientation SOR of the ultrahigh molecular weight polyolefin film layer was 1.01, the average thermal expansion coefficient was -221.5 x 10 cm / cm / ° C, and the shear modulus at the hot laminate temperature was 1.5. Xl〇5Pa ultra-high molecular weight polyethylene sheet (made of New Industry Co., Ltd., "Saxin new light film innovate", thickness 50 from m), and the average coefficient of thermal expansion of ϋ used as a reinforcing layer is 23xl (T6Cm/cm) / °C aluminum foil (made by Toyo Aluminum Co., Ltd., single bright type, thickness 50/zm) Forming a release film. Copolymer of p-hydroxybenzoic acid with 6-hydroxy-2-naphthoic acid (mole ratio of p-hydroxybenzoic acid unit and 6-hydroxy-2-naphthoic acid unit: 73 / 27), melting point The thermoplastic liquid crystal polymer of 280 ° C is melt-extruded, and the elongation ratio of the longitudinal direction and the transverse direction is controlled, and a film having a film thickness of 50 / / m and a melting point of 280 ° C is obtained by a blown film forming method. -24 - .201008770 Further, the obtained film was placed in a hot air dryer at 260 ° C for 3 hours, and a film having a melting point of 290 ° C was obtained by heat treatment. With this film as a base film, a copper foil having a thickness of 18 / zm was placed thereon. The base film was maintained at a pressurization temperature of 290 ° C, a pressurization pressure of 4 MPa, a pressurization time of 60 minutes, and then cooled to 100 ° C to obtain a copper-plated laminate under an open pressurization pressure. The printed circuit board is processed by IPC B-25 and printed as a printed circuit board. ® Copolymer of p-hydroxybenzoic acid with 6-hydroxy-2-naphthoic acid (p-hydroxybenzoic acid unit and 6-hydroxyl group) Mohr ratio of _2-naphthoic acid unit: 73 / 27 ), thermoplastic with melting point of 280 ° C The liquid crystal polymer is melt-extruded, and the longitudinal and lateral extension ratios are controlled, and a film having a film thickness of 25 Å and a melting point of 280 ° C is obtained by blow molding. On this film, five diameters are randomly opened. 20mm perforation, using this as a coating film. (Creation of flexible printed circuit board) Φ The above-mentioned release film, coating film, printed circuit board, and release film are stacked in this order. Unit, 10 units are set on the hot plate, maintained at a pressurization temperature of 280 ° C, a pressurization pressure of 2 MPa, a pressurization time of 60 minutes, and then cooled to 100 ° C under the conditions of open pressurization pressure, vacuum addition After press forming, the release film is peeled off to obtain a flexible printed circuit board. The release property of the release film and the circuit dimensional change rate of the flexible printed circuit board are shown in Table 6. (Example 2) -25- 201008770 The molecular orientation SOR of the ultrahigh molecular weight polyolefin film layer was 1.02, and the average thermal expansion coefficient was 85.4xl (T0cm / cm / °C, and the temperature of the hot laminate layer). An ultrahigh molecular weight polyethylene sheet having a shear modulus of 1.5 X 105 Pa (for "new industry", "Saxinnewlight film innovate", thickness 30; um), and an average of 27 x 1 for the coefficient of thermal expansion used as a reinforcing layer (T6cm/cm / °C polyimide film (Don Pont "Kapton", "25" thick), which forms a release film, and the real example A flexible printed circuit board is obtained in the same manner. The release property of the release film and the circuit dimensional change rate of the flexible printed circuit board are shown in Table 6. (Example 3) In addition to the reinforcing layer system The average thermal expansion coefficient is 16xl (aluminum foil of T6Cm / cm / °C ("SUS304H", thickness: 50/im), which is the same as that of the first embodiment except for the constituent material of the release film. A flexible printed circuit board is produced by the method. The release film is separated from the type and the flexible printed circuit The circuit dimensional change rate of the panel is as shown in Table 6. (Example 4) Except that the sheet used in Example 1 was laminated to a thickness of 150 to be an ultrahigh molecular weight polyolefin film layer, and A flexible printed circuit board was produced in the same manner as in Example 1. The release property of the release film and the circuit dimensional change rate of the flexible printed circuit board were as shown in Table 6 -26-201008770 (Comparative Example 1) In addition to the high-density polyethylene sheet using a molecular orientation S OR of 1.20, an average thermal expansion coefficient of 27 0xl (T6cm/cm/°C, and a shear modulus at a thermocomposite temperature of 1x10Pa) (Dazura Industry Co., Ltd.) A flexible printed circuit board was produced in the same manner as in Example 1 except that the ultrahigh molecular weight polyolefin film layer was replaced by a super high molecular weight polyolefin film layer to form a release film. Release property and flexibility of the release film. The circuit dimensional change rate of the printed circuit board is shown in Table 6. ® (Comparative Example 2) The average thermal expansion coefficient is 100xl (T6cm/cm/°C, and hot pressing, except that the molecular orientation SOR is 1.00. The fluorinated resin sheet with a shear modulus of laminating temperature of lxl 08Pa (Nitto Denko A flexible printed circuit board was produced in the same manner as in Example 2 except that "NITOFLON", thickness 100 "m) was used instead of the ultrahigh molecular weight polyolefin film layer to form a release film. The release ratio and the circuit size change rate of the flexible printed circuit board are shown in Table 6. • (Comparative Example 3) The ultrahigh molecular weight polyolefin film layer was used with a molecular orientation SOR of 1.00 and a thermal expansion coefficient. An ultra-high molecular weight polyethylene sheet (manufactured by Yodogawa Hu-Tech Co., Ltd., "UPE", thickness 100/zm) having an average shear modulus of 2x10 6 Pa at a thermocomposite temperature of 295 x 10 0 6 cm / cm / ° C A flexible printed circuit board was produced in the same manner as in Example 1 except for the release film. The release property of the release film and the circuit size change rate of the flexible printed circuit board are as shown in Table 6 of -27-.201008770. (Comparative Example 4) An ultrahigh molecular weight polyethylene sheet having a molecular orientation degree SOR of 1.00, a thermal expansion coefficient of 295 x 10 6 cm/cm/° C. and a shear modulus of 2x106 Pa at a thermocompression layer temperature. A flexible printed circuit board was produced in the same manner as in Example 1 except that the film was formed by a film of "1" and "11". The release properties of the release film and the electrical ® dimensional change rate of the flexible printed circuit board are shown in Table 6. (Comparative Example 5) A liquid crystal polymer film (manufactured by Kuraray Co., Ltd., "FA thickness 50//m") having an average thermal expansion coefficient of -5xl ("FA thickness 50/m") was used as the release film. In addition to the constituent materials, a flexible printed circuit board was produced in the same manner as in Example 1. The release film release property and the circuit dimensional change rate of the flexible printed circuit board were as shown in Table 6. Road cm ”1 shi -28- 201008770 参e (嗽9濉) Comparative example ultra high molecular weight polyethylene 8 1-H s Τ -221.5 1.5xl05 LCP r- I 1 κη 1 X Good 0.30 inch 1.00 〇Ό CS沄m vn CN 2xl06 m I 1 1 1 X Good 0.20 CO γ2 1.00 I 〇OJ CO ma 2xl06 s cn cs CO <N <3 Good 0.10 CN Fluoro Resin ______ J 8 »—Η 1.00 8 p Η 8 8 lxlO8 Polyimine X Good 0.30 > High Density Polyethylene j § S inch go CS 1x10s s cn cs CO <NX Bad 0.25 Example Inch Ultra High Molecular Weight Polyethylene gr~H ι_ _Η s inch-221.5 1.5x10s ssm Cs 〇 good 0.01 m r-Η s inch-221.5 1.5x10s stainless steel VO VO V〇〇 good 0.02 1.02 Oq τ o H — 85.4 1.5x10s Polyimine CN 〇 Good 0.03 Γ· < «'ws inch-221.5 1.5x10s m CN 〇Good S 〇 resin i 1 Thickness (Aim) SOR QS Average /-N Ph SwX » Φ BtoL έπ τΠΤ\ Material thickness ("m) 1 e Average coating film deformation release circuit size change rate (%) Molecular alignment degree thermal expansion coefficient (xl0~6cm/cm /°C) Thermal expansion coefficient H oa T° /°C) Overview _ m 4Π<Beet m -6ζ-.201008770 As shown in Table 6, in Example 1 and Example 2, a combination of a resin layer having a specific thermal expansion coefficient and a reinforcing layer is used. Therefore, even if hot press forming is performed, the circuit size change rate is low, and the dimensional stability of the circuit board before and after hot press forming can be improved. Further, when the material of the reinforcing layer is stainless steel (Example 3)' or when the thickness of the ultrahigh molecular weight polyolefin film layer is increased (Example 4), the circuit dimensional change rate can be further improved. When the release film of Examples 1 to 4 was used, it was possible to carry out hot pressing without any deformation of the coating film. Therefore, when the release film of the above embodiment is used for the 0-coated film having the opening portion, it is possible to effectively prevent the opening portion of the coating film from being deformed after hot pressing. On the other hand, in Comparative Examples 1 to 5, the rate of change in circuit size due to hot press forming was higher than that in the examples, and the rate of change was three times or more that of Examples 1 and 2 even when the circuit size did not change. A circuit size change of 10 times or more of Embodiment 4 may also occur. Further, when the release film of Comparative Examples 1 to 5 was used, after the hot pressing, slight defects such as wrinkles, deformation, cracking, and collapse were caused to the coating film. φ [Simple description of the diagram] None. [Main component symbol description] None. -30-

Claims (1)

201008770 VII. Patent Application Range·· 1. A release film which is a film obtained by using a thermoplastic liquid crystal polymer which forms an optically anisotropic molten phase as a (ruthenium substrate, (π) coating film or (iii) in the manufacturing step of the printed circuit board of both the substrate and the cover film, a release film which is used in the hot press forming, wherein the release film overlaps the ultrahigh molecular weight polyolefin film layer and the reinforcing layer The ultrahigh molecular weight polyolefin film layer has a molecular φ orientation SOR of 0.95 or more and less than 1.05 in the longitudinal direction of the film, and the average thermal expansion coefficient of the film in the plane direction is negative 値, and the reinforcing layer is The average coefficient of thermal expansion of the reinforcing layer in the planar direction is positive. 2. The release film according to claim 1, wherein the ultrahigh molecular weight polyolefin film layer has an average coefficient of thermal expansion (MUP) in the plane direction. A 1x10-6 cm/cm/°C or less. 3. The release film of claim 1 or 2, wherein the ultrahigh molecular weight polyolefin film constituting the ultrahigh molecular weight polyolefin film layer The viscosity average molecular weight is more than 1 million. 4. The release film according to any one of claims 1 to 3, wherein the average coefficient of thermal expansion (MRE) of the reinforcing layer in the plane direction is lxl (T f to The release film of any one of claims 1 to 4, wherein the ultrahigh molecular weight polyolefin film layer has a thickness (A) of 30 to 200/. The release film according to any one of claims 1 to 5, wherein the thickness (B) of the reinforcing layer is 10 to 10 gm. -31 - 201008770 7. The release film of any one of the six, wherein the ratio of the thickness of the reinforcing layer (B) to the thickness (A) of the ultrahigh molecular weight polyolefin film layer, (B) / (A), is 60 / 40 to 10 /90. 8. A method of manufacturing a printed circuit board by using a film formed of a thermoplastic liquid crystal polymer forming an optically anisotropic molten phase as (i) a substrate, a (Π) coating film or (iii) a method of manufacturing a printed circuit board by hot press forming of both a substrate and a cover film, wherein in hot press forming, The reinforcing layer is attached to the hot plate and is configured as a release film according to any one of claims 1 to 7. 9 _ The method of manufacturing a printed circuit board according to claim 8 wherein the hot press forming is performed It is selected from a temperature lower than the melting point of the thermoplastic liquid crystal polymer forming the optical phase of the optically anisotropic melting phase by a temperature of 15 volts or more and a temperature lower than the melting point by a temperature of 15 ° C. The method of manufacturing a printed circuit board according to Item 8 or 9, wherein the hot press forming temperature is 250 to 320 °C. A printed circuit board manufactured by the method of any one of claims 8 to 10 of the patent application. 12. A material for lamination, which is formed into a printed circuit board and covered. a thin film, or a film of a thermoplastic liquid crystal polymer having an optically anisotropic melt phase of both the substrate and the cover film, and placed on the circuit board and the cover film to make the printed circuit board and The coating film is sandwiched and combined with a reinforcing layer having a uniform thermal expansion coefficient in the planar direction of the reinforcing layer to form an ultrahigh molecular weight polyolefin film of the release film, and the composition is a type of sandwiched hot plate. In order to carry out the hot press forming product -32-201008770 layer material, the ultrahigh molecular weight polyolefin film has an orientation SOR of 0.95 or more, and the layer of thermal expansion coefficient in the plane direction is molecules in the longitudinal direction of the film and is lower than In the range of 1.05, the film is also negatively averaged. Reference -33- 201008770 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ 参 五 5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: