JP4965216B2 - 4-methyl-1-pentene polymer release film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a single or multilayered 4-methyl-1-pentene polymer releasing film capable of solving the plating problem while keeping the releasing performance and the heat-resistance of a 4-methyl-1-pentene polymer, causing little contamination with the film and useful for a printed circuit board, a thermosetting resin, a synthetic leather, etc. <P>SOLUTION: The 4-methyl-1-pentene polymer releasing film is a single layer film or a multilayer film, wherein the single layer film or the outer layer of the multilayer film is composed of (A) 100 pts.wt. of a 4-methyl-1-pentene polymer and (B) 0.01-0.5 pt.wt. of a phosphorus-containing antioxidant having an SP value of 8.0-10.2 (cal/cm<SP>3</SP>)<SP>1/2</SP>calculated by the Fedors method, a melting point of 20-160&deg;C and a molecular weight of 400-800. More preferably, the composition is combined with (C) a specific hindered phenol antioxidant and/or (D) a hydrotalcite at specific ratios. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  In the present invention, since there are few transitions from a film to a flexible wiring board (FPC) or the like, the outer layer of a single layer film or a multilayer film that can be suitably used in the manufacturing process of FPC or the like is a 4-methyl-1-pentene-based heavy layer. The present invention relates to a release film composed of a combination.

  4-Methyl-1-pentene polymer (PMP) has a melting point of 220 to 240 ° C. and is excellent in heat resistance and excellent in properties such as mechanical properties, chemical resistance, electrical insulation and releasability. Therefore, the 4-methyl-1-pentene polymer film is, for example, a release film for FPC, a release film for a rigid substrate, a release film for a thermosetting resin, a release film for a synthetic leather, or the like. Widely used in applications such as mold films and electric wire covering films (for example, Patent Document 1). And as this release film, not only a single layer film but a multilayer film is also used, for example in manufacture of FPC. That is, when a coverlay film with adhesive applied to FPC is thermally bonded, the release film requires appropriate cushioning and release properties to prevent contamination of the electrical circuit with the melted and discharged adhesive. Is done. Therefore, in this application, for example, a soft polyolefin such as an ethylene / acrylic acid copolymer is used as an intermediate layer to provide cushioning properties, and a 4-methyl-1-pentene polymer is used as an outer layer to provide release properties. A multilayer film or the like is used.

By the way, the 4-methyl-1-pentene polymer film is a film having extremely excellent releasability and heat resistance, but depending on the use conditions, the surface of FPC or the like is contaminated by organic substances that migrate from the film. For this reason, there may be a problem that the plating performance to be performed thereafter is reduced, and it has been desired to reduce the amount of transition from the film in applications for release films for FPC and rigid substrates. Therefore, for example, there is also a technique for improving the transition by blending 4-methyl-1-pentene polymer with polyphenylene sulfide resin (PPS) or filler having excellent heat resistance (for example, Patent Document 2) to increase the surface hardness. It has been taken. However, because 4-methyl-1-pentene polymer has poor affinity with PPS and filler, a release film blended in an amount sufficient to increase surface hardness causes the blended resin to fall off the film surface. There is a high possibility that the contamination of the FPC and the rigid substrate will be promoted. In addition, the moldability and the appearance of the resulting film are not sufficient, such as unevenness in thickness during film formation. Recently, it has been proposed to improve the plating property by using a release film having a polyester film as an outer layer (for example, Patent Document 3) instead of a 4-methyl-1-pentene polymer film. However, although this improves the plating property, it is considered that the application is limited because the releasability and heat resistance are not sufficient.
Japanese Patent No. 2619034 JP-A-3-33140 JP 2006-148081 A

  The present invention solves the plating property while maintaining the releasability and heat resistance of the 4-methyl-1-pentene polymer, and is less contaminated with a film for printed circuit boards, for thermosetting resins, And a monolayer or multilayer 4-methyl-1-pentene polymer release film useful for synthetic leather and the like.

  As a result of intensive studies to solve the above problems, the present inventor has found that 4-methyl-1-pentene polymer (A) and a specific phosphorus-containing antioxidant (B), more preferably a specific hindered phenol. The present invention finds that the above-mentioned problems can be solved by making a 4-methyl-1-pentene polymer obtained by combining a series antioxidant (C) at a specific ratio into an outer layer of a single layer film or a multilayer film. Arrived.

The present invention is specified by the following (1) to (6).
(1) 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous Acid salt, 6- [3- (3-tert-butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2 ] If selected from the group consisting of -dioxaphosphepine, the SP value calculated by the method of Fedors is 8.0 to 10.2 (cal / cm3) 1/2 and the melting point is 20 to 160 ° C. And a 4-methyl-1-pentene-based polymer release compound, which is blended with 0.01 to 0.5 parts by weight of at least one phosphorus-containing antioxidant (B) having a molecular weight of 400 to 800. Mold film.
(2) The 4-methyl-1-pentene polymer (A) contains 85 to 100 mol% of 4-methyl-1-pentene and has a melt flow rate (MFR) (temperature 260 ° C., load 5 kg) of 5 to 5. The 4-methyl-1-pentene polymer release film according to (1), which is 150 g / 10 minutes.
(3) Further, the SP value calculated by the method of Fedors is 8.0 to 10.8 (cal / cm ³ ) ^{1/2 with} respect to 100 parts by weight of the 4-methyl-1-pentene polymer (A). 4-methyl as described in (1) or (2), which is blended with 0.01 to 0.15 parts by weight of a hindered phenol antioxidant (C) having a melting point of 20 to 160 ° C. -1-pentene polymer release film.
(4) Further, 0.01 to 0.5 parts by weight of hydrotalcite (D) is blended with respect to 100 parts by weight of 4-methyl-1-pentene polymer (A), (1) To 4-methyl-1-pentene polymer release film according to any one of (3) to (3).
(5) The hindered phenol antioxidant (C) is pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], hexamethylene bis [3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1 -Dimethylethyl} -2,4,8,10-tetraoxaspiro [5 · 5] undecane, 2,6-di-tert-butyl-4-methylphenol, which is at least one selected from the group ( The 4-methyl-1-pentene polymer release film according to 3) or (4).

  The release film in which the outer layer of the monolayer film or multilayer film according to the present invention is made of a 4-methyl-1-pentene polymer has few transitions from the film and is excellent in release properties at high temperatures. Therefore, it can be suitably used for release film applications such as a release film for printed circuit boards, a release film for thermosetting resins, and a release film for synthetic leather. For this reason, since the yield of a product improves, improvement in productivity can be expected.

  Hereinafter, the release film in which the outer layer of the single layer film or the multilayer film according to the present invention is made of a 4-methyl-1-pentene polymer will be specifically described.

  The release film in which the outer layer of the monolayer film or multilayer film of the present invention is composed of a 4-methyl-1-pentene polymer is composed of a 4-methyl-1-pentene polymer (A) and a phosphorus-containing antioxidant (B ), More preferably, a hindered phenol antioxidant (C) and / or hydrotalcites (D).

  The 4-methyl-1-pentene polymer (A) used in the present invention is specifically a homopolymer of 4-methyl-1-pentene or 4-methyl-1-pentene and ethylene or the number of carbon atoms. A copolymer with 3 to 20 other α-olefins such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-tetradecene, 1-octadecene, etc. It is a polymer mainly composed of 4-methyl-1-pentene containing methyl-1-pentene in an amount of 85 mol% or more, preferably 90 mol% or more.

  According to ASTM D1238, the melt flow rate (MFR) of the 4-methyl-1-pentene polymer (A) measured under conditions of a load of 5 kg and a temperature of 260 ° C. is 5 to 150 g / 10 minutes, preferably 7 It is -120g / 10min, More preferably, it is the range of 10-100g / 10min. It is preferable that the MFR of the poly-4-methyl-1-pentene (A) is in the above range because the film formability and the appearance of the resulting film are good and there are few transitions from the film.

The melting point of poly-4-methyl-1-pentene (A) is 210 to 240 ° C, preferably 215 to 235 ° C, and more preferably 220 to 235 ° C. It is preferable that the melting point of poly-4-methyl-1-pentene is in the above range because there are few transitions from the film and high heat resistance.

  Such poly-4-methyl-1-pentene polymer (A) can be produced by a conventionally known method. For example, as described in JP-A-59-206418, a catalyst It can be obtained by polymerizing 4-methyl-1-pentene and the above ethylene or α-olefin in the presence.

The phosphorus-containing antioxidant (B) used in the present invention has an SP value calculated by the method of Fedors (R. F. Fedors., Polym. Eng. Sci. 14 147 (1974)) of 8.0-10. 2 (cal / cm ³ ) ^1/2 , preferably 8.0 to 10.1 (cal / cm ³ ) ^1/2 , more preferably 8.0 to 10.0 (cal / cm ³ ) ^1/2 Range. If the SP value of the phosphorus-containing antioxidant (B) is within this range, it is preferable because there are few transitions from the film.

  The phosphorus-containing antioxidant (B) has a melting point of 20 to 160 ° C, preferably 30 to 150 ° C, and more preferably 40 to 140 ° C. It is preferable for the phosphorus-containing antioxidant (B) to have a melting point within this range because there are few transitions from the film and the antioxidant can be easily handled.

  The phosphorus-containing antioxidant (B) has a molecular weight of 400 to 800, preferably 430 to 750, more preferably 450 to 700. If the molecular weight of the phosphorus-containing antioxidant (B) is within this range, it is preferable because there are few transitions from the film.

  The amount of the phosphorus-containing antioxidant (B) is 0.01 to 0.5 parts by weight, preferably 0.02 with respect to 100 parts by weight of the 4-methyl-1-pentene polymer (A). It is -0.4 weight part, More preferably, it is the range of 0.03-0.3 weight part. When the amount of the phosphorus-containing antioxidant (B) is within this range, the MFR of the film can be kept low, the mechanical strength of the film is excellent, and there are few transitions from the film, which is preferable.

Specific examples of such phosphorus-containing antioxidant (B) are given below.
2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite (Asahi Denka Kogyo Co., Ltd., ADK STAB HP-10), bis [2,4-bis (1,1-dimethylethyl) -6 -Methylphenyl] ethyl ester phosphite (manufactured by Ciba Specialty Chemicals, Irgaphos 38), bis- (2,4-di-tert-butylphenyl) pentaerythritol diphosphite (manufactured by Ciba Specialty Chemicals, Irgaphos) 126), distearyl [(3,5-di-tert-butyl-4-hydroxyphenyl) methyl] phosphonate (manufactured by Ciba Specialty Chemicals, Irgaphos 1093), diethyl {[((3,5-bis (1,1 -Dimethylethyl) -4-hydroxyphenyl) methyl] phosphone G} (manufactured by Ciba Specialty Chemicals, Irgammed 295), 6- [3- (3-tert-butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [D, f] [1,3,2] -Dioxaphosphine (Sumitomo Chemical, Sumilizer GP), bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite (GE, West 624). Among them, 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite (Asahi Denka Kogyo Co., Ltd., ADK STAB HP-10), bis [2,4-bis (1,1-dimethylethyl) ) -6-methylphenyl] ethyl ester phosphite (manufactured by Ciba Specialty Chemicals, Irgaphos 38), 6- [3- (3-tert-butyl-4-hydroxy-5-methyl) propoxy] -2, 4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] -dioxaphosphine (Sumitomo Chemical Co., Sumitizer GP), bis (2,4-di-tert-butylphenyl) ) Pentaerythritol diphosphite (GE, Weston 624) is preferred, and 2,2′-methylenebis (4,6-di-tert-butylpheny ) Octyl phosphite (Asahi Denka Kogyo, ADK STAB HP-10), bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphite (manufactured by Ciba Specialty Chemicals) Irgaphos 38), 6- [3- (3-tert-butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3 , 2] -dioxaphosphepine (Sumitomo Chemical, Sumilizer GP) is particularly preferable.
Of course, a phosphorus-containing antioxidant satisfying the conditions that the SP value other than the above is 8.0 to 10.3 (cal / cm ³ ) ^1/2 , the melting point is 20 to 160 ° C., and the molecular weight is 400 to 800. In the present invention , 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis [2,4] can be used as the phosphorus-containing antioxidant (B). -Bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphite and 6- [3- (3-tert-butyl-4-hydroxy-5-methyl) propoxy] -2,4 , 8,10-tetra-tert-butyldibenz [d, f] [1,3,2] -dioxaphosphine is selected as an essential component.

Next, the hindered phenol antioxidant (C) used in the present invention has an SP value calculated by the Fedors method of 8.0 to 10.8 (cal / cm ³ ) ^1/2 , preferably 8 ^{.0~10.6 (cal / cmcm 3) 1/2} , more preferably in the range of ^{8.0~10.4 (cal / cm 3) 1/2} . When the SP value of the hindered phenol-based antioxidant (C) is within this range, it is preferable because there are few transferred substances from the film.

  The hindered phenol-based antioxidant (C) has a melting point of 20 to 160 ° C, preferably 30 to 150 ° C, and more preferably 40 to 140 ° C. If the melting point of the hindered phenol antioxidant (C) is within this range, it is preferable because there are few transitions from the film.

  The amount of the hindered phenol antioxidant (C) is 0.01 to 0.15 parts by weight, preferably 0 with respect to 100 parts by weight of the 4-methyl-1-pentene polymer (A). The range is 0.02 to 0.15 parts by weight, and more preferably 0.03 to 0.12 parts by weight. When the blending amount of the hindered phenol antioxidant (C) is within this range, the thermal decomposition of the 4-methyl-1-pentene polymer (A) can be suppressed to a low level in the film forming step. This is preferable because of its excellent mechanical strength and few transitions from the film.

Specific examples of such a hindered phenol antioxidant ( C ) are given below.
Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals, Irganox 1010), thiodiethylenebis [3- (3,5-di- tert-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals, Irganox 1035), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Ciba Specialty Chemicals) Chemicals, Irganox 1076), 4,6-bis (dodecylthiomethyl) -o-cresol (Ciba Specialty Chemicals, Irganox 1726), hexamethylenebis [3- (3,5-di-tert- Butyl-4-hydroxy Phenyl) propionate] (manufactured by Ciba Specialty Chemicals, Irganox 259), 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1 , 1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5 · 5] undecane (manufactured by Sumitomo Chemical, Smither GA80), 2,6-di-tert-butyl-4-methylphenol, and the like. be able to. Among these, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Ciba Specialty Chemicals, Irganox 1010), octadecyl-3- (3,5-di -Tert-butyl-4-hydroxyphenyl) propionate (Ciba Specialty Chemicals, Irganox 1076), hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Ciba・ Specialty Chemicals, Irganox 259), 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5.5 Undecane (manufactured by Sumitomo Chemical Co., Sumilizer GA80) and 2,6-di-tert-butyl-4-methylphenol are preferable, and in particular, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl]. ) Propionate] (Ciba Specialty Chemicals, Irganox 1010), hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Ciba Specialty Chemicals, Irganox) 259), 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10 -Tetraoxaspiro [5.5] undecane (Sumitomo Chemical Co., Sumilizer GA8 ), 2,6-di -tert- butyl-4-methylphenol is particularly preferred.
Of course, hindered phenolic antioxidants other than those described above that satisfy the conditions that the SP value is 8.0 to 10.8 (cal / cm ³ ) ^1/2 and the melting point is 20 to 160 ° C. can also be used. .

The hydrotalcite used in the present invention is a water-containing double salt compound composed of magnesium, zinc, aluminum or the like represented by the general formula (1).
Zn _X1 Mg _X2 Al ₂ (CO ₃ ) (OH) _{2 (X1 + X2 + 2)} · nH ₂ O (1)
(0≤X1≤2, 0≤X2≤6, n≥6)

  In the present invention, the hydrotalcite (D) may be a natural product or a synthetic product. Further, the surface is made of higher fatty acid such as stearic acid, higher fatty acid metal salt such as alkali metal oleate, organic sulfonic acid metal salt such as alkali metal dodecylbenzenesulfonate, higher fatty acid amide, higher fatty acid ester or wax. A coated one can also be used.

  The amount of the hydrotalcite (D) is 0.01 to 0.5 parts by weight, preferably 0.02 to 0 parts per 100 parts by weight of the 4-methyl-1-pentene polymer (A). .4 parts by weight, more preferably 0.03 to 0.3 parts by weight. When the blending amount of the hydrotalcites (D) is within this range, it is preferable because there are few transitions from the film.

  The 4-methyl-1-pentene polymer release film of the present invention comprises 100 parts by weight of a 4-methyl-1-pentene polymer (A) and a phosphorus-containing antioxidant (B) 0.01-0. .5 parts by weight, and further various ratios of 0.01 to 0.15 parts by weight of hindered phenolic antioxidant (C) and / or 0.01 to 0.5 parts by weight of hydrotalcite (D). A known method, for example, a V-blender, a ribbon blender, a Henschel mixer, a tumbler blender, or after mixing with the blender, it is melt-kneaded with a single screw extruder, a double screw extruder, a kneader, a Banbury mixer, etc. And then granulated or pulverized, and then formed into a film by a known method such as a single screw extruder, a double screw extruder, or inflation molding. Moreover, the mold release film which provided further mechanical strength can be obtained by extending | stretching the obtained film.

  Of course, a multilayer film having a 4-methyl-1-pentene polymer as an outer layer and a soft polyolefin such as an ethylene / acrylic acid ester copolymer as an intermediate layer, which is one use form of the present invention, is of course separated. A multilayer film using 4-methyl-1-pentene polymer is included only in the outer layer used as the mold surface, but there is no particular limitation on the manufacturing method of these multilayer films, and a T-die apparatus is used. It can be produced by a known method such as laminating a single layer of each layer formed by an extrusion molding method, a hot pressing method, or a solvent casting method, and laminating and thermocompression bonding. Among these, the coextrusion method using a T-die apparatus is excellent in that a wide multilayer film can be easily obtained. Furthermore, a wide multilayer film formed by a coextrusion molding method is preferable as a method for producing a release film for FPC because it can be easily slit in accordance with a wide variety of FPC widths.

  The thickness of the single layer release film comprising the 4-methyl-1-pentene polymer of the present invention is usually 10 to 200 μm, preferably 20 to 150 μm. If it is such a range, it is preferable from the viewpoint of being excellent in film productivity, producing no pinholes at the time of film formation, and obtaining sufficient strength.

  The total thickness of the multilayer release film comprising the 4-methyl-1-pentene polymer of the present invention as an outer layer is usually 30 to 200 μm, preferably 50 to 180 μm, and the thickness of the intermediate layer made of flexible polyolefin is usually The thickness is 10 to 120 μm, preferably 20 to 100 μm. Within such a range, the multilayer release film is preferable because it has an appropriate cushioning property, does not cause pinholes during film formation, and provides sufficient strength.

  In addition, the 4-methyl-1-pentene polymer release film in the present invention is usually added to a polyolefin such as a hydrochloric acid absorbent, a weathering stabilizer, a rust inhibitor, a slip agent, a pigment, and a dye. You may add a compounding agent in the range which does not impair the objective of this invention.

  The release film in which the outer layer of the monolayer film or multilayer film of the present invention is a poly-4-methyl-1-pentene polymer is a release film for printed circuit boards, a release film for thermosetting resins, and a release film for synthetic leather. It can be used for release films that require excellent release properties, such as mold films, but especially as release films for FPC and rigid plates, where there are few transitions from the film, and contamination due to transitions is a major problem It can be used suitably.

  The present inventor washed a copper foil obtained by hot pressing under a predetermined condition with a poly-4-methyl-1-pentene polymer film sandwiched between copper foils, and heated chloroform from the chloroform solution. The residual amount obtained by distilling off was weighed to measure the amount of transfer from the film, and the MFR of the film was also measured to verify the effect. EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.

The amount of transferred material and the MFR of the film were evaluated by the following methods.
[Transition volume]
A film of A4 size cut out from a film molded using a cast film molding machine with a T-die was hot-pressed with the same size of copper foil, and then the copper foil was washed with chloroform. The chloroform solution thus obtained was heated to distill off the chloroform, and the remaining amount was weighed to obtain the amount transferred from the film. The hot pressing was carried out under conditions of 180 ° C., 5 MPa, 60 minutes, n = 5, and after washing the obtained 10 copper foils with chloroform, these solutions were processed together and the remaining amount was weighed. .

[MFR]
The single layer film was measured as it is according to ASTM D1238 under the conditions of a load of 5 kg and a temperature of 260 ° C. On the other hand, in the case of a multilayer film, the outer layer 4-methyl-1-pentene / decene-1 copolymer was peeled off and then sampled and measured under the same conditions.

[Example 1]
A copolymer of 4-methyl-1-pentene and decene-1 (decene-1 content: 3% by weight, MFR: 5 g / 10 min, melting point: 235 ° C.) and 100 parts by weight as a phosphorus-containing antioxidant -[3- (3-tert-Butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] -dioxa Phosphepine (Sumitomo Chemical Co., Ltd., Sumilizer GP, SP value: 9.9, melting point: 115 ° C., molecular weight: 549) 0.15 parts by weight, and further, 0.03 part by weight of calcium stearate was dry blended. The pellets were granulated by melt mixing at a cylinder temperature of 280 ° C. using a shaft extruder. Next, this pellet was film-formed at a cylinder temperature of 280 ° C. using a cast film molding machine with a 40 mmφ T-die to obtain a film having a thickness of 50 μm. The transfer amount and MFR of the obtained film were measured. The results are shown in Table 1.

[Example 2]
6- [3- (3-tert-butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1, as phosphorus-containing antioxidant 3,2] -Dioxaphosphepine (Sumitomo Chemical Co., Sumilizer GP, SP value: 9.9, melting point: 115 ° C., molecular weight: 549) instead of bis [2,4-bis (1,1-dimethyl) Ethyl) -6-methylphenyl] ethyl ester phosphite (manufactured by Ciba Specialty Chemicals, Irgaphos 38, SP value: 8.8, melting point: 89 ° C., molecular weight: 514) 0.15 part by weight, and The pellets were granulated in the same manner as in Example 1 except that 0.05 part by weight of hydrotalcite was mixed. Further, a film having a thickness of 50 μm was formed in the same manner as in Example 1, and the amount of transferred matter and MFR of the obtained film were measured. The results are shown in Table 1.

[Example 3]
Copolymer of 4-methyl-1-pentene, dodecene and tetradecene (dialene 124 content: 5% by weight, MFR: 1 g / 10 min, melting point: 235 ° C.) and 100 parts by weight as phosphorus-containing antioxidant 6- [3- (3-tert-butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] -dioxaphos Fepin (manufactured by Sumitomo Chemical Co., Ltd., Sumilizer GP, SP value: 9.9, melting point: 115 ° C., molecular weight: 549) 0.15 parts by weight, and 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5 · 5] undecane ( Sumitomo Chemical, Sumilizer GA80, SP value: 10.9, melting point: 124 ° C., molecular weight: 741) 0.05 parts by weight After dry blending the calcium stearate 0.03 parts by weight, melt-mixed at a cylinder temperature of 300 ° C. using a 45mmφ twin-screw extruder was granulated pellets. The pellets were then film-formed at a cylinder temperature of 280 ° C. using a cast film molding machine with a 40 mmφ T-die to obtain a film having a thickness of 50 μm. The transfer amount and MFR of the obtained film were measured. The results are shown in Table 1.

[Example 4]
6- [3- (3-tert-butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1, as phosphorus-containing antioxidant 3,2] -Dioxaphosphepine (Sumitomo Chemical Co., Sumilizer GP, SP value: 9.9, melting point: 115 ° C., molecular weight: 549) instead of bis [2,4-bis (1,1-dimethyl) Ethyl) -6-methylphenyl] ethyl ester phosphite (manufactured by Ciba Specialty Chemicals, Irgaphos 38, SP value: 8.8, melting point: 89 ° C., molecular weight: 514) 0.10 parts by weight, hinder 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4 as a dophenol antioxidant , 8,10-tetraoxaspiro [5 · 5] undecane (manufactured by Sumitomo Chemical, Sumilizer GA80, SP value: 10.9, melting point: 12 Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Ciba Specialty Chemicals, Irganox 1010, SP value: 10 instead of 4 ° C., molecular weight: 741) .5, melting point: 110 ° C., molecular weight: 1178) 0.10 parts by weight, and a film having a thickness of 50 μm was obtained in the same manner as in Example 3 except that 0.05 part by weight of hydrotalcite was blended. The amount of transferred material and MFR of the film were measured. The results are shown in Table 1.

[Example 5]
6- [3- (3-tert-butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1, as phosphorus-containing antioxidant 3,2] -Dioxaphosphepine (Sumitomo Chemical Co., Sumilizer GP, SP value: 9.9, melting point: 115 ° C., molecular weight: 549) instead of 2,2′-methylenebis (4,6-di- tert-butylphenyl) octyl phosphite (Asahi Denka Kogyo Co., Ltd., ADK STAB HP-10, SP value: 8.9, melting point: 148 ° C., molecular weight: 583) 0.10 parts by weight, hindered phenol antioxidant 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetra Oxaspiro [5,5] undecane (manufactured by Sumitomo Chemical Co., Ltd., Sumilizer GA80, SP value: 10.9, melting point: 124 ° C., molecular weight: 741) Instead, hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals, Irganox 259, SP value: 9.8, melting point: 104 ° C., molecular weight : 639) A film having a thickness of 50 μm was formed in the same manner as in Example 3 except that 0.10 parts by weight was blended, and the amount of transferred material and MFR of the obtained film were measured. The results are shown in Table 1.

[Example 6]
As hindered phenolic antioxidant, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1, as hindered phenolic antioxidant 1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5 · 5] undecane (manufactured by Sumitomo Chemical, Smither GA80, SP value: 10.9, melting point: 124 ° C., molecular weight: 741) Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Ciba Specialty Chemicals, Irganox 1010, SP value: 10.5, melting point: 110 ° C., molecular weight: 1178) A pellet was granulated in the same manner as in Example 3 except that 0.05 part by weight and 0.05 part by weight of hydrotalcite were mixed. Using these pellets and ethylene / acrylic acid ester (EEA) pellets, a three-layer, three-layer T-die apparatus was used to create a 4-methyl-1-pentene polymer / EEA / 4-methyl-1-pentene heavy polymer. A three-layer film of a combined body (thickness: 30/60/30 μm) was molded, and the amount of transferred material and MFR of the obtained film were measured. The results are shown in Table 1.

[Comparative Example 1]
Bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphite as a phosphorus-containing antioxidant (manufactured by Ciba Specialty Chemicals, Irgaphos 168, SP value: 8.9) , Melting point: 183 ° C., molecular weight: 646) 0.10 parts by weight, and pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] as a hindered phenol antioxidant (Ciba Specialty Chemicals, Irganox 1010, SP value: 10.5, melting point: 110, molecular weight: 1178) A 50 μm thick film was formed in the same manner as in Example 3 except that 0.20 part by weight was blended. Then, the amount of transferred substance and MFR of the obtained film were measured. The results are shown in Table 1.

[Comparative Example 2]
Three layers as in Example 6 except that 0.25 part by weight of Irganox 1010, SP value: 10.5, melting point: 110, molecular weight: 1178), a hindered phenol antioxidant, was added as an antioxidant. The film was molded, and the amount of transferred material and MFR of the obtained film were measured. The results are shown in Table 1.

  The release film in which the outer layer of the monolayer film or multilayer film of the present invention is a poly-4-methyl-1-pentene polymer is a release film for printed circuit boards, a release film for thermosetting resins, and a release film for synthetic leather. It can be used for release films that require excellent release properties, such as mold films, but especially as release films for FPC and rigid plates, where there are few transitions from the film, and contamination due to transitions is a major problem It can be used suitably. As a result, the industrial defect value is extremely high because the defect rate of the product due to the decrease in plating strength can be greatly improved.

Claims (5)

The outer layer of the single layer film or the multilayer film is composed of 100 parts by weight of 4-methyl-1-pentene polymer (A), 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, Bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphite, 6- [3- (3-tert-butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] -dioxaphosphine is selected from the group consisting of SP value calculated by Fedors method is 8 1.0 to 10.2 (cal / cm ³ ) 1/2, a melting point of 20 to 160 ° C., and a molecular weight of 400 to 800, at least one kind of phosphorus-containing antioxidant (B). 01-0 And 5 parts by weight, and characterized by being blended, 4-methyl-1-pentene polymer release film.   The 4-methyl-1-pentene polymer (A) contains 85 to 100 mol% of 4-methyl-1-pentene, and the melt flow rate (MFR) (temperature 260 ° C., load 5 kg) is 5 to 150 g / 10. The 4-methyl-1-pentene polymer release film according to claim 1, wherein the release film is a minute. Furthermore, with respect to 100 parts by weight of the 4-methyl-1-pentene polymer (A), the SP value calculated by the Fedors method is 8.0 to 10.8 (cal / cm 3) 1/2, and 4. The 4- component according to claim 1, wherein 0.01 to 0.15 part by weight of a hindered phenol antioxidant (C) having a melting point of 20 to 160 ° C. is blended. 4. Methyl-1-pentene polymer release film. Furthermore, 0.01 to 0.5 parts by weight of hydrotalcite (D) is blended with 100 parts by weight of 4-methyl-1-pentene polymer (A). The 4-methyl-1-pentene polymer release film according to any one of claims 1 to 3.   The hindered phenol-based antioxidant (C) is pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3 -Tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,6-di -Tert-butyl-4-methylphenol, hexamethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], at least one selected from the group The 4-methyl-1-pentene polymer release film according to claim 3 or 4.