JP7044521B2 - Release film - Google Patents

Description

The present invention relates to a single-layer or multi-layered release film having a layer containing a 4-methyl-1-pentene polymer.

The 4-methyl-1-pentene / α-olefin copolymer containing 4-methyl-1-pentene as a main constituent monomer is widely used in various applications because of its excellent heat resistance, mold release property, and chemical resistance. ing. For example, the film containing the copolymer makes use of its features such as good mold release property, and various mold release films such as a mold release film for manufacturing a printed wiring substrate, a mold release film for molding a composite material, and a mold release paper for manufacturing synthetic leather. (See Patent Document 1), and the molded product containing the copolymer is used for laboratory equipment and mandrel for rubber hose manufacturing by taking advantage of its features such as heat resistance, chemical resistance, acid resistance, and transparency. ing.

On the other hand, printed wiring boards are often used with the development of electronic devices. A printed wiring board is one of the main components of an electronic device for fixing and wiring an electronic component, and includes a rigid substrate, a flexible printed circuit board, and a rigid flexible substrate.

For example, when manufacturing a flexible printed circuit board (hereinafter, also referred to as “FPC”), a step of laminating a coverlay film on a substrate on which a circuit pattern is formed, and a step of laminating the obtained laminated body with a hot press plate. A hot press forming step of sandwiching, heating and pressurizing is usually provided.

In the hot press molding step, in order to prevent the coverlay film and the hot press plate from adhering to each other, usually polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, or polyvinyl fluoride are in between. A fluorofilm made of vinyl fluoride or the like, or a release film made of polymethylpentene film, polybutylene terephthalate, syndiotactic polystyrene or the like is used (see Patent Document 2).

As the release film, a film made of poly-4-methyl-1-pentene resin is used because it has excellent heat resistance and mold release property after heating and pressurization, and also has excellent followability to the substrate circuit. Has been proposed. Since poly-4-methyl-1-pentene has a high melting point of 235 ° C, it has excellent heat resistance and releasability even in the molding of copper-clad laminates performed at a temperature of about 180 ° C (patented). See Document 3).

Patent Document 4 discloses a release film having excellent heat resistance and stain resistance.
On the other hand, a protect film composed of a 4-methyl-1-pentene polymer and an olefin elastomer (Patent Document 5), and a film formed from a composition of a 4-methylpentene polymer and an olefin elastomer (Patent). Document 6), release paper for producing synthetic leather (Patent Document 7) and the like are known.

Japanese Unexamined Patent Publication No. 2010-0277445 Japanese Unexamined Patent Publication No. 2005-350601 Japanese Unexamined Patent Publication No. 2014-098138 Japanese Unexamined Patent Publication No. 2016-098257 International Publication No. 2015/012274 International Publication No. 2013/099876 Japanese Unexamined Patent Publication No. 2017-07475

However, although a higher level is required for the unevenness followability and the releasability, this requirement cannot be achieved by the above-mentioned conventional releasable film.
The present invention has been made in view of the above circumstances, and an object of the present invention is to solve the above-mentioned problems. That is, an object of the present invention is to provide a release film having excellent unevenness followability and releasability.

An example of a specific means for solving the above-mentioned problem is as follows.

[1] A 4-methyl-1-pentene (co) polymer (A) 50 to 95% by mass satisfying the following requirements (Aa) to (Ac).
Of the 4-methyl-1-pentene copolymer (B) 5 to 50% by mass ((co) polymer (A) and copolymer (B)) satisfying the following requirements (B) to (Bd). A single-layer or multi-layered release film having a layer composed of the composition (X) containing (the total amount is 100% by mass).
(Aa) The content of the structural unit (P) derived from 4-methyl-1-pentene is 90 to 100 mol%, and the α-olefin having 2 to 20 carbon atoms (4-methyl-1-pentene). The content of the constituent unit (AQ) derived from (excluding) is 0 to 10 mol% (the total content of the constituent unit (P) and the constituent unit (AQ) is 100 mol%) (A). -B) The ultimate viscosity [η] measured in 135 ° C. decalin is 0.5 to 5.0 dl / g. (Ac) The melting point (Tm) measured by DSC is in the range of 200 to 250 ° C. (A-c). B-a) An α-olefin (4-methyl-1-pentene) having a content of the structural unit (P) derived from 4-methyl-1-pentene of 80 to 97 mol% and having 2 to 20 carbon atoms. The content of the constituent unit (BQ) derived from (excluding) is 3 to 20 mol% (the total content of the constituent unit (P) and the constituent unit (BQ) is 100 mol%) (B-). b) The ultimate viscosity [η] measured in 135 ° C. decalin is 0.5 to 5.0 dl / g (B-c) and the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC). The molecular weight distribution (Mw / Mn), which is the ratio to the number average molecular weight (Mn), is 1.0 to 3.5. (Bd) The melting point (Tm) measured by DSC is in the range of 100 to 199 ° C.

[2] The release film according to [1], wherein the (co) polymer (A) satisfies the following requirement (Ad), and the copolymer (B) satisfies the following requirement (B-e). ..
(Ad) The density is 820 to 850 kg / m ³ (B) The density is 825 to 860 kg / m ³ .

[3] The release film according to [1] or [2], wherein the structural unit (BQ) is a structural unit derived from an α-olefin having 2 to 4 carbon atoms.

[4] The blocking coefficient is in the range of 0.5 to 150 mN / cm, and the 80 ° C. storage elastic modulus E'measured by a solid viscoelastic device is in the range of 0.5 to 130 MPa, [1] to [ 3] The release film according to any one of.

[5] The release film according to any one of [1] to [4], which is used for a flexible printed substrate.

According to the present invention, it is possible to provide a release film having excellent unevenness followability and releasability.

Hereinafter, specific embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and the present invention is carried out with appropriate modifications within the scope of the object of the present invention. be able to.

≪Release film≫
The release film according to the present invention is
It has 90 mol% or more and 100 mol% or less of a structural unit (P) derived from 4-methyl-1-pentene (hereinafter, may be simply referred to as “constituent unit (P)”) and 4-methyl-1. -Constituent unit (AQ) derived from α-olefin having 2 to 20 carbon atoms other than pentene (hereinafter, may be simply referred to as "constituent unit (AQ)") is 0 mol% or more and 10 mol% or less ( However, the 4-methyl-1-pentene (co) polymer (A) having a total of the structural unit (P) and the structural unit (AQ) is 100 mol% (hereinafter, simply "polymer (A)". ) ”),
A structural unit (BQ) derived from an α-olefin having 80 mol% or more and 97 mol% or less of a structural unit (P) and having 2 to 20 carbon atoms other than 4-methyl-1-pentene (hereinafter, simply "constituent"). Unit (BQ) ”) is 3 mol% or more and 20 mol% or less (however, the total of the constituent unit (P) and the constituent unit (BQ) is 100 mol%), 4-. It contains a methyl-1-pentene copolymer (B) (hereinafter, also simply referred to as “copolymer (B)”).
From the composition (X) in which the content of the polymer (A) is 50% by mass or more and 95% by mass or less with respect to the total 100% by mass of the polymer (A) and the copolymer (B). Has a layer of

[Composition (X)]
The composition (X) is a composition containing the polymer (A) and the copolymer (B).
Hereinafter, each of the polymer (A) and the copolymer (B) will be described.

<Polymer (A)>
The polymer (A) satisfies the following requirements (A) to (Ac). The polymer (A) contained in the composition (X) may be one kind or two or more kinds.
Requirement (A-a): The content of the structural unit (P) in the polymer (A) is 90 mol% or more and 100 mol% or less, preferably 95 mol% or more and 100 mol% or less, and the constituent unit (AQ). The content rate (when the constituent unit (AQ) is 2 or more, the total content of the 2 or more) is 0 mol% or more and 10 mol% or less, preferably 0 mol% or more and 5 mol% or less (however). , The total content of the constituent unit (P) and the constituent unit (AQ) is 100 mol%).

When the content of the structural unit (P) in the polymer (A) is 90 mol% or more, there is an advantage that a release film having an excellent heat resistance and an elastic modulus suitable for handling can be obtained.

Examples of α-olefins having 2 to 20 carbon atoms other than 4-methyl-1-pentene forming the structural unit (AQ) include ethylene, propylene, 1-butene, 1-hexene, 1-heptene, and 1 Includes octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-heptene, 1-octadecene and 1-eikosen. The α-olefin may be one kind or two or more kinds.
As the α-olefin forming the structural unit (AQ), an olefin having 8 or more carbon atoms and 18 or less carbon atoms (for example, from the viewpoint of imparting an appropriate elastic modulus, flexibility, and flexibility to the layer of the composition (X)). , 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-heptadecene and 1-octadecene) are preferred.

The polymer (A) may contain other structural units other than the structural unit (P) and the structural unit (AQ) as long as the effects of the present invention are not impaired. The content of the other constituent units is, for example, 0 to 10 mol% (however, the total content of the constituent units (P) and the constituent units (AQ) is 100 mol%).

The specific examples of the monomers forming the other structural units are the same as the specific examples of the monomers forming the other structural units that can be contained in the copolymer (B) described later.
The value of the content (mol%) of each structural unit in the polymer (A) is a value measured by a measurement method by ¹³ C-NMR, similarly to the copolymer (B) described later.

Requirement (A-b): The ultimate viscosity [η] of the polymer (A) measured at 135 ° C. in a decalin solvent is 0.5 to 5.0 dl / g, preferably 1.0 to 4.0 dl. / G, more preferably 1.0 to 3.5 dl / g, still more preferably 1.0 to 3.0 dl / g. When the ultimate viscosity [η] of the polymer (A) is within the above range, the number of low molecular weight substances is small, so that the layer made of the composition (X) is less sticky, and the laminate is molded by the extrusion laminating method. Is possible.

The ultimate viscosity [η] of the polymer (A) is a value measured by the following method using a Ubbelohde viscometer.
A decalin solution is obtained by dissolving 20 mg of the polymer (A) in 25 ml of decalin, and then the specific viscosity η _sp is measured in an oil bath at 135 ° C. using a Ubbelohde viscometer. This decalin solution is diluted by adding 5 ml of decalin, and then the specific viscosity η _sp is measured in the same manner as described above. This dilution operation is repeated twice more, and the value of η _sp / C when the concentration (C) is extrapolated to 0 is defined as the ultimate viscosity [η] (unit: dl / g) (see the formula below).
[Η] = lim (η _sp / C) (C → 0)

Requirement (Ac): The melting point (Tm) of the polymer (A) is in the range of 200 to 250 ° C, preferably 200 to 245 ° C, more preferably 200 to 240 ° C. By using the polymer (A) having Tm in the above range, it has an appropriate elastic modulus as compared with the case where Tm is higher than the above range, and has better heat resistance than when Tm is lower than the above range. It is possible to obtain a release film which is.

The Tm of the polymer (A) is a value measured by the following method in accordance with JIS K7121 using a differential scanning calorimetry (DSC).

Approximately 5 mg of the polymer (A) is sealed in an aluminum pan for measurement of a differential scanning calorimeter (DSC220C type) manufactured by Seiko Instruments Co., Ltd. at room temperature, and the temperature is increased from room temperature to 200 ° C. at a rate of 10 ° C./min. Heat. To completely melt the polymer (A), hold at 200 ° C. for 5 minutes and then cool to −50 ° C. at a rate of 10 ° C./min. After holding at −50 ° C. for 5 minutes, the polymer is heated to 200 ° C. at a rate of 10 ° C./min for the second time, and the temperature at which the peak is observed by this second heating is defined as the melting point (Tm) of the polymer. When a plurality of peaks are detected, the peak detected on the highest temperature side is adopted.

The polymer (A) preferably satisfies any of the following requirements in addition to the above requirements (Aa) to (Ac).

Requirement (Ad): The density of the polymer (A) measured in accordance with JIS K7112 (density gradient tube method) is preferably 820 to 850 kg / m ³ , more preferably 825 to 840 kg / m ³ , Particularly preferably, it is 830 to 835 kg / m ³ . When the density is in the above range, the mechanical strength of the layer made of the composition (X) is higher than in the case where the density is smaller than the above range, and it is made up of the composition (X) as compared with the case where the density is higher than the above range. The impact strength of the layer tends to be high.

Requirement (AF): The melt flow rate (MFR) of the polymer (A) measured at 260 ° C. and a 5.0 kg load according to ASTM D1238 is extruded with the copolymer (B) described later. The range is preferably 0.5 to 200 g / 10 min, more preferably 1 to 150 g / 10 min, and particularly preferably 1 to 100 g / 10 min, although it is easy to mix in the machine and can be coextruded. When the MFR is in the above range, the composition (X) can be easily extruded to a relatively uniform film thickness.

Requirement (Ag): The molecular weight distribution (Mw / Mn) of the polymer (A) is preferably 1.0 to 7.0, more preferably 2.0 to 6.0. The molecular weight distribution (Mw / Mn) of the polymer (A) is a value calculated by the method described in Examples.

Requirement (Ah): The polymer (A) is preferably a polymer having high crystallinity from the viewpoint of obtaining a layer made of the composition (X) which is hard to break. The polymer having a high crystallinity may be either a polymer having an isotactic structure or a polymer having a syndiotactic structure, but a polymer having an isotactic structure is particularly preferable, and a polymer having an isotactic structure is also available. It's easy. Further, the steric regularity of the polymer (A) is not particularly limited, but the steric regularity is such that the composition (X) can be molded into a film shape and a film having strength enough to withstand the desired use can be obtained. It is preferable to have it.

(Method for producing polymer (A))
The polymer (A) may be produced by polymerizing olefins, or may be produced by thermally decomposing a high molecular weight 4-methyl-1-pentene polymer. Further, the polymer (A) may be purified by a method such as solvent separation in which the polymer (A) is separated by the difference in solubility in the solvent, or molecular distillation in which the polymer (A) is separated by the difference in boiling point.

When the polymer (A) is produced by a polymerization reaction, for example, the amount of 4-methyl-1-pentene and α-olefin to be copolymerized as needed, the type of polymerization catalyst, the polymerization temperature, and the amount of hydrogen added during polymerization. By adjusting the above, the melting point, stereoregularity, molecular weight, etc. can be controlled. The method for producing the polymer (A) by a polymerization reaction may be a known method. The polymer (A) can be produced, for example, by a method using a known catalyst such as a Chigra natta catalyst or a metallocene catalyst, and preferably can be produced using a metallocene catalyst. On the other hand, when the polymer (A) is produced by thermal decomposition of a higher molecular weight 4-methyl-1-pentene polymer, the molecular weight can be set to a desired value by controlling the temperature and time of the thermal decomposition. Can be controlled.
The polymer (A) may be a commercially available polymer such as TPX manufactured by Mitsui Chemicals, Inc., in addition to the polymer produced as described above.

<Copolymer (B)>
The copolymer (B) satisfies the following requirements (B) to (Bd). The copolymer (B) contained in the composition (X) may be one kind or two or more kinds.
Requirement (BA): The copolymer (B) has a constituent unit (P) in a proportion of 80 to 97 mol% and a constituent unit (BQ) in a proportion of 3 to 20 mol% (provided that it has a constituent unit (BQ) in a proportion of 3 to 20 mol%. The total content of the constituent unit (P) and the constituent unit (BQ) is 100 mol%).

The content of the structural unit (P) is preferably 80 mol% or more and 93 mol% or less, and more preferably 82 mol% or more and 90 mol% or less.

When the content of the structural unit (P) is within the above range, the film is excellent in releasability and heat resistance.

The content of the constituent unit (BQ) (when the constituent unit (BQ) is two or more, the total content of the two or more) is preferably 7 mol% or more and 20 mol% or less, more preferably 10 mol. % Or more and 18 mol% or less.

When the content of the structural unit (BQ) in the copolymer (B) is within the above range, the unevenness-following property of the obtained film is improved.

As an α-olefin having 2 or more and 20 or less carbon atoms other than 4-methyl-1-pentene, which forms a structural unit (BQ), the anisotropy of tensile elongation at break and the anisotropy of tear strength of the obtained film Ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-hexadecene, 1-octadecene are preferable, and carbon atoms are preferable from the viewpoint of further reducing the amount of Alpha-olefins of numbers 2-4, ie ethylene, propylene, 1-butene, are more preferred, with propylene being particularly preferred.
As the α-olefin forming the structural unit (BQ), only one kind may be used, or two or more kinds may be used.
When the polymer (A) contains the structural unit (AQ), the structural unit (BQ) may be the same as or different from the structural unit (AQ).

The copolymer (B) may contain other structural units other than the structural unit (P) and the structural unit (BQ) as long as the effects of the present invention are not impaired. The content of the other constituent units is, for example, 0 to 10 mol% (however, the total content of the constituent units (P) and the constituent units (BQ) is 100 mol%).

Examples of the monomer forming the other structural unit include cyclic olefins, aromatic vinyl compounds, conjugated dienes, non-conjugated polyenes, functional vinyl compounds, hydroxyl group-containing olefins, halogenated olefins and the like.

As the cyclic olefin, aromatic vinyl compound, conjugated diene, non-conjugated polyene, functional vinyl compound, hydroxyl group-containing olefin and halogenated olefin, for example, the compounds described in paragraphs 0035 to 0041 of JP2013-169685A. Can be done.

Vinyl cyclohexane and styrene are particularly preferable as the monomers forming the other structural units.
When the copolymer (B) contains the other structural units, the copolymer (B) may contain only one type of the other structural units, or may contain two or more types of the other structural units.

The value of the content (mol%) of each structural unit in the copolymer (B) is the one measured by the measurement method by ¹³ C-NMR under the following conditions.

~ Conditions ~
Measuring device: Nuclear magnetic resonance device (ECP500 type, manufactured by JEOL Ltd.)
Observation nucleus: ¹³ C (125 MHz)
Sequence: Single pulse Proton decoupling Pulse width: 4.7 μsec (45 ° pulse)
Repeat time: 5.5 seconds Number of integrations: 10,000 times or more Solvent: Ortodichlorobenzene / Deuterated benzene (volume ratio: 80/20) Mixed solvent Sample concentration: 55 mg / 0.6 mL
Measurement temperature: 120 ° C
Reference value for chemical shift: 27.50 ppm

Requirement (Bb): The ultimate viscosity [η] of the copolymer (B) measured at 135 ° C. in a decalin solvent is 0.5 to 5.0 dl / g, preferably 0.5 to 4. It is 0 dl / g, more preferably 0.5 to 3.5 dl / g, and particularly preferably 1.0 to 3.5 dl / g.
The ultimate viscosity [η] of the copolymer (B) is a value measured by the same method as the ultimate viscosity [η] of the polymer (A).

Requirement (B-c): The molecular weight distribution (Mw / Mn) of the copolymer (B) is 1.0 to 3.5, preferably 1 from the viewpoint of stickiness and appearance of the layer composed of the composition (X). It is 1 to 3.0.
The weight average molecular weight (Mw) of the copolymer (B) is preferably 1 × 10 ⁴ to 2 × 10 ⁶ , more preferably 1 × 10 ⁴ to, from the viewpoint of moldability of the layer composed of the composition (X). It is 1 × 10 ⁶ .
The Mw and Mw / Mn of the copolymer (B) are values calculated by the method described in Examples.

Requirement (Bd): The melting point (Tm) of the copolymer (B) is in the range of 100 to 199 ° C, preferably 110 to 180 ° C, more preferably 110 to 160 ° C, and particularly preferably 125 to 150 ° C. be.
The Tm of the copolymer (B) is a value measured by the same method as the Tm of the polymer (A).

The copolymer (B) preferably satisfies any of the following requirements in addition to the above requirements (Ba) to (Bd).

Requirement (B): The density of the copolymer (B) measured in accordance with JIS K7112 (density gradient tube method) is preferably 825 to 860 kg / m ³ from the viewpoint of handleability, and more preferably. It is 830 to 860 kg / m ³ , particularly preferably 830 to 850 kg / m ³ .

Requirement (BF): The melt flow rate (MFR) of the copolymer (B) as measured at 230 ° C. with a load of 2.16 kg according to ASTM D1238 is during the molding of the composition (X). From the viewpoint of fluidity, it is preferably 0.1 to 100 g / 10 min, more preferably 0.5 to 50 g / 10 min, and particularly preferably 0.5 to 30 g / 10 min.

Requirement (Bg): When showing the maximum value of loss tangent (tan δ) in the dynamic viscoelasticity measurement (temperature range: -40 ° C to 150 ° C, frequency: 10 rad / s) of the copolymer (B). The temperature is preferably in the range of −40 to 50 ° C., more preferably 0 to 45 ° C., still more preferably 0 to 43 ° C., and the maximum value of loss tangent (tan δ) is preferably 0.4 or more. It is more preferably 0.6 or more, still more preferably 0.8 or more, and particularly preferably 1.0 or more. When the maximum value of the loss tangent (tan δ) of the copolymer (B) is within the temperature range and the maximum value is 0.4 or more, the copolymer (B) is more excellent in stress relaxation property, and therefore, due to the unevenness followability. An excellent release film can be obtained.

The maximum value of the loss tangent (tan δ) of the copolymer (B) and the temperature at which the maximum value is shown are the following conditions, and a sheet having a thickness of 3 mm is formed from the copolymer (B) to form the sheet. It is a value when measured after 3 days.

~ Sheet formation conditions ~
Using a hydraulic heat press machine set at 200 ° C., a pressure of 10 MPa is applied to the copolymer (B) to form a sheet. Specifically, in the case of a 3 mm thick sheet (spacer shape; 45 x 45 x 3 mm, 4 pieces on a 240 x 240 x 3 mm thick plate), the residual heat is 5 minutes and the copolymer (B) is 10 MPa. After pressurizing for 2 minutes with, compress at 10 MPa using another hydraulic hot press machine set at 20 ° C. and cool for about 5 minutes to prepare a press sheet. A brass plate having a thickness of 5 mm is used as the hot plate.

~ Measurement conditions ~
A strip of 45 mm × 10 mm × 3 mm is cut out from the press sheet as a measurement sample. Using MCR301 manufactured by ANTONPaar, -40 ~ at a frequency of 10 rad / s
The temperature dependence of dynamic viscoelasticity up to 150 ° C. is measured, and the temperature at which the loss tangent (tan δ) due to the glass transition temperature reaches the maximum value (peak value), and the loss tangent (tan δ) at that time. Measure the value.

(Method for producing copolymer (B))
The copolymer (B) is synthesized by a conventionally known metallocene catalyst system, for example, by the methods described in International Publication No. 2005/121192, International Publication No. 2011/055803, International Publication No. 2014/050817, and the like. can do.

<Composition (X)>
In the composition (X), the content of the polymer (A) with respect to the total of 100% by mass of the polymer (A) and the copolymer (B) is 50 to 95% by mass, preferably 60 to 93% by mass, and further. It is preferably 70 to 90% by mass. The content of the copolymer (B) is 5 to 50% by mass, preferably 7 to 40% by mass, and more preferably 10 to 30% by mass.

When the content of the polymer (A) is in the above range, the mold release property and the heat resistance are excellent as compared with the case where the content is less than the above range, and the unevenness followability is excellent as compared with the case where the content is more than the above range. A film is obtained.

The composition (X) preferably has a TMA softening temperature of 200 ° C. or higher (for example, 200 to 240 ° C.) measured in accordance with JIS K7196 from the viewpoint of heat resistance. The TMA softening temperature can be increased, for example, by reducing the content of the copolymer (B) or reducing the content of the structural unit (AQ) in the polymer (A).

The composition (X) is obtained by mixing the polymer (A) and the copolymer (B) in the above ratio, but the composition (X) may be obtained, for example, by a polymerization reaction of olefins.
When the composition (X) is obtained by mixing the polymer (A) and the copolymer (B), the mixing method is not particularly limited, but for example, a compound by a twin-screw extruder, dry blending of pellets and the like, etc. Examples thereof include a method of mixing by mixing.

The composition (X) further comprises, for example, a weather-resistant stabilizer, a heat-resistant stabilizer, an antioxidant, an ultraviolet absorber, an antioxidant, an antioxidant, an anti-slip agent, and an anti-blocking agent, within a range not impairing the object of the present invention. Clouding agents, nucleating agents, lubricants, pigments, dyes, antioxidants, hydrochloric acid absorbers, inorganic or organic fillers, organic or inorganic foaming agents, cross-linking agents, cross-linking aids, adhesives, softeners, difficult It may contain various additives such as a fuel agent and a resin other than the polymer (A) and the copolymer (B). The content of the components other than the polymer (A) and the copolymer (B) in the composition (X) is preferably 10 with respect to a total of 100 parts by mass of the polymer (A) and the copolymer (B). By mass or less, more preferably 5 parts by mass or less.

[Release film]
In the present invention, "film" is a name for convenience, and "film" is a general term for planar molded products, which is a concept including sheets, membranes, tapes, and the like.

The composition (X) can be processed into a target molded product, for example, a film, a sheet, or the like by various molding methods such as an extrusion cast molding method, an extrusion laminating molding method, a calendar molding method, an inflation molding, and a roll molding. .. Further, it is also preferable that the molded body obtained by the above-mentioned molding processing method is further uniaxially stretched or biaxially stretched.

<Laminated film>
Further, as the film of the present invention, in addition to the single-layer film obtained from the above-mentioned composition (X), a laminated film in which at least one layer of the outermost surface layer is composed of the composition (X) is also a preferable embodiment.

The layer structure of the laminated film is, for example, five layers including an A layer (surface layer), a B layer (adhesive layer), a C layer (base layer), a B'layer (adhesive layer), and an A'layer (surface layer). A film having a structure is mentioned, and in this case, it is preferable that the A layer (surface layer) and the A'layer (surface layer) are layers composed of the composition (X).

Examples of the resin constituting the base material include low-density polyethylene, linear low-density polyethylene, high-density polyethylene, homopolymers of propylene, ethylene / propylene copolymers, ethylene / propylene / butene copolymers, and butene. Homopolymer, ethylene / butene copolymer, propylene / butene copolymer, poly4-methyl-1-pentene, ethylene / α-olefin copolymer, propylene / α-olefin copolymer, 1-butene / Polyolefin-based resins such as α-olefin copolymers and cyclic olefin copolymers, resins obtained by graft-modifying these resins with unsaturated carboxylic acids or derivatives thereof, polyamide 6, polyamide 11, polyamide 12, polyamide 612, polyamide 66, Polypolymer resin such as polyamide 610, polyamide 46, polyamide MXD6, polyamide 6T, polyamide 6I, polyamide 9T, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate resin, vinyl chloride, vinylidene chloride, polyurethane, ethylene / acrylic acid. Examples thereof include ester copolymers, ethylene / methacrylic acid ester copolymers, ethylene / vinyl acetate copolymers, ethylene / acrylic acid copolymers, ethylene / methacrylic acid copolymers, and partially ionized crosslinked products thereof.
As the resin constituting the base material layer, the above-mentioned resin may be used alone or in combination of two or more.

Examples of the adhesive layer include a modified polyolefin resin with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride, and more specifically, a resin containing a modified poly4-methyl-1-pentene polymer.

The method for obtaining the laminated film is not particularly limited, but a method of laminating on a surface layer film previously obtained by extrusion casting or inflation molding by a known laminating method such as extrusion lamination or extrusion coating, or a plurality of methods. Examples thereof include a method in which the films are independently molded and then laminated by dry lamination. From the viewpoint of productivity, coextrusion molding in which a plurality of components are subjected to a multi-layer extruder is preferable.

The thickness of the release film of the present invention is not particularly limited, but is usually 500 μm or less, preferably 10 to 500 μm, more preferably 20 to 250 μm, still more preferably 20 to 100 μm.

[Physical characteristics of release film]
The physical characteristics that the release film of the present invention preferably satisfies are described below.

<Blocking coefficient>
As an index of releasability, it can be evaluated by the blocking coefficient.
The blocking coefficient of the release film in the present invention is preferably 0.5 to 150 (mN / cm), more preferably 0.5 to 100 (mN / cm), and further preferably 0.5 to 80 (mN / cm). ), Particularly preferably 0.5 to 50 (mN / cm). A film having a blocking coefficient within the above range is excellent in releasability.
The blocking factor is measured according to ASTM D1893. The specific test method will be described in the column of Examples.

<Storage modulus E'at 80 ° C.>.
As an index of unevenness followability, it can be evaluated by the storage elastic modulus E'at 80 ° C.
The storage elastic modulus E'at 80 ° C. of the release film of the present invention is preferably in the range of 0.5 to 130 MPa.
The specific measurement method can be carried out by the method described in the column of Examples.

[Use]
Specific uses of the release film of the present invention include, but are not limited to, the following uses.
Release film for flexible printed substrate (FPC), release film for ACM substrate, release film for rigid substrate, release film for rigid flexible substrate, release film for advanced composite material, release film for curing carbon fiber composite material , Glass fiber composite material curing release film, Aramid fiber composite material curing release film, Nano composite material curing release film, Filler filler curing release film, Semiconductor encapsulation release film, Plate plate Release film, release film for diffusion sheet, release film for prism sheet, release film for reflection sheet, cushion film for release film, release film for fuel cell, release film for various rubber sheets, urethane curing Release film, release film for epoxy curing, release film for silicon resin, mold release film for LED encapsulant, release film for acrylic adhesive, release film for protect film, release film for synthetic leather Release film, such as
Pellicle film, polarizing plate film, polarizing plate protective film, liquid crystal panel protective film, optical component protective film, lens protective film, electrical component / electrical product protective film, mobile phone protective film, personal computer protection Examples thereof include a film, a protective film for a touch panel, a protective film for a window glass, a film for baking coating, and a masking film.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded.

[Polymer (A)]
Physical properties shown in Table 1 by changing the proportions of 4-methyl-1-pentene, 1-hexadecene, 1-octadecene, and hydrogen according to the polymerization method described in Comparative Example 9 of International Publication No. 2006/054613. The polymer A-1 having the above was obtained. The methods for measuring various physical properties of the polymer are shown below, and the measurement results are shown in Table 1.

(1) Composition The composition of the polymer was determined by the above-mentioned measurement method by ¹³ C-NMR.

(2) Extreme viscosity [η]
Using a Ubbelohde viscometer, the ultimate viscosity [η] was determined at 135 ° C. in a decalin solvent by the above-mentioned method.

(3) Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
Liquid chromatograph: ALC / GPC 150-C plus type (integrated differential refractometer detector) manufactured by Waters is used, and GMH6-HT x 2 and GMH6-HTL x 2 manufactured by Toso Co., Ltd. are connected in series as columns. Then, using o-dichlorobenzene as a mobile phase medium, gel permeation chromatography (GPC) measurement was performed at a flow rate of 1.0 ml / min and 140 ° C. The obtained chromatogram was analyzed by a known method using a calibration curve using a standard polystyrene sample to determine the weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn).

(4) Melt flow rate (MFR)
The melt flow rate (MFR) measured at 260 ° C. and a 5.0 kg load was determined according to ASTM D1238.

(5) Density The density was determined according to JIS K7112 (Density Gradient Tube Method).

(6) Melting point (Tm)
It was measured by the method described above according to JIS K7121 and determined from the peak temperature.

[Copolymer (B)]
23 ml of n-hexane (dried on activated alumina in a dry nitrogen atmosphere) and 450 ml of 4-methyl-1-pentene were placed in a SUS autoclave with a stirring blade having a capacity of 1.5 L and sufficiently nitrogen-substituted. After charging at ° C, 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL) was charged and the stirrer was rotated.

Next, the autoclave was heated to an internal temperature of 60 ° C. and pressurized with propylene so that the total pressure (gauge pressure) was 0.19 MPa.
Subsequently, 1 mmol of methylaluminoxane and 0.01 mmol of diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7-di-t-butyl) prepared in advance in terms of Al were used. -0.34 ml of a toluene solution containing (fluorenyl) zirconium dichloride was pressed into an autoclave with nitrogen to initiate a polymerization reaction. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C.

60 minutes after the start of the polymerization, 5 ml of methanol was press-fitted into the autoclave with nitrogen to stop the polymerization reaction, and then the inside of the autoclave was depressurized to atmospheric pressure. After decompression, acetone was added to the reaction solution while stirring the reaction solution to obtain a polymerization reaction product containing a solvent. Then, the obtained polymerization reaction product containing the solvent was dried under reduced pressure at 130 ° C. for 12 hours to obtain 44.0 g of a powdery polymer B-1 as the copolymer (B).

Table 1 shows the measurement results of various physical properties of the polymer B-1. The measuring method is the same as the measuring method of the polymer (A) except that the measuring conditions of the melt flow rate (MFR) are changed to 230 ° C. and a 2.16 kg load.

[Composition (X)]
<Preparation of composition (X)>
90 parts by mass of polymer A-1, 10 parts by mass of polymer B-1, and 0.1 parts by weight of tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant. And 0.1 part by weight of n-octadecyl-3- (4'-hydroxy-3', 5'-di-t-butylphenyl) propinate as a heat-resistant stabilizer was blended. After that, it was manufactured using a twin-screw extruder BT-30 (screw system 30 mmφ, L / D = 46) manufactured by Plastic Engineering Laboratory Co., Ltd. under the conditions of a set temperature of 270 ° C., a resin extrusion rate of 60 g / min, and 200 rpm. Granulation was performed to obtain composition X1.

Further, the compositions X2, X3 and X'1 were obtained in the same manner as the composition X1 except that the ratio of the polymer A-1 to the polymer B-1 was changed as shown in Table 2.

[Preparation of film]
<Example 1>
Using the composition X1, a coat hanger type T-type die (lip shape; 270 x 0.8 mm) is attached to a single-screw extruder (screw diameter 20 mmφ · L / D = 28) manufactured by Thermo Plastic Co., Ltd. A film having a thickness of 50 μm was obtained by molding under the conditions of a die temperature of 260 ° C., a roll temperature of 80 ° C., and a winding speed of 2.0 m / min.

<Example 2>
A film was produced by the same method as in Example 1 except that the composition X1 was changed to the composition X2.

<Example 3>
A film was produced by the same method as in Example 1 except that the composition X1 was changed to the composition X3.

<Comparative Example 1>
A film was prepared by the same method as in Example 1 except that the composition X1 was changed to the polymer A-1.

<Comparative Example 2>
A film was produced by the same method as in Example 1 except that the composition X1 was changed to the composition X'1.

[Evaluation of film]
The obtained film was measured and evaluated as follows. The results are shown in Table 2.

<Blocking coefficient>
Evaluated according to ASTM D1893. Specifically, films cut into 70 mm × 100 mm are stacked, pressurized at a temperature of 170 ° C. with a load of 5 MPa for 30 minutes, cooled to room temperature to obtain a measurement sample, and then a universal tensile tester 3380 manufactured by Instron. Evaluated at a speed of 200 mm / min.

<Storage modulus E'at 80 ° C>
Using RSA-III manufactured by TA-Instruments, the storage elastic modulus (E') at 80 ° C. was measured in a tensile mode, a heating rate of 4 ° C./min, a frequency of 1 Hz, and a strain of 0.1.

Claims (4)

4-Methyl-1-pentene (co) polymer (A) satisfying the following requirements (Aa) to (Ac) is 50% by mass or more and less than 70% by mass .
4-Methyl-1-pentene copolymer (B) exceeding 30% by mass and 50% by mass or less ((co) polymer (A) and copolymer (B) satisfying the following requirements (B-a) to (B-d) The total amount of B) is 100% by mass.)
A release film satisfying the following requirement (F), which has a layer comprising the composition (X) and satisfying the following requirement (x).
(Aa) The content of the structural unit (P) derived from 4-methyl-1-pentene is 90 to 100 mol%, and the α-olefin having 2 to 20 carbon atoms (4-methyl-1-pentene). The content of the constituent unit (AQ) derived from (excluding) is 0 to 10 mol% (the total content of the constituent unit (P) and the constituent unit (AQ) is 100 mol%) (A). -B) The ultimate viscosity [η] measured in 135 ° C. decalin is 0.5 to 5.0 dl / g. (Ac) The melting point (Tm) measured by DSC is in the range of 200 to 250 ° C. (A-c). B-a) An α-olefin (4-methyl-1-pentene) having a content of the structural unit (P) derived from 4-methyl-1-pentene of 80 to 97 mol% and having 2 to 20 carbon atoms. The content of the constituent unit (BQ) derived from (excluding) is 3 to 20 mol% (the total content of the constituent unit (P) and the constituent unit (BQ) is 100 mol%) (B-). b) The ultimate viscosity [η] measured in 135 ° C. decalin is 0.5 to 5.0 dl / g (B-c) and the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC). The molecular weight distribution (Mw / Mn), which is the ratio to the number average molecular weight (Mn), is 1.0 to 3.5. (Bd) The melting point (Tm) measured by DSC is in the range of 100 to 199 ° C. (X) The blocking coefficient of the layer composed of the composition (X) measured as follows is in the range of 0.5 to 150 mN / cm, and the frequency is 1 Hz and 80 ° C. measured by a solid viscoelastic apparatus. The storage elasticity E'in the above range is in the range of 0.5 to 130 MPa.
Blocking coefficient: According to ASTM D1893, a layer consisting of the composition (X) cut out to 70 mm × 100 mm is layered, pressurized at a temperature of 170 ° C. with a load of 5 MPa for 30 minutes, and then cooled to room temperature to prepare a measurement sample. After obtaining, the value evaluated at a speed of 200 mm / min with a universal tensile tester.
(F) The release film is a single-layer release film having a layer made of the composition (X), or a layer made of the composition (X), an adhesive layer, a resin base material layer, an adhesive layer, and the like. A release film having a five-layer structure composed of a layer composed of the composition (X). The release film according to claim 1, wherein the (co) polymer (A) satisfies the following requirement (Ad), and the copolymer (B) satisfies the following requirement (B).
(Ad) The density is 820 to 850 kg / m ³ (B) The density is 825 to 860 kg / m ³ . The release film according to claim 1 or 2, wherein the structural unit (BQ) is a structural unit derived from an α-olefin having 2 to 4 carbon atoms. The release film according to any one of claims 1 to 3, which is for a flexible printed substrate.