JP2019093551A - Release film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a mold release film having excellent unevenness followability and mold releasability. 4-Methyl-1-pentene (co) polymer satisfying (1) to (3) 50 to 95% by mass and 4-methyl-1- satisfying (4) to (7). A single-layer or multi-layered release film having a layer composed of a composition containing 5 to 50% by mass of the penten copolymer (B) (the total of these polymers is 100% by mass). (1) Composition derived from 4-methyl-1-pentene The content of the unit (P) is 90 to 100 mol%, and the composition is derived from α-olefin having 2 to 20 carbon atoms other than 4-methyl-1-pentene. The content of the unit (AQ) is 0 to 10 mol% (2) The ultimate viscosity is 0.5 to 5.0 dl / g (3) The melting point is 200 to 250 ° C. (4) The content of the structural unit (P) is 80. ~ 97 mol%, content of structural unit (AQ) 3 ~ 20 mol% (5) Extreme viscosity 0.5 ~ 5.0 dl / g (6) Mw / Mn 1.0 ~ 3.5 (7) ) Melting point is 100 to 199 ° C [Selection diagram] None

Description

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

  4-Methyl-1-pentene / α-olefin copolymer mainly composed of 4-methyl-1-pentene is widely used in various applications because it is excellent in heat resistance, releasability and chemical resistance. ing. For example, various types of release films such as a release film for printed wiring board production, a release film for composite material molding, a release paper for synthetic leather production, etc., taking advantage of the features such as good release properties of films containing the copolymer (See Patent Document 1), and a molded article containing the copolymer is used for experimental instruments, rubber hoses for manufacturing rubber hoses, etc., taking advantage of features such as heat resistance, chemical resistance, acid resistance and transparency. ing.

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

  For example, when manufacturing a flexible printed circuit (hereinafter referred to as "FPC"), a step of laminating a coverlay film on a substrate on which a circuit pattern is formed, and the obtained laminated body by a heat press plate A heat press molding process is generally provided which sandwiches, heats and presses.

  In the heat press molding step, in order to prevent adhesion between the coverlay film and the heat press plate, a polytetrafluoroethylene, a tetrafluoroethylene-hexafluoropropylene copolymer, and a polyvinyl fluoride are usually interposed between them. A fluorine-based film made of vinyl chloride 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 is excellent in the heat resistance and the releasability after heating and pressing, and the followability to the substrate circuit. It 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 formation of a copper-clad laminate which is carried out at a temperature of about 180 ° C. (patented) Reference 3).

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

Unexamined-Japanese-Patent No. 2010-027745 JP 2005-350601 A JP, 2014-098138, A JP, 2016-098257, A WO 2015/012274 International Publication No. 2013/099876 JP, 2017-074775, A

However, although higher levels are required with respect to the unevenness followability and the releasability, the above conventional release film can not achieve this requirement.
The present invention has been made in view of the above circumstances, and an object thereof is to solve the above-mentioned problems. That is, an object of the present invention is to provide a release film which is excellent in unevenness followability and releasability.

  An example of the specific means for solving the said subject is as follows.

[1] 50 to 95 mass% of 4-methyl-1-pentene (co) polymer (A) satisfying the following requirements (A-a) to (A-c),
4-Methyl-1-pentene copolymer (B) 5 to 50% by mass ((co) polymer (A) and copolymer (B) satisfying the following requirements (B-a) to (B-d) A single layer or multilayer release film having a layer comprising the composition (X) containing 100% by mass as the total amount.
(A-a) The content of structural unit (P) derived from 4-methyl-1-pentene is 90 to 100 mol%, and α-olefin having 2 to 20 carbon atoms (4-methyl-1-pentene) The content of the structural unit (AQ) derived from (1) is 0 to 10 mol% (the total of the content of the structural unit (P) and the structural unit (AQ) is 100 mol%) (A -B) The intrinsic 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. B-a) The content of the structural unit (P) derived from 4-methyl-1-pentene is 80 to 97 mol%, and an α-olefin having 2 to 20 carbon atoms (4-methyl-1-pentene) The content of the structural unit (BQ) derived from The total content of the structural unit (P) and the structural unit (BQ) is 100 mol%.) (Bb) The limiting viscosity [[] measured in 135 ° C. decalin is 0.5 to 5. The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC), is 0 dl / g. 0 to 3.5 (Bd) 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 (A-d) and the copolymer (B) satisfies the following requirement (B-e) .
(Ad) density is 820 to 850 kg / m ³ (Be) 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 the solid viscoelastic device is in the range of 0.5 to 130 MPa. The release film as described in any one of 3].

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

  ADVANTAGE OF THE INVENTION According to this invention, the release film which is excellent in uneven | corrugated following property and releasability can be provided.

  Hereinafter, although specific embodiments of the present invention will be described in detail, the present invention is not limited to the following embodiments at all, and can be implemented 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
4-methyl-1 having 90 mol% or more and 100 mol% or less of a structural unit (P) derived from 4-methyl-1-pentene (hereinafter sometimes simply referred to as “structural unit (P)”) 0 to 10 mol% (hereinafter, referred to simply as “structural unit (AQ)”) derived from an α-olefin having 2 to 20 carbon atoms other than pentene (0 to 10 mol%) Provided that 4-methyl-1-pentene (co) polymer (A) (hereinafter referred to simply as “polymer (A) having a total of 100 mol% of structural unit (P) and structural unit (AQ)) Also referred to as
Structural unit (BQ) having structural unit (P) of 80 to 97 mol% and derived from α-olefin having 2 to 20 carbon atoms other than 4-methyl-1-pentene (hereinafter referred to simply as “configuration 4) having a unit (BQ) ratio of 3 to 20 mol% (however, the total of the structural unit (P) and the structural unit (BQ) is 100 mol%), 4- 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 based on 100% by mass in total of the polymer (A) and the copolymer (B) Layer.

[Composition (X)]
Composition (X) is a composition containing polymer (A) and copolymer (B).
Hereinafter, each of a polymer (A) and a copolymer (B) is demonstrated.

<Polymer (A)>
The polymer (A) satisfies the following requirements (A-a) to (A-c). The polymer (A) contained in the composition (X) may be one type, or two or more types.
Requirement (A-a): The content of the structural unit (P) in the polymer (A) is 90 to 100 mol%, preferably 95 to 100 mol%, and the structural unit (AQ) The content (when the structural unit (AQ) is two or more, the total content of the two or more) is 0 mol% or more and 10 mol% or less, preferably 0 mol% or more and 5 mol% or less The total content of the structural unit (P) and the structural 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 excellent heat resistance and an elastic modulus suitable for handling can be obtained.

Examples of the α-olefin having 2 to 20 carbon atoms other than 4-methyl-1-pentene which forms the structural unit (AQ) include ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 1 -Octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene and 1-eicosene. 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 to 18 carbon atoms (eg, for example, from the viewpoint of imparting appropriate elasticity, 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.

  A polymer (A) may contain other structural units other than a structural unit (P) and a structural unit (AQ) in the range which does not impair the effect of this invention. The content of the other constituent unit is, for example, 0 to 10 mol% (however, the total content of the constituent unit (P) and the constituent unit (AQ) is 100 mol%).

Specific examples and the like of the monomer forming the other structural unit are the same as specific examples and the like of the monomer forming the other structural unit which may be contained in the copolymer (B) described later.
In addition, the value of the content rate (mol%) of each structural unit in a polymer (A) is a value measured by the measuring method by < ¹³ > C-NMR similarly to the copolymer (B) mentioned later.

  Requirement (A-b): The limiting 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, further preferably 1.0 to 3.0 dl / g. When the intrinsic viscosity [η] of the polymer (A) is in the above range, the amount of low molecular weight is small, so that the layer consisting of the composition (X) has less stickiness, and molding of a laminate by the extrusion laminating method Is possible.

The intrinsic viscosity [η] of the polymer (A) is a value measured by the following method using a Ubbelohde viscometer.
After dissolving 20 mg of the polymer (A) in 25 ml of decalin to obtain a decalin solution, the specific viscosity η _sp is measured in an oil bath at 135 ° C. using an Ubbelohde viscometer. After diluting this decalin solution with 5 ml of decalin, the specific viscosity _{sp sp} is measured in the same manner as described above. This dilution operation is further repeated twice, and the value of _{sp sp} / C when the concentration (C) is extrapolated to 0 is defined as the limiting viscosity [η] (unit: dl / g) (see the following formula).
[Η] = lim (( _sp / C) (C → 0)

  Requirement (A-c): 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 compared to the case where Tm is higher than the above range, and heat resistance is better than when Tm is lower than the above range A release film that is

  Tm of a polymer (A) is a value measured by the following method based on JISK7121 using a differential scanning calorimeter (DSC: Differential scanning calorimetry).

  About 5 mg of the polymer (A) is sealed at room temperature in an aluminum pan for measurement by a differential scanning calorimeter (DSC 220 C type) manufactured by Seiko Instruments Inc., and from room temperature to 200 ° C. at a rate of 10 ° C./min. Heat up. In order to completely melt the polymer (A), it is kept at 200 ° C. for 5 minutes and then cooled to −50 ° C. at a rate of 10 ° C./min. After holding for 5 minutes at −50 ° C., heating is performed a second time to 200 ° C. at a rate of 10 ° C./minute, and the temperature at which a peak is observed in the second heating is taken as the melting point (Tm) of the polymer. When a plurality of peaks are detected, the peak detected at the highest temperature is employed.

  The polymer (A) preferably satisfies any of the following requirements in addition to the requirements (A-a) to (A-c).

Requirement (A-d): The density of the polymer (A) measured according to 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 comprising the composition (X) is higher than in the case where it is smaller than the above range, and it is composed of the composition (X) as compared with the case where it is larger than the above range. The impact strength of the layer tends to be high.

  Requirement (A-f): The melt flow rate (MFR) of the polymer (A) measured at 260 ° C. under a load of 5.0 kg in accordance with ASTM D 1238 is a copolymer with the copolymer (B) described later and extruded. It is preferable that mixing is easy in a machine or the like and coextrusion is possible, but it 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. When the MFR is in the above range, the composition (X) can be easily extruded to have a relatively uniform film thickness.

  Requirement (A-g): The molecular weight distribution (Mw / Mn) of the polymer (A) is preferably 1.0 to 7.0, more preferably 2.0 to 6.0. In addition, molecular weight distribution (Mw / Mn) of a polymer (A) is a value calculated by the method as described in an Example.

  Requirement (A-h): The polymer (A) is preferably a polymer having high crystallinity from the viewpoint of obtaining a layer composed of the composition (X) which is not easily broken. The highly crystalline polymer 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 it is also possible to obtain one. It is easy. Furthermore, the stereoregularity of the polymer (A) is not particularly limited, but the stereoregularity can be such that the composition (X) can be formed into a film, and a film having strength to end the intended use can be obtained. It is preferable to have.

(Method of producing polymer (A))
The polymer (A) may be produced by polymerizing olefins, or may be produced by thermal decomposition of a high molecular weight 4-methyl-1-pentene polymer. In addition, the polymer (A) may be purified by a method such as solvent fractionation in which fractionation is performed by difference in solubility in a solvent, or molecular distillation in which fractionation is performed by difference in boiling point.

When the polymer (A) is produced by a polymerization reaction, for example, the charged amount of 4-methyl-1-pentene and optionally α-olefin to be copolymerized, kind of polymerization catalyst, polymerization temperature, hydrogenation amount at the time of polymerization The melting point, stereoregularity, molecular weight and the like can be controlled by adjusting the etc. The method for producing the polymer (A) by a polymerization reaction may be a known method. The polymer (A) is produced, for example, by a method using a known catalyst such as a Ziegler-Natta catalyst, a metallocene-based catalyst, or the like, and can preferably be produced using a metallocene-based 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, for example, a commercially available polymer such as Mitsui Chemical Co., Ltd. TPX, which is other than one produced as described above.

<Copolymer (B)>
The copolymer (B) satisfies the following requirements (Ba) to (Bd). The copolymer (B) contained in the composition (X) may be of one type or of two or more types.
Requirement (Ba): The copolymer (B) has 80 to 97 mol% of the structural unit (P) and 3 to 20 mol% of the structural unit (BQ) (however, The total content of the structural unit (P) and the structural unit (BQ) is 100 mol%.

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

  When the content rate of a structural unit (P) is the said range, it is excellent in the mold release property and heat resistance of a film.

  The content of the structural unit (BQ) (the total content of the two or more when the structural unit (BQ) is 2 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 in the above range, the unevenness followability of the obtained film is improved.

As the α-olefin having 2 to 20 carbon atoms other than 4-methyl-1-pentene which forms the structural unit (BQ), the anisotropy of tensile elongation at break and the anisotropy of tear strength of the obtained film From the viewpoint of further reducing the impact resistance and also improving the impact resistance, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-hexadecene, 1-octadecene are preferable, and carbon atoms The number of α-olefins of the numbers 2 to 4, that is, ethylene, propylene and 1-butene is more preferable, and propylene is particularly preferable.
As alpha-olefin which forms a structural unit (BQ), only 1 type may be used and 2 or more types 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 unit is, for example, 0 to 10 mol% (however, the total content of the constituent unit (P) and the constituent unit (BQ) is 100 mol%).

  As a monomer which forms the said other structural unit, cyclic olefin, an aromatic vinyl compound, a conjugated diene, nonconjugated polyene, a functional vinyl compound, a hydroxyl-containing olefin, a halogenated olefin etc. are mentioned.

  As the cyclic olefin, the aromatic vinyl compound, the conjugated diene, the nonconjugated polyene, the functional vinyl compound, the hydroxyl group-containing olefin and the halogenated olefin, for example, the compounds described in paragraphs 0035 to 0041 of JP-A-2013-169685 may be used. Can.

As a monomer which forms the said other structural unit, vinyl cyclohexane and styrene are especially preferable.
When the copolymer (B) includes the other structural unit, the other structural unit may be contained alone or in combination of two or more.

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

~conditions~
Measurement device: Nuclear magnetic resonance device (ECP 500 type, manufactured by Nippon Denshi Co., Ltd.)
Observation nucleus: ¹³ C (125 MHz)
Sequence: Single pulse proton decoupling Pulse width: 4.7 μs (45 ° pulse)
Repeating time: 5.5 seconds Number of integrations: 10,000 or more Solvent: ortho-dichlorobenzene / 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 (B-b): The intrinsic viscosity [η] of the copolymer (B) measured at 135 ° C. in 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, particularly preferably 1.0 to 3.5 dl / g.
The limiting viscosity [η] of the copolymer (B) is a value measured by the same method as the limiting viscosity [η] of the polymer (A).

Requirement (Bc): The molecular weight distribution (Mw / Mn) of the copolymer (B) is preferably 1.0 to 3.5, preferably 1 from the viewpoint of the stickiness and appearance of the layer comprising the composition (X). .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 ⁶ from the viewpoint of the moldability of the layer comprising the composition (X). It is 1 × 10 ⁶ .
In addition, Mw and Mw / Mn of a copolymer (B) are values calculated by the method as described in an Example.

Requirement (B-d): 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., particularly preferably 125 to 150 ° C. is there.
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 requirements (Ba) to (Bd).

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

  Requirement (B-f): The melt flow rate (MFR) of the copolymer (B) measured at 230 ° C. and a load of 2.16 kg according to ASTM D 1238 is at the time of molding of the composition (X) From the viewpoint of fluidity of the above, 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 (B-g): Copolymer (B) showing the maximum value of loss tangent (tan δ) in dynamic viscoelasticity measurement (temperature range: −40 ° C. to 150 ° C., frequency: 10 rad / s) 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 the loss tangent (tan δ) is preferably 0.4 or more, More preferably, it is 0.6 or more, more preferably 0.8 or more, and particularly preferably 1.0 or more. The copolymer (B) is excellent in the stress relaxation property when the maximum value of the loss tangent (tan δ) is within the above temperature range and the maximum value is 0.4 or more, so 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 the time of indicating the maximum value are 3 mm in thickness from the copolymer (B) under the following conditions to form a sheet It is a value when measured three days later.

Sheet formation conditions
Using a hydraulic heat press 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 × 45 × 3 mm in a 240 × 240 × 3 mm thick plate, taken four pieces), the residual heat is 5 minutes, and the copolymer (B) is 10 MPa After pressing for 2 minutes, compression is performed at 10 MPa using another hydraulic heat press set at 20 ° C., and cooling is performed for about 5 minutes to prepare a pressed sheet. A 5 mm thick brass plate is used as the heat plate.

~Measurement condition~
From the press sheet, a 45 mm × 10 mm × 3 mm strip piece is cut out as a measurement sample. Using MCR301 manufactured by ANTON Paar, at a frequency of 10 rad / s
The temperature dependence of the dynamic viscoelasticity up to 150 ° C. is measured, and the temperature at which the loss tangent (tan δ) resulting from 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 method described in WO 2005/121192, WO 2011/055803, WO 2014/050817, etc. can do.

<Composition (X)>
In the composition (X), the content of the polymer (A) is 50 to 95% by mass, preferably 60 to 93% by mass, based on 100% by mass in total of the polymer (A) and the copolymer (B) Preferably it is 70-90 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, it is excellent in releasability and heat resistance as compared with the case where the content is less than the above range, and excellent in unevenness followability as compared with the case where it is more than the above range. A film is obtained.

  From the viewpoint of heat resistance, 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. 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).

Although composition (X) is obtained by mixing a polymer (A) and a copolymer (B) in the said ratio, you may obtain composition (X) by the polymerization reaction of olefins, for example.
When the composition (X) is obtained by mixing the polymer (A) and the copolymer (B), the mixing method is not particularly limited. And the like.

  The composition (X) is, for example, a weathering stabilizer, a heat-resistant stabilizer, an antioxidant, an ultraviolet absorber, an antistatic agent, an antislip agent, an antiblocking agent, or the like within the range not impairing the object of the present invention. Clouding agents, nucleating agents, lubricants, pigments, dyes, anti-aging agents, hydrochloric acid absorbents, inorganic or organic fillers, organic or inorganic foaming agents, crosslinking agents, crosslinking assistants, adhesives, softeners, hard You may contain various additives, such as a flame retardant, and resin other than a polymer (A) and a copolymer (B). The content of 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). The content is at most parts by mass, more preferably at most 5 parts by mass.

[Release film]
In the present invention, “film” is a name for convenience, and “film” is a general term for planar molded products, and is a concept including a sheet, a membrane (membrane), a tape and the like.

  The composition (X) can be processed into a target molded article, for example, a film, a sheet, etc. by various molding methods such as extrusion cast molding, extrusion lamination, calendar molding, inflation molding, roll molding and the like. . Moreover, it is also preferable that it is a thing obtained by further uniaxially stretching or biaxially stretching the molded object obtained by the above-mentioned shaping | molding processing method.

<Laminated film>
In addition to the single layer film obtained from the composition (X) described above, the film of the present invention is also a preferred embodiment in which a laminated film in which at least one outermost surface layer comprises the composition (X).

  As a layer configuration of the laminated film, for example, 5 layers comprising A layer (surface layer), B layer (adhesive layer), C layer (base layer), B ′ layer (adhesive layer) and A ′ layer (surface layer) The film which has a structure is mentioned, In this case, it is preferable that A layer (surface layer) and A 'layer (surface layer) are layers which consist of a composition (X).

Examples of the resin constituting the base material layer include low density polyethylene, linear low density polyethylene, high density polyethylene, homopolymer of propylene, ethylene / propylene copolymer, ethylene / propylene / butene copolymer, butene Homopolymers of ethylene, butene copolymer, propylene / butene copolymer, poly 4-methyl-1-pentene, ethylene / α-olefin copolymer, propylene / α-olefin copolymer, 1-butene Polyolefin resins such as α-olefin copolymers and cyclic olefin copolymers, resins obtained by graft-modifying these resins with unsaturated carboxylic acids and derivatives thereof, polyamide 6, polyamide 11, polyamide 12, polyamide 12, polyamide 612, polyamide 66, Polyamide 610, Polyamide 46, Polyamide MXD6, Polyamide Polyamide resin such as 6T, polyamide 6I, polyamide 9T, polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate resin, vinyl chloride, vinylidene chloride, polyurethane, ethylene-acrylic acid ester copolymer, ethylene methacrylic acid ester Examples thereof include copolymers, ethylene / vinyl acetate copolymers, ethylene / acrylic acid copolymers, ethylene / methacrylic acid copolymers, and partial ion cross-linked products thereof.
As a resin which comprises a base material layer, said resin may be used individually by 1 type, and 2 or more types may be used.

  Examples of the adhesive layer include polyolefin resins modified with unsaturated carboxylic acid or unsaturated carboxylic acid anhydride, more specifically, resins containing modified poly 4-methyl-1-pentene polymer.

  The method of obtaining the laminated film is not particularly limited, but a method of laminating by a known laminating method such as extrusion lamination or extrusion coating on a surface layer film obtained in advance by extrusion casting or inflation molding, or a plurality of methods Although a method such as laminating each film by dry lamination after the film is formed independently may be mentioned, co-extrusion in which a plurality of components are subjected to a multilayer extruder and formed is preferable from the viewpoint of productivity.

  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, and still more preferably 20 to 100 μm.

[Physical properties of release film]
Physical properties which the release film of the present invention preferably satisfies are described below.

<Blocking factor>
As an index of releasability, it is possible to evaluate by a blocking factor.
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), still more preferably 0.5 to 80 (mN / cm) And particularly preferably 0.5 to 50 (mN / cm). A film having a blocking coefficient in the above range is excellent in releasability.
The blocking factor is measured in accordance with ASTM D1893. The specific test method is described in the column of Example.

<Storage elastic modulus E ′ at 80 ° C.>.
It is possible to evaluate by the storage elastic modulus E ′ at 80 ° C. as an index of unevenness followability.
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.
About a specific measuring method, it can carry out by the method as described in the column of an Example.

[Use]
Although the following applications can be mentioned as a specific application of the release film of this invention, for example, It is not specifically limited to these.
Release film for flexible printed circuit (FPC), release film for ACM substrate, release film for rigid substrate, release film for rigid flexible substrate, release film for tip composite material, release film for carbon fiber composite material curing Release film for curing glass fiber composite material, Release film for curing aramid fiber composite material, Release film for curing nanocomposite material, Release film for curing filler filler, Release film for semiconductor encapsulation, for polarizing plate Release film, release film for diffusion sheet, release film for prism sheet, release film for reflective sheet, cushion film for release film, release film for fuel cell, release film for various rubber sheets, release film for urethane curing Release film, Release film for epoxy curing, Release film for silicone resin, Mold release for LED sealing body Film, release film for acrylic pressure-sensitive adhesive, protective film for release film, release film, such as synthetic leather for release film,
Films for pellicles, films for polarizing plates, protective films for polarizing plates, protective films for liquid crystal panels, protective films for optical parts, protective films for lenses, protective films for electric parts and electric products, protective films for mobile phones, protective for personal computers A film, a protective film for a touch panel, a window glass protective film, a film for baking coating, a masking film and the like can be mentioned.

  Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is not limited to the following examples as long as the gist thereof 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 WO 2006/054613 Polymer A-1 which has is obtained. The measuring method of the various physical properties of a polymer is shown below, and a measurement result is shown in Table 1.

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

(2) Intrinsic viscosity [η]
The limiting viscosity [η] was determined at 135 ° C. in a decalin solvent using the Ubbelohde viscometer according to the method described above.

(3) Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
Liquid chromatograph: Waters ALC / GPC 150-C plus type (differential refractometer / detector integrated type), as a column, Tosoh Corp. GMH 6-HT x 2 and GMH 6-HTL x 2 are connected in series as a column Then, gel permeation chromatography (GPC) measurement was performed at 140 ° C. at a flow rate of 1.0 ml / min using o-dichlorobenzene as a mobile phase medium. The obtained chromatogram was analyzed by a known method using a calibration curve using a standard polystyrene sample to determine a weight average molecular weight (Mw) and a molecular weight distribution (Mw / Mn).

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

(5) Density The density was determined in accordance with JIS K7112 (density gradient tube method).

(6) Melting point (Tm)
It measured by the method mentioned above based on JISK7121, and calculated | required from peak temperature.

[Copolymer (B)]
In an autoclave made of SUS with a stirring blade with a capacity of 1.5 L fully purged with nitrogen, 300 ml of n-hexane (dried on activated alumina under a dry nitrogen atmosphere) and 450 ml of 4-methyl-1-pentene 23 After charging at .degree. C., 0.75 ml of a 1.0 mmol / ml solution of triisobutylaluminum (TIBAL) in toluene was charged, and the stirrer was turned.

Next, the autoclave was heated until the internal temperature reached 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) in terms of Al, which have been prepared beforehand, are prepared. 0.34 ml of a toluene solution containing -fluorenyl) zirconium dichloride was pressurized with nitrogen into an autoclave to initiate a polymerization reaction. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C.

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

  The measurement results of various physical properties of the polymer B-1 are shown in Table 1. In addition, the measuring method is the same as the measuring method of a polymer (A) except having changed the measurement conditions of the melt flow rate (MFR) into 230 degreeC and a 2.16-kg load.

[Composition (X)]
<Preparation of Composition (X)>
90 parts by weight of polymer A-1, 10 parts by weight 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 parts by weight of n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propinate as a heat resistant stabilizer. Thereafter, using a twin-screw extruder BT-30 (screw system 30 mmφ, L / D = 46) manufactured by Plastic Engineering Research Institute, Inc., manufactured under the conditions of a set temperature of 270 ° C. and a resin extrusion amount of 60 g / min and 200 rpm. Granulate to obtain composition X1.

  Further, 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.

[Production of film]
Example 1
Using the composition X1, a coat hanger type T-die (lip shape: 270 × 0.8 mm) was attached to a single-screw extruder (screw diameter 20 mmφ · L / D = 28) manufactured by Thermo Plastics Co., Ltd. The film was formed at a roll temperature of 80 ° C. and a winding speed of 2.0 m / min under conditions of a die temperature of 260 ° C. to obtain a film of 50 μm in thickness.

Example 2
A film was produced in the same manner as in Example 1 except that the composition X1 was changed to the composition X2.

Example 3
A film was produced in the same manner as in Example 1 except that the composition X1 was changed to the composition X3.

Comparative Example 1
A film was produced in the same manner as in Example 1 except that the composition X1 was changed to the polymer A-1.

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

[Evaluation of film]
The following measurements and evaluations were performed on the obtained film. The results are shown in Table 2.

<Blocking factor>
It evaluated based on ASTMD1893. Specifically, a film cut out to 70 mm × 100 mm is stacked, pressurized at a temperature of 170 ° C. and a load of 5 MPa for 30 minutes, and cooled to room temperature to obtain a sample for measurement. And evaluated at a speed of 200 mm / min.

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

Claims (5)

4-methyl-1-pentene (co) polymer (A) 50 to 95% by mass satisfying the following requirements (A-a) to (A-c),
4-Methyl-1-pentene copolymer (B) 5 to 50% by mass ((co) polymer (A) and copolymer (B) satisfying the following requirements (B-a) to (B-d) A single layer or multilayer release film having a layer comprising the composition (X) containing 100% by mass as the total amount.
(A-a) The content of structural unit (P) derived from 4-methyl-1-pentene is 90 to 100 mol%, and α-olefin having 2 to 20 carbon atoms (4-methyl-1-pentene) The content of the structural unit (AQ) derived from (1) is 0 to 10 mol% (the total of the content of the structural unit (P) and the structural unit (AQ) is 100 mol%) (A -B) The intrinsic 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. B-a) The content of the structural unit (P) derived from 4-methyl-1-pentene is 80 to 97 mol%, and an α-olefin having 2 to 20 carbon atoms (4-methyl-1-pentene) The content of the structural unit (BQ) derived from The total content of the structural unit (P) and the structural unit (BQ) is 100 mol%.) (Bb) The limiting viscosity [[] measured in 135 ° C. decalin is 0.5 to 5. The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC), is 0 dl / g. 0 to 3.5 (Bd) Melting point (Tm) measured by DSC is in the range of 100 to 199 ° C. The release film according to claim 1, wherein the (co) polymer (A) satisfies the following requirement (A-d), and the copolymer (B) satisfies the following requirement (B-e).
(Ad) density is 820 to 850 kg / m ³ (Be) 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 blocking coefficient is in the range of 0.5 to 150 mN / cm, and the 80 ° C. storage elastic modulus E ′ measured by the solid viscoelastic device is in the range of 0.5 to 130 MPa. The release film as described in 1 item. The release film according to any one of claims 1 to 4, which is for a flexible printed circuit board.