JP5840064B2 - Composition, film, and method for producing said film - Google Patents

Description

  The present invention relates to a composition that can produce a film having high heat resistance and high electrical insulation, a film that can be produced using the composition, a method for producing the film, and the like.

  Various coating agents for protection, insulation, flattening, heat resistance, light resistance, weather resistance, etc. are used for display devices, semiconductor devices, optical members, printed circuit boards and the like. Films produced using these coating agents are often subjected to processes exceeding 200 ° C. such as solder reflow and fine processing in the production of the above devices and the like, and thus high heat resistance is required. Furthermore, characteristics such as transparency and electrical insulation are required depending on the application. In particular, a film formed using a coating agent on the electrode surface of a capacitor is required to have high electrical insulation properties in order to prevent leakage of stored electricity and voltage drop as well as heat resistance.

  In the pressing process of circuit boards such as printed wiring boards, flexible printed wiring boards, and multilayer printed wiring boards, a release film is used to prevent the circuit board from adhering to the backing plate. For example, in the case of a flexible printed circuit board, in order to protect the circuit part of a base material (polyimide film etc.) having a predetermined circuit part, the circuit part is covered with a resin film with an adhesive, and a release film is further laminated. Pressing is performed (for example, Patent Document 1).

  From such a background, a coating agent capable of forming a film having high heat resistance and electrical insulation that can be used for a release film or the like is demanded. In response to such demands, coating agents containing acrylic resin, polycarbonate resin, fluororesin, polyacetal resin, polyester resin, silicone resin, polyethersulfone resin, polyimide resin, polyarylate resin, cyclic olefin resin, etc. have been proposed. However, a film having a good balance between heat resistance and electrical insulation could not be formed.

  In recent years, cyclic olefin addition polymers containing silyl groups have been proposed as transparent resins for coating having a glass transition temperature of 200 ° C. or more and excellent heat resistance (for example, Patent Documents 2 and 3). However, although the cyclic olefin addition polymer has high heat resistance, it is rigid and poor in flexibility, and when it is made into a film, it tends to cause cracks and cracks. For this reason, during use as a release film or the like, the film may be damaged and the electrical insulation may be lowered. Further, when a large amount of silyl groups are introduced and crosslinked, there is a concern about warping due to shrinkage, and there are problems such as water absorption and high dielectric constant.

JP 2004-339491 A US Pat. No. 5,912,313 JP 2004-58339 A

  An object of this invention is to provide the composition which can form the film which shows high heat resistance and favorable electrical insulation by coating etc.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that copolymer A containing a structural unit derived from 4-methyl-1-pentene and / or 3-methyl-1-pentene having specific physical properties. And the present invention has been completed by finding that the above-mentioned problems can be solved by a composition containing a solvent.

That is, the first invention of the present application relates to the following composition.
[1] A composition comprising a copolymer (A) that satisfies the following requirements (i) to (v) and a solvent.
(I) a copolymer containing 80 to 99 mol% of structural units derived from 4-methyl-1-pentene and / or 3-methyl-1-pentene and 1 to 20 mol% of structural units derived from propylene (Ii) Intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.5 to 5.0 (dl / g) (iii) Melting point (Tm) measured by DSC is in the range from 160 ° C. to 240 ° C. (Iv) having a density of 820 to 850 (kg / m 3) (v) a weight average molecular weight (GPC) measured by gel permeation chromatography (GPC) (
The molecular weight distribution (Mw / Mn), which is the ratio of Mw) to the number average molecular weight (Mn), is 1.0 to 3.5.
Ru Der
[2 ] The copolymer (A) is contained in an amount of 0.1 to 25% by weight with respect to 100% by weight of the composition .
The composition according to.
[ 3 ] The composition according to [1] or [2] , wherein the solvent is a solvent having a relative dielectric constant of 5 or less at 25 ° C.
[ 4 ] The solvent is at least one solvent selected from the group consisting of n-hexane, n-heptane, n-octane, cyclohexane, methylcyclohexane, ethylcyclohexane, toluene and xylene [1] to [ 3 ] The composition as described in any one of these.
[ 5 ] A coating agent comprising the composition according to any one of [1] to [ 4 ].
The second invention of the present application relates to the following films.
[ 6 ] A film comprising a copolymer (A) satisfying the following requirements (i) to (v) and a solvent, wherein the solvent is added to 0.001 to 100% by weight of the film. Film containing 0.5% by weight.
(I) a copolymer containing 80 to 99 mol% of structural units derived from 4-methyl-1-pentene and / or 3-methyl-1-pentene and 1 to 20 mol% of structural units derived from propylene (Ii) Intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.5 to 5.0 (dl / g) (iii) Melting point (Tm) measured by DSC is in the range from 160 ° C. to 240 ° C. (Iv) having a density of 820 to 850 (kg / m 3) (v) a weight average molecular weight (GPC) measured by gel permeation chromatography (GPC) (
The molecular weight distribution (Mw / Mn), which is the ratio of Mw) to the number average molecular weight (Mn), is 1.0 to 3.5.
The first step of applying the composition or coating agent according to any one of [ 7 ] [1] to [ 4 ], and the second step of removing the solvent in the composition. A method for producing a film.
[ 8 ] A capacitor comprising the film according to [ 6 ].
[ 9 ] A release film comprising the film according to [ 6 ] on at least a part of the outermost surface.

  By using the composition of the present invention as a coating agent in particular, a film having high heat resistance and good electrical insulation can be easily produced.

1. Composition The composition of the present invention is a composition comprising a copolymer (A) and a solvent. Below, the composition of this invention is demonstrated in detail.

  In the present invention, a numerical range is defined using “to”, but “to” in the present invention includes a boundary value. For example, “1 to 100” means 10 or more and 100 or less. Moreover, in this application, a copolymer may be described as a polymerization and a copolymer may be described as a polymer.

(1) Copolymer (A)
The copolymer (A) of the present invention comprises (i) 80 to 99 mol% of a structural unit derived from 4-methyl-1-pentene and / or 3-methyl-1-pentene, and contains ethylene and 3 carbon atoms. It is a copolymer containing 1 to 20 mol% of structural units derived from at least one olefin selected from the group consisting of α-olefins of ˜4, and (ii) the intrinsic viscosity [η] measured in decalin at 135 ° C. 0.5 to 5.0 (dl / g), (iii) the melting point (Tm) measured by DSC is in the range of 160 ° C. to 240 ° C., and (iv) the density is 820 to 850 (kg / m ^3). (V) The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC), is 1.0-3. (I) to (v) Meet at the same time. Each requirement will be described below.

(1-1) Requirements (i)
The copolymer (A) of the present invention contains 80 to 99 mol% of structural units derived from 4-methyl-1-pentene and / or 3-methyl-1-pentene, and has ethylene and 3 to 4 carbon atoms. It is a copolymer containing 1 to 20 mol% of structural units derived from at least one olefin selected from the group consisting of α-olefins.

  Here, the upper limit of the structural unit derived from 4-methyl-1-pentene and / or 3-methyl-1-pentene is preferably 99 mol%, more preferably 98 mol%, and the lower limit is preferably 80 mol%. More preferably, it is 85 mol%, still more preferably 87 mol%. The mol% of the structural unit derived from 4-methyl-1-pentene and / or 3-methyl-1-pentene means the mol% of the structural unit derived only from 4-methyl-1-pentene and 3-methyl- This is the sum of mol% of structural units derived only from 1-pentene.

  The copolymer (A) may contain either one of a structural unit derived from 4-methyl-1-pentene or a structural unit derived from 3-methyl-1-pentene, and both are included. It may be. The ratio of the structural unit derived from 4-methyl-1-pentene and the structural unit derived from 3-methyl-1-pentene is not particularly limited, but the structural unit derived from 4-methyl-1-pentene is preferably, It is preferable that it is a ratio of 80-100 mol% with respect to a total of 100 mol% of the structural unit derived from 3-methyl-1-pentene and 4-methyl-1-pentene.

  The upper limit of the structural unit derived from at least one olefin selected from the group consisting of ethylene and an α-olefin having 3 to 4 carbon atoms is preferably 20 mol%, more preferably 15 mol%, still more preferably 13 mol%. The lower limit is preferably 1 mol%, more preferably 2 mol%.

  Here, the structural unit derived from 4-methyl-1-pentene and / or 3-methyl-1-pentene is 100 mol% (at least one selected from the group consisting of ethylene and an α-olefin having 3 to 4 carbon atoms) The constituent unit derived from the olefin of 0 mol%) indicates that the copolymer (A) is a polymer of 4-methyl-1-pentene and / or 3-methyl-1-pentene only. It is.

  When each structural unit is in the above range, the heat resistance and electrical insulation of a film prepared from the composition containing the copolymer (A) are improved. Furthermore, the affinity with the solvent described later is improved, and the stability of the composition of the present invention tends to be improved. This is because a bulky constituent unit of 4-methyl-1-pentene and / or 3-methyl-pentene is contained in a certain amount with respect to olefins such as propylene, hexadecene, octadecene and hexene which are easily crystallized. It is considered that (A) is difficult to crystallize and is easily developed and uniformly dispersed in a solvent. In addition, the stability of the composition as used in this invention means that a copolymer (A) melt | dissolves uniformly in the solvent mentioned later, and the remarkable precipitation of the said copolymer (A) is not seen.

  Suitable examples of the α-olefin having 3 to 4 carbon atoms include propylene and 1-butene. Of these, propylene is preferred from the viewpoints of copolymerizability and physical properties of the resulting copolymer. These ethylene and α-olefin having 3 to 4 carbon atoms can be used alone or in combination of two or more.

  The copolymer (A) may contain structural units derived from other polymerizable compounds as long as the object of the present invention is not impaired. Examples of such other polymerizable compounds include vinyl compounds having a cyclic structure such as styrene, vinylcyclopentene, vinylcyclohexane, and vinylnorbornane; vinyl esters such as vinyl acetate; unsaturated organic acids such as maleic anhydride or the like Derivatives; Conjugated dienes such as butadiene, isoprene, pentadiene, 2,3-dimethylbutadiene; 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5- Heptadiene, 7-methyl-1,6-octadiene, dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylene norbornene, 5-vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5- Isopropylidene-2-norbol , 6-chloromethyl-5-isopropylene-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, etc. Non-conjugated polyenes.

  In the copolymer (A) in the present invention, the units derived from such other polymerizable compounds are added to a total of 100 mol% of structural units derived from all the polymerizable compounds contained in the copolymer (A). On the other hand, it may be contained in an amount of 10 mol% or less, preferably 5 mol% or less, more preferably 3 mol% or less.

The content of 4-methyl-1-pentene, 3-methyl-1-pentene, ethylene, α-olefin and the like in the copolymer (A) can be measured by ¹³ C-NMR with the following apparatus and conditions. it can. Specifically, using an ECP500 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd., a solvent mixture of orthodichlorobenzene / heavy benzene (80/20% by volume), sample (copolymer (A)) concentration of 55 mg / 0.6 mL, measuring temperature 120 ° C., observation nucleus ¹³ C (125 MHz), sequence single pulse proton decoupling, pulse width 4.7 μs (45 ° pulse), repetition time 5.5 seconds, integration number More than 10,000 times, 27.50 ppm can be measured as a reference value for chemical shift.

(1-2) Requirements (ii)
The intrinsic viscosity [η] measured in 135 ° C. decalin of the copolymer (A) of the present invention is 0.5 to 5.0 (dl / g). Here, from the viewpoint of the stability of the composition of the present invention, the upper limit of the intrinsic viscosity [η] is preferably 4.0 or less, and more preferably 2.5 or less. Moreover, it is more preferable that the lower limit of intrinsic viscosity [η] is 0.6 or more from the viewpoint of the shape stability of a film prepared using the composition of the present invention. The value of the intrinsic viscosity [η] can be adjusted by the amount of hydrogen added in the polymerization step when the copolymer (A) is produced.

  The intrinsic viscosity [η] is a value measured at 135 ° C. using a decalin solvent. Specifically, about 20 mg of the copolymer (A) can be dissolved in 15 ml of decalin, and the specific viscosity ηsp can be measured in an oil bath at 135 ° C. After adding 5 ml of decalin solvent to the decalin solution and diluting, the specific viscosity ηsp is measured in the same manner, and the value of ηsp / C can be obtained as the limiting viscosity by extrapolating the concentration (C) to 0. .

(1-3) Requirements (iii)
The melting point (Tm) measured by the copolymer (A) DSC of the present invention is in the range of 160 ° C to 240 ° C, preferably in the range of 170 to 220 ° C. The value of the melting point (Tm) tends to depend on the stereoregularity of the polymer and the content of ethylene and an α-olefin structural unit having 3 to 4 carbon atoms. For this reason, melting | fusing point (Tm) can be adjusted by using the catalyst for olefin polymerization mentioned later, and also controlling the content rate of a C3-C4 alpha olefin structural unit.

The melting point (Tm) can be measured by the following method. Using a DSC measuring apparatus (DSC220C) manufactured by Seiko Instruments Inc., about 5 mg of the sample (copolymer (A)) is filled in an aluminum pan for measurement, the temperature is raised to 290 ° C. at 10 ° C./min, and 5 at 290 ° C. After holding for a minute, the temperature is lowered to −50 ° C. at 10 ° C./min. The melting point (T _m ) can be calculated from the peak apex of the crystallization melting peak at this time. In addition, the crystallization temperature (Tc) mentioned later can be calculated | required from the temperature of the peak vertex of the crystallization peak measured by the method similar to Tm.

  The copolymer (A) having a melting point (Tm) in the above range is preferable from the viewpoint of heat resistance, so that the film obtained from the composition containing the copolymer (A) is also excellent in heat resistance and has uniform film properties. Tends to be obtained.

(1-4) Requirements (iv)
The density of the copolymer (A) of the present invention is 820 to 850 (kg / m ³ ). Preferably it is 825-850 kg / m < ³ >, More preferably, it is 825-845 kg / m < ³ >, More preferably, it is 825-840 kg / m < ³ >. The value of the density of the copolymer (A) can be adjusted by selecting the type and content of other olefins polymerized with 4-methyl-1-pentene and / or 3-methyl-1-pentene. Is possible. The density can be measured according to JIS K6268. Since the copolymer (A) having a density value in the above range is preferable from the viewpoint of heat resistance, a film obtained from a composition containing the copolymer (A) tends to have high heat resistance.

(1-5) Requirements (v)
The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of the copolymer (A) of the present invention, is 1.0. It is -3.5, Preferably it is 1.3-3.0, More preferably, it is 1.5-2.5.

The value of the molecular weight distribution (Mw / Mn) can be adjusted according to the type of olefin polymerization catalyst, particularly a metallocene catalyst described later. The molecular weight distribution (Mw / Mn) can be measured by using a gel permeation chromatograph Alliance GPC-2000 manufactured by Waters. For example, as the separation column, two TSKgel GNH6-HT and two TSKgel GNH6-HTL can be used (both column sizes are 7.5 mm in diameter and 300 mm in length). The column temperature is 140 ° C., o-dichlorobenzene (manufactured by Wako Pure Chemical Industries, Ltd.) is used as the mobile phase, and 0.025% by weight of BHT (manufactured by Takeda Pharmaceutical Company Limited) is used as the antioxidant, and 1.0 ml / Move in minutes. Next, the concentration of the copolymer (A) can be adjusted to 15 mg / 10 mL, and the sample injection amount can be 500 microliters and measured with a detector (differential refractometer). The standard polystyrene can be measured by using Tosoh Corporation for the range of molecular weight Mw <1000 or Mw> 4 × 10 ⁶ , and by using Pressure Chemical Co. for the range of 1000 ≦ Mw ≦ 4 × 10 ⁶ .

  The copolymer (A) having a molecular weight distribution (Mw / Mn) in the above range is preferable from the viewpoints of transparency and mechanical properties, and therefore a film obtained from a composition containing the copolymer (A) is also excellent in transparency. It tends to be obtained. Moreover, when the molecular weight distribution of the copolymer (A) is within the above range, the affinity with the solvent described later is increased, and the stability of the composition of the present invention is improved. Furthermore, the surface smoothness and uniformity of a film produced using the composition of the present invention tend to be improved, and the tackiness tends to be reduced.

(1-6) Crystallization temperature (Tc)
In the present invention, the crystallization temperature (Tc) measured by DSC of the copolymer (A) is preferably 110 to 220 ° C, more preferably 120 to 210 ° C.

  The value of the crystallization temperature (Tc) tends to depend on the stereoregularity of the polymer and the content of ethylene or an α-olefin structural unit having 3 to 4 carbon atoms. Further, it can be adjusted by controlling the content of ethylene or an α-olefin structural unit having 3 to 4 carbon atoms. Since the copolymer (A) having a crystallization temperature (Tc) in the above range is preferable from the viewpoint of moldability, a film obtained from a composition containing the copolymer (A) tends to have excellent moldability. is there.

(1-7) Method for Producing Copolymer (A) The copolymer (A) in the present invention comprises 4-methyl-1-pentene and / or 3-methyl-1-pentene in the presence of an olefin polymerization catalyst. And the above-mentioned specific olefin and, if necessary, the other polymerizable compound can be used for polymerization.

  Among the above-mentioned catalysts for olefin polymerization, a metallocene catalyst can be mentioned as a preferred embodiment of the catalyst for producing the copolymer (A). Preferred metallocene catalysts include those described in WO 01/53369, WO 01/27124, JP-A-3-19396, JP-A-02-41303, or WO 06/025540. And metallocene catalysts described in the above.

  The content of the copolymer (A) in the composition of the present invention is preferably 0.1 to 30% by weight, more preferably 0.1 to 20% by weight, with respect to 100% by weight of the composition. ˜15% by weight is particularly preferred. When the content of the solvent is within the above range, there is a balance between the handleability of the composition when the composition of the present invention is used as a coating agent and the like and the ease of removal of the solvent when producing a film from the composition. It becomes good and it becomes easy to adjust the film thickness of the film manufactured from a coating agent.

(2) Solvent The composition of the present invention contains a solvent. In particular, a solvent having a relative dielectric constant of 5 or less at 25 ° C. is preferably included. The solvent of the present invention may be any liquid substance in which the copolymer (A) is partly soluble, and is not particularly limited. Specific examples of the solvent having a relative dielectric constant of 5 or less at 25 ° C. include aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, cyclohexane, methylcyclohexane, and ethylcyclohexane; toluene, xylene, and the like And aromatic hydrocarbons. By adding a solvent having a relative dielectric constant of 5 or less to the composition of the present invention, the copolymer (A) is uniformly developed, and when a film is produced using the composition of the present invention, the surface of the film is smoothed. There is a tendency to improve the uniformity and uniformity.

  Moreover, it is preferable that the boiling point of the solvent which the composition of this invention contains is 10-150 degreeC, and 20-120 degreeC is more preferable. When there is a boiling point in this range, the balance between the handleability of the composition and the production efficiency when a film is produced using the composition is good.

  In addition, the solvent which the composition of this invention contains is not restricted to the solvent whose relative dielectric constant in 25 degreeC is 5 or less. For example, in order to make it easy to apply the composition of the present invention to a highly polar substrate, a mixed solvent of a solvent having a relative dielectric constant of 5 or less at 25 ° C. and a highly polar solvent having a relative dielectric constant exceeding 5 is used. It can also be used. Examples of the highly polar solvent include ethyl methyl ketone, diethyl ether, dichloromethane, chlorobenzene, 1,2-dichloroethylene, 1,1-dichloroethylene, tetrachloroethylene, dichlorobenzene and the like. The amount of the highly polar solvent added is preferably 40% by weight or less, and more preferably 30% by weight or less, when the weight of all the solvents in the composition of the present invention is 100% by weight.

  The composition of the present invention preferably contains 0.1 to 25% by weight of the copolymer (A) when the total weight of the composition is 100% by weight. When it is within the above range, when a film is produced using the composition of the present invention, a film having a sufficient thickness can be obtained, and the stability (solvent solubility) of the composition tends to be improved.

  The solvent content of the composition of the present invention is preferably 70 to 99.9% by weight, more preferably 80 to 99.9% by weight, and 85 to 99.9% by weight with respect to 100% by weight of the composition. Particularly preferred. When the content of the solvent is within the above range, there is a balance between the handleability of the composition when the composition of the present invention is used as a coating agent and the like and the ease of removal of the solvent when producing a film from the composition. It becomes good.

(3) Other components In the composition of the present invention, the heat stabilizer, the weather stabilizer, the antistatic agent, the slip agent, the leveling agent, and the reinforcing agent are further added as necessary without departing from the object of the present invention. Antiblocking agents, antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, fillers and the like can be blended. In addition, when it is necessary to increase the adhesion and adhesion between a film prepared using the composition of the present invention and a base film described later or a circuit board to which the composition is applied, the composition of the present invention is used. A) a thermoplastic adhesive resin, b) a resin having an adhesive component, c) a component obtained by graft-modifying the copolymer (A) with a polar compound (hereinafter also referred to as a graft-modified copolymer (A)) ) Can also be blended.

a) Thermoplastic adhesive resin a) Thermoplastic adhesive resins include known thermoplastic adhesives, including polyolefins, ionomer resins, ethylene or ethylene having functional groups introduced in the main chain. It is preferable to use a monomer selected from a copolymer of a monomer containing glycidyl methacrylate. The polyolefin having a functional group introduced into the main chain is preferably a polyolefin having a carboxyl group introduced into the main chain by a graft reaction. For example, a commercially available thermoplastic resin “Admer” (registered trademark) (manufactured by Mitsui Chemicals, Inc. or Mitsui Chemicals Tosero Co., Ltd.) and polyolefin adhesive resins (trade name Modic; manufactured by Mitsubishi Chemical Co., Ltd.) can be used. The addition amount of the adhesive resin is preferably 0 to 20% by weight, more preferably 0.1 to 15% by weight with respect to 100% by weight of the copolymer (A) in the composition.

b) Resin having an adhesive component b) The resin having an adhesive component is not particularly limited as long as it is an adhesive resin. For example, a thermoplastic resin having a melting point (Tm) measured by DSC of less than 110 ° C., And conventionally known thermoplastic elastomers. Specifically, a polyolefin-based thermoplastic resin or a polyolefin-based thermoplastic elastomer is preferable. Specific examples of the polyolefin-based thermoplastic resin or the polyolefin-based thermoplastic elastomer include an ethylene-based polymer, a propylene-based copolymer, and a butene. Examples thereof include a system copolymer. More specifically, a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, a copolymer of ethylene, an α-olefin having 3 to 20 carbon atoms and a cyclic olefin, styrene, vinyl acetate, (meta ) Ethylene copolymer having various vinyl compounds such as acrylic acid and (meth) acrylic acid ester as a comonomer, copolymer of propylene and α-olefin having 4 to 20 carbon atoms, propylene and having 4 to 20 carbon atoms Examples include copolymers of α-olefins and cyclic olefins, and ethylene copolymers having various vinyl compounds such as styrene, vinyl acetate, (meth) acrylic acid, and (meth) acrylic acid esters as comonomers.

  In addition, examples of the thermoplastic elastomer include a polystyrene-based elastomer. Polystyrene elastomers include block copolymers (SBS) of polystyrene blocks that become hard parts (crystal parts) and diene monomer blocks that become soft parts, hydrogenated styrene / butadiene / styrene blocks (HSBR), styrene / Examples thereof include an ethylene / propylene / styrene block copolymer (SEBS), a styrene / isobutylene / styrene copolymer (SIBS), and a styrene / isobutylene copolymer (SIB). Polystyrene elastomers are used alone or in combination of two or more.

  The styrene / ethylene / propylene / styrene block copolymer is obtained by hydrogenating a styrene / isoprene / styrene block copolymer (SIS). Specific examples of SIS include: JSR Corporation as trade name: JSR SIS (registered trademark), Kuraray Co., Ltd. as trade name: Hibler (registered trademark), or Shell Corporation as trade name: Clayton D (registered trademark) The thing marketed etc. are mentioned.

  Specific examples of SEPS include those commercially available from Kuraray Co., Ltd. under the trade name: Septon (registered trademark). Specific examples of SIBS include those commercially available from Kaneka Corporation under the trade name: Shibustar (registered trademark).

Furthermore, an elastomer made of an olefin block copolymer can be used as an example of the thermoplastic resin or the thermoplastic elastomer. As an elastomer made of a polyolefin block copolymer, for example, a block copolymer of a polyolefin block that forms a polymer with high crystallinity such as polypropylene that becomes a hard part, and a monomer copolymer that shows amorphousness that becomes a soft part Specifically, olefin (crystalline) / ethylene / butylene / olefin block copolymer, polypropylene / polyolefin (amorphous) / polypropylene block copolymer and the like can be exemplified. Specific examples include those commercially available from JSR Corporation under the trade name DYNARON.
The addition amount of the resin having the adhesive component b) is preferably 0 to 50% by weight, more preferably 0.1 to 20% by weight with respect to 100% by weight of the copolymer (A) in the composition.

c) Graft-modified copolymer (A)
When the copolymer (A) is mixed with a polar resin, or when it is necessary to increase the adhesive force between the film of the present invention and the substrate film in contact with the film of the present application, the copolymer (A) It is preferable to add the graft-modified copolymer (A), which is at least partially graft-modified with a polar compound, to the composition of the present invention.

  Examples of polar compounds used for graft modification include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids or their derivatives, and vinyl esters. Compounds, vinyl chloride, vinyl group-containing organosilicon compounds, carbodiimide compounds and the like can be mentioned. Of these, unsaturated carboxylic acids or derivatives thereof and vinyl group-containing organosilicon compounds are particularly preferred.

  Examples of the unsaturated carboxylic acid or a derivative thereof include an unsaturated compound having one or more carboxylic acid groups, an ester of a compound having a carboxylic acid group and an alkyl alcohol, and an unsaturated compound having one or more carboxylic anhydride groups. Examples of the unsaturated group include a vinyl group, a vinylene group, and an unsaturated cyclic hydrocarbon group. Conventionally known compounds can be used, and there are no particular limitations, but specific compounds include, for example, acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, Unsaturated carboxylic acids such as nadic acid [registered trademark] (endocis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid); or derivatives thereof such as acid halides, amides, imides, anhydrous Products, esters and the like. Specific examples of such derivatives include maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like. These unsaturated carboxylic acids and / or derivatives thereof can be used singly or in combination of two or more. Among these, unsaturated dicarboxylic acids or acid anhydrides thereof are suitable, and maleic acid, nadic acid [registered trademark] or acid anhydrides thereof are particularly preferably used.

  As the vinyl group-containing organosilicon compound, conventionally known compounds can be used, and there is no particular limitation, but specific examples include vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β-methoxyethoxysilane), γ-glycol. Sidoxypropyl-tripirtrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxy Silane, 3-glycidoxypropylmethylethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethylmethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3- Acro Cypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3 -Aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureido Propyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, etc. can be used. Preferably, γ-glycidoxypropyltripyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane More preferably, vinyltriethoxysilane, vinyltrimethoxysilane, and 3-acryloxypropyltrimethoxysilane having small steric hindrance and high graft modification efficiency can be used.

  In the present invention, the graft-modified copolymer (A) is graft-reacted in an amount of usually 1 to 100 parts by weight, preferably 5 to 80 parts by weight with respect to 100 parts by weight of the copolymer (A). Can be obtained. This grafting reaction is usually performed in the presence of a radical initiator.

  Examples of the radical initiator used for graft polymerization include organic peroxides and azo compounds. The radical initiator can be used as it is mixed with the copolymer (A) and the polar compound, but can also be used after being dissolved in a small amount of an organic solvent. Any organic solvent that can dissolve the radical initiator can be used without particular limitation.

  Further, when the polar compound is grafted to the copolymer (A), a reducing substance may be used. If a reducing substance is used, the graft amount of the polar compound may be improved.

  The graft modification reaction of the copolymer (A) with the polar compound can be performed by a conventionally known method. For example, the copolymer (A) is dissolved in an organic solvent, then a polar compound and a radical initiator are added to the solution, and a temperature of 70 to 200 ° C., preferably 80 to 190 ° C., for 0.5 to 15 hours, preferably Can mention the method of making it react for 1 to 10 hours.

  Moreover, a copolymer (A) and a polar compound can also be made to react by solvent-free using an extruder. This reaction is usually preferably performed at a temperature equal to or higher than the melting point (Tm) of the copolymer (A), specifically at a temperature of 160 to 290 ° C., usually for 0.5 to 10 minutes.

  The modification amount of the graft-modified copolymer (A) thus obtained (the graft amount of the polar compound) is usually 0.1 to 100% by weight of the copolymer (A) subjected to the graft modification reaction. 50% by weight, preferably 0.2-30% by weight, more preferably 0.2-10% by weight.

  A known antioxidant can be used as the antioxidant. Specifically, a hindered phenol compound, a sulfur-based antioxidant, a lactone-based antioxidant, an organic phosphite compound, an organic phosphonite compound, or a combination of these can be used.

  Examples of the lubricant include sodium, calcium and magnesium salts of saturated or unsaturated fatty acids such as lauric acid, palmitic acid, oleic acid and stearic acid, and these may be used alone or in combination of two or more. it can. The amount of the lubricant is usually 0.1 to 3 parts by weight, preferably about 0.1 to 2 parts by weight, based on 100 parts by weight of the composition of the present invention.

  As the slip agent, it is preferable to use amides of saturated or unsaturated fatty acids such as lauric acid, palmitic acid, oleic acid, stearic acid, erucic acid and hebenic acid, or bisamides of these saturated or unsaturated fatty acids. Of these, erucic acid amide and ethylene bisstearamide are particularly preferred. These fatty acid amides are preferably blended in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the copolymer (A) in the composition of the present invention.

  Examples of the anti-blocking agent include fine powder silica, fine powder aluminum oxide, fine powder clay, powdered or liquid silicon resin, tetrafluoroethylene resin, fine powder cross-linked resin such as cross-linked acrylic and methacrylic resin powder. be able to. Of these, fine powder silica and crosslinked acrylic and methacrylic resin powders are preferred.

  Moreover, when using the composition of this invention as a coating agent so that it may mention later, it is also a preferable aspect to add a leveling agent to the composition of this invention. As a leveling agent for reducing the surface roughness of a film prepared from the composition of the present invention, a fluorine-based nonionic surfactant, a special acrylic resin leveling agent, a silicone leveling agent, and the like can be used, and are compatible with a solvent. Are preferable, and the amount added is in the range of 1 to 50,000 ppm relative to the copolymer (A) in the composition.

  Examples of the reinforcing agent include metal oxides such as silicon, titanium, aluminum, and zirconium, polyfunctional alkoxy compounds or oligomers thereof, and clay minerals in an amount of 5 to 50 with respect to 100 parts by weight of the copolymer (A) in the composition. A weight part can also be mix | blended and the hardness and elasticity modulus of the film (in this case also called a coating layer) created using the composition of this invention as a coating agent can be raised. If the addition amount is less than 5 parts by weight, the effect is too low, and if it exceeds 50 parts by weight, the transparency and mechanical strength of the coat layer may be impaired.

(4) Manufacturing method of composition The manufacturing method of the composition of this invention is not specifically limited, It can manufacture by the method used normally. For example, it can be produced by adding the copolymer (A) to the solvent and stirring for a predetermined time at a temperature not higher than the boiling point of the solvent.

(5) Use of composition Since the composition of the present invention can produce a film having high heat resistance and high electrical insulation using the composition, a coating agent, particularly a liquid crystal display element, an electroluminescence display element, etc. Various display devices; semiconductor devices; optical members such as light guide plates, polarizing films, light diffusion films, retardation films, antireflection films; surface protection, printed circuit boards, etc., for surface protection, insulation, planarization, heat resistance, It can be suitably used as various coating agents for light resistance and weather resistance.

  In particular, since the composition of the present invention can form a protective layer on a substrate having a complicated shape, it can be suitably used as a coating agent for forming a protective layer on the electrode surface of a printed wiring board or capacitor. Moreover, the said other film can also be made into a mold release film by apply | coating the composition of this invention on another film, and removing a solvent.

2. Film (1) Film The film of the present invention is a film containing the copolymer (A) and a solvent. Below, the film of this invention is demonstrated in detail. The term “film” as used in the present application is a name for convenience and is a general term for a planar molded product. In addition to a film, this includes a sheet, a film, a tape, a layer formed on a substrate, and the like. It is a concept that includes. The “film” is not limited to a molded product having a continuous plane.

  As for the film of this invention, when the said whole film is 100 weight%, it is normal that content of a solvent is 0.001-0.5 weight%. When it is in this range, it is easy to maintain the shape as a film, and the flexibility of the film is increased. For this reason, when it uses as a release film of a circuit board, for example, it can prevent that a film is damaged by press work etc. and electrical insulation property falls. The normalized breakdown voltage (kV / μm) obtained by dividing the breakdown voltage (BDV) of the film of the present invention by the thickness of the film is preferably 0.05 or more.

Further, when the copolymer (A) is molded by an extrusion method or the like, the copolymer (A) needs to be heated and melted at a temperature equal to or higher than its melting point (T _m ). When a film is produced by coating, the film can be produced at a temperature lower than the melting point (Tm), so that the decomposition product due to thermal degradation of the copolymer is reduced, and the releasability may be increased. Examples of the decomposition products include low molecular weight components such as dimers to pentamers of monomer components constituting the copolymer (A) obtained by decomposing the copolymer (A) at high temperatures, Heat stabilizer, weather stabilizer, antistatic agent, slip agent, leveling agent, reinforcing agent, antiblocking agent, antifogging agent, lubricant, dye, pigment, natural oil, synthetic oil, wax, filling And oxides such as agents, and some of the components that have undergone oxidative decomposition.

(2) Manufacturing method of film The film of this invention can be manufactured using the composition of this invention. Specifically, by applying the composition of the present invention on a predetermined substrate and heating to a temperature close to the boiling point of the composition, the solvent in the composition is removed to some extent to produce a film. it can. When the film of the present invention is used as a self-supporting film separated from the substrate, the substrate to which the composition of the present invention is applied is preferably composed of a material having high releasability.

  When the film of the present invention is used as a specific layer in a laminated film, the composition of the present invention is applied to the film to be laminated as a coating agent, and the solvent in the composition is removed to some extent. A laminated film including the film of the present invention as a layer can also be obtained. The method for applying the composition of the present invention is not particularly limited, but application using a brush or brush, spraying by spraying, screen printing method, flow coating, spin coating, dipping method, bar coater, T die, Examples thereof include a method of applying to a roll or flat plate using a T-die with a bar, a doctor knife, a roll coat, a die coat, or the like.

  The removal of the solvent in the present application does not only mean that the solvent is completely removed from the composition of the present invention, but that the solvent is removed to such an extent that the composition of the present invention can be formed into a film. Say. Specifically, it means that the solvent is removed until the solvent becomes about 0.001 to 0.5% by weight with respect to 100% by weight of the film prepared using the composition of the present invention.

  A method for removing the solvent is not particularly limited, and the solvent may be dried by allowing it to stand, but is generally removed by heating at 30 to 220 ° C. and drying. In order to prevent thermal deterioration and thermal decomposition of the copolymer (A), it is preferable to remove the solvent at a temperature not higher than the melting point (Tm) of the copolymer (A). On the other hand, if the drying temperature is too low, the drying time becomes long and productivity is deteriorated. If it is too high, problems such as foaming and deterioration occur. In order to dry in a short time while preventing foaming, drying may be performed while increasing the temperature in two or more steps or continuously. Further, after the drying step, the coating layer is subjected to a step of immersing in a solvent in which the copolymer (A) is difficult to dissolve, such as water, methanol, ethanol, acetone, methylene chloride, or a step of exposing to a vapor atmosphere of the solvent. The remaining solvent can also be reduced. The solvent remaining in the coating layer after drying is 0.5% by weight or less, preferably 0.05% by weight or less, more preferably 0.01% by weight or less.

  When using the film of the present invention as a protective layer for various display devices, semiconductor devices, optical members, printed circuit boards, capacitors, etc., the composition of the present invention is applied to a predetermined position of the device or circuit, A film (in this case, also referred to as a coating layer) can be formed by heating at a temperature at which the device or the like does not deteriorate and removing a certain amount of the solvent in the composition.

(3) Use of film Since the film of the present invention is excellent in heat resistance and electrical insulation as described above, it is particularly suitably used as a protective layer for various display devices, semiconductor devices, optical members, printed circuit boards, capacitors and the like. be able to. The film of the present invention is suitably used as a release film or a release layer for a release film. Hereinafter, an example in which the film of the present invention is used for the release layer of the release film will be described.

  A release film can be produced by laminating the film of the present invention with a base film described later. The material of the base film is not particularly limited, and may be a single layer or a multilayer, and the thickness is not particularly limited, but preferably includes a thermoplastic resin that can be easily formed into a film. Examples of the thermoplastic resin include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, linear low density polyethylene such as high density polyethylene, medium density polyethylene, low density polyethylene, and ethylene-α-olefin copolymer, polypropylene, 4- Examples thereof include polyolefin resins such as methyl-1-pentene polymer and polybutene. Moreover, the shaping | molding method of a base film may be general methods, such as extrusion, uniaxial or biaxial stretching, and is not specifically limited.

  In addition, heat-resistant stabilizers, weather-resistant stabilizers, ultraviolet absorbers, lubricants, slip agents, nucleating agents, anti-blocking agents, antistatic agents, antifogging agents, pigments, dyes, inorganic or organic fillers are added to these base films. In general, various additives used for polyolefin may be added within a range not impairing the object of the present invention. Although the thickness of these base film is 10-100 micrometers normally, it is not specifically limited.

  Applying the composition of the present invention to the surface of the base film and removing the solvent of the composition to create a release film by laminating the film of the present invention on the surface of the base film Can do. In addition, since the film of this invention should just be arrange | positioned to at least one part of the outermost surface of the said release film, it is not necessary to apply | coat the composition of this invention to the whole surface of a base film.

  When it is necessary to increase the adhesion and adhesion between the base film and the film of the present invention, the above-mentioned a) thermoplastic adhesive resin and b) a resin having an adhesive component are used. C) The graft-modified copolymer (A) is preferably selected and added as appropriate. Only one kind of these components a to c may be added to the film of the present invention, or may be added in combination. Although the method of adding these components to the film of the present invention is not limited, specifically, the film is formed by the above method using a composition obtained by adding and mixing the components a to c to the composition of the present invention. It can also be added by the method.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the examples, each physical property was measured and evaluated under the following conditions.

[Intrinsic viscosity [η]]
It measured at 135 degreeC using the decalin solvent. That is, about 20 mg of polymer powder, pellets or resin mass was dissolved in 15 ml of decalin, and the specific viscosity ηsp was measured in an oil bath at 135 ° C. After diluting the decalin solution with 5 ml of decalin solvent, the specific viscosity ηsp was measured in the same manner. This dilution operation was further repeated twice, and the value of ηsp / C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity. The calculation formula is shown below.
"Formula 1"
[Η] = lim (ηsp / C) (C → 0)

[MFR]
The MFR of the copolymer (A) was measured according to JIS K7210 at a load of 5 kg at 260 ° C. or a load of 230 ° C. and 2.16 kg. Copolymers 6 and 7 were measured under conditions of 260 ° C. and 5 kg load.

[Number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (Mw / Mn)]
The number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) were measured as follows using a gel permeation chromatograph Alliance GPC-2000 manufactured by Waters. As the separation column, two TSKgel GNH6-HT and two TSKgel GNH6-HTL were used. Each of these columns has a diameter of 7.5 mm and a length of 300 mm. The column temperature is 140 ° C., o-dichlorobenzene (Wako Pure Chemical Industries, Ltd.) is used as the mobile phase, and 0.025% by weight of BHT (Takeda Pharmaceutical Co., Ltd.) is used as the antioxidant, at 1.0 ml / min. Moved. The concentration of the sample (measuring object: copolymer (A)) was adjusted to 15 mg / 10 mL, 500 microliters were injected, and detection was performed using a differential refractometer. As the standard polystyrene, those manufactured by Tosoh Corporation were used for samples having molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and those manufactured by Pressure Chemical Co. were used for 1000 ≦ Mw ≦ 4 × 10 ⁶ .

[Content of olefin and the like in copolymerization (A)]
The contents of 4-methyl-1-pentene, 3-methyl-1-pentene and α-olefin in the copolymer were measured by ¹³ C-NMR using the following apparatus and conditions. Using an ECP500 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd., a mixed solvent of orthodichlorobenzene / heavy benzene (80/20 vol%) as a solvent, sample concentration 55 mg / 0.6 mL, measuring temperature 120 ° C., observation nucleus ¹³ C (125 MHz), sequence is single pulse proton decoupling, pulse width is 4.7 μs (45 ° pulse), repetition time is 5.5 seconds, integration number is 10,000 times or more, 27.50 ppm as standard for chemical shift Measured as a value. From the obtained 13C-NMR spectrum, the compositions of 4-methyl-1-pentene, 3-methyl-1-pentene and α-olefin were quantified.

[Melting point (T _m ), crystallization temperature (T _c ))]
Using a DSC measuring device (DSC220C) manufactured by Seiko Instruments Inc., a sample of about 5 mg was put in an aluminum pan for measurement, heated to 290 ° C. at 100 ° C./min, held at 290 ° C. for 5 minutes, 10 ° C. / The crystallization temperature (T _c ) was calculated from the peak apex of the crystallization peak when the temperature was lowered to −100 ° C. in min, and the melting point (T _m ) was calculated from the peak apex of the crystal melting peak. It means that heat resistance is so high that melting | fusing point ( _Tm ) is high.

[density]
For the density measurement, the 1 mm-thick press sheet obtained by the above method was cut into 30 mm square, and was measured by an underwater substitution method using an electronic hydrometer according to JIS K6268.

[Dissolved state (composition stability)]
In the synthesis of the composition of the present invention to be described later, the copolymer (A) and the solvent were stirred at 200 rpm for 1 hour at 200 ° C., and then the composition was synthesized. After that, the composition was visually transparent under visible light. The case was evaluated as ◯, when it appeared cloudy but fluidity was observed, Δ when it was cloudy and fluidity was not observed.

[Film coatability]
When the composition of the present invention is applied on a glass substrate at 25 ° C. and uniformly stretched with an applicator, and then dried at 25 ° C. for 30 minutes and further at 80 ° C. for 1 hour, a film is obtained. ◯ when the unevenness is 0.02 mm or less, x when there is an unevenness greater than 0.02 mm, and when the film is pressed with a finger, there is tackiness when the components of the film adhere to the finger As △. Here, irregularities were counted as a result of unmelted residue.

[Dielectric breakdown voltage (BDV)]
The dielectric breakdown voltage (V / μm) was measured using a dielectric breakdown tester manufactured by Yamayo Tester Co., Ltd. according to ASTM-D149. A voltage was applied to the film obtained by the above method at a boosting rate of 500 V / sec to measure a breakdown voltage, and a breakdown voltage characteristic was obtained. Moreover, the thickness of the part of the film for which the breakdown voltage was obtained was measured, and the value obtained by dividing the breakdown voltage (BDV) by the thickness was defined as the normalized breakdown voltage kV (/ μm). The larger the normalized breakdown voltage, the higher the electrical insulation.

[Measurement of water contact angle]
The contact angle of water was measured by using a DropMaster 500 image processing system and a solid-liquid interface analysis system to measure a contact angle value when a water droplet was dropped on the obtained film. The larger the contact angle value, the higher the releasability for a material with higher polarity.

[Critical interfacial tension]
The critical interfacial tension is measured by using a DropMaster500 image processing type, solid-liquid interface analysis system, and using a liquid mixture for a wetting tension reagent (manufactured by Wako Pure Chemical Industries, Ltd.) in an environment of 23 ° C. and 50% humidity. Below, the contact angle of the film obtained in the Example was measured, and the critical interfacial tension was calculated based on it. It means that the smaller the critical interfacial tension, the higher the releasability for a material with higher polarity.

[Solvent content, decomposition product content]
The solvent contained in the film, the decomposition product of the copolymer (A), and the like were carried out with reference to test methods such as JP2011-88352A and JP2007-224311A. Specifically, a film having a thickness of 50 μm was cut into a 20 × 2 mm strip, 10 mg of which was precisely weighed, and then heated at 180 ° C. for 30 minutes in a helium stream. Gas components generated during the heating were collected by a dynamic headspace method and measured with a thermal desorption GC / MS spectrum analyzer (HP6890 / HP5975 manufactured by Agilent Technologies). Next, the obtained MS spectrum was converted into a converted quantitative value using decane as a standard sample, and the peak derived from the solvent was defined as the amount of solvent, and the peak not derived from the solvent was defined as the amount of decomposition product.

  The synthesis method of the copolymer used by the Example and the comparative example by the following synthesis examples is demonstrated. Synthesis examples 1 to 4 are copolymers (A) as used in the present invention.

Synthesis Example 1 Preparation of Copolymer (A) -1 750 ml of 4-methyl-1-pentene was charged at 23 ° C. into a 1.5-liter stirring SUS autoclave sufficiently purged with nitrogen. The autoclave was charged with 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL), 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 was 0.18 MPa (gauge pressure). Subsequently, 1 mmol of methylaluminoxane prepared in advance, 1 mmol of diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7-di-t-butyl-fluorenyl) zirconium dichloride in terms of Al. Was introduced into an autoclave with nitrogen to initiate polymerization. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C. Sixty minutes after the start of polymerization, 5 ml of methanol was injected into the autoclave with nitrogen to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Acetone was poured into the reaction solution with stirring.

The obtained powdery polymer containing the solvent was dried at 130 ° C. under reduced pressure for 12 hours. The obtained polymer was 45.9 g, and the 4-methyl-1-pentene content in the polymer was 91.3 mol% and the propylene content was 8.7 mol%. The melting point (T _m ) of the polymer was 172 ° C., and the intrinsic viscosity [η] was 1.62 dl / g.

(Synthesis Example 2) Preparation of Copolymer (A) -2 750 ml of 4-methyl-1-pentene was charged at 23 ° C. into a SUS autoclave with a stirring blade having a volume of 1.5 liters sufficiently substituted with nitrogen. The autoclave was charged with 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL), 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 was 0.15 MPa (gauge pressure). Subsequently, 1 mmol of methylaluminoxane prepared in advance, diphenylmethylene (1-ethyl-3-tert-butyl-cyclopentadienyl) (2,7-di-tert-butyl-fluorenyl) zirconium in terms of Al Polymerization was initiated by injecting 0.34 ml of a toluene solution containing 0.005 mmol of dichloride into an autoclave with nitrogen. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C. Sixty minutes after the start of polymerization, 5 ml of methanol was injected into the autoclave with nitrogen to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Acetone was poured into the reaction solution with stirring.

The obtained powdery polymer containing the solvent was dried at 130 ° C. under reduced pressure for 12 hours. The obtained polymer was 39.2 g, and the 4-methyl-1-pentene content in the polymer was 92 mol% and the propylene content was 8 mol%. The melting point (T _m ) of the polymer was 177 ° C., and the intrinsic viscosity [η] was 1.7 dl / g. Table 1 shows the measurement results of various physical properties.

(Synthesis Example 3) Preparation of Copolymer (A) -3 750 ml of 4-methyl-1-pentene was charged at 23 ° C. into a SUS autoclave with a stirring blade having a volume of 1.5 liters sufficiently purged with nitrogen. The autoclave was charged with 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL), and the stirrer was rotated.

Next, the autoclave was heated to an internal temperature of 60 ° C., pressurized with propylene so that the total pressure became 0.15 MPa (gauge pressure), and 100 ml of hydrogen gas was further added to adjust the molecular weight. Subsequently, 1 mmol of methylaluminoxane prepared in advance, diphenylmethylene (1-ethyl-3-tert-butyl-cyclopentadienyl) (2,7-di-tert-butyl-fluorenyl) zirconium in terms of Al Polymerization was initiated by injecting 0.34 ml of a toluene solution containing 0.003 mmol of dichloride into the autoclave with nitrogen. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C. Five minutes after the start of polymerization, 5 ml of methanol was pressed into the autoclave with nitrogen to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Acetone was poured into the reaction solution with stirring. The obtained powdery polymer containing the solvent was dried at 130 ° C. under reduced pressure for 12 hours. The obtained polymer was 19.9 g, and the 4-methyl-1-pentene content in the polymer was 92.4 mol% and the propylene content was 7.6 mol%. The melting point (T _m ) of the polymer was 180 ° C., and the intrinsic viscosity [η] was 0.77 dl / g. Table 1 shows the measurement results of various physical properties.

(Synthesis Example 4) Preparation of Copolymer (A) -4 750 ml of 4-methyl-1-pentene was charged at 23 ° C. into a SUS autoclave with a stirring blade having a volume of 1.5 liters sufficiently purged with nitrogen. The autoclave was charged with 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL), 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 was 0.12 MPa (gauge pressure). Subsequently, 1 mmol of methylaluminoxane prepared in advance, diphenylmethylene (1-ethyl-3-tert-butyl-cyclopentadienyl) (2,7-di-tert-butyl-fluorenyl) zirconium in terms of Al Polymerization was initiated by injecting 0.34 ml of a toluene solution containing 0.005 mmol of dichloride into an autoclave with nitrogen. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C. Sixty minutes after the start of polymerization, 5 ml of methanol was injected into the autoclave with nitrogen to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Acetone was poured into the reaction solution with stirring. The obtained powdery polymer containing the solvent was dried at 130 ° C. under reduced pressure for 12 hours. The obtained polymer was 34.7 g, and the 4-methyl-1-pentene content in the polymer was 94 mol% and the propylene content was 6 mol%. The melting point (T _m ) of the polymer was 200 ° C., and the intrinsic viscosity [η] was 1.6 dl / g. Table 1 shows the measurement results of various physical properties.

(Synthesis Example 5) Preparation of Copolymer 5 750 ml of 4-methyl-1-pentene was charged at 23 ° C. into a SUS autoclave with a stirring blade having a capacity of 1.5 liters sufficiently substituted with nitrogen. To this autoclave, 0.94 ml of a 1.0 mmol / ml toluene solution of triethylaluminum (TEA) was charged, 240 ml of hydrogen gas was introduced, 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 was 0.18 MPa (gauge pressure). Subsequently, 4.7 ml of a toluene solution containing 0.013 mmol of a solid titanium catalyst prepared based on JP-A-2008-144155 was pressed into the autoclave with nitrogen to initiate polymerization. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C. Sixty minutes after the start of polymerization, 5 ml of methanol was injected into the autoclave with nitrogen to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Acetone was poured into the reaction solution with stirring.

The obtained powdery polymer containing the solvent was dried at 130 ° C. under reduced pressure for 12 hours. The obtained polymer was 67.1 g, and the 4-methyl-1-pentene content in the polymer was 90 mol% and the propylene content was 10 mol%. The melting point (T _m ) of the polymer was 174 ° C., and the intrinsic viscosity [η] was 1.4 dl / g. Table 1 shows the measurement results of various physical properties.

(Synthesis Example 6) Production of Copolymer 6 According to the methods of Comparative Example 7 and Comparative Example 9 of International Publication No. 2006/054613, the ratios of 4-methyl 1-pentene, 1-hexadecene, 1-octadecene and hydrogen are determined. By changing, a copolymer 6 having physical properties shown in Table 1 was obtained.

(Synthesis example 7) Manufacture of the copolymer 7 According to the method of Unexamined-Japanese-Patent No. 2008-144155, the physical property shown in Table 1 is changed by changing the ratio of 4-methyl 1-pentene, 1-hexene, and hydrogen. The copolymer 7 which has this was obtained. In Table 1, the physical-property value regarding the copolymer (A) -1 to (A) -4 and the copolymer 5-7 is shown.

(Example 1)
0.1% by weight of tri (2,4-di-tert-butylphenyl) phosphate as an antioxidant and n-octadecyl-3 as a heat stabilizer for 10 g of copolymer (A) -1 -(4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propionate was added in an amount of 0.1% by weight, and toluene (manufactured by Wako Pure Chemical Industries, Ltd.) was prepared so that the solid content concentration became 5% by weight. ) Was added and stirred at 200 rpm for 1 hour at 40 ° C. to prepare a composition containing the copolymer (A) -1. This solution was applied onto a glass substrate at 25 ° C. and uniformly stretched with an applicator, and then dried at 25 ° C. for 30 minutes and further at 80 ° C. for 1 hour to obtain a film.
(Example 2)
A film was obtained in the same manner as in Example 1 except that the copolymer (A) -2 was used.
(Example 3)
A film was obtained in the same manner as in Example 1 except that the copolymer (A) -3 was used.
Example 4
A film was obtained in the same manner as in Example 1 except that the copolymer (A) -4 was used.
(Comparative Example 1)
A film was obtained in the same manner as in Example 1 except that the copolymer 5 was used.
(Comparative Example 2)
A film was obtained in the same manner as in Example 1 except that the copolymer 6 was used.
(Comparative Example 3)
A film was obtained in the same manner as in Example 1 except that the copolymer 7 was used.

(Reference Example 1)
Copolymer (A) -2 and 0.1 part by weight of secondary antioxidant tri (2,4-di-t-butylphenyl) phosphate with respect to 100 parts by weight of copolymer (A) -2 , 0.1 parts by weight of heat stabilizer n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propinate and 0.1 part by weight of hydrochloric acid absorbent calcium stearate A resin composition was obtained. Next, 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, The resin composition was granulated to obtain evaluation pellets. Furthermore, the pellet for evaluation was melt cast molded at a die temperature of 250 ° C. using a single-axis sheet molding machine manufactured by Tanaka Iron Works Co., Ltd. to obtain a film having a thickness of 20 μm.

  Table 2 shows the compositions and coating properties of Examples 1-4, Comparative Examples 1-3, and Reference Example 1, and the thicknesses and dielectric breakdowns measured by the methods described above for the films prepared using the compositions. The voltage (BDV), the normalized breakdown voltage (BDV) obtained by dividing BDV by the film thickness, the contact angle of water, and the critical interfacial tension (mN / m) are shown.

  The amount of the solvent contained in the films obtained in Examples 1 to 4, Comparative Examples 1 to 3, and Reference Example 1 is 0.001 to 0.2% by weight when the film is 100% by weight. Met. Moreover, the solvent contained in the film obtained in Reference Example 1 was 0.003% by weight or less, and the amount of the decomposed product contained was 0.3% by weight.

  As apparent from the results in Table 2, Comparative Example 1 in which the molecular weight distribution (Mw / Mn) of the copolymer (A) exceeds 3.5, and a configuration derived from the α-olefin in the copolymer (A) It can be seen that the comparative example 2 of hexadecene or octadecene having a unit carbon number of 4 or more is inferior in dissolution state (composition stability) to the examples of the present application. Moreover, it turns out that the comparative example 3 using the hexene whose carbon number of the structural unit derived from the alpha olefin in a copolymer (A) is 6 is inferior to an Example.

  This is a bulky constituent unit, and 4-methyl-1-pentene and / or 3-methyl-pentene, which has heat resistance when made into a polymer, has a constant α-olefin, such as propylene, which tends to lower the crystallinity. The inclusion of the above indicates that the crystallinity of the copolymer (A) is moderately lowered and is easily developed in a solvent. In addition, it is considered that the narrower the molecular weight distribution of the copolymer (A), the lower the proportion of high molecular weight components that are difficult to dissolve in the solvent, so that the dissolved state and film coatability are improved.

  Moreover, even if the comparative example 1 which made the copolymer (A) into the film by the extrusion method and Examples 1-4 are compared, a big difference is not looked at by the normalization breakdown voltage or the contact angle of water. From this, it can be seen that by using the composition of the present invention, a film comparable to the extrusion method can be produced by a coating method having higher moldability and workability.

  By using the composition of the present invention as a coating agent in particular, a film having high heat resistance and good electrical insulation can be easily produced. The film has a particularly high industrial applicability as a protective film for various display devices, semiconductor devices, optical members, and printed circuit boards that require heat resistance and electrical insulation in the manufacturing process.

Claims (9)

A copolymer (A) that satisfies the following requirements (i) to (v);
And a solvent.
(I) a copolymer containing 80 to 99 mol% of structural units derived from 4-methyl-1-pentene and / or 3-methyl-1-pentene and 1 to 20 mol% of structural units derived from propylene (Ii) Intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.5 to 5.0 (dl / g) (iii) Melting point (Tm) measured by DSC is in the range from 160 ° C. to 240 ° C. (Iv) The density is 820 to 850 (kg / m ³ ). (V) The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC). Molecular weight distribution (Mw / Mn) is 1.0 to 3.5 The composition of Claim 1 which contains a copolymer (A) 0.1 to 25weight% with respect to 100 weight% of compositions. The composition according to claim 1 or 2 , wherein the solvent is a solvent having a relative dielectric constant at 25 ° C of 5 or less. The solvent, n- hexane, n- heptane, n- octane, cyclohexane, methylcyclohexane, ethylcyclohexane, any one of claims 1 to 3 is at least one solvent selected from the group consisting of toluene and xylene The composition according to item. The coating agent containing the composition as described in any one of Claims 1-4 . A copolymer (A) that satisfies the following requirements (i) to (v);
A film containing 0.001 to 0.5% by weight of the solvent with respect to 100% by weight of the film.
(I) a copolymer containing 80 to 99 mol% of structural units derived from 4-methyl-1-pentene and / or 3-methyl-1-pentene and 1 to 20 mol% of structural units derived from propylene (Ii) Intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.5 to 5.0 (dl / g) (iii) Melting point (Tm) measured by DSC is in the range from 160 ° C. to 240 ° C. (Iv) The density is 820 to 850 (kg / m ³ ). (V) The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC). Molecular weight distribution (Mw / Mn) is 1.0 to 3.5 A first step of applying the composition according to any one of claims 1 to 4 or the coating agent according to claim 5 and a second step of removing the solvent in the composition. , Film manufacturing method. A capacitor comprising the film according to claim 6 . A release film comprising the film according to claim 6 on at least a part of the outermost surface.