JP6474201B2 - Polyamide film - Google Patents

Description

  The present invention relates to a film made of a polyamide resin or a composition containing the resin, which is effective for uses requiring high heat resistance such as a film for a printed wiring board.

  In addition to film productivity, heat-resistant films for printed wiring boards used in various products such as mobile phones, portable music devices, printers, personal computers, etc. are deformed in the temperature range of 240-260 ° C in the reflow soldering process. High heat resistance that does not occur is required.

  A polyimide film is generally used for a printed wiring board or the like. The polyimide film has excellent heat resistance, but has a problem that it is expensive and difficult to obtain a transparent film in addition to the difficulty of melt molding.

  On the other hand, amorphous films typified by polycarbonate, polysulfone, and polyetherimide are excellent in optical properties, electrical properties, and humidity properties. On the other hand, the films soften at temperatures above the glass transition temperature, and their functions are reduced. I can't show it. In order to improve this, a heat-resistant film using a semi-aromatic polyamide has been proposed (Patent Document 1), but the heat resistance is not sufficiently satisfactory.

  Furthermore, although a film using a composition comprising a polyamide and polyphenylene ether whose dicarboxylic acid units mainly consist of 1,4-cyclohexanedicarboxylic acid units has been proposed (Patent Document 2), heat resistance, transparency, film There was room for improvement in formability and the like.

JP 2000-186141 A International Publication No. 2008/149862

  Accordingly, an object of the present invention is to provide a film made of a polyamide resin excellent in heat resistance and transparency, having few foreign matters and excellent in appearance, or a composition containing the resin.

According to the invention, the object is
[1] Monomer derived from the end-capping agent containing 25 mol% or more of 1,4-cyclohexanedicarboxylic acid unit as a monomer unit constituting polyamide and 25 mol% or more of aliphatic diamine unit having 4 to 12 carbon atoms A film comprising a polyamide resin (A) containing 0.6 to 2.8 mol% of a unit,
A film having a thickness of 1 to 200 μm, wherein the content of trans isomer structural units derived from 1,4-cyclohexanedicarboxylic acid in the film is 70 to 90 mol% and the melting peak temperature (Tm) is 310 ° C. or higher;
[2] The film according to the above [1], wherein the solution viscosity (η _inh ) measured at 30 ° C. of a 0.2 g / dl concentrated sulfuric acid solution of the polyamide resin (A) is 1.1 to 3.0 dl / g;
[3] The aliphatic diamine unit having 4 to 12 carbon atoms is at least one selected from the group consisting of 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine and 1,12-dodecanediamine. The film of [1] or [2], which is
[4] The film according to any one of [1] to [3], wherein the aliphatic diamine unit having 4 to 12 carbon atoms is 1,9-nonanediamine.
[5] The film according to [4], further containing 1 to 25 mol% of 2-methyl-1,8-octanediamine as the aliphatic diamine unit having 4 to 12 carbon atoms;
[6] The film according to any one of [1] to [5], wherein the phosphorus atom concentration in the polyamide resin (A) is 10 to 100 ppm;
[7] The film according to any one of [1] to [6], further containing 0.1 to 10 parts by mass of the compound (B) acting as a Lewis base with respect to 100 parts by mass of the polyamide resin (A);
[8] A method for producing a stretched film including a step of further stretching the film of any one of [1] to [7]; and [9] a step of reflowing the film of any of [1] to [7]. A method for producing a flexible printed circuit board,
Is achieved by providing

  ADVANTAGE OF THE INVENTION According to this invention, the film which consists of a polyamide resin excellent in heat resistance and transparency, few foreign materials, and the external appearance or the composition containing this resin can be provided.

  Hereinafter, the present invention will be described in detail.

[Polyamide resin (A)]
The monomer unit constituting the polyamide resin (A) used in the film of the present invention contains 25 mol% or more of 1,4-cyclohexanedicarboxylic acid units and 25 mol% or more of aliphatic diamine units having 4 to 12 carbon atoms. And 0.6 to 2.8 mol% of a monomer unit derived from the end-capping agent. In addition, since it becomes easy to achieve desired solution viscosity when the molar ratio of the amino group with respect to the carboxyl group of these monomer units exists in the range of 0.95-1.05, it is preferable.

  1,4-Cyclohexanedicarboxylic acid and units derived therefrom include Hyundai Organic Chemistry (4th Edition), Volume 1 (KPC Volhardt, NE Schole, Kagaku Dojin, April 2004 1 day issue, p. 174), there are trans isomers and cis isomers, and when both substituents occupy an axial position or an equatorial position, the trans isomer, respectively the axial position, When occupying the equatorial position, it becomes a cis body.

  Since the trans-cis rearrangement of the 1,4-cyclohexanedicarboxylic acid unit in the polyamide resin (A) proceeds reversibly, the ratio of the trans-isomer to the cis-isomer is the condition for producing the polyamide resin (A), polyamide It may vary depending on the conditions for producing the resin composition and the conditions for molding the film. For this reason, the trans isomer ratio of the 1,4-cyclohexanedicarboxylic acid raw material may be in any range, but the trans isomer ratio of 50 mol% or less is preferable because the water solubility of the nylon salt with the diamine raw material becomes good. The content of the trans isomer structural unit derived from 1,4-cyclohexanedicarboxylic acid in the film of the present invention is 70 to 90 mol%, preferably 75 to 90 mol%. When the trans isomer structural unit content is less than 70 mol%, the heat resistance is lowered, and when it is more than 90 mol%, the moldability is lowered.

  The 1,4-cyclohexanedicarboxylic acid unit contained in the polyamide resin (A) is usually 25 mol% or more, preferably 40 to 52 mol%, more preferably 45 to 50 mol% (provided that dicarboxylic acid is used). The total amount of monomer units derived from the acid unit, diamine unit and end-capping agent does not exceed 100 mol%.). When the 1,4-cyclohexanedicarboxylic acid unit contained in the polyamide resin (A) is less than 25 mol%, the heat resistance, transparency and appearance of the resulting film are deteriorated.

  The polyamide resin (A) may contain dicarboxylic acid units other than 1,4-cyclohexanedicarboxylic acid units as long as the effects of the present invention are not hindered. Examples of dicarboxylic acid units other than 1,4-cyclohexanedicarboxylic acid units include 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and 1,4- (2-methyl). ) Units derived from cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid and 1,4- (3-methyl) cyclohexanedicarboxylic acid; oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2 Units derived from aliphatic dicarboxylic acids such as methyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, suberic acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid Terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6- Phthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid, diphenic acid, 4,4′-oxydibenzoic acid, diphenylmethane-4,4 Examples thereof include units derived from aromatic dicarboxylic acids such as' -dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, and 4,4'-biphenyldicarboxylic acid. These may be used alone or in combination of two or more. A unit derived from a trivalent or higher polyvalent carboxylic acid such as trimellitic acid, trimesic acid, and pyromellitic acid may be contained within a range not impairing the effects of the present invention. When the 1,4-cyclohexanedicarboxylic acid unit contained in the monomer unit constituting the polyamide resin (A) is less than 25 mol%, the heat resistance, transparency and appearance of the resulting film are deteriorated. When a dicarboxylic acid unit other than 1,4-cyclohexanedicarboxylic acid unit is contained, it is preferably 25 mol% or less.

  A C4-C12 aliphatic diamine unit contained in a polyamide resin (A) is 25 mol% or more normally, Preferably it is 40-52 mol%, More preferably, it is 45-50 mol%. In the monomer unit constituting the polyamide resin (A), when the aliphatic diamine unit having 4 to 12 carbon atoms is less than 25 mol%, the heat resistance of the resulting film is lowered.

  Examples of the aliphatic diamine unit having 4 to 12 carbon atoms include 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexamethylenediamine, 1,7-heptanediamine, 1,8-octanediamine, Units derived from linear aliphatic diamines such as 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine and 1,12-dodecanediamine; 2-methyl-1,5-pentane Diamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 2,4-diethyl-1,6-hexanediamine, 2,2-dimethyl -1,7-heptanediamine, 2,3-dimethyl-1,7-heptanediamine, 2,4-dimethyl-1,7-heptanediamine, 2,5-dimethyl 1,7-heptanediamine, 2-methyl-1,8-octanediamine, 3-methyl-1,8-octanediamine, 4-methyl-1,8-octanediamine, 1,3-dimethyl-1,8- Octanediamine, 1,4-dimethyl-1,8-octanediamine, 2,4-dimethyl-1,8-octanediamine, 3,4-dimethyl-1,8-octanediamine, 4,5-dimethyl-1, 8-octanediamine, 2,2-dimethyl-1,8-octanediamine, 3,3-dimethyl-1,8-octanediamine, 4,4-dimethyl-1,8-octanediamine, 5-methyl-1, Examples thereof include a diamine unit derived from a branched aliphatic diamine such as 9-nonanediamine. These may be used alone or in combination of two or more. Among the aliphatic diamine units having 4 to 12 carbon atoms, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine, and 1,12 -At least 1 sort (s) chosen from the group which consists of dodecanediamine is preferable.

  Among the diamine units, the monomer unit constituting the polyamide resin (A) is at least selected from the group consisting of 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, and 1,12-dodecanediamine. More preferably, one type contains 25 mol% or more, and more preferably contains 25 mol% or more 1,9-nonanediamine units. Furthermore, it is particularly preferable to use 2-methyl-1,8-octanediamine units in a proportion of 25 mol% or less, and most preferable to use them in a proportion of 1 to 25 mol%. By setting the diamine unit to such a configuration, a film having excellent heat resistance can be obtained.

  The polyamide resin (A) may contain a diamine unit other than the aliphatic diamine unit having 4 to 12 carbon atoms as long as the effects of the present invention are not hindered. Examples of the diamine unit other than the aliphatic diamine unit having 4 to 12 carbon atoms include 1,4-cyclohexanediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, -Amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) Units derived from alicyclic diamines such as propane, bis (aminopropyl) piperazine, and aminoethylpiperazine; derived from aromatic diamines such as metaxylylenediamine, paraxylylenediamine, and 1,4-phenylenediamine Units. These can be used alone or in combination of two or more.

  Polyamide resin (A) is a unit derived from lactam or aminocarboxylic acid such as ε-caprolactam, ω-laurolactam, 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid May be included.

The film of the present invention needs to have a melting peak temperature (Tm) of 310 ° C. or higher from the viewpoint of ensuring heat resistance. In addition, Tm can be measured by the method described in the Example mentioned later.
As a guideline for selecting the monomer raw material constituting the polyamide resin (A), the melting point of the obtained film is set to 310 ° C. or higher. This is because if the melting point of the film is less than 310 ° C., the resulting film has insufficient heat resistance.

The polyamide resin (A) preferably has a solution viscosity (η _inh ) measured at 30 ° C. using a concentrated sulfuric acid solution of 0.2 g / dl in the range of 1.1 to 3.0 dl / g. More preferably within the range of 1 to 2.0 dl / g, and still more preferably within the range of 1.1 to 1.5 dl / g. When η _inh is within the above range, a film having excellent formability into a film and excellent mechanical properties and heat resistance can be obtained.

  The polyamide resin (A) contains 0.6 to 2.8 mol% of monomer units derived from the end-capping agent. If the unit derived from the end-capping agent is less than 0.6 mol%, the viscosity at the time of melt molding will increase and it will be difficult to form a film. On the other hand, if the unit derived from the end-capping agent exceeds 2.8 mol%, the melt viscosity becomes low and it becomes difficult to form a film. The end-capping agent can be added at any stage when polymerizing the polyamide.

  The end capping agent may be a monofunctional compound having reactivity with the amino group or carboxyl group at the end of the polyamide. For example, acid anhydrides such as monocarboxylic acid, monoamine, and phthalic anhydride, monoisocyanate, monoester Acid halides, monoesters, monoalcohols, and the like can be used, but monocarboxylic acids or monoamines are preferable from the viewpoints of reactivity and stability of the sealing end, and monocarboxylic acids are preferable from the viewpoint of ease of handling. More preferred.

  Examples of the monocarboxylic acid used as the end-capping agent include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecyl acid, myristic acid, palmitic acid, stearic acid, pivalic acid and the like. Aliphatic monocarboxylic acid; alicyclic monocarboxylic acid such as cyclohexanecarboxylic acid; aromatic monocarboxylic acid such as benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid Etc. These can use 1 type (s) or 2 or more types. Among them, in terms of reactivity, stability of the sealing end, price, etc., acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecyl acid, myristic acid, palmitic acid, stearic acid, cyclohexane Carboxylic acid and benzoic acid are preferred.

  Examples of monoamines used as end-capping agents include aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine. Alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine. These can use 1 type (s) or 2 or more types. Of these, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are preferable from the viewpoints of reactivity, high boiling point, stability of the sealing end, and price.

  10-100 ppm is preferable and, as for the phosphorus atom concentration in a polyamide resin (A), it is still more preferable that it is 20-75 ppm. When the phosphorus atom concentration exceeds 100 ppm, the filter is likely to be clogged when the molten resin is filtered with a filter during film molding or the like, which may cause problems such as foreign matter being easily generated on the film. . When the phosphorus atom concentration is less than 10 ppm, the film is easily colored.

  In this invention, you may add a phosphorus compound as a catalyst at the time of polyamide resin (A) manufacture. When adding a phosphorus compound, it is preferable to add it with a raw material monomer at the time of polyamide resin (A) manufacture. Examples of phosphorus compounds include phosphoric acid, phosphorous acid, hypophosphorous acid, salts or esters thereof, and specifically, phosphoric acid, phosphorous acid or hypophosphorous acid and potassium, sodium, magnesium, vanadium. , Calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, antimony and other salts; phosphoric acid, phosphorous acid or hypophosphorous acid ammonium salt; phosphoric acid, phosphorous acid or hypophosphorous acid Examples include acid ethyl ester, isopropyl ester, butyl ester, hexyl ester, isodecyl ester, octadecyl ester, decyl ester, stearyl ester, and phenyl ester. Preferably, a phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid and hypophosphorous acid, and a metal salt consisting of them and a metal of Group 1 of the periodic table, more preferably hypophosphorous acid and periodic rule. It is a metal salt or phosphorous acid composed of a metal of Table 1 and more preferably sodium hypophosphite or a hydrate thereof, or phosphorous acid. The amount of the phosphorus compound used is not particularly limited, but when the phosphorus atom concentration in the polyamide resin (A) is 100 ppm or less, it is preferably 0.05% by weight or less, and 0.02% by weight or less based on the total of the polyamide raw materials. Is more preferable.

  The polyamide resin (A) can be produced using any method known as a method for producing polyamide. For example, it can be produced by a solution polymerization method or an interfacial polymerization method using acid chloride and diamine as raw materials, a melt polymerization method using dicarboxylic acid and diamine as raw materials, a solid phase polymerization method, a melt extrusion polymerization method, or the like.

  As a manufacturing method of a polyamide resin (A), for example, raw materials such as diamine and dicarboxylic acid, a compound such as sodium hypophosphite monohydrate and phosphorous acid, and water are charged into an autoclave, and the temperature is 100 to 180 ° C. A prepolymer can be obtained by forming a nylon salt aqueous solution, then raising the temperature to 200 to 300 ° C. and proceeding with polymerization while dehydrating. As a method of obtaining a polyamide resin having a target polymerization degree from the obtained prepolymer, dehydration is performed while raising the temperature to a temperature higher than the melting point, or treatment is performed under an inert gas stream or under reduced pressure while applying heat in a solid state below the melting point. The method of doing is mentioned. As described above, the 1,4-cyclohexanedicarboxylic acid unit contained in the polyamide resin (A) used in the present invention has a cis isomer and a trans isomer, but under the conditions for producing the polyamide resin (A), -The trans rearrangement reaction occurs reversibly, and generally, the energy level of the trans isomer is more stable. Therefore, the cis isomer increases as the final temperature of the production process of the polyamide resin (A) increases.

[Compound (B) acting as a Lewis base]
The film of the present invention may contain 0.1 to 10 parts by mass of the compound (B) acting as a Lewis base with respect to 100 parts by mass of the polyamide resin (A) constituting the film. It is more preferable to contain 5 parts by mass. By setting the amount of the compound (B) acting as a Lewis base within the above range, the content of the trans isomer derived from the 1,4-cyclohexanedicarboxylic acid unit constituting the polyamide resin (A) in the film can be increased. A polyamide resin composition having a high melting point, that is, excellent heat resistance and durability at high temperatures can be obtained. Furthermore, when the trans isomer content is increased, the crystal structure of the obtained film becomes stronger and the mechanical properties are improved.

  The compound (B) acting as a Lewis base is selected from the group consisting of alkali metal oxides, alkali metal hydroxides, alkaline earth metal oxides, alkaline earth metal hydroxides, zinc oxide and zinc hydroxide. It is preferable to use at least one kind.

  Examples of the alkali metal oxide and alkaline earth metal oxide include potassium oxide, magnesium oxide, and calcium oxide. Examples of the alkali metal hydroxide and alkaline earth metal hydroxide include potassium hydroxide, water, and the like. Examples thereof include magnesium oxide and calcium hydroxide. These may be used individually by 1 type and may use 2 or more types together.

[Other ingredients]
In the composition containing the polyamide resin (A) or the polyamide resin (A) used in the film of the present invention, in order to further improve various properties of the film finally obtained, the effects of the present invention are not impaired. Inside, pigments and dyes such as carbon black, nigrosine and titanium oxide as necessary; UV absorbers; light stabilizers such as hindered amines; organic systems such as hindered phenols, thios, phosphoruss and amines Antioxidants; inorganic antioxidants such as combinations of copper halides such as copper iodide and copper bromide and alkali metal halides such as potassium iodide and potassium bromide; antistatic agents; fluorescent brighteners; bromine Brominated polymers such as fluorinated polystyrene, flame retardant aids such as antimony oxide; fatty acid amides, fatty acid esters, fatty acid metal salts, polyethylene wax, polypropylene wax, Lubricants such as Rica; other polymers such as polyphenylene sulfide, liquid crystal polymer, polyethylene, polystyrene, polyester, aliphatic polyamide, semi-aromatic polyamide, polyphenylene oxide, polyolefin elastomer, styrene elastomer, polyester elastomer, polyamide elastomer; organic In addition, various inorganic powdery or fibrous fillers may be added.

  Examples of the method of adding the various additives include a method of adding at the time of polymerization of the polyamide resin, a method of dry blending to the polyamide resin and melt-kneading, a method of adding at the time of forming into a film, and the like.

[Method for producing film]
Although the film of the present invention can be made into a single sheet, it is preferably in the form of a film roll from the viewpoint of productivity when used in various applications.

  The polyamide resin (A) or a composition containing the polyamide resin (A) is melt-extruded by an extruder, and the melted composition containing the polyamide resin or the polyamide resin (A) (hereinafter simply referred to as “molten polymer”). ) Is discharged in a sheet form from a flat die such as a T die or an I die, and brought into contact with the cooling surface of a moving cooling body such as a cooling roll or a steel belt to cool the unstretched film. At this time, the extrusion temperature is preferably not less than the melting peak temperature (Tm) of the polyamide resin (A) and not more than 370 ° C. If the extrusion temperature is Tm or less, the viscosity may increase and extrusion may not be possible. If it exceeds 370 ° C, the polyamide resin (A) may be decomposed. The unstretched film has a thickness of usually 1 to 500 μm, preferably 5 to 200 μm.

  The temperature of the moving cooling body is preferably 40 to 125 ° C, more preferably 45 to 90 ° C, still more preferably 45 to 60 ° C. Normally, polyamide has a high crystallization speed, and when it is slowly cooled, crystals grow and it becomes difficult to stretch. Therefore, in order to achieve both cooling efficiency and suppression of condensation of water droplets on the moving cooling body, near room temperature. It is preferable to cool rapidly.

  When the temperature of the moving cooling body exceeds 125 ° C., it takes a long time until the molten polymer develops an appropriate hardness on the moving cooling body, and it is difficult to come off the moving cooling body. As a result, for example, when the moving cooling body is a roll, it breaks and winds around the roll, or even if it does not break, the pulsation occurs due to the momentum when the film comes off the roll. In addition, crystals with different sizes may be generated in the unstretched film, and stretching unevenness may occur or stretching may become difficult.

  When the polyamide resin (A) used in the film of the present invention was rapidly cooled with a moving cooling body of less than 40 ° C., the portion of the molten polymer that was not yet in contact with the moving cooling body (cooling roll) was hardened and hardened. The portion does not adhere to the moving cooling body (cooling roll). As a result, a portion that is in close contact with the moving cooling body and a portion that is not in close contact appear in the unstretched film, which makes it impossible to operate stably. Further, in the subsequent stretching step, breakage or non-uniform stretching occurs.

  In order to obtain an unstretched film by uniformly cooling and solidifying the molten polymer, a method for bringing the molten polymer into close contact with the moving cooling body and cooling and solidifying, for example, an air knife casting method, an electrostatic application method, a vacuum chamber method, etc. Can be used.

  Although the obtained unstretched film usually has excellent properties such as heat resistance and transparency even if it is as it is, various properties such as heat resistance and chemical resistance are further improved by biaxial stretching.

  As a film stretching method, for example, a flat sequential biaxial stretching method, a flat simultaneous biaxial stretching method, a tubular method, or the like can be used. Among them, the flat simultaneous biaxial stretching method is optimal because the film thickness accuracy is good and the physical properties in the film width direction are uniform. As a stretching apparatus for the flat simultaneous biaxial stretching method, a screw type tenter, a pantograph type tenter, a linear motor driven clip type tenter, or the like can be used.

  The stretching temperature needs to be a temperature equal to or higher than the glass transition temperature (Tg), and more preferably exceeds Tg and is equal to or lower than (Tg + 50) ° C. When the stretching temperature is less than Tg, the film is easily broken and stable production cannot be performed. On the other hand, if it exceeds (Tg + 50) ° C., stretching unevenness may occur.

  After performing the stretching as described above, it is preferable to perform a heat setting treatment as necessary while holding the film with a clip for stretching. A preferable heat setting treatment temperature is 200 ° C to (Tm-5) ° C, and more preferably 240 ° C to (Tm-10) ° C. Further, after the heat setting treatment, it is preferable to perform 1 to 10% relaxation treatment as needed while holding the film, and more preferably 3 to 7% relaxation treatment. Sufficient strength can be obtained by performing the relaxation treatment.

  After performing heat setting treatment or relaxation treatment as desired, the polyamide stretched film roll is obtained by cooling and winding up on a take-up roll. The obtained stretched polyamide film roll can be slit again to a desired width to form a stretched polyamide film roll again.

  The film of the present invention may be provided with a coat layer or a vapor deposition layer on the surface as needed, laminated with other polymers, laminated with paper, metal foil, woven fabric, nonwoven fabric, wood, etc., printed Can be used.

  The film of the present invention may be subjected to corona treatment, plasma treatment, acid treatment, flame treatment, coating treatment and the like in order to improve the adhesion of the film surface.

  Various coating agents may be applied to the surface of the film in order to impart functions such as easy adhesion, antistatic properties, releasability, and gas barrier properties. The coating can be applied to the film after stretching, or can be applied to the film before stretching, or it can be coated immediately before the stretching machine, and dried and formed into a film in the preheating section of the stretching machine. .

  Examples of paints that form the coating layer include gas barrier paints (polyvinyl alcohol aqueous solution, polyvinylidene chloride, etc.), easy-adhesion paints (urethane-based, ester-based, olefin-based dispersions), antistatic paints (surface-active) Agent system, conductive polymer system, carbon system, metal oxide system, etc.), UV-absorbing paint (HALS system, zinc oxide system, etc.), hard coat paint (acrylic system, silane coupling agent system, etc.), release Examples include mold paints (silicone type, olefin type, etc.).

  Examples of the vapor deposition layer include inorganic layers such as alumina and silica, and organic layers such as melamine.

  Examples of the polymer to be laminated include high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, ultrahigh molecular weight polyethylene, polypropylene, ethylene / propylene copolymer (EPR), and ethylene / butene copolymer ( EBR), ethylene / vinyl acetate copolymer (EVA), ethylene / vinyl acetate copolymer saponified product (EVOH), ethylene / acrylic acid copolymer (EAA), ethylene / methacrylic acid copolymer (EMAA), ethylene / Polyolefin resins such as methyl acrylate copolymer (EMA), ethylene / methyl methacrylate copolymer (EMMA), ethylene / ethyl acrylate copolymer (EEA); glycidyl acrylate, glycidyl methacrylate, ethacrylic acid Glycidyl, glycidyl itaconate, Polyolefin resin having a functional group such as a carboxyl group or a metal salt thereof, an acid anhydride group, or an epoxy group introduced by an epoxy group-containing unsaturated compound such as glycidyl laconate; polybutylene terephthalate, polyethylene terephthalate, Polyester resins such as polyethylene isophthalate, PET / PEI copolymer, polyarylate, polybutylene naphthalate, polyethylene naphthalate, and liquid crystalline polyester; polyether resins such as polyacetal and polyphenylene oxide; polysulfones such as polysulfone and polyethersulfone Polythioether resins such as polyphenylene sulfide and polythioethersulfone; polyketone resins such as polyetheretherketone and polyallyletherketone; polyacryloni Ril, polymethacrylonitrile, acrylonitrile / styrene copolymer, methacrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS), methacrylonitrile / styrene / butadiene copolymer (MBS), etc. Polynitrile resins; polymethacrylate resins such as polymethyl methacrylate and polyethyl methacrylate; polyvinyl ester resins such as polyvinyl acetate; polyvinylidene chloride, polyvinyl chloride, vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / Polyvinyl chloride resins such as methyl acrylate copolymers; Cellulosic resins such as cellulose acetate and cellulose butyrate; Polycarbonate resins such as polycarbonate; Polyimides such as thermoplastic polyimide, polyamideimide, and polyetherimide Mido resin: polyvinylidene fluoride, polyvinyl fluoride, ethylene / tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene / Hexafluoropropylene copolymer (TFE / HFP, FEP), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (TFE / HFP / VDF, THV), tetrafluoroethylene / fluoro (alkyl vinyl ether) copolymer Fluorine resins such as (PFA); thermoplastic polyurethane resins; polyurethane elastomers, polyester elastomers, polyamide elastomers, and the like.

  The film of the present invention is excellent in heat resistance and transparency, has few foreign matters, and is excellent in appearance. Therefore, pharmaceutical packaging materials; food packaging materials such as retort foods; electronic parts packaging materials for semiconductor packages, etc .; electrical insulation materials for motors, transformers, cables, etc .; dielectric materials for capacitor applications, etc .; cassette tapes, digital Magnetic tape materials for data storage for data storage, magnetic tape materials such as video tapes; protective plates for solar cell substrates, liquid crystal plates, conductive films, display devices, etc .; electronics such as LED mounting boards, flexible printed boards, flexible flat cables, etc. Substrate materials; heat-resistant adhesive tapes such as FPC coverlay films, heat-resistant masking tapes, industrial process tapes; heat-resistant barcode labels; heat-resistant reflectors; various release films; heat-resistant adhesive base films; photographic films; Materials; medical materials; civil engineering, building materials; filtration Film and the like; domestic, as a film or the like for industrial materials can be suitably used. As such an embodiment, for example, there is a method for producing a flexible printed circuit board including a step of performing reflow soldering between electronic components on a substrate including a film made of the polyamide resin composition of the present invention.

  EXAMPLES Hereinafter, although an Example and a comparative example (henceforth an Example etc.) demonstrate this invention in detail, this invention is not limited to these. The evaluation methods of various physical properties in the following examples were as follows.

[Evaluation of physical properties of polyamide resin (A)]
<1,4-cyclohexanedicarboxylic acid unit>
The polyamide resin (A) 20-30 mg was dissolved in trifluoroacetic acid -d (CF ₃ COOD) 1ml, using JEOL Ltd. nuclear magnetic resonance apparatus JNM-ECX400, ¹ at room temperature, accumulated number 256 conditions 1 H-NMR measurement was performed. The content of 1,4-cyclohexanedicarboxylic acid unit (CHDA unit) was calculated from the integral value of the characteristic signal. Table 1 shows the assignment of polyamide in ¹ H-NMR.

<C4-C12 aliphatic diamine unit>
Similarly to the CHDA unit, the content of the aliphatic diamine unit having 4 to 12 carbon atoms was calculated.

<End sealant unit>
Similar to the CHDA unit, the content of the unit derived from the end capping agent (terminal capping unit) was calculated.

<Phosphorus atom concentration>
The polyamide resin (A) was subjected to radio frequency inductively coupled plasma (ICP) emission analysis using Thermo Jarrel Ash IRIS / IP, and the phosphorus atom concentration was determined using a peak at a wavelength of 213.618 nm.

<Solution viscosity (η _inh )>
50 mg of polyamide resin (A) was dissolved in 25 ml of concentrated sulfuric acid. The test solution was measured for drop time (t) at 30 ° C. using an Ubbelohde viscometer, and calculated from the drop time (t ₀ ) of concentrated sulfuric acid by the following formula (1).
η _inh (dl / g) = {ln (t ÷ t ₀ )} ÷ 0.2 (g / dl) (1)

<Melting filterability>
Using polyamide resin composition, a “labo plast mill 2D25W” single screw extruder manufactured by Toyo Seiki Seisakusho with a filter of 20 μm mesh between screw and die, cylinder temperature 20 ° C. higher than melting point, screw rotation speed 30 rpm Extrusion was performed at a discharge rate of 1 kg per hour under the following conditions. The melt filterability was evaluated by ◯ when the torque did not exceed 100 N · m within 3 hours and x when the torque exceeded 100 N · m within 3 hours.

[Evaluation of physical properties of film]
<Trans isomer structural unit content>
20-30 mg is cut out from the film, dissolved in 1 mL of CF ₃ COOD, filtered through a glass filter to remove insoluble matters, and a measurement sample is prepared. Using a nuclear magnetic resonance apparatus JNM-ECX400 (400 MHz) manufactured by JEOL Ltd. ¹ H-NMR was measured under conditions of room temperature and 256 times of integration. From the ratio of the peak area of 2.10 ppm derived from β hydrogen of the cis isomer of the 1,4-cyclohexanedicarboxylic acid structural unit and the peak area of 2.20 ppm derived from β hydrogen of the trans isomer structural unit, trans isomerism The body structural unit content was determined.

<Melting point>
When 10 mg was cut out from the film and the temperature was increased from 30 ° C. to 360 ° C. at a rate of 10 ° C./min under a nitrogen atmosphere using a differential scanning calorimeter (DSC822) manufactured by METTLER TOLEDO Co., Ltd. It calculated | required by making the peak temperature of the melting peak which appears into melting | fusing point (degreeC). When there are a plurality of melting peaks, the melting point is the peak temperature of the melting peak on the highest temperature side.

<Reflow characteristics>
The film is mounted on an SMT scope (Sanyo Seiko Co., Ltd.) and observed for shape change after being held at 250 ° C. for 1 minute. Reflowability is indicated by ○ when the film is hardly deformed and × when the film is clearly deformed. Was used as an index of heat resistance.

<Appearance>
The film after stretching was visually observed, (1) ○ when no foreign matter such as fish eye was observed, x when foreign matter such as fish eye was clearly recognized, (2) ○ when the case was colorless, The appearance was evaluated as x for the colored case. All films obtained in Examples and the like were transparent.

  The polyamide resin (A) used in each Example etc., the compound (B) which acts as a Lewis base, and other components are shown below.

<Polyamide resin (A)>
Polyamide 1 to polyamide 7 obtained in the following Production Examples 1 to 7 were used.

[Production Example 1]
10197.5 g of 1,4-cyclohexanedicarboxylic acid having a cis: trans ratio of 70:30, 8158.6 g of 1,9-nonanediamine, 1439.7 g of 2-methyl-1,8-octanediamine, benzoic acid as a terminal blocking agent 222.2 g, 4.0 g of sodium hypophosphite monohydrate, and 5 L of distilled water were placed in an autoclave with an internal volume of 40 L and purged with nitrogen. The internal temperature was raised to 200 ° C. over 2 hours. At this time, the autoclave was pressurized to 2 MPa. Then, for 2 hours, the internal temperature was kept at 215 ° C., and the reaction was carried out while gradually removing water vapor and keeping the pressure at 2 MPa. Next, the pressure was reduced to 1.2 MPa over 30 minutes to obtain a prepolymer. The prepolymer was pulverized to a size of 6 mm or less and dried at 120 ° C. under reduced pressure for 12 hours. This was subjected to solid phase polymerization at 230 ° C. and 13.3 Pa for 10 hours to obtain a polyamide resin (polyamide 1).

[Production Example 2]
Polymerization was carried out in the same manner as in Production Example 1 except that sodium hypophosphite monohydrate was changed to 4.0 g of phosphorous acid to obtain a polyamide resin (polyamide 2).

[Production Example 3]
1023,3 g of 1,4-cyclohexanedicarboxylic acid having a cis: trans ratio of 70:30, 8204.9 g of 1,9-nonanediamine, 1447.9 g of 2-methyl-1,8-octanediamine, and acetic acid 109 as a terminal blocking agent Polymerization was carried out in the same manner as in Production Example 1 except that 0.9 g, 4.0 g of sodium hypophosphite monohydrate, and 5 L of distilled water were used to obtain a polyamide resin (polyamide 3).

[Production Example 4]
9764.2 g of 1,4-cyclohexanedicarboxylic acid having a cis: trans ratio of 70:30, 10022.7 g of 1,10-decanediamine, 213.1 g of benzoic acid as a terminal blocking agent, sodium hypophosphite monohydrate Polymerization was carried out in the same manner as in Production Example 1 except that 4.0 g and 5 L of distilled water were used to obtain a polyamide resin (polyamide 4).

[Production Example 5]
10000.7 g of terephthalic acid, 8307.1 g of 1,9-nonanediamine, 1466.0 g of 2-methyl-1,8-octanediamine, 226.2 g of benzoic acid as an end-capping agent, sodium hypophosphite monohydrate 4 Polymerization was carried out in the same manner as in Production Example 1 except that 0.0 g and 5 L of distilled water were used to obtain a polyamide resin (polyamide 5).

[Production Example 6]
1,4-cyclohexanedicarboxylic acid 10356.9 g with a cis: trans ratio of 70:30, 8123.9 g of 1,9-nonanediamine, 1435.4 g of 2-methyl-1,8-octanediamine, benzoic acid as end-capping agent Polymerization was performed in the same manner as in Production Example 1 except that 73.8 g, 4.0 g of sodium hypophosphite monohydrate, and 5 L of distilled water were used, to obtain a polyamide resin (polyamide 6).

[Production Example 7]
1,4-Cyclohexanedicarboxylic acid with a cis: trans ratio of 70:30 9.84.9 g, 1,9-nonanediamine 827.4 g, 1450.1 g of 2-methyl-1,8-octanediamine, benzoic acid as end-capping agent Polymerization was performed in the same manner as in Production Example 1 except that 447.5 g, 4.0 g of sodium hypophosphite monohydrate, and 5 L of distilled water were used to obtain a polyamide resin (polyamide 7).

<Compound (B) acting as a Lewis base>
Magnesium oxide: manufactured by Kyowa Chemical Industry Co., Ltd., “Kyowa Mag MF-150” (average particle size: 0.71 μm)

<Other ingredients>
Phenol-based antioxidant: “Sumilyzer GA-80” (3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy}-, manufactured by Sumitomo Chemical Co., Ltd.) 1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane)

[Examples 1 to 5 and Comparative Examples 1 to 3]
According to the blending ratio shown in Table 2, the polyamide resin (A), the compound (B) acting as a Lewis base, and the Sumilizer GA-80 were dry blended, and the resulting mixture was twin-screw extruder (screw diameter: 30 mm, L / L). D = 28, cylinder temperature 350 ° C., rotation speed 150 rpm) was fed from a hopper, melted and kneaded, extruded into a strand, and then cut by a pelletizer to obtain a pellet-like polyamide resin composition.
Next, the obtained polyamide resin composition was supplied to a single-screw extruder (“Lab Plast Mill 2D25W” manufactured by Toyo Seiki Seisakusho), heated and melted at a temperature 10 to 40 ° C. higher than the melting point of polyamide, and from a T-die. Extrusion was performed to produce a polyamide unstretched film having a width of 30 cm and a thickness of 200 μm.
Further, a sample piece of 5 cm in length and 5 cm in width was cut out from the center portion of the obtained unstretched film, and it was 3 times in length and 3 times in width at 155 ° C. with a biaxial stretching machine (“Small stretching device” manufactured by Shibayama Scientific Instruments) Biaxial stretching was performed at the same magnification. This biaxially stretched film was heat-fixed at 270 ° C. for 5 minutes to obtain films for various evaluations.
The evaluation results are shown in Table 2.

  As shown in Table 2 above, the resin composition of the present invention is excellent in melt filterability during film molding, and the resulting film is excellent in heat resistance and transparency, has few foreign matters, and has a good appearance. In Comparative Example 2, an unstretched film having a predetermined thickness could not be obtained. Further, in Comparative Example 3, the molten resin that exited the T die dropped vertically and an unstretched film could not be obtained.

  The film of the present invention is excellent in heat resistance and transparency, has few foreign matters, and is excellent in appearance. Therefore, pharmaceutical packaging materials; food packaging materials such as retort foods; electronic parts packaging materials for semiconductor packages, etc .; electrical insulation materials for motors, transformers, cables, etc .; dielectric materials for capacitor applications, etc .; cassette tapes, digital Magnetic tape materials such as magnetic tape for data storage and data tape for data storage; protective plates for solar cell substrates, liquid crystal plates, conductive films, display devices; LED mounting substrates, flexible printed wiring boards, flexible flat cables, etc. Electronic substrate materials; heat-resistant adhesive tapes such as FPC coverlay films, heat-resistant masking tapes, industrial process tapes; heat-resistant barcode labels; heat-resistant reflectors; various release films; heat-resistant adhesive base films; Agricultural materials; medical materials; civil engineering and building materials; Filtration membrane or the like; domestic, it can be suitably used for films for industrial materials.

Claims (11)

The monomer unit constituting the polyamide contains 25 mol% or more of 1,4-cyclohexanedicarboxylic acid units, 25 mol% or more of aliphatic diamine units having 4 to 12 carbon atoms, and 0 monomer units derived from the end-capping agent. A film made of polyamide resin (A) containing 6 to 2.8 mol%,
The content of the trans isomer structural unit derived from 1,4-cyclohexanedicarboxylic acid in the film is 70 to 90 mol%, the phosphorus atom concentration in the polyamide resin (A) is 64 to 100 ppm, and the melting peak A film having a thickness of 1 to 200 μm and a temperature (Tm) of 310 ° C. or higher. The film of Claim 1 whose solution viscosity ((eta) _inh ) measured at 30 degreeC of the 0.2 g / dl concentrated sulfuric acid solution of a polyamide resin (A) is 1.1-3.0 dl / g.   The aliphatic diamine unit having 4 to 12 carbon atoms is at least one selected from the group consisting of 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, and 1,12-dodecanediamine. The film according to claim 1 or 2.   The film according to any one of claims 1 to 3, wherein the aliphatic diamine unit having 4 to 12 carbon atoms is 1,9-nonanediamine.   The film according to claim 4, further comprising 1 to 25 mol% of 2-methyl-1,8-octanediamine as the aliphatic diamine unit having 4 to 12 carbon atoms. The film in any one of Claims 1-5 whose phosphorus atom concentration in a polyamide resin (A) is 64-83 ppm. A test solution prepared by dissolving 50 mg of polyamide resin (A) in 25 ml of concentrated sulfuric acid was measured for the drop time (t) at 30 ° C. using an Ubbelohde viscometer, and the fall time of concentrated sulfuric acid (t ₀ ) Solution viscosity (η calculated from the following formula (1) _inh ) Is in the range of 1.1 to 1.5 dl / g.
η _inh (Dl / g) = {ln (t ÷ t ₀ )} ÷ 0.2 (g / dl) (1) The solution viscosity (η _inh ) In the range of 1.13 to 1.16 dl / g. Furthermore, 0.1-10 mass parts of compounds (B) which act as a Lewis base with respect to 100 mass parts of polyamide resins (A) are contained, The film in any one of Claims 1-8 . Method for producing a stretched film comprising a step of further stretching the film according to any one of claims 1-9. Method of manufacturing a flexible printed circuit board comprising the step of reflowing the film according to any one of claims 1-9.