JP2021176973A - Polyamide resin composition and release film using the same - Google Patents

Abstract

To provide a polyamide resin composition which is improved in releasability when formed into a film, and a release film using the same.SOLUTION: A polyamide resin composition according to the present invention is for forming a release film and contains a polyamide resin, an unmodified polypropylene resin and a polyolefin wax, the content of the unmodified polypropylene resin being 0.1-10 mass% and the content of the polyolefin wax being 0.1-8 mass%. A release film according to the present invention contains the polyamide resin composition.SELECTED DRAWING: None

Description

The present invention relates to a polyamide resin composition having improved releasability when made into a film, and a releasable film using the same.

Tennis and badminton racket frames, golf shafts, fishing rods, etc. are hollow for the purpose of weight reduction. An internal pressure molding method is known as a method for producing a tubular structure having a hollow inside. In the internal pressure molding method, for example, a prepreg is wound around a tubular film, the surrounding prepreg is molded while applying high pressure to the inside of the tube, and then the tube is removed to form a tubular structure in which the inside is hollow. You get things. As the tubular film, a polyamide film is used.

Patent Document 1 describes a tubular body made of fiber reinforced plastic having a thermoplastic film inside the fiber reinforced plastic layer, wherein the thickness of the thermoplastic film is 5 μm or more and 30 μm or less. There is. Further, Patent Document 2 describes a method for manufacturing a racket frame for manufacturing a hollow racket frame made of a fiber reinforced resin by mold molding, wherein a flexible tube for internal pressure filling used at the time of heat molding in a mold is used. A method for manufacturing a racket frame is described, wherein a mold release layer made of a silicone polymer or a fluoropolymer is formed on the surface thereof, and the flexible tube is removed from the frame after molding.

Japanese Unexamined Patent Publication No. 2000-238152 JP-A-11-244424

However, when a tube made of a polyamide film is to be removed from a tubular structure after molding, it may be torn, and improvement in releasability has been required.

Therefore, an object of the present invention is to provide a polyamide resin composition having improved releasability when made into a film, and a releasable film using the same.

The present invention is a polyamide resin composition containing a polyamide resin, an unmodified polypropylene resin, and a polyolefin wax.
The content of the unmodified polypropylene resin is 0.1 to 10% by mass.
A polyamide resin composition for forming a release film having a polyolefin wax content of 0.1 to 8% by mass, and a release film containing the same.

According to the present invention, it is possible to provide a polyamide resin composition having improved releasability when made into a film and a releasable film using the same.

<Polyamide resin>
The polyamide resin used in the present invention is polymerized or copolymerized by a known method such as melt polymerization, solution polymerization, solid phase polymerization, etc. using a nylon salt composed of lactam, aminocarboxylic acid, or diamine and dicarboxylic acid as a raw material. Obtained by

Examples of lactam include caprolactam, enantractum, undecane lactam, dodecane lactam, α-pyrrolidone, α-piperidone and the like. Examples of the aminocarboxylic acid include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like. These can be used alone or in combination of two or more.

Examples of the diamines constituting the nylon salt include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, and undecamethylenediamine. Dodecamethylenediamine, tridecamethylenediamine, tetradecamethylenediamine, pentadecamethylenediamine, hexadecamethylenediamine, heptadecamethylenediamine, octadecamethylenediamine, nonadecamethylenediamine, eicosamethylenediamine, 2- / 3-methyl Aliamines such as -1,5-pentanediamine, 2-methyl-1,8-octanediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methyl-1,9-nonandamine Diamine; 1,3- / 1,4-cyclohexanediamine, 1,3- / 1,4-cyclohexanediamine, bis (4-aminocyclohexamethylene) methane, bis (4-aminocyclohexamethylene) propane, bis (3-methyl -4-Aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) propane, 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine, 5-amino-1,3,3- Alicyclic diamines such as trimethylcyclohexamethylenediamine (isophoronediamine), bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, norbornanedimethylamine, tricyclodecanedimethylamine; aromatics such as m- / p-xylylenediamine Examples include family diamine. These can be used alone or in combination of two or more.

On the other hand, as the dicarboxylic acids constituting the nylon salt, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid and hexadecanedioic acid , Octadecanedioic acid, aliphatic dicarboxylic acid such as eicosandioic acid; alicyclic dicarboxylic acid such as 1,3- / 1,4-cyclohexanedicarboxylic acid, dicyclohexanemethane-4,4'-dicarboxylic acid, norbornandicarboxylic acid. Examples include aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid, and 1,4- / 2,6- / 2,7-naphthalenedicarboxylic acid. These can be used alone or in combination of two or more.

In the polyamide resin, these monopolymers or copolymers derived from lactam, aminocarboxylic acid, or nylon salt composed of diamine and dicarboxylic acid can be used alone or in the form of a mixture, respectively.

Specific examples of the polyamide resin used in the present invention include polycaprolactam (polyamide 6), polyundecanelactam (polyamide 11), polydodecanelactam (polyamide 12), polyethylene adipamide (polyamide 26), and polytetramethylene adhi. Pamide (polyamide 46), polyhexamethylene adipamide (polyamide 66), polyhexamethylene azelamide (polyamide 69), polyhexamethylene sebacamide (polyamide 610), polyhexamethylene undecamide (polyamide 611), Polyhexamethylene dodecamide (polyamide 612), polyhexamethylene terephthalamide (polyamide 6T), polyhexamethylene isophthalamide (polyamide 6I), polyhexamethylene hexahydroterephthalamide (polyamide 6T (H)), polynonamethylene azi. Pamide (polyamide 96), polynonamethylene azelamide (polyamide 99), polynonamethylene sebacamide (polyamide 910), polynonamethylene dodecamide (polyamide 912), polynonamethylene terephthalamide (polyamide 9T), poly Trimethylhexamethylene terephthalamide (polyamide TMHT), polynonamethylene hexahydroterephthalamide (polyamide 9T (H)), polynonamethylene naphthalamide (polyamide 9N), polydecamethylene adipamide (polyamide 106), polydeca Methylene azelamide (polyamide 109), polydecamethylene decamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), polydecamethylene terephthalamide (polyamide 10T), polydecamethylene hexahydroterephthalamide (polyamide 10T) (H)), Polydecamethylene naphthalamide (polyamide 10N), Polydodecamethylene adipamide (Polyamide 126), Polydodecamethylene azelamide (Polyamide 129), Polydodecamethylene sebacamide (Polyamide 1210), Polydodecamethylene Dodecamide (polyamide 1212), polydodecamethylene terephthalamide (polyamide 12T), polydodecamethylene hexahydroterephthalamide (polyamide 12T (H)), polydodecamethylene naphthalamide (polyamide 12N), polymethoxylylen adipamide (Polyamide MXD6), Polymethoxylylence veramide (Polyamide MXD8), Polymethoxylylene azelamide (Polyami) Do MXD9), polymethoxylylene sevacamido (polyamide MXD10), polymethoxylylend decamide (polyamide MXD12), polymethoxylylene terephthalamide (polyamide MXDT), polymethoxylylene isophthalamide (polyamide MXDI), polymethoxylylene Naphthalamide (polyamide MXDN), polybis (4-aminocyclohexyl) methadodecamide (polyamide PACM12), polybis (4-aminocyclohexyl) methaneterephthalamide (polyamide PACMT), polybis (4-aminocyclohexyl) methaneisophthalamide (polyamide PACMT) Polyamide PACMI), polybis (3-methyl-4-aminocyclohexyl) methadodecamide (polyamide dimethyl PACM12), polyisophorone adipamide (polyamide IPD6), polyisophorone terephthalamide (polyamide IPDT) and their raw material monomers are used. Examples thereof include the polyamide copolymer used. These can be used alone or in combination of two or more.

Considering the heat resistance, mechanical strength, transparency, economy, availability, etc. of the obtained film, the polyamide resin is derived from caprolactam-derived units (caprolactam units), hexamethylenediamine and adipic acid. It is preferably a homopolymer or copolymer composed of at least one selected from the group consisting of a unit (hexamethylene adipamide unit) and a unit derived from dodecantactam (dodecalactam unit). .. Specifically, polyamide 6, polyamide 12, polyamide 66, polyamide 6/66 copolymer (polymer of polyamide 6 and polyamide 66, hereinafter, the copolymer is described in the same manner), polyamide 6/69 copolymer. , Polyamide 6/610 copolymer, Polyamide 6/611 copolymer, Polyamide 6/612 copolymer, Polyamide 6/12 copolymer, Polyamide 6/66/12 copolymer, Polyamide 6 / 6T copolymer , Polyamide 6 / 6I Copolymer, Polyamide 6 / IPD6 Copolymer, Polyamide 6 / IPDT Copolymer, Polyamide 66 / 6T Copolymer, Polyamide 66 / 6I Copolymer, Polyamide 6T / 6I Copolymer, Polyamide It is preferably at least one selected from the group consisting of 66 / 6T / 6I copolymer and polyamide MXD6, and is preferably polyamide 6, polyamide 12, polyamide 66, polyamide 6/66 copolymer, and polyamide 6/12 copolymer. , Polypolymer 6 / IPD6 copolymer, Polyamide 6 / IPDT copolymer, Polyamide 6/66/12 copolymer, at least one selected from the group. It is more preferable that it is at least one selected from the group consisting of polyamide 6, polyamide 6/66 copolymer, polyamide 6/12 copolymer, and polyamide 6/66/12 copolymer.

The relative viscosity of the polyamide resin measured according to JIS K-6920 is preferably 2.0 to 5.0, more preferably 2.5 to 4.5. When the relative viscosity of the polyamide resin is at least the above lower limit value, the mechanical properties of the obtained polyamide film are good. On the other hand, when the relative viscosity of the polyamide resin is not more than the above upper limit value, the viscosity at the time of melting becomes low, and the film can be easily molded.

The polyamide resin is produced by polymerizing or copolymerizing the raw material of the polyamide resin by a known method such as melt polymerization, solution polymerization or solid phase polymerization in the presence of amines. Alternatively, it is produced by melt-kneading in the presence of amines after polymerization. As described above, amines can be added at any stage during polymerization or at any stage during melt-kneading after polymerization, but when considering the melt stability during film formation, at the stage during polymerization. It is preferable to add it.

Examples of the amines include monoamines, diamines, polyamines and the like. In addition to amines, carboxylic acids such as monocarboxylic acids and dicarboxylic acids may be added, if necessary. These amines and carboxylic acids may be added at the same time or separately. Further, as the amines and carboxylic acids exemplified below, one kind or two or more kinds can be used.

Specific examples of the monoamine to be added include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine and tridecylamine. , Tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, octadecyleneamine, eicosylamine, docosylamine and other aliphatic monoamines; cyclohexylamine, methylcyclohexylamine and other alicyclic monoamines; benzylamine, β- Aromatic monoamines such as phenylmethylamine; N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutylamine, N, N-dihexylamine, N, N-dioctyl Symmetrical secondary amines such as amines; N-methyl-N-ethylamine, N-methyl-N-butylamine, N-methyl-N-dodecylamine, N-methyl-N-octadecylamine, N-ethyl-N-hexadecyl Examples thereof include mixed secondary amines such as amines, N-ethyl-N-octadecylamines, N-propyl-N-hexadecylamines and N-propyl-N-benzylamines.

Specific examples of the diamine to be added include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, and dodecamethylene. Diamine, Tridecamethylenediamine, Hexamethylenediamine, Pentadecamethylenediamine, Hexamethylenediamine, Hexamethylenediamine, Octadecamethylenediamine, Nonadecamethylenediamine, Eikosamethylenediamine, 2- / 3-Methyl-1 , 5-Pentanediamine, 2-methyl-1,8-octanediamine, 2,2,4- / 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9-nonandamine, etc. Hexamethylenediamine; 1,3- / 1,4-cyclohexamethylenediamine, bis (4-aminocyclohexamethylene) methane, bis (4-aminocyclohexamethylene) propane, bis (3-methyl-4-aminocyclohexamethylene) methane, bis ( 3-Methyl-4-aminocyclohexamethylene) propane, 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine, 5-amino-1,3,3-trimethylcyclohexanemethylamine, bis (aminopropyl) Examples thereof include alicyclic diamines such as piperazine, bis (aminoethyl) piperazine, norbornandimethylamine and tricyclodecanedimethylamine; and aromatic diamines such as m- / p-xylylenediamine.

The polyamine to be added _{may be a compound having a plurality of primary amino groups (-NH 2} ) and / or secondary amino groups (-NH-), for example, polyalkyleneimine, polyalkylenepolyamine, polyvinylamine, polyallylamine and the like. Can be mentioned. The amino group with active hydrogen is the reaction site for polyamines.

Polyalkyleneimine is produced by a method of ion-polymerizing an alkyleneimine such as ethyleneimine or propyleneimine, or a method of polymerizing an alkyloxazoline and then partially or completely hydrolyzing the polymer. Examples of the polyalkylene polyamine include diethylenetriamine, triethylenetetramine, pentaethylenehexamine, and a reaction product of ethylenediamine and a polyfunctional compound. Polyvinylamine can be obtained, for example, by polymerizing N-vinylformamide to obtain poly (N-vinylformamide), and then partially or completely hydrolyzing the polymer with an acid such as hydrochloric acid. Polyallylamine is generally obtained by polymerizing a hydrochloride salt of an allylamine monomer and then removing hydrochloric acid. These can be used alone or in combination of two or more. Among these, polyalkyleneimine is preferable.

As the polyalkyleneimine, one or more of 2 to 8 alkyleneimines having 2 to 8 carbon atoms such as ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, and 1,1-dimethylethyleneimine can be used. Examples thereof include homopolymers and copolymers obtained by polymerization by a conventional method. Among these, polyethyleneimine is more preferable. The polyalkyleneimine is obtained by ring-opening polymerization of an alkyleneimine as a raw material, and a branched polyalkyleneimine containing a primary amine, a secondary amine and a tertiary amine, or an alkyloxazoline as a raw material, which is polymerized. It may be either a linear polyalkyleneimine containing only the primary amine and the secondary amine obtained above, or a three-dimensionally crosslinked structure. Further, it may contain ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine, bisaminopropylethylenediamine and the like. Polyalkyleneimines are usually derived from the reactivity of active hydrogen atoms on the contained nitrogen atoms, and in addition to tertiary amino groups, primary amino groups and secondary amino groups (imino) having active hydrogen atoms. Group).

The number of nitrogen atoms in the polyalkyleneimine is not particularly limited, but is preferably 4 to 3,000, more preferably 8 to 1,500, and even more preferably 11 to 500. The number average molecular weight of polyalkyleneimine is preferably 100 to 20,000, more preferably 200 to 10,000, and even more preferably 500 to 8,000.

On the other hand, as the carboxylic acids to be added, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, capric acid, capric acid, pelargonic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, myristoleic acid, Adicyclic monocarboxylic acids such as palmitic acid, stearic acid, oleic acid, linoleic acid, araquinic acid, bechenic acid and erucic acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid and methylcyclohexanecarboxylic acid, benzoic acid and toluic acid. , Ethylbenzoic acid, aromatic monocarboxylic acids such as phenylacetic acid; malonic acid, succinic acid, glutaric acid, adipic acid, pimelliic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, hexadecadioic acid , Hexadecenodic acid, Octadecadioic acid, Octadecenoic acid, Eikosandioic acid, Eikosendioic acid, Docosandioic acid, Diglycolic acid, 2,2,4- / 2,4,4-trimethyladiponic acid and other aliphatic dicarboxylic acids Acids; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and norbornandicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, m- / p-xylylene dicarboxylic acid, 1,4- / 2,6- / Examples thereof include aromatic dicarboxylic acids such as 2,7-naphthalenedicarboxylic acid.

Therefore, it is preferable to add diamine and / or polyamine at the time of polymerization without deteriorating the productivity at the time of producing the polyamide resin, and from the viewpoint of suppressing gel generation, it is more than the group consisting of aliphatic diamines, alicyclic diamines, and polyamines. It is more preferable to add at least one selected.

Further, the polyamide resin may be a mixture of two or more kinds of polyamide resins having different terminal group concentrations. In this case, the terminal amino group concentration and the terminal group carboxyl concentration of the polyamide resin mixture are determined by the terminal amino group concentration, the terminal carboxyl group concentration and the blending ratio thereof of the polyamide resin constituting the mixture.

For the polyamide resin, the water extraction amount measured according to the method for measuring the content of low molecular weight substances specified in JIS K-6920 is preferably 1.0% or less, preferably 0.5% or less. Is more preferable. When the amount of water extracted exceeds the above value, the oligomer component adheres remarkably to the vicinity of the die, and the appearance is likely to be deteriorated due to the generation of die lines and fish eyes due to these deposits. Further, the polyamide resin has a higher hygroscopicity than the olefin resin, and if a hygroscopic resin is used, hydrolysis occurs when the raw material is melt-extruded, so that oligomers are generated, which makes it difficult to produce a film. It is preferably dried and has a water content of 0.1% by mass or less.

<Unmodified polypropylene resin>
The unmodified polypropylene resin used in the present invention is mainly composed of unmodified polypropylene. The polypropylene may be a propylene homopolymer or a copolymer of propylene and an olefin other than propylene. Examples of olefins other than propylene include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and other olefins having 2 to 8 carbon atoms (excluding propylene). Be done. Of these, ethylene is preferable. That is, the polypropylene includes a propylene homopolymer such as isotactic polypropylene; a propylene-α-olefin random copolymer such as a propylene-ethylene random copolymer and a propylene-butene random copolymer; and a propylene-ethylene block copolymer. Examples thereof include propylene-α-olefin block copolymers such as coalescing and propylene-butene block copolymers; and propylene-containing ternary copolymers such as propylene-ethylene-butene copolymers. Further, the polypropylene may be one kind or two or more kinds. The three-dimensional regularity (tacticity) includes isotactics, syndiotactics, tactical structures, and the like, and is not particularly limited. Isotactic is preferable from the viewpoint of rigidity and the like.

The unmodified polypropylene resin is preferably composed of only unmodified polypropylene, but may contain a small amount of other components as long as its properties are not impaired. The content of unmodified polypropylene in the unmodified polypropylene resin is preferably 95% by mass or more, more preferably 97% by mass or more, and even more preferably 99% by mass or more.

The unmodified polypropylene resin preferably has a melt flow rate (MFR: 230 ° C., 2160 g) measured according to ASTM D1238 of 0.1 to 80 g / 10 minutes, preferably 1 to 75 g / 10 minutes. Is more preferable.

<Polyolefin wax>
The polyolefin wax used in the present invention is, for example, composed of a homopolymer or copolymer of an α-olefin having 2 to 20 carbon atoms, has a melting point of 50 to 170 ° C., and has a viscosity at a temperature 10 ° C. higher than the melting point. Is as low as 10 Pa · s or less. Examples of the polyolefin wax include polyethylene wax composed mainly of ethylene and polypropylene wax composed mainly of propylene. The polyolefin wax may be unmodified or modified. Examples of the modified polyolefin wax include vinyl ester-modified polyolefin wax, acid-modified polyolefin wax, and oxide polyolefin wax.

The polyethylene wax may be made of an ethylene homopolymer or may be made of an ethylene-α-olefin copolymer. Examples of α-olefins include propylene, 1-butene, isobutylene, 1-pentene, 1-hexene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene, 4-methyl-. Examples thereof include α-olefins having 3 to 20 carbon atoms such as 1-pentene. The content of ethylene units in the ethylene-α-olefin copolymer wax is preferably more than 50 mol%. The polyethylene wax may be unmodified or modified. Examples of the unmodified polyethylene wax include Licowax (registered trademark) PE520, PE130, PE190; Licocene (registered trademark) PE3101TP, PE4201, PE5301; Ceridust (registered trademark) 3620, and 3610 manufactured by Clariant Chemicals. Can be mentioned.

The polypropylene wax may be made of a propylene homopolymer or a propylene-α-olefin copolymer. Examples of α-olefins include ethylene, 1-butene, isobutylene, 1-pentene, 1-hexene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene, 4-methyl-. Examples thereof include α-olefins having 3 to 20 carbon atoms such as 1-pentene. The content of the propylene unit in the propylene-α-olefin copolymer wax is preferably more than 50 mol%. The polypropylene wax may be unmodified or modified. Examples of the unmodified polypropylene wax include Licocene (registered trademark) PP6102, PP6502, PP7502, PP1302, PP1502, PP1602, PP2602, PP3602; Celidust (registered trademark) 6050M manufactured by Clariant Chemicals. Be done.

The vinyl ester-modified polyolefin wax can be obtained by copolymerizing a monomer constituting the corresponding unmodified polyolefin wax with a vinyl ester such as vinyl acetate or vinyl propionate. Examples of the vinyl acetate-modified polyethylene wax include Licowax (registered trademark) 371FP manufactured by Clariant Chemicals.

The acid-modified polyolefin wax can be obtained by acid-modifying the corresponding unmodified polyolefin wax with an unsaturated carboxylic acid or an acid anhydride thereof. Specific examples of unsaturated carboxylic acids or acid anhydrides thereof include maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, maleic anhydride, and itaconic anhydride. , Sis-4-cyclohexene-1,2-dicarboxylic acid anhydride and the like, but maleic anhydride is preferable. Derivatives such as acid amides and acid esters can also be used instead of unsaturated carboxylic acid anhydrides. Examples of the maleic anhydride-modified polyethylene wax include Licocene (registered trademark) PE MA 4221 and PE MA 4351 manufactured by Clariant Chemicals. Examples of the maleic anhydride-modified polypropylene wax include Licocene (registered trademark) PP MA 1332, PP MA 6252, PP MA 6452, and PP MA 7452 manufactured by Clariant Chemicals.

The oxidized polyolefin wax can be obtained by oxidizing the corresponding unmodified polyolefin wax. Examples of the polyethylene oxide wax include Licowax (registered trademark) PED521, PED522, and PED121; Ceridust (registered trademark) 3715 manufactured by Clariant Chemicals.

<Modified polyethylene resin>
The modified polyethylene resin used in the present invention is obtained by modifying a (unmodified) polyethylene resin during or after polymer synthesis. Examples of the unmodified polyethylene resin include high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE).

Examples of the modified polyethylene resin include vinyl ester-modified polyethylene resin, acid-modified polyethylene resin, and oxidized polyethylene resin. The vinyl ester-modified polyethylene resin can be obtained by copolymerizing ethylene with a vinyl ester such as vinyl acetate or vinyl propionate. The acid-modified polyethylene resin can be obtained by acid-modifying the polyethylene resin with an unsaturated carboxylic acid or an acid anhydride thereof. Specific examples of unsaturated carboxylic acids or acid anhydrides thereof include maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, maleic anhydride, and itaconic anhydride. , Sis-4-cyclohexene-1,2-dicarboxylic acid anhydride and the like, but maleic anhydride is preferable. Derivatives such as acid amides and acid esters can also be used instead of unsaturated carboxylic acid anhydrides. The polyethylene oxide resin can be obtained by oxidizing the polyethylene resin. Examples of the maleic anhydride-modified polyethylene resin include a trade name F3000 manufactured by Ube-Maruzen Polyethylene Co., Ltd. and a trade name Admer NF528T manufactured by Mitsui Chemicals.

The modified polyethylene resin preferably has a melt flow rate (MFR: 190 ° C., 2160 g) measured in accordance with ASTM D1238 of 0.1 to 60 g / 10 minutes, preferably 0.5 to 55 g / 10 minutes. More preferably.

<Polyamide resin composition>
The polyamide resin composition according to the present invention contains a polyamide resin, an unmodified polypropylene resin, a polyolefin wax and / or a modified polyethylene resin.

The content of the unmodified polypropylene resin is 0.1 to 10% by mass with respect to the polyamide resin composition. With this content, the releasability when made into a film can be improved. The content of the unmodified polypropylene resin is preferably 0.5 to 8% by mass, more preferably 1 to 5% by mass, based on the polyamide resin composition.

The content of the polyolefin wax and / or the modified polyethylene resin is 0.1 to 8% by mass with respect to the polyamide resin composition. With this content, the releasability when made into a film can be improved. The content of the polyolefin wax and / or the modified polyethylene resin is preferably 0.2 to 6% by mass, more preferably 0.3 to 5% by mass, based on the polyamide resin composition.

The polyamide resin composition of the present invention contains various additives and modifiers that are usually blended, such as heat stabilizers, ultraviolet absorbers, light stabilizers, and oxidations, as long as the characteristics of the obtained film are not impaired. Inhibitors, antistatic agents, lubricants, anti-blocking agents, fillers, tackifiers, sealability improvers, antifogging agents, crystal nucleating agents, mold release agents, plasticizers, cross-linking agents, foaming agents, colorants (pigments) , Dyes, etc.), bending fatigue resistance improving materials, etc. can be added. The polyamide resin composition of the present invention preferably contains an antiblocking agent and / or an antioxidant.

The anti-blocking agent is a substance added to suppress adhesion between films by imparting unevenness to the surface when the film is formed. The shape of the antiblocking agent is not particularly limited as long as surface protrusions are formed on the surface and a polyamide film having excellent slipperiness can be obtained, and the shape is not particularly limited, and is powdery, particulate, flake-like, plate-like, or fibrous. , Needle-shaped, cloth-shaped, mat-shaped, or any other shape, but particle-shaped or plate-shaped is preferable. The average particle size of the antiblocking agent is preferably 0.5 to 10 μm. It is desirable that the particles having a particle size of 10 μm or more are not substantially contained. If a large amount of particles having a particle size of 10 μm or more is contained, fish eye gel may be generated and the appearance of the film may be impaired. Further, even if the slipperiness improving effect is exhibited, the transparency of the film may be deteriorated. On the other hand, if the average particle size is less than 0.5 μm, secondary agglutination is likely to occur, and on the contrary, fish eye gel may be generated. Further, even if the agglomeration can be prevented, it is difficult to obtain the unevenness effect on the film surface, and the slipperiness may not be improved. Therefore, when the particle size of the antiblocking agent does not conform to the present invention, it is desirable to perform pulverization treatment or classification in advance.

Specific examples of these anti-blocking agents include gel-type silica, precipitated-type silica, spherical silica and other silica, talc, kaolin, montmorillonite, zeolite, mica, glass flakes, wollastonite, potassium titanate, magnesium sulfate, sepiolite, etc. Examples thereof include zonolite, aluminum borate, glass beads, calcium silicate, calcium carbonate, titanium oxide, barium sulfate, zinc oxide and magnesium hydroxide. These can be used alone or in combination of two or more. Among these, talc, kaolin, zeolite, and silica are preferable from the viewpoint of easy dispersibility. These can be used alone or in combination of two or more.

In particular, silica as an anti-blocking agent is more preferable because the obtained film is excellent in transparency and slipperiness. Silica is _{mainly composed of silicon dioxide represented by SiO 2} · nH ₂ O, and is roughly classified into two types, wet method silica and dry method silica, depending on the production method thereof. Either of them should be used. Can be done. In particular, the average particle size of silica is preferably 0.1 to 20 μm, more preferably 0.3 to 15 μm, and even more preferably 0.5 to 10 μm. Further, the primary particles include soft silica in which these primary particles are aggregated to form secondary particles or tertiary particles in the so-called submicron order, and hard silica in which the size of the primary particles is already 1 μm or more. When stretching the film, soft silica is more preferable.

Although it is possible to use unsurface-treated silica, it is also possible to use surface-treated silica. When an anti-blocking agent treated with a silane-based or titanium-based surface treatment agent is used, the dispersibility is further improved, and the transparency of the obtained film is further improved. The surface treatment method is not particularly limited, and for example, a method described in JP-A-63-251460, in which a silane coupling agent diluted with heated stirring sewage is added to fine silica for treatment is applied. Can be done.

The content of the antiblocking agent is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, and 0.1 to 1% by mass with respect to the polyamide resin composition. It is more preferable to do so.

The antioxidant is a substance added to suppress the oxidation of each component. Examples of the antioxidant include phosphorus-based antioxidants, phenol-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, amide-based antioxidants, potassium halides, and copper compounds. Among these, it is preferable to use potassium iodide and / or potassium bromide in combination with copper iodide. In addition, these may use 1 type or 2 or more types. The content of the antioxidant is preferably 0.001 to 5% by mass, more preferably 0.003 to 3% by mass, and 0.005 to 1% by mass with respect to the polyamide resin composition. It is more preferable to do so.

The polyamide resin composition according to the present invention is preferably used for forming a release film because it has good releasability when formed into a film.

<Release film>
The release film according to the present invention (hereinafter, may be simply referred to as "film") contains the above-mentioned polyamide resin composition.

The film can be obtained by forming a film by a known film manufacturing method. For example, a raw polyamide resin composition is melt-kneaded with an extruder, extruded into a flat film by a T-die or a coated hanger die, cast on a casting roll surface, cooled to produce a film, or a ring-shaped die. There is a tubular method or the like in which a tubular material melt-extruded into a tubular shape is air-cooled or water-cooled to produce a film. The produced film may be in a substantially unoriented, unstretched state, or may be in a stretched state.

When the unstretched film is stretched, a conventionally known industrial method can be used. For example, a simultaneous biaxial stretching method in which an unstretched sheet produced by a casting method is simultaneously stretched vertically and horizontally with a tenter type simultaneous biaxial stretching machine, and an unstretched sheet melt-extruded from a T die is stretched in the longitudinal direction with a roll type stretching machine. After that, there are a sequential biaxial stretching method in which stretching is performed in the lateral direction with a tenter type stretching machine, and a tubular stretching method in which a tubular sheet formed from an annular die is stretched simultaneously in the vertical and horizontal directions by an inflation type with gas pressure. The stretching step may be continuously carried out following the production of the film, or the manufactured film may be wound once and stretched as a separate step.

The thickness of the film may be appropriately determined depending on the intended use, and is not particularly limited. For example, if the thickness of the film is thick, the film strength is improved, but the transparency and bending fatigue resistance are lowered, so that the thickness of the film can be determined in consideration of these. In the case of a single-layer film, the thickness of the film is preferably 5 to 200 μm, more preferably 10 to 150 μm, and even more preferably 15 to 100 μm.

Hereinafter, the present invention will be specifically described with reference to Examples.

<Example 1>
A polyamide resin composition containing the components shown in Table 1 was prepared and extruded at 270 ° C. and 50 rpm with a single-screw T-die film molding machine to obtain a release film having a thickness of 50 μm. The blending amount of the component whose unit is described as "mass ppm" is the amount added to a total of 100 parts by mass of the component whose unit is described as "parts by mass" (hereinafter, the same applies). Polyethylene 6 (PA6, manufactured by Ube Kosan Co., Ltd., trade name: 1030B) is used as the polyamide resin, and polypropylene homopolymer (isotactic PP, manufactured by Prime Polymer Co., Ltd., trade name: J108M, melt) is used as the unmodified polypropylene resin. Florate: 45 g / 10 minutes, 230 ° C.), and as the modified polyethylene resin, maleic anhydride-modified polyethylene resin (MAH-g-PE, manufactured by Ube Maruzen Polyethylene Co., Ltd., trade name: F3000) is used, and an anti-blocking agent (anti-blocking agent) is used. As AB), gel-type silica having no surface treatment (with an average particle size of 1 to 4 μm) was used, and as the antioxidant (AO), copper iodide and potassium iodide were used.

<Examples 2 to 9>
A release film was obtained in the same manner as in Example 1 except that the compounding ratio of each component was changed as shown in Table 1.

<Examples 10 to 13>
A release film was obtained in the same manner as in Example 1 except that the type of the unmodified polypropylene resin was changed and the compounding ratio of each component was changed as shown in Table 1. As the unmodified polypropylene resin, in Example 10, a polypropylene homopolymer (isotactic PP, manufactured by Prime Polymer Co., Ltd., trade name: J106MG, melt flow rate: 15 g / 10 minutes, 230 ° C.) was used, and Example 11 In Example 12, a polypropylene homopolymer (isotactic PP, manufactured by Prime Polymer Co., Ltd., trade name: J105G, melt flow rate: 9.0 g / 10 minutes, 230 ° C.) was used, and in Example 12, a polypropylene homopolymer (isotactic PP, Made by Prime Polymer Co., Ltd., trade name: E-100GPL, melt flow rate: 1.0 g / 10 minutes, 230 ° C.), and in Example 13, polypropylene homopolymer (isotactic PP, manufactured by Prime Polymer Co., Ltd., trade name: F113G, melt flow rate: 3.0 g / 10 minutes, 230 ° C.) was used.

<Examples 14 to 16>
A release film was obtained in the same manner as in Example 1 except that a polyolefin wax was used instead of the maleic anhydride-modified polyethylene resin and the compounding ratio of each component was changed as shown in Table 1. In Example 14, unmodified polyethylene wax (PE-wax, manufactured by Clarianto Chemicals Co., Ltd., trade name: Licowax (registered trademark) PE520) was used, and in Example 15, unmodified polypropylene wax (PP-wax, manufactured by Clariant Chemicals Co., Ltd.) was used. , Trade name: Licocene (registered trademark) PP6102), and in Example 16, maleic anhydride-modified polypropylene wax (MAH-PP-wax, manufactured by Clarianto Chemicals, trade name: Licocene (registered trademark) PP MA 6452) is used. board.

<Comparative example 1>
A release film was obtained in the same manner as in Example 1 except that the compounding ratio of each component was changed as shown in Table 2 without using the maleic anhydride-modified polyethylene resin.

<Comparative example 2>
Instead of maleic anhydride-modified polyethylene resin, maleic anhydride-modified polypropylene resin (MAH-PP, manufactured by Prime Polymer Co., Ltd., trade name: ZP648, melt flow rate: 55 g / 10 minutes, 230 ° C.) is used, and the compounding ratio of each component is used. A release film was obtained in the same manner as in Example 1 except that the above was changed as shown in Table 2.

<Comparative Examples 3 to 11>
Examples except that components generally used for imparting releasability were used instead of the unmodified polypropylene resin and the maleic anhydride-modified polyethylene resin, and the compounding ratio of each component was changed as shown in Table 2. A release film was obtained in the same manner as in 1. In Comparative Example 3, low-density polyethylene (LDPE, manufactured by Ube Maruzen Polyethylene, trade name: C470) was used, and in Comparative Example 4, metallocene-catalyzed linear short-chain branched polyethylene (LLDPE, manufactured by Ube Maruzen Polyethylene, trade name: C470) was used. : 2040F), a fluororesin (FR, manufactured by Asahi Glass Co., Ltd., trade name: AH-2000) was used in Comparative Example 5, and a fluororesin (FR, manufactured by Asahi Glass Co., Ltd., trade name: LM730AP) was used in Comparative Example 6. In Comparative Example 7, a silicone resin (SR, manufactured by Toray Dow Corning Co., Ltd., trade name: MB50-011) was used, and in Comparative Examples 8 and 9, a mold release agent (manufactured by Nitto Kasei Kogyo Co., Ltd., trade name: Ca-Beh) was used. ), In Comparative Example 10, ethylene bisstearoamide (EBS, manufactured by Kyoeisha Chemical Industry Co., Ltd., trade name: WH-100), and in Comparative Example 11, ethylene bisbechenic acid amide (EBB, manufactured by Nihon Kasei Co., Ltd., trade name: WH-100). Slipax B) was used.

<Comparative Example 12>
A release film was obtained in the same manner as in Example 1 except that the compounding ratio of each component was changed as shown in Table 2 without using the unmodified polypropylene resin and the maleic anhydride-modified polyethylene resin.

<Appearance>
The appearance of the obtained release film was visually observed and judged according to the following criteria.
◯: No problem ×: Some incompatible parts are seen XX: In addition to the incompatible parts, film streaks are also seen

<Peelability test (Peel Test)>
The CFRP prepreg is sandwiched between the release films obtained above, heat-cured at 150 ° C for 2 hours under pressure in an autoclave, and the release film is peeled off from the sample taken out after cooling to improve the release property. evaluated.
◎: Extremely good ○: Good △: Normal ×: Damaged

As described above, it can be seen that the polyamide resin composition containing the polyamide resin, the unmodified polypropylene resin, the polyolefin wax and / or the modified polyethylene resin has improved releasability when formed into a film (Example). 1-16). In particular, the technical significance of the present invention is extremely great because the releasability is not improved even if a component generally used for imparting releasability is added to the polyamide resin (Comparative Examples 3 to 11).

Claims (4)

A polyamide resin composition containing a polyamide resin, an unmodified polypropylene resin, and a polyolefin wax.
The content of the unmodified polypropylene resin is 0.1 to 10% by mass.
A polyamide resin composition for forming a release film having a polyolefin wax content of 0.1 to 8% by mass. The polyamide resin composition according to claim 1, further comprising an anti-blocking agent. The polyamide resin composition according to claim 1 or 2, further comprising an antioxidant. A release film containing the polyamide resin composition according to any one of claims 1 to 3.