JP7267784B2 - multilayer release film - Google Patents

Description

The present invention provides a release film for molding a fiber-reinforced composite material placed between the mold when molding a fiber-reinforced composite prepreg in the mold, a semiconductor chip, or an LED element in the mold. The present invention relates to a multilayer release film that can be used as a release film for a semiconductor or LED element encapsulation process that is placed between a semiconductor chip or LED element and the inner surface of a mold when resin is injected and molded after the film is placed.

When molding a fiber-reinforced resin, a prepreg is generally used in which reinforcing fibers such as carbon fibers or glass fibers are impregnated with a resin. Then, this prepreg is heated and molded into a desired shape.

In this case, a fluorine-based material such as polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, or polyvinyl fluoride is placed between the prepreg and the mold so that the molded prepreg and the mold do not adhere to each other. Release films such as polymer films and polymethylpentene films are used.

A semiconductor chip is usually used as a semiconductor resin package sealed with a sealing material. A semiconductor resin package is generally obtained by transfer molding, in which a semiconductor chip is loaded into a mold cavity and the cavity is filled with a sealing material containing epoxy resin as a main component.

In conventional transfer molding, the sealing material may contaminate the inner surface of the mold, which reduces work efficiency, and damages the inner surface of the mold, shortening the life of the mold. There are problems such as the fact that burrs are likely to occur in the molded semiconductor resin package.

In this case, in order to improve the above problems, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, fluorine-based polymer films such as polyvinyl fluoride, and release films such as polymethylpentene films are used. It is

When a multi-layer polymethylpentene release film is used as the release film, the multilayer film deforms according to the unevenness of the surface and shape, but peeling occurs between the layers of the multilayer film, and the film does not separate. There is a risk that the film may tear or wrinkle the film, and the peeling, tearing, or wrinkles may be transferred to the molded product, deteriorating the appearance of the molded product and impairing the reliability of the molded product itself. .

As for the release film, not only a single-layer film but also a release film having crystalline polymethylpentene layers formed on both inner and outer surfaces has been proposed (Patent Documents 1 and 2).
On the other hand, since 4-methyl-1-pentene polymer films have a low elastic modulus at high temperatures, polyamides and aromatic polyesters are added to 4-methyl-1-pentene polymers in order to improve the elastic modulus at high temperatures. A method of laminating with an aromatic polyester block copolymer layer (Patent Document 4) has been proposed.
However, since the 4-methyl-1-pentene polymer film is inferior in adhesiveness, it tends to be inferior in interlayer adhesive strength to an aromatic polyester block copolymer layer or the like.

Japanese Patent No. 2619034 Japanese Patent Application Laid-Open No. 2003-211602 Japanese Patent No. 5297233 Japanese Patent No. 5335731

SUMMARY OF THE INVENTION An object of the present invention is to develop a multi-layer release film that is free from tearing and has excellent heat resistance and interlayer adhesive strength.

The present invention is a multilayer film having at least three layers, a release layer (X), an intermediate layer (Y), and a heat-resistant layer (Z),
The release layer (X) comprises 50 to 100 parts by mass of a 4-methyl-1-pentene (co)polymer (A) that satisfies the following requirements (a) to (d), and the following requirements (a1) to (e1): 4-methyl-1-pentene copolymer (B) 50 to 0 parts by mass (provided that the total of components (A) and (B) is 100 parts by mass), and 4-methyl -Consisting of a 1-pentene (co)polymer composition (L),
[4-methyl-1-pentene (co)polymer (A)]
(a) 100 to 90 mol% of structural units derived from 4-methyl-1-pentene, at least one selected from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene); Structural units derived from seeds are 0 to 10 mol% [however, the total amount of structural units derived from 4-methyl-1-pentene and structural units derived from ethylene and α-olefins having 3 to 20 carbon atoms is 100 mol %. ]
(b) the intrinsic viscosity [η] measured in decalin at 135°C is in the range of 0.5 to 5.0 dl/g;
(c) a melting point (Tm) measured by DSC in the range of 200-250° C.; and (d) a density in the range of 820-850 kg/m ³ .
[4-methyl-1-pentene copolymer (B)]
(a1) 97 to 60 mol % of structural units derived from 4-methyl-1-pentene, and 3 to 40 mol of structural units derived from at least one selected from ethylene and α-olefins having 3 to 4 carbon atoms; % [However, the total amount of structural units derived from 4-methyl-1-pentene and structural units derived from ethylene and an α-olefin having 3 to 4 carbon atoms is defined as 100 mol %. ]
(b1) Intrinsic viscosity [η] measured in decalin at 135°C in the range of 0.5 to 5.0 dl/g,
(c1) a melting point (Tm) measured by DSC of 199° C. or less, or substantially not observed;
(d1) the molecular weight distribution (Mw/Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC), is in the range of 1.0 to 3.5; and (e1) the density is in the range of 825-860 kg/m ³ .

The intermediate layer (Y) contains 10 to 45 parts by mass of the 4-methyl-1-pentene copolymer (B), 45 to 75 parts by mass of the propylene polymer (C), and the ethylene polymer (D). 5 to 15 parts by mass [However, the total amount of components (B), (C) and (D) is 100 parts by mass. ] Consists of an olefin polymer composition (M) containing
The multilayer release film is characterized in that the heat-resistant layer (Z) is polyester or polyamide having a melting point of 160° C. or higher.

In the multilayer release film of the present invention, the release layer is a 4-methyl-1-pentene (co)polymer composition, so the release property and heat resistance which are the features of poly-4-methyl-1-pentene In addition, since the intermediate layer is an olefin polymer composition, the film does not tear or delaminate during use, so molding can be performed at higher temperatures, improving work efficiency. Also, the yield of the molded article obtained can be improved.
In addition, the multilayer release film of the present invention suppresses the transfer of impurities to the surface of the molded article, and does not contain a halogen-based resin, so it has excellent recyclability and low environmental load.

The multilayer release film of the present invention is a multilayer film having at least three layers: a release layer (X), an intermediate layer (Y), and a heat-resistant layer (Z).
The release layer (X), the intermediate layer (Y), the heat-resistant layer (Z) and the polymers forming these layers, which constitute the multilayer film, will be described below.

<Release layer (X)>
The release layer constituting the multilayer release film of the present invention is 4-methyl-1-pentene (co)polymer (A), or 4-methyl-1-pentene (co)polymer (A) and 4- A composition with methyl-1-pentene copolymer (B) [4-methyl-1-pentene (co)polymer composition (L)].

[4-methyl-1-pentene (co)polymer (A)]
4-methyl-1-pentene which is one of the components constituting the 4-methyl-1-pentene (co)polymer composition (L) forming the release layer (X) of the multilayer release film of the present invention (Co)Polymer (A) [hereinafter sometimes referred to as "polymer (A)". ] is a homopolymer of 4-methyl-1-pentene or a copolymer of 4-methyl-1-pentene and an α-olefin that satisfies the following requirements (a) to (d).
(a) 100 to 90 mol%, preferably 99.9 to 92 mol%, more preferably 99 to 95 mol% of structural units derived from 4-methyl-1-pentene, ethylene and C 3 to 20 0 to 10 mol%, preferably 0.1 to 8 mol%, more preferably 1 to 5 mol% of structural units derived from at least one selected from α-olefins (excluding 4-methyl-1-pentene) [However, the total amount of structural units derived from 4-methyl-1-pentene and structural units derived from ethylene and an α-olefin having 3 to 20 carbon atoms is 100 mol%. ].
(b) The intrinsic viscosity [η] measured in decalin at 135°C is 0.5 to 5.0 dl/g, preferably 0.5 to 4.0 dl/g, more preferably 0.7 to 3.5 dl/g. in the range of
(c) a melting point (Tm) measured by DSC in the range of 200 to 250°C, preferably 210 to 245°C, more preferably 220 to 240°C;
(d) Density is in the range of 820-850 kg/m ³ , preferably 825-845 kg/m ³ , more preferably 830-840 kg/m ³ .

The 4-methyl-1-pentene (co)polymer (A) satisfying the above requirements (a) to (d) has excellent fluidity and heat resistance, and the polymer (A) is used as a release layer. can be used to obtain a multilayer release film having an excellent balance with releasability.

[4-methyl-1-pentene copolymer (B)]
4-methyl-1, which is another component constituting the 4-methyl-1-pentene (co)polymer composition (L) forming the release layer (X) of the multilayer release film of the present invention - Pentene copolymer (B) [hereinafter sometimes referred to as "copolymer (B)". ] is a copolymer of 4-methyl-1-pentene and an α-olefin that satisfies the following requirements (a1) to (e1).
(a1) 97 to 60 mol%, preferably 90 to 60 mol%, more preferably 88 to 70 mol% of structural units derived from 4-methyl-1-pentene, ethylene or α- having 3 to 4 carbon atoms; Structural units derived from at least one selected from olefins are in the range of 3 to 40 mol%, preferably 10 to 40 mol%, more preferably 12 to 30 mol% [provided that from 4-methyl-1-pentene The total amount of derived structural units, ethylene and structural units derived from α-olefins having 3 to 4 carbon atoms is defined as 100 mol %. ].
(b1) intrinsic viscosity [η] measured in decalin at 135°C of 0.5 to 5.0 dl/g, preferably 0.7 to 4.0 dl/g, more preferably 1.0 to 3.0 dl/g in the range.
(c1) The melting point (Tm) measured by DSC is 199° C. or lower, preferably 180° C. or lower, more preferably 160° C. or lower, or is substantially not observed.
(d1) the molecular weight distribution (Mw/Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC), is 1.0 to 3.5, preferably It ranges from 1.5 to 3.0.
(e1) Density is in the range of 825-860 kg/m ³ , preferably 830-850 kg/m ³ , more preferably 833-845 kg/m ³ .
The 4-methyl-1-pentene (co)polymer (B) according to the present invention has excellent compatibility with the 4-methyl-1-pentene (co)polymer (A) and has flexibility and elongation. Excellent for

[4-methyl-1-pentene (co)polymer composition (L)]
The 4-methyl-1-pentene (co)polymer composition (L) constituting the release layer (X) of the multilayer release film of the present invention contains 50 to 100 parts by mass of the polymer (A), preferably 60 to 95 parts by mass, more preferably 70 to 90 parts by mass, and 50 to 0 parts by mass, preferably 40 to 5 parts by mass, more preferably 30 to 10 parts by mass of the copolymer (B) [however, ( The sum of component A) and component (B) is 100 parts by mass. ].

When the 4-methyl-1-pentene (co)polymer composition (L) constituting the release layer (X) according to the present invention contains the above copolymer (B), and the obtained multilayer release film While maintaining heat resistance and releasability, the stretchability and elongation of the film are increased, and the adhesive strength with the intermediate layer (Y) is increased.

The 4-methyl-1-pentene (co)polymer composition (L) according to the present invention, in addition to the polymer (A) and the copolymer (B), has the effect of the present invention depending on its use. Other resins or polymers and/or additives for resins can be arbitrarily added as long as they do not impair the

Such resin additives include, for example, pigments, dyes, fillers, lubricants, plasticizers, release agents, antioxidants, flame retardants, ultraviolet absorbers, antibacterial agents, surfactants, antistatic agents, weather resistant agent, heat stabilizer, anti-slip agent, anti-blocking agent, foaming agent, crystallization aid, anti-fogging agent, (transparent) nucleating agent, anti-aging agent, hydrochloric acid absorber, impact modifier, cross-linking agent, co-cross-linking agent , cross-linking aids, adhesives, softeners, processing aids, and the like. These additives can be used singly or in combination of two or more.

Other resins or polymers to be added include polystyrene, acrylic resin, polyphenylene sulfide resin, polyetheretherketone resin, polyester resin, polysulfone, polyphenylene oxide, polyimide, polyetherimide, acrylonitrile-butadiene-styrene copolymer (ABS ), ethylene/α-olefin copolymer rubber, conjugated diene rubber, phenol resin, melamine resin, polyester resin, silicone resin, and epoxy resin. The amount of these resins or polymers added is preferably 0.1 to 30% by mass relative to the total mass of the 4-methyl-1-pentene (co)polymer composition (L).

Examples of pigments include inorganic pigments (titanium oxide, iron oxide, chromium oxide, cadmium sulfide, etc.) and organic pigments (azo lake-based, thioindigo-based, phthalocyanine-based, anthraquinone-based). Examples of dyes include azo dyes, anthraquinone dyes, and triphenylmethane dyes. The amount of these pigments and dyes to be added is not particularly limited. .1 to 3% by weight.

Fillers include glass fiber, carbon fiber, silica fiber, metal (stainless steel, aluminum, titanium, copper, etc.) fiber, carbon black, silica, glass beads, silicate (calcium silicate, talc, clay, etc.), metal oxide ( iron oxide, titanium oxide, alumina, etc.), metal carbonates (calcium sulfate, barium sulfate) and various metals (magnesium, silicon, aluminum, titanium, copper, etc.) powders, mica, glass flakes and the like. These fillers may be used singly or in combination of two or more.

Lubricants include waxes (carnauba wax, etc.), higher fatty acids (stearic acid, etc.), higher alcohols (stearyl alcohol, etc.), higher fatty acid amides (stearic acid amide, etc.), and the like.

Plasticizers include aromatic carboxylic acid esters (dibutyl phthalate, etc.), aliphatic carboxylic acid esters (methyl acetyl ricinoleate, etc.), aliphatic dicarboxylic acid esters (adipic acid-propylene glycol polyester, etc.), aliphatic tricarboxylic acids. Examples include esters (triethyl citrate, etc.), phosphate triesters (triphenyl phosphate, etc.), epoxy fatty acid esters (epoxybutyl stearate, etc.), petroleum resins, and the like.

Release agents include lower (C1-4) alcohol esters of higher fatty acids (butyl stearate, etc.), polyhydric alcohol esters of fatty acids (C4-30) (hydrogenated castor oil, etc.), glycol esters of fatty acids, liquid paraffin, etc. is mentioned.

Examples of antioxidants include phenolic (2,6-di-t-butyl-4-methylphenol, etc.), polycyclic phenolic (2,2′-methylenebis(4-methyl-6-t-butylphenol, etc.), Phosphorus-based (tetrakis(2,4-di-t-butylphenyl)-4,4-biphenylenediphosphonate, etc.) and amine-based (N,N-diisopropyl-p-phenylenediamine, etc.) antioxidants can be mentioned. be done.

Flame retardants include organic flame retardants (nitrogen-containing, sulfur-containing, silicon-containing, phosphorus-containing, etc.) and inorganic flame retardants (antimony trioxide, magnesium hydroxide, zinc borate, red phosphorus, etc.). mentioned.

Examples of ultraviolet absorbers include benzotriazole-based, benzophenone-based, salicylic acid-based, and acrylate-based.
Antibacterial agents include quaternary ammonium salts, pyridine compounds, organic acids, organic acid esters, halogenated phenols, organic iodine, and the like.

Surfactants may include nonionic, anionic, cationic or amphoteric surfactants. Examples of nonionic surfactants include polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, polypropylene glycol ethylene oxide adducts, polyethylene oxide, and fatty acid esters of glycerin. , fatty acid esters of pentaerythritol, fatty acid esters of sorbit or sorbitan, alkyl ethers of polyhydric alcohols, and polyhydric alcohol nonionic surfactants such as fatty amides of alkanolamine. Examples include sulfate ester salts such as alkali metal salts of higher fatty acids, sulfonates such as alkylbenzenesulfonates, alkylsulfonates, and paraffin sulfonates, and phosphate ester salts such as higher alcohol phosphates. Examples of cationic surfactants include quaternary ammonium salts such as alkyltrimethylammonium salts. Examples of amphoteric surfactants include amino acid-type double-sided surfactants such as higher alkylaminopropionates, and betaine-type amphoteric surfactants such as higher alkyldimethylbetaines and higher alkylhydroxyethylbetaines.

Examples of antistatic agents include the surfactants, fatty acid esters, and polymeric antistatic agents described above. Examples of fatty acid esters include esters of stearic acid and oleic acid, and examples of polymeric antistatic agents include polyether ester amides.

Addition amounts of various additives such as fillers, lubricants, plasticizers, release agents, antioxidants, flame retardants, ultraviolet absorbers, antibacterial agents, surfactants, and antistatic agents impair the purpose of the present invention. Although it is not particularly limited depending on the application within the range, it is 0.1 to 30% by mass with respect to the total mass of the 4-methyl-1-pentene (co)polymer composition (L). is preferred.

When producing a multilayer release film using the 4-methyl-1-pentene (co)polymer composition (L) according to the present invention, the polymer (A) and the copolymer (B) etc. may be mixed in a predetermined amount and used, or after being mixed, they may be kneaded and prepared.

<Intermediate layer (Y)>
The intermediate layer (Y) constituting the multilayer release film of the present invention is an olefin containing the 4-methyl-1-pentene copolymer (B), the propylene polymer (C) and the ethylene polymer (D). It consists of a polymer composition (M).

[Propylene polymer (C)]
The propylene-based polymer (C), which is one of the components constituting the olefin polymer composition (M) that forms the intermediate layer (Y) that constitutes the multilayer release film of the present invention, is a propylene homopolymer or propylene and ethylene or 4 to 20 carbon atoms, preferably ethylene or 4 to 8 carbon atoms. The monomer to be copolymerized with propylene may be a single monomer or two or more monomers.

The propylene-based polymer (C) according to the present invention usually contains 85 to 100 mol %, preferably 92 to 99 mol % of units derived from propylene [provided that units derived from propylene and α-olefin The total amount of units derived from (including ethylene) is 100 mol%. ].

The propylene-based polymer (C) according to the present invention usually has an MFR (measured at 230° C. under a load of 2160 g) of 0.1 to 100 g/10 minutes, preferably 0.5 to 50 g/10 minutes, more preferably 1 .0 to 20 g/10 min.

The propylene-based polymer (C) according to the present invention is a modified propylene-based polymer (C1) partially or wholly graft-modified with an unsaturated carboxylic acid or a derivative thereof [hereinafter referred to as "modified propylene-based polymer ( C1)”. ] may be.

<Graft-modified propylene-based polymer (C1)>
In the modified propylene-based polymer (C1) according to the present invention, the graft amount of the unsaturated carboxylic acid or derivative thereof is usually 0.1 to 10% by mass with respect to 100% by mass of the modified propylene-based polymer (C1). %, preferably 1 to 10 mass %, more preferably 2 to 9 mass %.

The unsaturated carboxylic acid and/or derivative thereof according to the present invention includes an unsaturated compound having one or more carboxylic acid groups, an ester of a compound having a carboxylic acid group and an alkyl alcohol, or one or more carboxylic anhydride groups. Examples of unsaturated compounds include vinyl groups, vinylene groups, and unsaturated cyclic hydrocarbon groups. Specific compounds include, for example, acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid [trademark] (endosys-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid); or derivatives thereof such as acid halides, amides, imides, anhydrides, esters, and the like. Specific examples of such derivatives include malenyl 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 and their acid anhydrides are preferred, and maleic acid, nadic acid and their acid anhydrides are particularly preferred. The content of the unsaturated carboxylic acid and/or its derivative can be easily controlled, for example, by appropriately selecting the grafting conditions.

The method of grafting a graft monomer selected from unsaturated carboxylic acids and/or derivatives thereof to the propylene-based polymer is not particularly limited, and conventionally known graft polymerization methods such as a solution method and a melt-kneading method can be employed. can. For example, a method in which a propylene-based polymer is melted and a grafting monomer is added thereto for grafting reaction, or a propylene-based polymer is dissolved in a solvent to form a solution, and a grafting monomer is added thereto for grafting reaction. There are ways to make it work.

In these methods, if the graft polymerization is carried out in the presence of a radical initiator, the graft monomer such as the unsaturated carboxylic acid can be efficiently graft-polymerized. In this case, the radical initiator is usually used in an amount of 0.001 to 1 part by mass with respect to 100 parts by mass of the propylene-based polymer.

Organic peroxides, azo compounds and the like are used as such radical initiators. Specific examples of such radical initiators include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(peroxidobenzoate)hexyne- 3, 1,4-bis(t-butylperoxyisopropyl)benzene, lauroyl peroxide, t-butylperacetate, 2,5-dimethyl-2,5-di-(t-butylperoxide)hexyne-3, 2,5 -dimethyl-2,5-di(t-butylperoxide)hexane, t-butyl perbenzoate, t-butyl perphenylacetate, t-butyl perisobutyrate, t-butyl per-sec-octoate, t-butyl perpi Valate, cumyl perpivalate, t-butylperdiethyl acetate; azobisisobutyronitrile, dimethylazoisobutyrate and the like.

Among these are dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-di(t -Butylperoxy)hexane, 1,4-bis(t-butylperoxyisopropyl)benzene, and other dialkyl peroxides are preferably used.

The reaction temperature for the graft polymerization reaction using a radical initiator or the graft polymerization reaction performed without using a radical initiator is usually set within the range of 60 to 350.degree. C., preferably 150 to 300.degree.

When the propylene-based polymer (C) according to the present invention is used as one of the components of the olefin polymer composition (M), it may be used alone or in combination of two or more. When two or more propylene-based polymers (C) are used, they may be polymers having different physical properties. It may be a polymer (C1).

[Ethylene polymer (D)]
The ethylene polymer (D), which is one of the components constituting the olefin polymer composition (M) that forms the intermediate layer (Y) that constitutes the multilayer release film of the present invention, is an ethylene homopolymer or It is a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms.

The ethylene polymer (D) according to the present invention usually has a density of 850 to 960 kg/m ³ , preferably 850 to 930 kg/m ³ , more preferably 850 to 900 kg/m ³ , MFR (190°C, measured at a load of 2160 g) is in the range of 0.1 to 100 g/10 minutes, preferably 0.2 to 80 g/10 minutes, more preferably 0.5 to 20 g/10 minutes.

The ethylene-based polymer (D) according to the present invention is a modified ethylene-based polymer partially or wholly graft-modified with an unsaturated carboxylic acid or a derivative thereof, like the propylene-based polymer (C). There may be.

[Olefin polymer composition (M)]
The 4-methyl-1-pentene (co)polymer composition (M) constituting the intermediate layer (Y) of the multilayer release film of the present invention is the 4-methyl-1-pentene copolymer (B). 10 to 45 parts by mass, preferably 15 to 45 parts by mass, more preferably 20 to 40 parts by mass, 45 to 75 parts by mass, preferably 50 to 75 parts by mass, more preferably 50 to 70 parts by mass and 5 to 15 parts by mass, preferably 5 to 14 parts by mass, and more preferably 5 to 12 parts by mass of the ethylene polymer (D) [however, components (B), (C) and (D) Let the total amount be 100 parts by mass. ].

The 4-methyl-1-pentene (co)polymer composition (M) constituting the intermediate layer (Y) according to the present invention contains a predetermined amount of the copolymer (B), thereby forming the release layer ( An intermediate layer (Y) having excellent adhesion to X) can be obtained.

The propylene-based polymer (C) contained in the 4-methyl-1-pentene (co)polymer composition (M) is a component that contributes to adhesion with the heat-resistant layer (Z) described below. As (C), when the modified propylene-based polymer (C1) is used as at least a part thereof, the adhesive strength is further improved.

The ethylene-based polymer (D) contained in the 4-methyl-1-pentene (co)polymer composition (M) is a component necessary for maintaining the flexibility of the intermediate layer (Y) of the present invention. In particular, by using a polymer having a low density as the ethylene polymer (D), a multilayer release film having a better balance between flexibility and adhesive strength can be obtained.

The 4-methyl-1-pentene (co)polymer composition (M) according to the present invention comprises the 4-methyl-1-pentene copolymer (B), the propylene polymer (C) and the ethylene polymer. By including each of (D) in the above range, the intermediate layer (Y) has excellent adhesion strength to the release layer (X) and the heat-resistant layer (Z) described below.

The olefin polymer composition (M) according to the present invention contains the components (B), (C) and (D) in the same manner as the 4-methyl-1-pentene (co)polymer composition (L). In addition to these, other resins or polymers and/or additives for resins can be arbitrarily added depending on the application within a range that does not impair the effects of the present invention.

When producing a multilayer release film using the olefin polymer composition (M) according to the present invention, the components (B), (C) and (D) are mixed in predetermined amounts and used. Alternatively, the mixture may be prepared by kneading after mixing.

<Heat-resistant layer (Z)>
The heat-resistant layer (Z) constituting the multilayer release film of the present invention is made of polyester or polyamide having a melting point of 160° C. or higher.

[polyester]
Polyester constituting the heat-resistant layer (Z) according to the present invention is not particularly limited as long as it has a melting point of 160° C. or higher.

Specific examples of such polyester include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene terephthalate/isophthalate copolymer, and the like. Polymers, or polyester elastomers having the above-mentioned crystalline polymer as a hard segment, and the like can be mentioned.

As the polyester elastomer, for example, a block copolymer having a crystalline polymer segment composed of a crystalline aromatic polyester unit as a hard segment and an amorphous polymer segment composed of a polyether unit or an aliphatic polyester unit as a soft segment. coalescence is mentioned.

Examples of crystalline polymers composed of crystalline aromatic polyester units constituting hard segments of polyester elastomers include polybutylene terephthalate (PBT) and polybutylene naphthalate (PBN).

In addition, polytetramethylene ether glycol (PTMG) is included as an example of the amorphous polymer composed of polyether units that constitute the soft segment of the polyester elastomer. Examples of amorphous polymers composed of aliphatic polyester units constituting soft segments include aliphatic polyesters such as polycaprolactone (PCL).

Specific examples of thermoplastic polyester elastomers include block copolymers of polybutylene terephthalate (PBT) and polytetramethylene ether glycol (PTMG); block copolymers of polybutylene terephthalate (PBT) and polycaprolactone (PCL); Coalescence; block copolymers of polybutylene naphthalate (PBN) and aliphatic polyester, and the like.

[polyamide]
The polyamide constituting the heat-resistant layer (Z) according to the present invention is not particularly limited as long as it has a melting point of 160° C. or higher.

Such polyamides include, for example, PA6, PA66, PA46, polyamide 6I, PA610, PA612, PA6T, PA9, PA9T, PA10T, PA11, PA12, polyamide elastomer, polyamide MXD6 and the like.

Polyamide elastomers include block copolymers having polyamide as hard segments and polyester or polyether as soft segments.
Examples of polyamides constituting the hard segment include PA6, PA66, PA610, PA612, PA11 and the like.

Examples of polyethers that make up the soft segment include polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene glycol (PTMG), and the like.

The polyester or polyamide having a melting point of 160° C. or higher, which constitutes the heat-resistant layer (Z) according to the present invention, may be used in the same manner as the 4-methyl-1-pentene (co)polymer composition (L), depending on the application. Therefore, other resins or polymers and/or additives for resins can be added arbitrarily within a range that does not impair the effects of the present invention.

<Multilayer release film>
The multilayer release film of the present invention is a multilayer film having at least three layers: the release layer (X), the intermediate layer (Y), and the heat-resistant layer (Z).
In the multilayer release film of the present invention, since the release layer (X) is composed of the 4-methyl-1-pentene (co)polymer composition (L), the release property from the molded article and the mold is improved. Excellent.
Moreover, since it has a heat-resistant layer (Z), the multilayer release film can be used for molding at higher temperatures.

Moreover, since the multilayer release film of the present invention has the intermediate layer (Y) composed of the olefin polymer composition (M) between the release layer (X) and the heat-resistant layer (Z), It is characterized by being excellent in deformation and elongation of the film and preventing film tearing.

The thickness of the multilayer release film of the present invention can be appropriately determined as desired. The thickness of the intermediate layer (Y) is 10-50 μm, preferably 10-40 μm, more preferably 10-30 μm, and the thickness of the heat-resistant layer (Z) is 10-100 μm, preferably 20-80 μm, more It is preferably in the range of 20-70 μm, and the total thickness of the multilayer release film is in the range of 30-200 μm, preferably 50-170 μm, more preferably 50-150 μm.

The multilayer release film of the present invention may be a film in which the release layer (X), the intermediate layer (Y), and the heat-resistant layer (Z) are in direct contact, improving the adhesive strength between each layer. For this purpose, an adhesive layer may be provided between each layer.

Further, the multilayer release film of the present invention may be a three-layer film of the release layer (X), the intermediate layer (Y), and the heat-resistant layer (Z), and the release layer ( X), the intermediate layer (Y), and the heat-resistant layer (Z),
Further, the multilayer release film of the present invention includes three types of the release layer (X), the intermediate layer (Y), the heat-resistant layer (Z), the intermediate layer (Y), and the release layer (X). It may be a five-layer film, the release layer (X), the intermediate layer (Y), the heat-resistant layer (Z), the adhesive layer, the heat-resistant layer (Z′) and the intermediate layer (Y), The release layer (X) may be a five-kind seven-layer film. nine

<Method for producing multilayer release film>
The multilayer release film of the present invention can be produced by using various known film forming machines.
Specifically, for example, using a multilayer film molding machine equipped with a multilayer die and at least three extruders, 4-methyl-1-pentene (co)polymer used for the release layer (X) in one extruder The coalescing composition (L) is charged, and the olefin polymer composition (M) used for the intermediate layer (Y) and the polyester or polyamide having a melting point of 160° C. or higher used for the heat-resistant layer (Z) are fed into the other two extruders. A method for producing a multilayer release film using a multilayer T-die, a multilayer annular die, etc. so that the layers are charged respectively to form a release layer (X)/intermediate layer (Y)/heat-resistant layer (Z). After molding the heat-resistant layer (Z) in the second layer, the intermediate layer (Y) of the two-layer film obtained by coextrusion of the release layer (X) and the intermediate layer (Y) is laminated on the heat-resistant layer (Z) to form a multilayer release. A method for producing a mold film, or after individually producing a film to be a release layer (X), a film to be an intermediate layer (Y), and a film to be a heat-resistant layer (Z), each film is coated on the surface A multi-layer release film consisting of release layer (X)/intermediate layer (Y)/heat-resistant layer (Z) may be formed by treatment or by using an adhesive.

<Application of multilayer release film>
The multilayer release film of the present invention can be used for various known applications, specifically, for example, release films for flexible printed circuit boards (FPC), release films for ACM substrates, release films for rigid substrates, and for rigid flexible substrates. Release film, release film for advanced composite materials, process release film for manufacturing fiber reinforced composite materials, release film for curing carbon fiber composite materials, release film for molding carbon fiber composite materials, release film for curing glass fiber composite materials Mold film, release film for molding glass fiber composites, release film for curing aramid fiber composites, release film for molding aramid fiber composites, release film for curing nanocomposite materials, release film for curing filler filler , release film for semiconductor encapsulation, release film for polarizing plate, release film for diffusion sheet, release film for prism sheet, release film for reflection sheet, cushion film for release film, release film for fuel cell , release film for various rubber sheets, release film for urethane curing, release film for epoxy curing, release film for silicon resin, mold release film for LED encapsulant, release film for acrylic adhesive, protection Release films for films, release films for synthetic leather, release liner for synthetic leather, release liner for advanced composite materials, release liner for curing carbon fiber composite materials, release liner for curing glass fiber composite materials , release liner for curing aramid fiber composite material, release liner for curing nanocomposite material, release liner for curing filler filler, and release liner for heat and water resistant photographic paper.

EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.
Various polymers used in Examples and Comparative Examples are shown below.
(1) 4-methyl-1-pentene/1-decene copolymer (A-1) shown in Table 1 as 4-methyl-1-pentene (co)polymer (A) and 4-methyl-1- A pentene/1-hexadecene/1-octadecene copolymer (A-2) was used.

(2) 4-methyl-1-pentene/propylene copolymer (B-1) and 4-methyl-1-pentene/propylene copolymer shown in Table 1 as 4-methyl-1-pentene copolymer (B) Polymer (B-2) was used.

(3) The following propylene-based polymer was used as the propylene-based polymer (C).
<Maleic anhydride-modified propylene homopolymer (C1-1)>
MFR = 100 g/10 min, Density = 0.90 g/cm ³ , Maleic anhydride modified amount =
The amount of grafted maleic anhydride was measured by the following method using FT-IR. The sample was hot-pressed at 250°C for ³ minutes to form a sheet. An infrared absorption spectrum was measured. The measurement conditions were a resolution of 2 cm −1 and an integration count of 32 times.
<Propylene homopolymer (C-2)
MFR = 7.0 g/10 min, Density = 910 kg/ ^m3
<Propylene random copolymer (C-3)
MFR = 7.0 g/10 min, density = 900 kg/m ³ , ethylene content = 4.0 wt%.

(4) Ethylene polymer (D)
<Ethylene/propylene copolymer (D-1)
MFR = 0.8 g/10 min, density = 870 kg/m ³ , melting point = 42°C.

(5) The following polyamides were used as the polyamide (E).
<Polyamide 6 (E-1)> Manufactured by Ube Industries, Ltd., trade name 1030B, density = 1140 kg/m ³ .
<Polyamide 66 (E-2)> Trade name Zytel 45HSB manufactured by Dupont, density = 1140 kg/m ³ .

(6) The following ionomer resin was used as the modified resin (F-1).
<Ionomer resin> Trade name Himilan 1706, manufactured by DuPont Mitsui Polychemicals, MFR = 5.0, density = 960 kg/m ³ , melting point = 88°C.
The physical properties of various polymers used in Examples and Comparative Examples were measured by the following methods.

(1) Comonomer content of 4-methyl-1-pentene copolymer (mol%)
At least one olefin-derived structural unit (comonomer ) content was calculated from the ¹³ C-NMR spectrum using the following apparatus and conditions.

Using a Bruker Biospin AVANCEIIIcryo-500 type nuclear magnetic resonance apparatus, the solvent is o-dichlorobenzene/benzene-d6 (4/1 v/v) mixed solvent, the sample concentration is 55 mg/0.6 mL, the measurement temperature is 120°C, observation nucleus is 13C (125MHz), sequence is single-pulse proton broadband decoupling, pulse width is 5.0μs (45° pulse), repetition time is 5.5s, number of integrations is 64, benzene-d6 of 128 ppm was measured as a reference value for chemical shift. Using the integrated value of the main chain methine signal, the comonomer content was calculated by the following formula.

Comonomer content (mol%) = [P/(P+M)] x 100
where P denotes the total peak area of the comonomer backbone methine signal and M denotes the total peak area of the 4-methyl-1-pentene backbone methine signal.

(2) The comonomer content of the propylene-based polymer and ethylene-based polymer was calculated from the ¹³ C-NMR spectrum using the same equipment and conditions as above.
(3) Melting point (Tm)
Using a DSC measuring device (DSC220C) manufactured by Seiko Instruments Inc., about 5 mg of a sample was packed in an aluminum pan for measurement and heated to 280°C at a rate of 10°C/min. After holding at 280° C. for 5 minutes, the temperature was lowered to 20° C. at 10° C./min. After holding at 20°C for 5 minutes, the temperature was raised to 280°C at 10°C/min. The melting point (Tm) was defined as the apex of the crystal melting peak observed during the second heating.

[Multilayer release film molding]
Using a three-layer T-die film molding machine manufactured by Thermo Plastics Co., Ltd. with a die width of 300 mm, which has two 25 mmφ single screw extruders and one 30 mmφ single screw extruder, the surface layer (X), the intermediate The composition or polymer is charged from the raw material supply hoppers connected to the layer (Y) and the heat-resistant layer (Z), and the resin pellets are melted through the cylinder in the single-screw extruder, and then the multilayer film is formed from the T-die. , release layer (Z): 20 μm, intermediate layer (Y): 10 μm, heat-resistant layer (Z): 40 μm, all layers: 70 μm.

By changing the adapter part of the above molding machine, a three-kind five-layer release film consisting of a release layer (X1), an intermediate layer (Y1), a heat-resistant layer (Z), an intermediate layer (Y2), and a release layer (X2) got Release layer (Z1) and release layer (Z2): 20 μm each, intermediate layer (Y1) and intermediate layer (Y2): 10 μm each, heat-resistant layer (Z): 40 μm, all layers: 100 μm multilayer release film Obtained.
The physical properties of the multilayer release film were measured by the following methods.

[Blocking factor]
Two films of 70 mm × 100 mm cut out from the multilayer release film were superimposed so that the respective chill roll surfaces were in contact with each other, sandwiched between two metal plates whose surfaces were mirror-finished, and heated at 170 ° C. and 5 MPa. After heating and pressurizing with a load for 30 minutes, the sample was cooled to room temperature to obtain a sample for measurement. A measurement sample is placed between two stacked films using an aluminum rod of 7 mm diameter using a universal tensile tester 3380 manufactured by Instron, and pulled at a speed of 200 mm / min while peeling off the film. Testing was performed to evaluate the blocking coefficient.

[Interlayer adhesive strength]
Cut the multilayer release film into a width of 15 mm and use a tensile tester (Model IM-20ST manufactured by Intesco Co., Ltd.) to measure the interlayer adhesion (peel strength) was measured at room temperature 23°C.
The crosshead speed was set at 200 mm/min.
The unit of interlayer adhesion is N/10 mm.

[Stretchability]
[Film stretchability]
The film obtained by the film forming method was cut into 60 mm × 60 mm, and was preheated at 170°C for 1 minute using a batch-type biaxial stretching machine manufactured by Imoto Seisakusho Co., Ltd., and then simultaneously stretched at a speed of 50 mm/min. It was biaxially stretched to obtain a biaxially stretched film. The draw ratio was 2.0×2.0 times (machine direction (MD): 2 times, vertical direction (Transverse Direction: TD): 2 times). From the state of the film after stretching, stretchability was evaluated as follows.
◯: Uniform stretching, no delamination.
Δ: Uniform stretching, partial delamination.
x: Uniform stretching, delamination.

[Example 1] to [Example 6]
Using each polymer described above and the blending amount of the polymer shown in Table 2 and the amount thereof, a multilayer release film is formed by the multilayer film molding method described above, and the multilayer release film is obtained. were evaluated by the methods described above. Table 2 shows the results.

[Comparative Example 1] to [Comparative Example 3]
Using each polymer described above and the blending amount of the polymer shown in Table 2 and the amount thereof, a multilayer release film is formed by the multilayer film molding method described above, and the multilayer release film is obtained. were evaluated by the methods described above. Table 2 shows the results.

As is clear from Table 2, the multilayer release films obtained in Examples are all superior in peel strength and stretchability to the multilayer release films obtained in Comparative Examples. The multi-layer release film is a multi-layer release film that does not break during stretching and has excellent interlaminar adhesive strength.

Claims (6)

A multilayer film having at least three layers in which a release layer (X), an intermediate layer (Y), and a heat-resistant layer (Z) are laminated in that order ,
The release layer (X) comprises 50 to 100 parts by mass of a 4-methyl-1-pentene (co)polymer (A) that satisfies the following requirements (a) to (d), and the following requirements (a1) to (e1): satisfying 4-methyl-1-pentene copolymer (B) 50 to 0 parts by mass (provided that the total of components (A) and (B) is 100 parts by mass), and 4-methyl-1 - consists of a pentene (co)polymer composition (L),
[4-methyl-1-pentene (co)polymer (A)]
(a) 100 to 90 mol% of structural units derived from 4-methyl-1-pentene, at least one selected from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene); Structural units derived from seeds are 0 to 10 mol% [however, the total amount of structural units derived from 4-methyl-1-pentene and structural units derived from ethylene and α-olefins having 3 to 20 carbon atoms is 100 mol %. ]
(b) the intrinsic viscosity [η] measured in decalin at 135°C is in the range of 0.5 to 5.0 dl/g;
(c) a melting point (Tm) measured by DSC in the range of 200-250° C.; and (d) a density in the range of 820-850 kg/m ³ .
[4-methyl-1-pentene copolymer (B)]
(a1) 97 to 60 mol % of structural units derived from 4-methyl-1-pentene, and 3 to 40 mol of structural units derived from at least one selected from ethylene and α-olefins having 3 to 4 carbon atoms; % [However, the total amount of structural units derived from 4-methyl-1-pentene and structural units derived from ethylene and an α-olefin having 3 to 4 carbon atoms is defined as 100 mol %. ]
(b1) Intrinsic viscosity [η] measured in decalin at 135°C in the range of 0.5 to 5.0 dl/g,
(c1) a melting point (Tm) measured by DSC of 199° C. or less, or substantially not observed;
(d1) the molecular weight distribution (Mw/Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC), is in the range of 1.0 to 3.5; and (e1) the density is in the range of 825-860 kg/m ³ .
Propylene in which the intermediate layer (Y) comprises 10 to 45 parts by mass of the 4-methyl-1-pentene copolymer (B) and a propylene-based polymer graft-modified with an unsaturated carboxylic acid and/or a derivative thereof. 45 to 75 parts by mass of the polymer (C) and 5 to 15 parts by mass of the ethylene polymer (D) [However, the total amount of components (B), (C) and (D) is 100 parts by mass. do. ] Consists of an olefin polymer composition (M) consisting of
A multilayer release film, wherein the heat-resistant layer (Z) is polyester or polyamide having a melting point of 160° C. or higher. 2. The multilayer release film according to claim 1, which has a thickness in the range of 10 to 500 μm and a film blocking coefficient in the range of 0.5 to 150 (mN/mm). The 4-methyl-1-pentene (co)polymer composition (L) forming the release layer (X) contains 60 to 95 parts by mass of the 4-methyl-1-pentene (co)polymer (A), and 4-methyl-1-pentene copolymer (B) 40 to 5 parts by mass [where the total of components (A) and (B) is 100 parts by mass. ]. The multilayer release film according to claim 1 or 2, characterized by comprising: The multilayer delamination according to any one of claims 1 to 3, wherein the propylene-based polymer (C) constituting the intermediate layer (Y) is a propylene-based polymer containing 85 to 100 mol% of units derived from propylene. mold film. A process release film for producing a fiber-reinforced composite material, comprising the multilayer release film according to any one of claims 1 to 4 . A mold release film for manufacturing a semiconductor, comprising the multilayer release film according to any one of claims 1 to 4 .