TWI791597B - Release film, press molding method using same, manufacturing method of semiconductor package, and laminated film - Google Patents

Abstract

An object of the present invention is to provide an inexpensive release film having good peelability from a transfer layer such as a sealing material even after heating and pressing, and a release film having improved solvent resistance.

In order to achieve the above objects, the present invention has the following constitutions. That is, a release film having a release layer on at least one side of a base film, wherein the release layer is a hardened layer of the composition (I) or the composition (II).

Composition (I): A thermosetting composition containing a compound (a) containing an alkyl group having 8 or more carbon atoms and a crosslinking agent (b)

Composition (II): an active energy ray-curable composition containing a compound (α) containing an alkyl group having 8 or more carbon atoms

Description

Release film, press molding method using same, manufacturing method of semiconductor package, and laminated film

The present invention relates to a release film. Specifically, it relates to a release film (release film) for compression molding; and is suitable for molding adhesive sheets, green sheets, photosensitive resin sheets (photoresist sheets), etc. Release film as carrier film or protective film.

The release film is generally used as a carrier film or a protective film when forming an adhesive sheet, a green sheet, a photosensitive resin sheet (photoresist sheet), etc.; Used for molded release film (release film).

For example, compression molding methods for semiconductor devices and light emitting devices are known (Patent Documents 1 to 3). Compression molding is a method in which a semiconductor element or a light emitting element and a sealing material are placed between an upper mold and a lower mold, and heated and pressurized, whereby the semiconductor element or light emitting element is covered with a sealing material and sealed. In the above patent document, it is described that a release film (release film) is disposed between the mold and the sealing material.

In addition, as a carrier film or a protective film when an adhesive sheet, a green sheet, a photosensitive resin sheet (photoresist sheet), etc. Silicone release film. For example, there is a proposal to use a release film of a polymer containing a long-chain alkyl group as a non-polysiloxane release film (Patent Document 4).

[Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2009-51107

[Patent Document 2] Japanese Unexamined Patent Publication No. 2016-201573

[Patent Document 3] Japanese Patent Laid-Open No. 2017-115056

[Patent Document 4] Japanese Unexamined Patent Publication No. 2003-300283

For example, in the above-mentioned press molding, a release film (release film) comprising a fluororesin film is well known. Fluorine resin films are generally expensive. Release films other than fluororesin films are also described in the above-mentioned patent documents 1 to 3, but the peelability of the release film and the sealing material after heating and pressing of the other release films described in the above-mentioned patent documents 1 to 3 is not good. full.

Also, coating compositions used to form transfer layers such as adhesive layers, ceramic layers, and photosensitive resin layers usually contain organic solvents, and good solvent resistance is required for release layers. However, the release layer system described in Patent Document 4 has insufficient solvent resistance. If the solvent resistance of the release layer is insufficient, a part of the release layer will dissolve due to the solvent contained in the coating composition of the transfer layer, etc., and the adhesion between the release layer and the transfer layer will increase, and the peeling will occur. sexual deterioration.

Therefore, the first object of the present invention is to provide an inexpensive release film having good peelability after heating and pressing of a sealing material. The second object of the present invention is to provide a release film with improved solvent resistance.

The above objects are achieved by the following inventions.

[1] A release film having a release layer on at least one side of a base film, wherein the release layer is a hardened layer of the composition (I) or the composition (II).

Composition (I): A thermosetting composition containing a compound (a) containing an alkyl group having 8 or more carbon atoms and a crosslinking agent (b)

Composition (II): an active energy ray-curable composition containing a compound (α) containing an alkyl group having 8 or more carbon atoms

[2] The release film according to [1], wherein the crosslinking agent (b) in the composition (I) is a melamine-based crosslinking agent.

[3] The release film according to [1], wherein the compound (a) containing an alkyl group having 8 or more carbon atoms in the composition (I) is a polyvinyl resin containing an alkyl group having 8 or more carbon atoms or contains An alkyd resin with an alkyl group of 8 or more carbon atoms.

[4] The release film according to [1], wherein the compound (α) containing an alkyl group having 8 or more carbon atoms in the composition (II) is a compound (α) containing an ethylenically unsaturated group and a carbon number of 8 or more in the molecule. Alkyl Polymerization Compound (α1) containing a long-chain alkyl group.

[5] The release film according to [1], wherein the composition (II) further contains a polymerizable compound (β) that contains an ethylenically unsaturated group in its molecule and does not contain an alkyl group having 8 or more carbon atoms.

[6] The release film according to any one of [1] to [5], wherein the surface free energy of the release layer is 20 to 35 mJ/m ² .

[7] The release film according to any one of [1] to [5], wherein the centerline average roughness Ra of the surface of the release layer is 100 nm or more.

[8] The release film according to any one of [1] to [5], wherein the base film has a three-layer laminate structure.

[9] The release film according to any one of [1] to [5], wherein the base film has a three-layer laminate structure including A layer/B layer/A layer.

[10] The release film according to any one of [1] to [5], wherein the centerline average roughness Ra of the surface of the laminated release layer of the base film is 100 nm or more.

[11] The release film according to any one of [1] to [5], wherein the centerline average roughness Ra of the release film on the surface opposite to the laminated release layer is 20 nm or more.

[12] The release film according to any one of [1] to [5], wherein the centerline average roughness Ra of both surfaces of the base film is 100 nm or more.

[13] The release film according to any one of [1] to [5], wherein the stresses of the base film at 150°C in the longitudinal direction (MD direction) and the width direction (TD direction) of 100% elongation are respectively Below 60MPa.

[14] The release film according to any one of [1] to [5], which has a haze value of 1.5 to 8.0%.

[15] A compression molding method, which is a compression molding method in which a release film, a sealing material, and a semiconductor element as described in any one of [1] to [14] are sequentially arranged in a mold and heated and pressurized , wherein the release film is arranged in such a way that the release layer of the release film faces the sealing material.

[16] A method of manufacturing a semiconductor package using the compression molding method described in [15].

[17] A laminated film, which is on the release layer of the release film as described in any one of [1] to [14], and laminated with a ceramic layer, an adhesive layer, and a photosensitive resin layer. Any transfer layer of the group.

[18] A laminated film, which is on a support film, and any transfer layer selected from the group consisting of a ceramic layer, an adhesive layer, and a photosensitive resin layer is laminated, and further a release layer is formed on the transfer layer. The layer and the transfer layer are laminated in such a way that the release film described in any one of [1] to [14] is laminated.

According to the present invention, it is possible to provide an inexpensive release film having good peelability after heating and pressing of a sealing material. Moreover, according to this invention, the release film which improved solvent resistance can be provided.

1‧‧‧Semiconductor components (chips)

2‧‧‧substrate

3‧‧‧Sealing material

4‧‧‧Release film

10‧‧‧Lower mold

20‧‧‧upper mold

FIG. 1 is a schematic cross-sectional view showing an example of stamper molding used in the manufacture of semiconductor packages.

[Mode of Implementing the Invention]

Hereinafter, the present invention will be described in detail together with the embodiments.

The release film of the present invention has a release layer on at least one side of the base film, and the release layer is a hardened layer of the composition (I) or the composition (II).

Composition (I): A thermosetting composition containing a compound (a) containing an alkyl group having 8 or more carbon atoms and a crosslinking agent (b).

Composition (II): An active energy ray-curable composition containing a compound (α) containing an alkyl group having 8 or more carbon atoms.

A release film in which the above-mentioned release layer is provided on a base film has good releasability of the sealing material after heating and pressing, and also improves the solvent resistance of the release layer. And, release film of the present invention, as base film, can use general plastic film, the plastic film such as polyester film or polyolefin film etc., therefore can be manufactured relatively cheaply. Therefore, the release film of the present invention can be supplied at a lower cost than conventional release films containing fluororesin films. Details about the base film will be described later.

Hereinafter, the composition (I) and the composition (II) will be described in detail.

[Composition (I)]

Composition (I) is a thermosetting composition containing a compound (a) containing an alkyl group having 8 or more carbon atoms and a crosslinking agent (b).

The alkyl group in the compound (a) containing an alkyl group having 8 or more carbon atoms includes a linear or branched alkyl group. The number of carbon atoms in the alkyl group of the compound (a) is preferably 10 or more, more preferably 12 or more, from the viewpoint of improving the releasability of the sealing material after heating and pressing and improving the solvent resistance of the release layer. , preferably more than 14. The carbon number of the above-mentioned alkyl group is preferably 30 or less, more preferably 28 or less, particularly preferably 25 or less.

In the following description, an alkyl group having 8 or more carbon atoms may be referred to as a "long-chain alkyl group". Also, a compound (a) containing an alkyl group having 8 or more carbon atoms may be referred to as a "long-chain alkyl group-containing compound (a)".

As the long-chain alkyl group-containing compound (a), a compound having a long-chain alkyl group in a side chain is preferably used. Specifically, long-chain alkyl-containing polyethylene resin (polyvinyl resin), long-chain alkyl-containing alkyd resin, long-chain alkyl-containing acrylic resin, long-chain alkyl-containing polyester resin, Long-chain alkyl-containing ether compounds, long-chain alkyl-containing amine compounds, and the like.

Among the above-mentioned compounds, polyethylene resins containing long-chain alkyl groups and long-chain alkyl groups are preferred from the viewpoint of improving the peelability of the sealing material after heating and pressing and improving the solvent resistance of the release layer. Alkyl alkyd resins, particularly preferably polyethylene resins containing long chain alkyl groups.

Polyethylene resins containing long-chain alkyl groups can be obtained by making polyvinyl alcohol polymers (including partially saponified products of polyvinyl acetate), ethylene-vinyl alcohol polymers (including partially saponified products of ethylene-vinyl acetate copolymers) Or a vinyl alcohol-acrylic acid copolymer (including a partially saponified product of a vinyl acetate-acrylic acid copolymer) is synthesized by reacting an isocyanate compound containing a long-chain alkyl group.

Examples of isocyanate compounds containing a long-chain alkyl group include monoisocyanate compounds having an alkyl group having 8 or more carbon atoms, specifically, octyl isocyanate, nonyl isocyanate, and decyl isocyanate. , dodecyl isocyanate, tetradecyl isocyanate, cetyl isocyanate, octadecyl isocyanate, etc.

Examples of the long-chain alkyl group-containing alkyd resin include those modified with a condensate of a polybasic acid and a polyhydric alcohol having a long-chain alkyl group with a modifier such as fatty oil or fatty acid. Examples of polybasic acids include saturated polybasic acids such as phthalic anhydride, terephthalic acid, succinic acid, adipic acid, and sebacic acid; or maleic acid, maleic anhydride, fumaric acid, and itaconic acid. , unsaturated polyacids such as citraconic anhydride; other polybasic acids such as cyclopentadiene-maleic anhydride adducts, terpene-maleic anhydride adducts, rosin-maleic anhydride adducts, etc. Examples of the polyhydric alcohol include dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, and tetramethylene glycol; glycerin, trimethylolpropane, and the like; Trihydric alcohols; diglycerin, triglycerol, neopentylitol, dipenteoerythritol, mannitol, sorbitol, etc., alcohols with four or more hydric alcohols. Examples of modifying agents include soybean oil, linseed oil, tung oil, castor oil, dehydrated castor oil, coconut oil, and their fatty acids, stearic acid, oleic acid, linolenic acid, sublinolenic acid, and jatrophic acid. , ricinoleic acid, dehydrated ricinoleic acid and other oils and fatty acids; natural resins such as rosin, copal, amber, shellac, etc.; synthetic resins such as ester glue, phenol resin, urea resin, and melamine resin. Also, from the viewpoint of the balance between coatability and peelability, stearic acid-modified alkyd resins and/or stearic acid-modified acrylic resins and cured resins of amino resins are also preferable.

As an acrylic resin containing a long-chain alkyl group, an acrylic monomer or a methacrylic monomer having a long-chain alkyl group, such as octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, Homopolymer or copolymer of stearyl acrylate, stearyl methacrylate, etc.

As another monomer used for the said copolymer, acrylic acid, methacrylic acid, acrylamide, methacrylamide, styrene, etc. are mentioned, for example.

The aforementioned long-chain alkyl group-containing compounds (a) are commercially available, and these can be used. Examples of commercially available products include "K-256", "N-137", "P-677", "Q-472" of the Resem series manufactured by Chukyo Oil & Fat Co., Ltd. "RA-80", "RA-95H", "RA-585S" of the ASHIO RESIN (registered trademark)" series, "HT", "1050" of the "Piroiru (registered trademark)" series manufactured by LION SPECIALTY CHEMICALS ", "1010", "1070", "406", "ZF-15", "ZF-15H" manufactured by JAPAN VAM & POVAL, "Epomin (registered trademark)" manufactured by Nippon Shokubai Co., Ltd. "RP-20 "wait.

唑啉系交聯劑、碳二亞胺(carbodiimide)系交聯劑、三聚氰胺系交聯劑等。於此等之中，特佳使用三聚氰胺系交聯劑。 Examples of the crosslinking agent (b) contained in the composition (I) include epoxy-based crosslinking agents, isocyanate-based crosslinking agents,

An oxazoline-based crosslinking agent, a carbodiimide-based crosslinking agent, a melamine-based crosslinking agent, and the like. Among them, it is particularly preferable to use a melamine-based crosslinking agent.

As an epoxy type crosslinking agent, ethylene glycol diglycidyl ether, glycerol polyglycidyl ether (glycerol polyglycidyl ether), polybutadiene diglycidyl ether, etc. are mentioned, for example.

As an isocyanate crosslinking agent, hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, methylene diphenyl diisocyanate etc. are mentioned, for example.

唑啉系交聯劑，例如可舉出2,2’-雙(2-

唑啉)、2,2’-伸乙基-雙(4,4’-二甲基-2-

唑啉)、2,2’-對伸苯基-雙(2-

唑啉)、雙(2-

唑啉基環己烷)硫醚等之具有

唑啉基的化合物、或含有

唑啉基的聚合物。 as

An oxazoline-based crosslinking agent, for example, 2,2'-bis(2-

oxazoline), 2,2'-ethylidene-bis(4,4'-dimethyl-2-

oxazoline), 2,2'-p-phenylene-bis(2-

oxazoline), bis(2-

Azolinyl cyclohexane) sulfide, etc. have

Azoline-based compounds, or containing

Azoline-based polymers.

Examples of the carbodiimide-based crosslinking agent include p-phenylene-bis(2,6-xylylcarbodiimide), tetramethylene-bis(tertiary butylcarbodiimide), Compounds having carbodiimide groups such as cyclohexane-1,4-bis(methylene-tert-butylcarbodiimide), or polycarbodiimides having polymers having carbodiimide groups .

環的3個碳原子而成之所謂對於三聚氰胺[1,3,5-三

-2,4,6-三胺]之胺基施有各種的改質之化合物的總稱，亦包含三

環複數縮合者。 作為改質之種類，較佳為3個胺基的氫原子之至少1個經羥甲基化之羥甲基化三聚氰胺化合物，更佳為將羥甲基化三聚氰胺化合物的羥甲基以碳數為1~4的低級醇而部分或完全醚化之烷基醚化三聚氰胺化合物。 The melamine compound used as a melamine-based cross-linking agent is for the amine group to be bonded to three

The so-called melamine [1,3,5-tri

-2,4,6-Triamine] is a general term for compounds with various modifications applied to the amine group, including three

Cyclic plural condensors. As the type of modification, it is preferably a methylolated melamine compound with at least one of the hydrogen atoms of the 3 amine groups methylolated, and more preferably a methylolated melamine compound with the number of carbons in the methylolated melamine compound Alkyl-etherified melamine compounds partially or completely etherified for 1-4 lower alcohols.

Examples of the alcohol used for etherification include methanol, ethanol, propanol, and butanol.

A commercial item can be used for a melamine crosslinking agent. Examples of commercially available products include "Super Beckamine (registered trademark)" manufactured by DIC Co., Ltd. J-820-60, J-821-60, J-1090-65, J-110-60, Same as J-117-60, same as J-127-60, same as J-166-60B, same as J-105-60, same as G840, same as G821, "U-VAN (registered trademark)" manufactured by Mitsui Chemicals Co., Ltd. 20SB, same 20SE60, same 21R, same 22R, same 122, same 125, same 128, same 220, same 225, same 228, same 28-60, same 2020, same 60R, same 62, same 62E, same 360, same 165, same 166-60, same 169, same 2061, "Sumimal (registered trademark)" manufactured by Sumitomo Chemical Co., Ltd. M-100, same M-40S, same M-55, same M-66B, manufactured by Cytec Industries Japan "Cymel (registered trademark)" 303, Tong 325, Tong 327, Tong 350, Tong 370, Tong 235, Tong 202, Tong 238, Tong 254, Tong 272, Tong 1130, "Nikalac ( registered trademark)" MS17, same MX15, same MX430, same MX600, Bancemine SM-975 manufactured by HARIMA CHEMICALS Co., Ltd., same SM-960, "Melan (registered trademark)" manufactured by Hitachi Chemical Co., Ltd. 265, same 2650L wait.

Composition (I) preferably contains an acid catalyst (c) in order to accelerate curing. Examples of the acid catalyst (c) include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, p-toluenesulfonic acid, and the like. Among them, p-toluenesulfonic acid is preferably used.

The content of the long-chain alkyl group-containing compound (a) in the composition (I) is relative to The total solid content of the composition is 100% by mass, preferably at least 30% by mass, more preferably at least 50% by mass, and most preferably at least 70% by mass. On the other hand, if the content of the long-chain alkyl group-containing compound (a) becomes too much, the strength (hardness) of the release layer may decrease, and solvent resistance and heat resistance may decrease. The content of the compound (a) is preferably at most 98% by mass, more preferably at most 95% by mass, particularly preferably at most 90% by mass.

The content of the crosslinking agent (b) in the composition (I) is relative to the solid content of the composition from the viewpoint of improving the peelability of the sealing material after heating and pressing and improving the solvent resistance of the release layer. The total amount of components is 100% by mass, preferably at least 3% by mass, more preferably at least 5% by mass, and most preferably at least 10% by mass. On the other hand, if the content of the crosslinking agent (b) becomes too high, the release force on the surface of the release layer may increase, so the content of the crosslinking agent (b) is preferably 95% by mass or less, more preferably It is 90 mass % or less, especially preferably 80 mass % or less.

In particular, from the viewpoint of further improving the solvent resistance of the release layer, the content of the crosslinking agent (b) is preferably at least 1.0 times that of the long-chain alkyl group-containing compound (a), more preferably at least 2.0 times , the best is more than 3.0 times. The upper limit is about 20.0 times.

The content of the acid catalyst (c) in the composition (I) is relative to the solid content of the composition from the viewpoint of improving the peelability of the sealing material after heating and pressing and improving the solvent resistance of the release layer. The total amount of components is 100% by mass, preferably in the range of 0.1 to 10% by mass, more preferably in the range of 0.3 to 5% by mass, and most preferably in the range of 0.5 to 3% by mass.

The release layer comprising the cured layer of the composition (I) is formed by heating and curing the composition (I) coated on the base film. The conditions (heating temperature and time) for curing the composition (I) are not particularly limited, but the heating temperature is preferably 70°C or higher, more preferably 100°C or higher, and particularly preferably 150°C or higher. The upper limit is about 300°C. The heating time is preferably from 3 to 300 seconds, more preferably from 5 to 200 seconds.

Composition (I) can be applied by a wet coating method. Examples of wet coating methods include reverse coating, spray coating, bar coating, gravure coating, rod coating, die coating, and spin coating. Coating method, extrusion coating method, curtain coating method, etc.

[Composition (II)]

Composition (II) is an active energy ray-curable composition containing a compound (α) containing an alkyl group having 8 or more carbon atoms. Hereinafter, a compound (α) containing an alkyl group having 8 or more carbon atoms may be referred to as a “long-chain alkyl group-containing compound (α)”.

The alkyl group in the long-chain alkyl group-containing compound (α) includes linear or branched alkyl groups. The carbon number of the alkyl group of the compound (α) is preferably 10 or more, more preferably 12 or more, and especially Preferably 14 or more. The carbon number of the above-mentioned alkyl group is preferably 30 or less, more preferably 28 or less, particularly preferably 25 or less.

The composition (II) contains a compound (hereinafter, polymerizable compound) that is polymerized and hardened by active energy rays. Such a polymerizable compound includes a compound (monomer or oligomer) having at least one ethylenically unsaturated group in the molecule. Here, examples of the ethylenically unsaturated group include an acryl group, a methacryl group, an acryloxy group, a methacryloxy group, an allyl group, and a vinyl group.

The long-chain alkyl group-containing compound (α) may or may not be a polymerizable compound. That is, examples of the long-chain alkyl group-containing compound (α) include a polymerizable long-chain alkyl group-containing compound (α1) and a non-polymerizable long-chain alkyl group-containing compound (α2).

The polymerizable long-chain alkyl group-containing compound (α1) is a compound containing an ethylenically unsaturated group and an alkyl group having 8 or more carbon atoms in the molecule.

Examples of the non-polymerizable long-chain alkyl group-containing compound (α2) include the same compounds as the long-chain alkyl group-containing compound (a) contained in the aforementioned composition (I).

When the composition (II) contains only a non-polymerizable long-chain alkyl group-containing compound as the long-chain alkyl group-containing compound (α), it must contain no long-chain alkyl group (alkyl group having 8 or more carbon atoms) in the molecule. (hereinafter sometimes referred to as "polymerizable compound (β)"). Details of the polymerizable compound (β) will be described later.

In the composition (II), a polymerizable long-chain alkyl group-containing compound (α1) and a non-polymerizable long-chain alkyl group-containing compound (α2) may be used in combination, or a polymerizable long-chain alkyl group-containing compound ( α1) and a polymerizable compound (β), or a polymerizable long-chain alkyl group-containing compound (α1) and a non-polymerizable long-chain alkyl group-containing compound (α2) and a polymerizable compound (β) may be used in combination.

The composition (II) preferably contains a polymerizable long-chain alkyl group-containing compound (α1), and it is also preferable to use a polymerizable long-chain alkyl group-containing compound (α1) and a polymerizable compound (β) in combination. When the release layer is a cured layer of such an active energy ray curable composition, the peelability after heating and pressing of the sealing material is further improved, and the solvent resistance of the release layer is improved.

Specific examples of the polymerizable long-chain alkyl group-containing compound (α1) are shown below. In addition, in the following description, "‧‧‧(meth)acrylate" is a general term for "‧‧‧acrylate" and "‧‧‧methacrylate".

Examples of the polymerizable long-chain alkyl group-containing compound (α1) include octyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, pentadecyl (meth)acrylate, Cetyl (meth)acrylate, stearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, etc.

In particular, polymerizable long-chain alkyl group-containing compounds (α1) shown below are preferably used. Examples of such compounds include (meth)acrylate compounds each having one or more (meth)acryl groups and hydroxyl groups in the molecule, and polyisocyanates having two or more isocyanate groups in the molecule. A compound obtained by reacting a compound with a higher alcohol with a carbon number of 8 to 30.

Examples of the (meth)acrylate compounds include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth)acrylate ) 4-hydroxybutyl acrylate, glycerol mono(meth)acrylate, glycerol di(meth)acrylate, 2-hydroxy-3-acryloxypropyl methacrylate, 2-(methyl)phthalate base) acryloxyethyl-2-hydroxyethyl ester, 2-methacryloxyethyl-2-hydroxypropyl phthalate, 2-(meth)acryloxyethyl phosphate , Epoxy (meth)acrylate, neopentylthritol monoacrylate, neopentylthritol diacrylate, neopentylthritol triacrylate, diperythritol monoacrylate, diperythritol diacrylate ester, diperythritol triacrylate, diperythritol tetraacrylate, diperythritol pentaacrylate, with 2 to 30 alkoxyl groups in the molecule (for example, ethoxyl, alkene Propoxy, butoxy, etc.) (meth)acrylate, etc.

Among the above-mentioned compounds, it is preferable to use 2-hydroxyethyl (meth)acrylate, (meth) ) 2-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and (meth)acrylates with 2 to 30 alkoxyl groups in the molecule.

Examples of the polyisocyanate compound include hexamethylene diisocyanate, lysine diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate, tolidine diisocyanate, toluene diisocyanate, hydrogenated toluene diisocyanate, and Diisocyanate compounds such as isocyanate, hydrogenated diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, Further examples include biuret-type polyisocyanate compounds obtained by reacting these various diisocyanate compounds with water, and adduct-type polyisocyanate compounds obtained by reacting various diisocyanate compounds with polyols such as trimethylolpropane. Isocyanate compounds, polymers obtained by subjecting various compounds to isocyanurate, and the like are well known.

Among the above-mentioned polyisocyanate compounds, compounds with a molecular weight of 50-500 are preferred, compounds with a molecular weight of 100-400 are more preferred, and compounds with a molecular weight of 130-300 are particularly preferred. For example, hexamethylene diisocyanate (molecular weight: 168) and diphenylmethane diisocyanate (molecular weight: 250) can be illustrated as preferable compounds. In particular, diphenylmethane diisocyanate (molecular weight: 250) is preferable from the viewpoint of improving the peelability after heating and pressing of the sealing material and improving the solvent resistance of the release layer.

Examples of higher alcohols include octanol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, cetearyl alcohol, stearyl alcohol, behenyl alcohol, and behenyl alcohol. alcohol) etc., oleyl alcohol etc. can be enumerated for linear unsaturated higher alcohols, 2-hexyldecyl alcohol, 2-octyldodecanol, 2-octyl dodecyl alcohol can be enumerated for branched higher alcohols. -decyltetradecanol and the like.

As a higher alcohol, a commercial item can be used. For example, examples of linear saturated higher alcohols include "Conol (registered trademark)" 10WS, Conol 1098, Conol 1275, Conol 20F, Conol 20P, Conol 1495, Conol 1670, Conol 1695, Conol 30CK, Conol 30OC, Conol 30RC, Conol 30F, Conol 30S, Conol 30SS, Conol 30T, Conol 2265, Conol 2280 (trade name manufactured by Shin Nippon Chemical Co., Ltd.), "KALCOL (registered trademark)" 0898, KALCOL 0880, KALCOL 1098, KALCOL 2098, KALCOL 4098, KALCOL 6098, KALCOL 8098, KALCOL 200GD, KALCOL 2475, KALCOL 2474, KALCOL 2473, KALCOL 2463, KALCOL 2455, KALCOL 2450, KALCOL 4250, K ALCOL 6870, KALCOL 6850, KALCOL 8688, KALCOL 8665, KALCOL 220 -80 (trade name manufactured by Kao Co., Ltd.), "Rikacol (registered trademark)" 60B, Rikacol 70B, Rikacol 75BJ, Rikacol 85BJ, Rikacol 90B, Rikacol 90BR, Rikacol 90BHR, Rikacol 110BJ, "Unjecol (registered trademark)" 50A, Unjecol 60AN, Unjecol 70AN, Unjecol 80AN, Unjecol 85AN, Unjecol 90AN, Unjecol 90NR, Unjecol 90NHR (manufactured by Shin Nippon Chemical Co., Ltd. product name), Examples of branched higher alcohols include "Njcol (registered trademark)" 160BR, Njcol 200A, and Njcol 240A (trade names manufactured by Shin Nippon Chemical Co., Ltd.).

The composition (II) more preferably contains a polymerizable compound (β). The polymerizable compound (β) is a compound containing an ethylenically unsaturated group in a molecule and not containing an alkyl group having 8 or more carbon atoms.

Examples of the polymerizable compound (β) include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl di(meth)acrylate, Alcohol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethyl Glycol di(meth)acrylate, Dipropylene glycol di(meth)acrylate, Polyethylene glycol di(meth)acrylate, Polypropylene glycol di(meth)acrylate, Trimethylolpropane tri(meth)acrylate base) acrylate, di-trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, glycerol propoxy tri(meth)acrylate, neopentyl tetra Alcohol Mono(meth)acrylate, Neopentylthritol Di(meth)acrylate, Neopentylthritol Tri(meth)acrylate, Neopentylthritol Tetra(meth)acrylate, Dineopentylthritol Mono(meth)acrylate, diperythritol di(meth)acrylate, diperythritol tri(meth)acrylate, diperythritol tetra(meth)acrylate, dipenteopentyl Tetrol penta(meth)acrylate, dipenteopentylthritol hexa(meth)acrylate, trineopentylthritol tri(meth)acrylate, trineopentylthritol hexa(meth)acrylate, new Pentaerythritol tri(meth)acrylate hexamethylene diisocyanate urethane pre-oligomer, Neopentylthritol tri(meth)acrylate-toluene diisocyanate urethane oligomer, Neopentylthritol tri(meth)acrylate-isophorone diisocyanate urethane oligomer, etc.

Among the above compounds, compounds having 2 to 10 ethylenically unsaturated groups in the molecule are preferred, and compounds having 3 to 8 ethylenically unsaturated groups in the molecule are particularly preferred.

、2-氯氧硫

、2-甲基氧硫

等之硫化合物等。此等光聚合起始劑可單獨使用，也可2種以上組合使用。 The composition (II) preferably further contains a photopolymerization initiator. As specific examples of such a photopolymerization initiator, for example, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, diphenyl Base ketone, 2-chlorodiphenyl ketone, 4,4'-dichlorodiphenyl ketone, 4,4'-bisdiethylamino diphenyl ketone, Micheler's ketone, diphenyl ketone, Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, methyl benzoylformate, p-isopropyl-α-hydroxyisobutyl benzophenone (p-isopropyl Carbonyl compounds such as -α-hydroxyisobutylphenone), α-hydroxyisobutylphenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, etc., tetramethylkiura Monosulfide (tetramethylthiuram monosulfide), tetramethylthiuram disulfide, oxygen sulfur

, 2-sulfur oxychloride

, 2-Methylsulfur

and other sulfur compounds. These photopolymerization initiators may be used alone or in combination of two or more.

In addition, photopolymerization initiators are generally commercially available, and those can be used. For example, "Irgacure (registered trademark)" 184, Irgacure 907, Irgacure 379, Irgacure 819, Irgacure 127, Irgacure 500, Irgacure 754, Irgacure 250, Irgacure 1800, and Irgacure manufactured by Ciba Specialty Chemicals Co., Ltd. ure 1870, Irgacure OXE01, "DAROCUR (registered trademark)" TPO, DAROCUR 1173, etc., "Speedcure (registered trademark)" MBB manufactured by Nihon Siber Hegner Co., Ltd., Speedcure PBZ, Speedcure ITX, Speedcure CTX, Speedcure EDB, "Esacure (registered trademark) "ONE, Esacure KIP150, Esacure KTO46, etc., "KAYACURE (registered trademark)" DETX-S, KAYACURE CTX, KAYACURE BMS, KAYACURE DMBI manufactured by Nippon Kayaku Co., Ltd.

The content of the long-chain alkyl group-containing compound (α) in the composition (II) is relative to the composition from the viewpoint of improving the peelability of the sealing material after heating and pressing and improving the solvent resistance of the release layer. The total solid content of the product is 100% by mass, preferably at least 1% by mass, more preferably at least 5% by mass, and most preferably at least 7% by mass. On the other hand, if the content of the long-chain alkyl group-containing compound (α) becomes too much, the strength (hardness) of the release layer may decrease, and solvent resistance and heat resistance may decrease. The content of the compound (α) is preferably at most 70% by mass, more preferably at most 50% by mass, particularly preferably at most 30% by mass.

The content of the polymerizable compound (β) in the composition (II) increases the strength (hardness) of the release layer, improves the peelability of the sealing material after heating and pressing, and improves the solvent resistance of the release layer. In view of 100% by mass of the total solid content of the composition, it is preferably at least 10% by mass, more preferably at least 20% by mass, and most preferably at least 30% by mass. On the other hand, if the content of the polymerizable compound (β) becomes too high, the release force on the surface of the release layer may increase, so the content of the polymerizable compound (β) is preferably 90% by mass or less, more preferably It is 80 mass % or less, especially preferably 70 mass % or less.

The content of the photopolymerization initiator in the composition (II) is suitably in the range of 0.1 to 10 mass %, preferably 0.5 to 8 mass %, based on 100 mass % of the total solid content of the composition.

The release layer including the cured layer of the composition (II) is preferably formed by irradiating the composition (II) coated on the base film with active energy rays and curing it. That is, the composition (II) is preferably an active energy ray curable composition. Examples of active energy rays include ultraviolet rays, visible rays, infrared rays, electron beams, α rays, β rays, and γ rays. Among these active energy rays, ultraviolet rays and electron beams are preferable, and it is particularly preferable to use ultraviolet rays.

The light source for irradiating ultraviolet rays is not particularly limited, but for example, ultraviolet fluorescent lamps, low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, etc. can be used. Also, an ArF excimer laser, a KrF excimer laser, an excimer lamp, or synchrotron radiation may be used. Among them, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a xenon lamp, and a metal halide lamp can be preferably used. In addition, when irradiating ultraviolet rays, it is preferable to irradiate in an atmosphere with a low oxygen concentration, for example, an atmosphere with an oxygen concentration of 500 ppm or less, because it can be cured efficiently.

The amount of ultraviolet light irradiated is preferably at least 50 mJ/cm ² , more preferably at least 100 mJ/cm ² , and most preferably at least 150 mJ/cm ² . In addition, the irradiation light quantity of ultraviolet rays is preferably 2000 mJ/cm ² or less, more preferably 1000 mJ/cm ² or less.

Composition (II) can be applied by a wet coating method. Examples of wet coating methods include reverse coating, spray coating, bar coating, gravure coating, bar coating, die coating, spin coating, extrusion coating, and curtain coating.

[Common Components of Composition (I) and Composition (II)]

Hereinafter, composition (I) and composition (II) may be collectively referred to as "composition".

The composition may contain particles. By containing particles in the composition, the surface roughness of the release layer can be made relatively large. For example, in order to adjust the centerline average roughness Ra of the release layer to 100 nm or more, it is preferable to contain particles with an average particle diameter of 0.1 to 30 μm in the composition. The details of the centerline average roughness Ra of the release layer will be described later.

The average particle size of the particles contained in the composition is further preferably 0.3 to 20 μm, more preferably 0.5 to 10 μm, particularly preferably 1 to 5 μm.

From the point of view of adjusting the centerline average roughness Ra of the release layer to 100nm or more, the average particle size of the particles is preferably at least 1.1 times the thickness of the release layer, more preferably at least 1.5 times, and most preferably at least 2.0 more than double. Moreover, the above-mentioned ratio is preferably at most 10.0 times, more preferably at most 7.0 times, and most preferably at most 5.0 times.

The content of particles in the composition is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, and most preferably 3 to 30% by mass relative to 100% by mass of the total solid content of the composition.

As the particles, organic particles, inorganic particles, and organic-inorganic composite particles can be used. Examples of organic particles include acrylic resin particles, polystyrene resin particles, melamine resin particles, polyester resin particles, polyurethane resin particles, polyolefin resin particles, polycarbonate resin particles, and polyamide resin particles. particles, fluororesin particles, etc. Examples of the inorganic particles include silica, titanium oxide, aluminum oxide, zirconium oxide, calcium carbonate, zeolite and the like. Examples of organic-inorganic composite particles include acrylic-silica composite particles, melamine-silica composite particles, and the like.

Among the above-mentioned particles, melamine resin particles and melamine-silica composite particles, which have relatively good dispersion stability in compositions containing long-chain alkyl-containing compounds, are preferred.

Also, when the release film is used in the heating and pressing step of the sealing material, it is preferable to use particles with relatively high hardness. From this point of view, melamine resin particles or melamine‧silica composite particles are also preferable because of their relatively high hardness. Particularly preferred are melamine‧silica composite particles. Here, the hardness of the particles can be represented by 10% compressive strength. The 10% compressive strength can be measured using a micro compression tester (for example, "MCTM2000" manufactured by Shimadzu Corporation).

The 10% compressive strength of the particles is preferably at least 30 MPa, more preferably at least 40 MPa, and most preferably at least 50 MPa. The upper limit is about 150MPa.

The composition system may contain binder resin, antistatic agent, colorant, etc. Examples of the binder resin include polyurethane resins, acrylic resins, polyester resins, and the like. Here, the binder resin is a compound that does not contain a long-chain alkyl group.

The composition is preferably free of polysiloxane compounds. If the release layer contains a silicone compound, it may cause failure of precision electronic devices, and if the transfer layer is a silicone adhesive layer, the peeling force may become high, which may cause peeling failure. Therefore, when the composition contains the polysiloxane compound, it is preferably not more than 10 mass %, more preferably not more than 5 mass %, particularly preferably not more than 1 mass %, based on 100 mass % of the total solid content of the composition.

Here, the silicone compound refers to a silicone compound generally known as a silicone release agent. The so-called polysiloxane is a polymer comprising a main chain in which silicon and oxygen are alternately bonded with organic groups (such as alkyl groups or phenyl groups). For example, polysiloxane-based compounds having dimethylpolysiloxane as a basic skeleton are well known.

Also, the composition may contain a fluorine-based release agent, but from the viewpoint of cost reduction, the content of the fluorine-based release agent is preferably 10% by mass or less with respect to 100% by mass of the total solid content of the composition, and more preferably Preferably, it is 5 mass % or less, and especially preferably, it is 1 mass % or less. Here, the so-called fluorine-based release agent means a compound containing a fluorine atom.

[release layer]

The thickness of the release layer is preferably 10-3,000 nm, more preferably 20-2,000 nm, further preferably 30-1,000 nm, and particularly preferably 50-500 nm.

From the viewpoint of improving the releasability of the sealing material after heating and pressing, the viewpoint of improving the applicability of the transfer layer such as the adhesive layer, the ceramic layer, and the photosensitive resin layer, and the viewpoint of improving the releasability of the transfer layer, The surface free energy of the release layer is preferably 20~35mJ/m ² , more preferably 21~32mJ/m ² , particularly preferably 22~30mJ/m ² .

By forming a release layer with the above-mentioned composition (I) or composition (II), the surface free energy of a release layer can be made into the said range.

Here, the surface rough free energy can be measured using a contact angle meter, for example, "Drop Master DM501" manufactured by Kyowa Interface Science Co., Ltd. Details will be described later.

The surface roughness of the release layer is adjusted according to the application. For example, when the release film of the present invention is used as a supporting film or protective film for coating and forming a ceramic layer or a photosensitive resin layer, the surface of the release layer is preferably smoother, and the centerline average roughness Ra of the release layer is Be a smaller way of designing. Specifically, the centerline average roughness Ra of the release layer is preferably not more than 50 nm, more preferably not more than 30 nm, and most preferably not more than 15 nm. From the viewpoint of ensuring the slipperiness and take-up of the release film, the centerline average roughness Ra is preferably at least 1 nm, more preferably at least 3 nm, and particularly preferably at least 5 nm.

The release film whose centerline average roughness Ra of the release layer is 50 nm or less can be obtained, for example, by using a base film with a centerline average roughness Ra of 50 nm or less on the surface of the laminated release layer of the base film.

On the other hand, when forming the fine uneven structure on the surface of the transfer layer, such as a sealing material, it is designed so that the surface roughness of the release layer may become comparatively large. Specifically, the centerline average roughness Ra of the release layer is preferably at least 100 nm, more preferably at least 200 nm, and most preferably at least 300 nm. The upper limit is about 3,000nm.

As a method of adjusting the centerline average roughness Ra of the release layer to 100nm or more, the method of including particles in the release layer as described above, or using the centerline of the surface of the laminated release layer of the base film A method for a base film having an average roughness Ra of 100 nm or more, and a method for combining them.

The base film (polyester film) whose center line average roughness Ra is 100 nm or more is mentioned later in detail.

Here, the centerline average roughness Ra is the surface roughness specified in JIS B0601 (1982).

[Substrate film]

Various resin films can be used as the base film used for the release film of the present invention, but resin films other than fluororesin films are preferred from the viewpoint of cost. Examples of such resin films include polyester films such as polyethylene terephthalate films, polybutylene terephthalate films, and polyethylene naphthalate films, polypropylene films, polyethylene films, etc. Polyolefin films such as films, cellulose films such as diacetyl cellulose films and triacetyl cellulose films, polyethene films, polyether ether ketone films, polyether sulfide films, polyphenylene sulfide films, Polyetherimide film, polyimide film, polyamide film, acrylic film, cyclic olefin film, polycarbonate film, etc.

Among these resin films, polyimide films, polyester films, and cyclic olefin films having good heat resistance are preferable. From the viewpoint of cost reduction, a polyester film is preferable. In addition, from the viewpoint of suppressing the gas generated by the sealing material from penetrating the release film during heating and pressurization in compression molding, and suppressing mold contamination caused by gas penetrating, biaxially oriented polyester is preferred. The film, particularly preferably a biaxially oriented polyethylene terephthalate film.

In the past, the fluororesin film generally used in compression molding has the problem that the gas generated by the sealing material is easy to penetrate. However, by using a biaxially oriented polyester film, biaxially oriented polyethylene terephthalic acid is preferred. Ethylene glycol film, while suppressing the above problems.

Also, in compression molding, it is preferable that the release film can easily follow the concave portion of the mold. From this point of view, the base film is preferably one with a relatively high elongation. Specifically, the stress at 100% elongation in the longitudinal direction (MD direction) and width direction (TD direction) of the substrate film at 150°C is preferably 60 MPa or less, more preferably 50 MPa or less, and still more preferably 40 Ma or less. , especially preferably below 30MPa. If the above-mentioned stress at 100% elongation becomes too small, there is a possibility of fracture during elongation, so it is preferably at least 5 MPa, more preferably at least 10 MPa.

As the above-mentioned high-stretch base film, a biaxially oriented polyester film is preferable. High-stretch biaxially oriented polyester film (biaxially oriented polyester film for molding) can be referred to, for example, Japanese Patent Laid-Open No. 2016-190438, No. 2016-159537, No. 2015-10121, and No. 2012-126821. No. 2011-073151, No. 2011-057850, No. 2010-189593, WO2013/099608, No. 2012/005097, etc.

In addition, as the high-stretch biaxially oriented polyester film, "Softshine (registered trademark)" manufactured by Toyobo Co., Ltd. and "Teflex (registered trademark)" manufactured by Teijin DuPont Films Co., Ltd. can be used, for example.

The biaxially oriented polyester film is preferably composed of three laminated layers. As a three-layer laminate structure, A layer/B layer/A layer or A layer/B layer/C layer are mentioned. Here, A layer, B layer, and C layer mean that each composition is different. Among the above-mentioned three-layer laminated structures, the three-layer laminated structure of A layer/B layer/A layer is preferable from the viewpoint of simplification of production equipment and improvement of productivity.

As mentioned above, when forming a fine concave-convex structure on the surface of a transfer layer such as a sealing material, it is preferable to use a base film having a center line average roughness Ra of 100 nm or more. Examples of such a base film include a method of adding particles to the base film, a method of blasting the surface of the base film, and a method of embossing the surface of the base film. Among them, the method of including particles in the base film is preferable.

A base film (polyester film) having a center line average roughness Ra of 100 nm or more can be produced, for example, by including particles in layer A in the above three-layer structure. Specifically, by adjusting the average particle diameter and/or content of the particles contained in the A layer, the centerline average roughness Ra of the polyester film can be controlled.

Examples of particles that may be contained in the layer A include inorganic particles and organic particles. Examples of inorganic particles include silica, aluminum silicate, calcium carbonate, calcium phosphate, alumina and the like. Examples of organic particles include acrylic resin particles, polystyrene resin particles, silicone resin particles, polyester resin particles, melamine resin particles, and the like. These particles may be used alone or in combination of two or more.

The average particle size of the particles is preferably 1-10 μm, more preferably 2-8 μm, particularly preferably 3-7 μm.

The content of the particles in the layer A is preferably 1-10% by mass, more preferably 2-8% by mass, particularly preferably 3-7% by mass, based on 100% by mass of the total solid content of the layer A.

From the point of view of easily forming a fine concave-convex structure with a centerline average roughness Ra of 100 nm on the surface of the A layer, the thickness of the A layer is preferably 1 to 10 μm, more preferably 2 to 8 μm, and most preferably 3 μm. ~7 μm.

The thickness of the C layer is preferably 1-10 μm, more preferably 2-8 μm, particularly preferably 3-7 μm. The thickness of the B layer is appropriately set in response to the total thickness of the polyester film.

When the release film of the present invention is applied to compression molding, it is preferably a relatively thin film from the viewpoint of making it easy to follow the concave portion of the mold. Specifically, the thickness of the base film is preferably at most 150 μm, more preferably at most 100 μm, particularly preferably at most 75 μm. The aforementioned thickness is preferably at least 10 μm, more preferably at least 15 μm, and particularly preferably at least 20 μm.

Also, as described later, when using a release film as a support film (carrier film) or protective film for forming a ceramic layer, an adhesive layer, and a photosensitive resin layer (photoresist layer), sometimes the haze of the release film Adjust the value to 1.5~8.0%. At this time, it is preferable to adjust the haze value of the release film by controlling the haze value of the base film.

The haze value of the base film is preferably obtained by making layer A or layer C contain 0.001 to 5.0 mass % of particles with an average particle diameter of 0.1 to 1.5 μm are controlled relative to 100 mass % of the total solid content of layer A or layer C. Also, when used for the above purposes, the thickness of the substrate film is preferably less than 50 μm, more preferably less than 37 μm, and particularly preferably less than 30 μm. The thickness of the base film is preferably at least 5 μm, more preferably at least 10 μm, particularly preferably at least 12 μm.

The substrate film may be provided with a primer layer on one or both surfaces, and the primer layer is used to suppress the precipitation of oligomer components from the substrate film. Examples of the primer layer include organosilicon compounds containing organoaluminum compounds, polyvinyl alcohol, and the like.

Examples of organosilicon compounds containing organoaluminum compounds include organoalkoxysilanes containing γ-methacryloxy groups, organoalkoxysilanes containing epoxy groups, organoalkoxysilanes containing vinyl groups, Vinyl-containing acetoxysilanes and mixtures thereof, etc.

In addition, as the primer layer, a cured resin layer having a pencil hardness (pencil hardness specified in JIS K5600-5-4 (1999)) of F to 2H can be used. As this cured resin layer, conventionally well-known hard-coat components can be adjusted suitably and used.

The thickness of the primer layer is preferably 0.05-2.0 μm, more preferably 0.1-1.0 μm, particularly preferably 0.2-0.5 μm.

[Release film]

In the release film of the present invention, the release layer can be provided on one side or both sides of the base film. When the release layer is provided on only one side of the base film, it is necessary to provide the release layer composed of the aforementioned composition (I) or (II). When the release layer is arranged on both sides of the substrate film, the release layer on one side must be provided with a release layer composed of the aforementioned composition (I) or (II), but the release layer on the other side can be composed of the aforementioned composition The release layer formed by (I) or (II) can also be another different release layer.

Moreover, as for the release film, as mentioned above, a primer layer for suppressing the precipitation of oligomers may be provided on one or both surfaces of the base film. When the primer layer is provided on the release layer side, it is provided between the base film and the release layer.

[Application example of release film]

The release film of the present invention is suitable as an engineering film. For example, it can be used as a support film (carrier film) or a protective film for forming a ceramic layer, an adhesive layer, or a photosensitive resin layer (photoresist layer), or as a release film in a heating and pressing step.

As the heating and pressing step, for example, the heating and pressing step of semiconductor elements or light-emitting elements and sealing materials by compression molding, and flexible copper-clad laminates ( FCCL) and the heating and pressing steps of the cover layer.

[Example 1 of suitable application of release film]

The release film of the present invention is suitable as a release film in the heating and pressing step. In particular, it is suitable as a release film in the heating and pressing step of semiconductor elements or light-emitting elements and sealing materials by compression molding.

[press molding method]

Hereinafter, an example of a method of manufacturing a semiconductor package by a compression molding method will be described using FIG. 1 . FIG. 1 is a schematic cross-sectional view showing an example of stamper molding used in the manufacture of semiconductor packages.

The apparatus applying the compression molding method is composed of a lower mold 10 and an upper mold 20 . The lower mold 10 is a portion on which a substrate 2 (for example, a silicon wafer) on which a semiconductor element 1 (for example, a chip) is mounted, and has a flat surface in the illustrated example. The upper mold 20 is a mold facing the semiconductor element 1 and the sealing material 3 , and the upper mold 20 is provided with a concave portion with a trapezoidal cross section in the illustrated example. In the lower mold 10 and the upper mold 20 , heaters (not shown) for heating and hardening the sealing material 3 are incorporated.

On the lower surface of the upper mold 20, a release film 4 extending along the inner surface of the concave portion is installed. A suction mechanism (not shown) is provided on the upper mold 20 , and the release film 4 is sucked and held in the concave portion of the upper mold 20 . The release film 4 is a member interposed between the upper mold 20 and the sealing material 3 so that the sealing material 3 does not directly contact the upper mold 20 . The release film 4 is arranged such that its release layer (not shown) faces the sealing material 3 .

The upper mold 20 descends as indicated by the arrow and merges with the lower mold 10, and the sealing material 3 is heated (heated and pressurized) while being compressed. Thereby, the sealing material 3 hardens|cures so that it may follow the shape of the recessed part of the upper mold|die 20, and seals the semiconductor element 1 simultaneously. After hardening of the sealing material 3 , the upper mold 20 is separated from the lower mold 10 , and at the same time or thereafter, the release film 4 is peeled off from the sealing material 3 . As described above, the semiconductor element 1 mounted on the substrate 2 is sealed by the sealing material 3 .

The above-mentioned manufacturing method is an example of the press molding method, and the present invention is not limited thereto. As another compression molding method, for example, there is a method in which a release film and a sealing material are sequentially placed on a lower mold having a concave portion, and a device for sucking and holding a substrate on which a semiconductor element (wafer) is mounted is lowered. The upper mold, the lower mold and the upper mold are combined, and the substrate on which the semiconductor element is mounted and the sealing material are heated and pressurized to seal the semiconductor element with the sealing material.

The release film used in the compression molding method is preferably one with good mold followability. From this point of view, the stress at 100% elongation in the longitudinal direction (MD direction) and width direction (TD direction) of the release film at 150° C. is preferably 60 MPa or less, more preferably 50 MPa or less, further preferably 40 Ma or less , especially preferably below 30MPa. If the above-mentioned stress at 100% elongation becomes too small, there is a possibility of fracture during elongation, so it is preferably at least 5 MPa, more preferably at least 10 MPa. Such a release film is as described above. As the base film, it is preferable to use a base film whose stress is 60 MPa or less at 100% elongation in the longitudinal direction (MD direction) and width direction (TD direction) at 150° C., respectively. It is more preferable to use a base film of 50 MPa or less, further preferably to use a base film of 40 MPa or less, and particularly preferably to use a base film of 30 MPa or less.

For the release film used in the compression molding method, the surface of the release layer can be relatively smooth or roughened. In the compression molding method, the release film is arranged in such a way that the release layer and the sealing material face each other. Therefore, since the surface properties of the release layer affect the surface properties of the sealing material, the surface roughness of the release layer is appropriately set according to the purpose or application.

When imparting a fine concave-convex structure to the surface of the sealing material (imparting a mat tone), the center line average roughness Ra of the surface of the release layer is preferably at least 100nm, more preferably at least 200nm, and most preferably at least 300nm . The upper limit is about 3,000nm. As a method of adjusting the centerline average roughness Ra of the surface of the release layer to 100nm or more, as mentioned above, the method of including particles in the release layer, the centerline average roughness of the release layer layer using a base film, etc. A method for a base film having a roughness Ra of 100 nm or more and a method for combining them.

Also, in the compression molding method, the surface of the release film opposite to the release layer is adsorbed to the mold. Here, in order to smoothly adsorb the release film to the mold, it is preferable to perform the exhaust gas smoothly. For smooth exhaust, the centerline average roughness Ra of the release film opposite to the release layer is preferably at least 20nm, more preferably at least 50nm, further preferably at least 100nm, and most preferably at least 300nm. The upper limit is about 3,000nm.

In order to make the centerline average roughness Ra of the release film opposite to the release layer within the above range, it is preferable to use a centerline average roughness Ra of 20nm on the opposite surface of the release layer as the base film. The above base film is more preferably a base film having a centerline average roughness Ra of 50nm or more, further preferably a base film having a centerline average roughness Ra of 100nm or more, particularly preferably using the above-mentioned Base film whose centerline average roughness Ra is 300nm or more. The upper limit of the above-mentioned centerline average roughness Ra is about 3,000 nm.

When imparting a micro-concave-convex structure to the surface of the sealing material, it is preferable to set the centerline average roughness Ra of the release layer surface of the release film to 100 nm or more, and to set the centerline of the release film opposite to the release layer The average roughness Ra is set to be 100 nm or more. At this time, as the base film, it is preferable to use a base film having a center line average roughness Ra of 100 nm or more on both sides, more preferably a base film having a center line average roughness Ra of 200 nm or more on both sides, especially preferably A base film with a centerline average roughness Ra of 300 nm or more on both sides is used. As such a base film, for example, a polyester film composed of three laminated layers of A layer/B layer/A layer is preferable.

The release film of the present invention is particularly suitable as a release film (release film) in the compression molding method for sealing semiconductor elements with a sealing material. Compression molding method.

That is, the compression molding method of the present invention is a compression molding method in which the release film of the present invention, the sealing material, and the semiconductor element are sequentially arranged in a mold and heated and pressurized, and the release layer of the release film is Compression molding method of arranging the release film facing the sealing material.

Moreover, the manufacturing method of the semiconductor package of this invention is the manufacturing method of the semiconductor package using the compression molding method of this invention.

[sealing material]

The sealing material used in the compression molding method is not particularly limited, and well-known ones as sealing materials for semiconductor elements, light-emitting elements, and the like can be used. In the sealing material, it is preferable to contain a thermosetting resin. Examples of thermosetting resins include epoxy-based thermosetting resins, phenol-based thermosetting resins, melamine-based thermosetting resins, alkyd-based thermosetting resins, acrylic-based thermosetting resins, polyamine-based Formate-based thermosetting resins, polyimide-based thermosetting resins, polyamideimide-based thermosetting resins, and the like. Among them, epoxy-based thermosetting resins are preferable.

The sealing material preferably contains an inorganic filler. Examples of the inorganic filler include silica, aluminum hydroxide, calcium carbonate, aluminum oxide, boron nitride, silicon nitride, titanium oxide, barium titanate, and the like.

The inorganic filler is, for example, granular and has the function of adjusting the viscosity or hardness of the sealing material. The content of the inorganic filler in the sealing material is preferably 50% by mass to 90% by mass.

Sealing materials are already commercially available, and those can be used. For example, "CEL-9740" and "CEL-C-2902" manufactured by Hitachi Chemical Industry Co., Ltd., "SUMIKON (registered trademark)" manufactured by Sumitomo Bakelite Co., Ltd., "EME-A730", "EME- G770", "R4212" manufactured by Nagase ChemteX Co., Ltd., etc.

[Example 2 of suitable application of release film]

The release film of the present invention is suitable as a supporting film (carrying film) or protective film for forming a ceramic layer, an adhesive layer, and a photosensitive resin layer (photoresist layer).

When applied to the above purposes, the haze value of the release film is preferably 1.5~8.0%.

Apply a transfer layer including a ceramic layer, an adhesive layer, or a photosensitive resin layer on a release film, and if necessary, perform a transfer layer in a state where a protective film (release film) is laminated on the transfer layer The defect inspection. In addition, since the release film is finally peeled and removed, it may be visually confirmed whether the release film has been peeled or not.

That is, the release film applied to the above-mentioned application may require defect inspection suitability and visibility. The suitability and identification of this defect are good because the haze value of the release film is 1.5~8.0%.

From the viewpoint of improving the suitability for defect detection of the transfer layer, the haze value of the release film is preferably 7.0% or less, more preferably 6.5% or less, and most preferably 6.0% or less.

From the viewpoint of improving the visibility of the release film, the haze value of the release film is preferably at least 2.0%, more preferably at least 2.5%, further preferably at least 3.0%, and most preferably at least 3.5%.

As a method of adjusting the haze value of the release film to 1.5-8.0%, it is preferable to control the haze value of the base film. The haze value of the substrate film is preferably in the range of about 1.8-8.5%, more preferably in the range of 2.3-8.5%, further preferably in the range of 2.8-7.3%, and most preferably in the range of 3.3-6.8%.

The haze value of the base film can be controlled by including particles in the base film. As mentioned above, the base film is preferably composed of three laminated layers of A layer/B layer/A layer or A layer/B layer/C layer, and it is preferable that particles are contained in layer A or layer C.

Moreover, when it is applied to the above-mentioned application, it is preferable that the release layer has solvent resistance. A coating composition for forming a transfer layer including a ceramic layer, an adhesive layer, or a photosensitive resin layer usually contains an organic solvent, and the release layer may require good solvent resistance. If the solvent resistance of the release layer is insufficient, a part of the release layer will dissolve due to the solvent contained in the transfer layer coated on the release layer, etc., and the adhesion between the release layer and the transfer layer will decrease. Increased, detachability may deteriorate.

The solvent resistance of the release layer is improved when the release layer is a hardened layer of the aforementioned composition (I) or (II).

Regarding the composition (I), from the viewpoint of further improving the solvent resistance of the release layer, the content of the crosslinking agent (b) is preferably at least 1.0 times that of the long-chain alkyl group-containing compound (a), more preferably It is more than 2.0 times, and the best is more than 3.0 times. The upper limit is about 20.0 times.

Composition (II) preferably contains a polymerizable long-chain alkyl group-containing compound (α1) from the viewpoint of further improving the solvent resistance of the release layer, more preferably contains a polymerizable long-chain alkyl group-containing compound (α1). compound (α1) and polymeric compound (β).

The release film of the present invention is suitable for compression molding. In addition, the release film of the present invention is suitable as a support film (carrying film) for coating and forming a transfer layer such as a ceramic layer such as a green sheet, an adhesive layer, a photosensitive resin layer (photoresist layer), or a coating film. The protective film of the formed transfer layer.

The first aspect of the laminated film of the present invention is on the release layer of the release film of the present invention, and any transfer layer selected from the group consisting of a ceramic layer, an adhesive layer and a photosensitive resin layer is laminated. laminated film.

Also, the second aspect of the laminated film of the present invention is that any transfer layer selected from the group consisting of a ceramic layer, an adhesive layer, and a photosensitive resin layer is laminated on a support film, and further on the transfer layer The laminated film with the release film of the present invention is laminated on top of the transfer layer in such a way that the release layer faces the transfer layer. In the above laminated film, the support film may also be the release film of the present invention.

[Example]

Hereinafter, the present invention will be described in detail by examples, but the present invention is not limited by these examples.

[Embodiment of Application Example 1]

This example relates to an example of a release film used in compression molding.

The measurement method and evaluation method are shown below.

(1) Determination of the stress of the substrate film at 100% elongation at 150°C

<Preparation of test samples>

Cut the base film into a rectangle whose length and width are 150 mm long and 10 mm long, respectively, and prepare test samples a cut out in such a way that the length direction (MD direction) of the base film becomes the long side. , and the test sample b cut out so that the width direction (TD direction) of the base film becomes the long side.

<Measurement of Stress>

In the oven with a window, a tensile testing machine ("Tensilon UCT-100" manufactured by ORIENTEC Co., Ltd. ”), further allowing the tensile testing machine to be operated from outside the oven.

When the temperature of the oven reaches 150°C, open the oven, quickly set the test sample in the tensile testing machine, raise the temperature of the oven again, and after confirming that it is 150°C, set the tensile speed at 300mm/min and the initial distance between chucks at 50mm for measurement. When the test sample is elongated by 100% (when the distance between chucks becomes 100mm), read the load applied to the test sample, and divide the value obtained by dividing the cross-sectional area of the sample before the test (the thickness of the substrate film × 10mm) as Stress at 100% elongation. The measurement was performed 5 times for each of the test sample a and the test sample b, and the respective values were averaged to calculate the stress in the longitudinal direction (MD direction) and the stress in the width direction (TD direction).

(2) Determination of the centerline average roughness Ra of the substrate film and the release layer

Based on JIS B0601 (1982), it measured using the stylus type surface roughness measuring device SE-3400 (made by Kosaka Laboratories Co., Ltd.).

<Measurement conditions>

‧Feed speed: 0.5mm/second

‧Evaluation length: 8mm

‧Cut-off value λc:

When Ra is below 20nm, λc=0.08mm

When Ra is greater than 20nm and less than 100nm, λc=0.25mm

When Ra is greater than 100nm and less than 2000nm, λc=0.8mm

In addition, when measuring under the above-mentioned measurement conditions, first measure with the cut-off value λc=0.8mm, and if the result is Ra greater than 100nm, use the Ra. On the other hand, when the result of the above measurement is Ra is 100nm or less, measure again with λc=0.25mm, and if the result is Ra greater than 20nm, use the Ra. On the other hand, the above-mentioned re-measurement results are when Ra is 20nm or less, measured at λc=0.08mm, and the Ra is adopted.

(3) Determination of the surface free energy of the release layer

As three liquids whose surface free energy and the value of each component (dispersion force, polar force, hydrogen bond force) are known, use water, diiodomethane, 1-bromonaphthalene, at 23°C, 65%RH, The contact angle of each liquid on the release layer was measured with a contact angle meter Drop Master DM501 (manufactured by Kyowa Interface Science Co., Ltd.). The measurement was performed five times on one measurement surface, and the average value thereof was regarded as the contact angle (θ). From the value of the contact angle (θ) and the known value of each liquid (according to Panzer's method IV (Journal of the Japan Adhesive Association, Vol. 15, No. 3, page 96), the value obtained by Kitazaki‧Hata ( The value of each component is calculated by the following formula imported from the formula of Kitazaki and Hata).

(γSd‧γLd)1/2+(γSp‧γLp)1/2+(γSh‧γLh)1/2=γL(1+cosθ)/2

Here, γLd, γLp, and γLh represent the components of the dispersion force, polar force, and hydrogen bond force of the measurement liquid, respectively, θ represents the contact angle of the measurement liquid on the measurement surface, and γSd, γSp, and γSh represent the contact angle of the laminated film surface, respectively. The value of each component of dispersion force, polar force, and hydrogen bond force, and γL represents the surface energy of each liquid. Substitute the known value and θ into the above formula and solve the resulting simultaneous equations to obtain the values of the three components of the measurement surface (release layer surface).

The sum of the values of the dispersive force component, the polar force component, and the hydrogen bond force component obtained as shown in the following formula was taken as the value of the surface free energy (E).

E=γSd+γSp+γSh

(4) Evaluation of moldability

The silicon wafer is placed on the lower side mold of a compression molding device ("WCM-300MS" manufactured by APIC YAMADA Co., Ltd.), and an epoxy-based sealing material (Nagase ChemteX (Nagase ChemteX ( Co., Ltd. "R4212-2" (liquid resin)). The release film is installed on the upper mold, and the silicon wafer and the sealing material are hot-pressed under the following forming conditions, and the sealing material is then covered on the silicon wafer.

<Forming conditions>

‧Temperature: 120℃

‧Pressure: 4MPa

‧Time: 10 minutes

<Evaluation method of peelability of molded release film>

After molding, the peelability of the sealing material and the release film was evaluated by the following criteria.

A: Cases that can be easily peeled off

B: It cannot be easily peeled off, but it can be peeled off by applying a certain amount of force

C: The case where it cannot be peeled off unless it is forcibly peeled off

<Evaluation of Die Followability>

The state of suction and adsorption of the release film to the upper mold was observed visually, and evaluated by the following criteria.

A: The case where the release film can be adsorbed without wrinkles

B: There are cases where air leaks from the end, or when there are wrinkles on the release film during adsorption

(5) Determination of thickness of substrate film and release layer

Using a Micro-sampling system (FB-2000A manufactured by Hitachi) to produce a release film by the FIB method (specifically, based on the method described in "Polymer Surface Processing" (Akatsuki Iwamori) p.118~119) Sample for section observation. With a transmission electron microscope (H-9000UHRII manufactured by Hitachi), the acceleration voltage was set to 300 kV, the cross section of the sample for cross section observation was observed, and the thicknesses of the base film and the release layer were measured.

(6) Determination of the average particle size of the particles contained in the substrate film and the release layer

The section of the release film was observed with an electron microscope, and the maximum lengths of 30 particles randomly selected from the section photos were measured, and the arithmetic mean value was taken as the average particle diameter of the particles.

(7) Determination of 10% compressive strength of particles

Using the Micro Compression Tester "MCTM2000" manufactured by Shimadzu Corporation, one particle is compressed at a constant load speed of 0.98mN/sec, and the load when the particle is deformed by 10% and the particle diameter before compression are substituted into the following Calculated by formula 1. The measurement was performed on 5 randomly sampled samples, and the average value thereof was regarded as "10% compressive strength". The measurement conditions are shown below.

10% compressive strength (MPa)=2.8P/πD ² ‧‧‧Formula 1

(In Formula 1, P represents a load (N), and D represents a particle diameter (mm)).

<Measurement conditions>

‧Measurement environment: temperature 23±1℃, relative humidity 55±5%

‧Upper pressure head: flat head with a diameter of 50μm (material: diamond)

‧Lower pressure plate: SKS flat plate

[Preparation of substrate film]

The following biaxially aligned polyester film was prepared as a base film.

<Mylar 1>

A polyester film composed of three laminated layers of A layer/B layer/A layer was produced in the following manner. The raw materials for each layer are shown below.

‧A layer: Contains 94% by mass of the following polyester a, 5% by mass of the following polyester b, and 1% by mass of the following particle c1 masterbatch.

‧B layer: Contains 50% by mass of the following polyester a and 50% by mass of the following polyester b.

(modulation of polyester a)

Polyethylene terephthalate resin (intrinsic viscosity 0.65) with 100 mol % of terephthalic acid component as a dicarboxylic acid component and 100 mol % of ethylene glycol component as a diol component.

(modulation of polyester b)

Copolymerized polyester (GN001 manufactured by EASTMAN CHEMICAL Co., Ltd.) having 33 mol% of 1,4-cyclohexanedimethanol copolymerized with respect to the diol component was used as cyclohexanedimethanol copolymerized polyethylene terephthalate (Intrinsic viscosity 0.75).

(Preparation of particle masterbatch c1)

Polyethylene terephthalate particle masterbatch (intrinsic viscosity 0.65) containing agglomerated silica particles with a number average particle diameter of 2.2 μm in polyester a at a particle concentration of 2% by mass.

(Manufacture of polyester film 1)

The raw materials for layer A and the raw materials for layer B are respectively supplied to the co-rotating twin-screw extruder with the respective exhaust port whose oxygen concentration is set to 0.2% by volume. The barrel temperature of the layer A extruder is 270°C The B-layer extruder barrel temperature is 277°C for melting, the temperature of the short tube after the confluence of A layer and B layer is 277°C, and the nozzle temperature is 280°C, and it is extruded from the T-die in sheet form until the temperature is controlled. On a cooling roller at 25°C. At this time, static electricity was applied using a wire electrode with a diameter of 0.1 mm, and a three-layer laminated unstretched film including A layer/B layer/A layer in close contact with the cooling drum was obtained. Next, before stretching in the longitudinal direction, the temperature of the film is raised with a heating roller, stretched 3.6 times in the longitudinal direction at a preheating temperature of 80°C, and a stretching temperature of 85°C, and immediately controlled at a temperature of 40°C. Roll to cool.

Next, use a tenter-type transverse stretching machine to stretch 3.8 times in the width direction at a preheating temperature of 85°C and an extension temperature of 95°C, and heat treatment directly in the tenter at a temperature of 234°C for 5 seconds, and then While applying 5% relaxation in the width direction, heat treatment was performed at 150° C. for 3 seconds to obtain a biaxially oriented polyester film. The total thickness of the polyester film was 50 μm, the thickness of the A layer was 5 μm, and the thickness of the B layer was 40 μm. The center line average roughness Ra of this polyester film is 23nm on both sides.

<Mylar 2>

An easily formable polyester film ("Softshine (registered trademark)" manufactured by Toyobo Co., Ltd.) having a thickness of 50 µm was prepared. Centerline average roughness Ra is 5nm on both sides.

<Mylar 3>

A polyester film ("Lumirror (registered trademark)" S10 manufactured by Toray Co., Ltd.) having a thickness of 50 μm was prepared. Centerline average roughness Ra is 25nm on both sides.

<Mylar 4>

A polyester film composed of three laminated layers of A layer/B layer/A layer was produced in the following manner. The raw materials for each layer are shown below.

‧A layer: 70 mass % of the said polyester a, 5 mass % of the said polyester b, and 25 mass % of the following particle masterbatches c2 are contained.

-B layer: Contains 50% by mass of the above-mentioned polyester a and 50% by mass of the above-mentioned polyester b.

(Preparation of particle masterbatch c2)

Polyethylene terephthalate particle masterbatch (intrinsic viscosity 0.65) containing agglomerated silica particles with a number average particle diameter of 3.5 μm in polyester a at a particle concentration of 20% by mass.

(Manufacture of polyester film 4)

The raw materials for layer A and the raw materials for layer B are respectively supplied to the respective single-screw extruders with the oxygen concentration set to 0.2% by volume. The temperature of the cylinder is 270°C for melting, the temperature of the short tube after the confluence of layer A and B is set at 275°C, the temperature of the nozzle is set at 280°C, and the temperature of the resin is 280°C, and it is discharged from the T-die in a sheet form. Place on a cooling drum with temperature controlled at 25°C. At this time, static electricity was applied using a wire-shaped electrode with a diameter of 0.1 mm to obtain an unstretched sheet in close contact with the cooling drum. Next, before stretching in the longitudinal direction, the temperature of the film was raised with a heating roll, stretched 3.1 times in the longitudinal direction at a stretching temperature of 85°C, and immediately cooled with a metal roll whose temperature was controlled at 40°C. Then, use a tenter-type horizontal stretching machine to stretch 3.5 times in the width direction at a temperature of 110°C in the first half of stretching, a temperature of 125°C in the middle of stretching, and a temperature of 140°C in the second half of stretching. , Heat treatment second half After heat treatment at 240°C, heat treatment was performed at a slow cooling temperature of 170°C while applying 5% relaxation in the width direction to obtain a biaxially stretched polyester film with a total thickness of 50 μm. The thickness of A layer/B layer/A layer is 5 μm/40 μm/5 μm. The centerline average roughness Ra of this polyester film is 550 nm on both sides.

[Example 1]

On one side of the polyester film 1, the following composition p1 was coated as the composition (I) with a gravure coater, pre-dried at 100° C., and then heated and dried at 160° C. to form a release layer, and a release film was produced. The thickness of the release layer is 100nm.

<composition p1>

‧Compound (a) containing long-chain alkyl groups: 10 parts by mass of polyethylene resin a1 containing long-chain alkyl groups synthesized below

‧Crosslinking agent (b): 2.5 parts by mass of melamine-based crosslinking agent in terms of solid content ("Sumimal" M-55 manufactured by Sumitomo Chemical Co., Ltd.)

‧Acid catalyst (c): 1.3 parts by mass of p-toluenesulfonic acid in terms of solid content ("TAYCACURE" AC-700 manufactured by TAYCA Co., Ltd.)

‧Solvent: 400 parts by mass of toluene, 130 parts by mass of methyl ethyl ketone

<Synthesis of Polyethylene Resin a1 Containing Long Chain Alkyl Group>

200 parts by mass of xylene and 600 parts by mass of stearyl isocyanate were added to a 4-neck flask, followed by heating with stirring. From the time when xylene started to reflux, 100 parts by mass of polyvinyl alcohol (average degree of polymerization 500, degree of saponification 88 mol%) was added little by little at intervals of 10 minutes over about 2 hours.

After the polyvinyl alcohol was added, the reaction was further refluxed for 2 hours to complete the reaction. After the reaction mixture was cooled to about 80°C, it was added to methanol. As a result, the reaction product was precipitated as a white precipitate. Therefore, the precipitate was separated by filtration, and 140 parts by mass of xylene was added, heated to dissolve it completely, and again After adding methanol to precipitate, and repeating this operation several times, the precipitate was washed with methanol, dried and pulverized.

[Example 2]

Except having changed into the following composition p2, it carried out similarly to Example 1, and produced the release film.

<composition p2>

‧Long-chain alkyl group-containing compound (a): 10 parts by mass of long-chain alkyl group-containing polyethylene resin ("Piroiru" 1050 of LION SPECIALTY CHEMICALS Co., Ltd.) in terms of solid content

‧Crosslinking agent (b): 2.5 parts by mass of melamine-based crosslinking agent in terms of solid content ("Sumimal" M-55 manufactured by Sumitomo Chemical Co., Ltd.)

‧Acid catalyst (c): 1.3 parts by mass of p-toluenesulfonic acid in terms of solid content ("TAYCACURE" AC-700 manufactured by TAYCA Co., Ltd.)

‧Solvent: 400 parts by mass of toluene, 130 parts by mass of methyl ethyl ketone

[Example 3]

Except having changed into the following composition p3, it carried out similarly to Example 1, and produced the release film.

<composition p3>

‧Long-chain alkyl group-containing compound (a): 10 parts by mass of long-chain alkyl group-containing polyethylene resin ("Piroiru" 1050 manufactured by LION SPECIALTY CHEMICALS Co., Ltd.) in terms of solid content

‧Crosslinking agent (b): 2.5 parts by mass of melamine-based crosslinking agent (trade name "Super Beckamine G" 821 manufactured by DIC Co., Ltd.) in terms of solid content

‧Acid catalyst (c): 1.3 parts by mass of p-toluenesulfonic acid in terms of solid content ("TAYCACURE" AC-700 manufactured by TAYCA Co., Ltd.)

[Example 4]

A release film was prepared in the same manner as in Example 1 except for changing to the following composition p4.

<Composition p4>

‧Long-chain alkyl group-containing compound (a): 10 parts by mass of long-chain alkyl group-containing polyethylene resin ("Piroiru" 1050 manufactured by LION SPECIALTY CHEMICALS Co., Ltd.) in terms of solid content

‧Crosslinking agent (b): 2.5 parts by mass of melamine-based crosslinking agent in terms of solid content ("U-VAN" 28-60 manufactured by Mitsui Chemicals Co., Ltd.)

‧Acid catalyst (c): 1.3 parts by mass of p-toluenesulfonic acid in terms of solid content ("TAYCACURE" AC-700 manufactured by TAYCA Co., Ltd.)

‧Solvent: 400 parts by mass of toluene, 130 parts by mass of methyl ethyl ketone

[Example 5]

Except having changed into the following composition p5, it carried out similarly to Example 1, and produced the release film.

<Composition p5>

‧Compound (a) containing a long-chain alkyl group: 10 parts by mass of polyethylene resin a1 containing a long-chain alkyl group synthesized in Example 1

‧Crosslinking agent (b): 2.5 parts by mass of isocyanate-based crosslinking agent in terms of solid content ("Takenate" D-103H manufactured by Mitsui Chemicals Co., Ltd.)

‧Acid catalyst (c): 1.3 parts by mass of p-toluenesulfonic acid in terms of solid content ("TAYCACURE" AC-700 manufactured by TAYCA Co., Ltd.)

‧Solvent: 400 parts by mass of toluene, 130 parts by mass of methyl ethyl ketone

[Example 6]

Except having changed into the following composition p6, it carried out similarly to Example 1, and produced the release film.

<Composition p6>

‧Compound (a) containing a long-chain alkyl group: 10 parts by mass of polyethylene resin a1 containing a long-chain alkyl group synthesized in Example 1

‧Crosslinking agent (b): 2.5 parts by mass of epoxy-based crosslinking agent (ethylene glycol diglycidyl ether)

‧Acid catalyst (c): 1.3 parts by mass of p-toluenesulfonic acid in terms of solid content ("TAYCACURE" AC-700 manufactured by TAYCA Co., Ltd.)

‧Solvent: 400 parts by mass of toluene, 130 parts by mass of methyl ethyl ketone

[Example 7]

Except having changed into the following composition p7, it carried out similarly to Example 1, and produced the release film.

<Composition p7>

‧A mixture of a long-chain alkyl group-containing compound (a) and a cross-linking agent (b), a mixture of a long-chain alkyl group-containing alkyd resin and a melamine-based cross-linking agent (Hitachi Chemical Co., Ltd. "Tesfine 303")

‧Acid catalyst (c): 0.3 parts by mass of p-toluenesulfonic acid in terms of solid content ("Dryer 900" manufactured by Hitachi Chemical Co., Ltd.)

‧Solvent: 17 parts by mass of toluene, 6 parts by mass of methyl ethyl ketone

[Example 8]

Except having changed into the following composition p8, it carried out similarly to Example 1, and produced the release film.

<Composition p8>

‧Long-chain alkyl group-containing compound (a): 10 parts by mass of long-chain alkyl group-containing acrylic resin a2 synthesized below in terms of solid content

‧Crosslinking agent (b): 2.5 parts by mass of melamine-based crosslinking agent in terms of solid content ("Sumimal" M-55 manufactured by Sumitomo Chemical Co., Ltd.)

‧Acid catalyst (c): 1.3 parts by mass of p-toluenesulfonic acid in terms of solid content ("TAYCACURE" AC-700 manufactured by TAYCA Co., Ltd.)

‧Solvent: 400 parts by mass of toluene, 130 parts by mass of methyl ethyl ketone

<Synthesis of long-chain alkyl-containing acrylic resin a2>

In a 4-necked flask equipped with a stirrer, a nitrogen introduction pipe, a cooling pipe, and a rubber septum (rubber septum), add 70 parts by mass of stearyl methacrylate, 25 parts by mass of butyl acrylate, 5 parts by mass of acrylic acid and 150 parts by mass of toluene was used to replace nitrogen in the system. Therein, under a nitrogen flow, 0.4 parts by mass of 2,2-azobisisobutyronitrile was added, heated to 60°C, and polymerized for 24 hours to obtain a viscous solution of an acrylic polymer. This acrylic polymer is a random copolymer of octadecyl methacrylate, butyl acrylate and acrylic acid. It has octadecyl in the side chain as a long-chain alkyl group and a carboxyl group as a functional group. The number average molecular weight is 96,000.

[Example 9]

Except having changed the base film into the polyester film 2, it carried out similarly to Example 1, and produced the release film.

[Comparative example 1]

The polyester film 1 was used as a release film without laminating a release layer on the polyester film 1 .

[Comparative example 2]

Except having changed into the following composition p9, it carried out similarly to Example 1, and produced the release film.

<Composition p9>

40 parts by mass of addition reaction type curable silicone resin KS847H (manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.4 parts by mass of hardener were mixed with 500 parts by mass of toluene and 500 parts by mass of n-heptane. PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.).

[Comparative example 3]

In Comparative Example 2, a release film was produced in the same manner as in Comparative Example 2, except that the polyester film 1 was changed to the polyester film 3.

[Comparative example 4]

Except having changed into the following composition p10, it carried out similarly to Example 1, and produced the release film.

<Composition p10>

50 parts by mass of toluene and 50 parts by mass of cyclohexanone were mixed with 20 parts by mass of RP-50 (manufactured by Sanwa Laboratories Co., Ltd.) as a melamine resin and 4 parts by mass of PLUS COAT DEP Clear ( Hexin Chemical Industry Co., Ltd.).

[Comparative Example 5]

Except having changed into the following composition p11, it carried out similarly to Example 1, and produced the release film.

<Composition p11>

‧Compound (a) containing a long-chain alkyl group: 12.5 parts by mass of the acrylic resin a2 containing a long-chain alkyl group synthesized in Example 8 in terms of solid content

‧Acid catalyst (c): 1.3 parts by mass of p-toluenesulfonic acid in terms of solid content ("TAYCACURE" AC-700 manufactured by TAYCA Co., Ltd.)

‧Solvent: 400 parts by mass of toluene, 130 parts by mass of methyl ethyl ketone

[Example 10]

Except having changed the base film into the polyester film 4, it carried out similarly to Example 1, and produced the release film.

[Example 11]

Except having changed the base film into the polyester film 4, it carried out similarly to Example 4, and produced the release film.

[Example 12]

Except having changed into the following composition p12, and having changed the thickness of the release layer into 500 nm, it carried out similarly to Example 1, and produced the release film.

<Composition p12>

‧Long-chain alkyl group-containing compound (a): 10 parts by mass of long-chain alkyl group-containing polyethylene resin ("Piroiru" 1050 manufactured by LION SPECIALTY CHEMICALS Co., Ltd.) in terms of solid content

‧Crosslinking agent (b): 40 parts by mass of melamine-based crosslinking agent in terms of solid content ("U-VAN" 28-60 manufactured by Mitsui Chemicals Co., Ltd.)

‧Acid catalyst (c): 2.8 parts by mass of p-toluenesulfonic acid in terms of solid content ("TAYCACURE" AC-700 manufactured by TAYCA Co., Ltd.)

‧Particles: 1.5 parts by mass of melamine‧silica composite particles ("Optbeads (registered trademark)" manufactured by Nissan Chemical Industry Co., Ltd. 2000M; average particle size 2.0μm, 10% compressive strength 58MPa)

‧Solvent: 1500 parts by mass of toluene, 300 parts by mass of methyl ethyl ketone

[Example 13]

Except having changed into the following composition p13, and having changed the thickness of the release layer into 500 nm, it carried out similarly to Example 1, and produced the release film.

<Composition p13>

‧Long-chain alkyl group-containing compound (a): 10 parts by mass of long-chain alkyl group-containing polyethylene resin ("Piroiru" 1050 manufactured by LION SPECIALTY CHEMICALS Co., Ltd.) in terms of solid content

‧Crosslinking agent (b): 40 parts by mass of melamine-based crosslinking agent in terms of solid content ("U-VAN" 28-60 manufactured by Mitsui Chemicals Co., Ltd.)

‧Acid catalyst (c): 2.8 parts by mass of p-toluenesulfonic acid in terms of solid content ("TAYCACURE" AC-700 manufactured by TAYCA Co., Ltd.)

‧Particles: 3.5 parts by mass of melamine‧silica composite particles ("Optbeads (registered trademark)" manufactured by Nissan Chemical Industry Co., Ltd. 2000M; average particle size 2.0μm, 10% compressive strength 58MPa)

‧Solvent: 1500 parts by mass of toluene, 500 parts by mass of methyl ethyl ketone

[Example 14]

Except having changed into the following composition p14, and having changed the thickness of the release layer into 500 nm, it carried out similarly to Example 1, and produced the release film.

<Composition p14>

‧Long-chain alkyl group-containing compound (a): 10 parts by mass in terms of solid content of long-chain alkyl group-containing polyethylene resin ("Piroiru" 1050 manufactured by LION SPECIALTY CHEMICALS Co., Ltd.)

‧Crosslinking agent (b): 40 parts by mass of melamine-based crosslinking agent in terms of solid content ("U-VAN" 28-60 manufactured by Mitsui Chemicals Co., Ltd.)

‧Acid catalyst (c): 2.8 parts by mass of p-toluenesulfonic acid in terms of solid content ("TAYCACURE" AC-700 manufactured by TAYCA Co., Ltd.)

‧Particles: 8.5 parts by mass of melamine‧silica composite particles ("Optbeads (registered trademark)" manufactured by Nissan Chemical Industry Co., Ltd. 2000M; average particle size 2.0μm, 10% compressive strength 58MPa)

‧Solvent: 1500 parts by mass of toluene, 500 parts by mass of methyl ethyl ketone

[Example 15]

Except having changed into the following composition p15, it carried out similarly to Example 1, and produced the release film.

<Composition p15>

‧Long-chain alkyl group-containing compound (a): 10 parts by mass of long-chain alkyl group-containing polyethylene resin ("Piroiru" 1050 of LION SPECIALTY CHEMICALS Co., Ltd.) in terms of solid content

‧Crosslinking agent (b): 25 parts by mass of melamine-based crosslinking agent in terms of solid content ("U-VAN" 28-60 of Mitsui Chemicals Co., Ltd.)

‧Acid catalyst (c): 1.8 parts by mass of p-toluenesulfonic acid in terms of solid content ("TAYCACURE" AC-707 of TAYCA Co., Ltd.)

‧Solvent: 1000 parts by mass of toluene, 340 parts by mass of methyl ethyl ketone

[Example 16]

Except having changed into the following composition p16, it carried out similarly to Example 1, and produced the release film.

<Composition p16>

‧Long-chain alkyl group-containing compound (a): 10 parts by mass of long-chain alkyl group-containing polyethylene resin ("Piroiru" 1050 of LION SPECIALTY CHEMICALS Co., Ltd.) in terms of solid content

‧Crosslinking agent (b): melamine-based crosslinking agent ("U-VAN" 28-60 of Mitsui Chemicals Co., Ltd., 90 parts by mass in terms of solid content)

‧Acid catalyst (c): 6.3 parts by mass of p-toluenesulfonic acid in terms of solid content ("TAYCACURE" AC-707 of TAYCA Co., Ltd.)

‧Solvent: 3000 parts by mass of toluene, 980 parts by mass of methyl ethyl ketone

[Example 17]

Except having changed into the following composition p17, it carried out similarly to Example 1, and produced the release film.

<Composition p17>

‧Long-chain alkyl group-containing compound (a): 10 parts by mass of long-chain alkyl group-containing polyethylene resin ("Piroiru" 1050 of LION SPECIALTY CHEMICALS Co., Ltd.) in terms of solid content

‧Crosslinking agent (b): 190 parts by mass of melamine-based crosslinking agent in terms of solid content ("U-VAN" 28-60 of Mitsui Chemicals Co., Ltd.)

‧Acid catalyst (c): 13.3 parts by mass of p-toluenesulfonic acid in terms of solid content ("TAYCACURE" AC-707 of TAYCA Co., Ltd.)

‧Solvent: 6000 parts by mass of toluene, 2000 parts by mass of methyl ethyl ketone

[Example 21]

On one side of the base film made of polyester film 1, apply the following composition p21 as composition (II) with a gravure coater, dry it at 100°C, and then irradiate it with 300mJ/ ^cm2 of ultraviolet rays to cure it , Form a release layer to make a release film. The thickness of the release layer is 250nm.

<Composition p21>

Charge 25 parts by mass of the polymerizable long-chain alkyl-containing compound (α1-1) synthesized below, and 75 parts by mass of diperythritol hexaacrylate (Daicel-Cytec®) as the polymerizable compound (β). Co., Ltd. product name "DPHA"), 10 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.), heated to 100°C, and mixed for 1 hour to obtain an active energy ray-curable composition thing. This composition was prepared with a mixed solvent of toluene and isopropanol (IPA) (toluene:IPA=3:1 (mass ratio)) so that the solid content concentration was 4% by mass.

<Synthesis of polymerizable long-chain alkyl group-containing compound (α1-1)>

Into a flask equipped with a stirrer and a thermometer, 100 parts by mass of 2-hydroxyethyl acrylate ("BHEA" manufactured by Nippon Shokubai Co., Ltd.), 240 parts by mass of (meth)acrylate compound having a hydroxyl group were charged. 26 parts by mass of diphenylmethane diisocyanate ("Millionate MT" manufactured by Nippon Polyurethane Co., Ltd.) as a polyisocyanate compound, 26 parts by mass of stearyl alcohol ("Conol 30SS" manufactured by Shin Nippon Chemical Co., Ltd.) ”), the temperature was raised to 100°C, and the temperature was kept for 7 hours to allow the reaction. The result of IR measurement confirmed that the isocyanate group disappeared, and the reaction was terminated.

[Example 22]

Except having changed into the following composition p22, it carried out similarly to Example 21, and produced the release film.

<Composition p22>

Charge 15 parts by mass of the polymerizable long-chain alkyl-containing compound (α1-2) synthesized below, and 85 parts by mass of diperythritol hexaacrylate (Daicel-Cytec®) as the polymerizable compound (β). Co., Ltd. product name "DPHA"), 10 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.), heated to 100°C, and mixed for 1 hour to obtain an active energy ray-curable composition thing. This composition was prepared with a mixed solvent of toluene and isopropanol (IPA) (toluene:IPA=3:1 (mass ratio)) so that the solid content concentration was 4% by mass.

<Synthesis of polymerizable long-chain alkyl group-containing compound (α1-2)>

Into a flask equipped with a stirrer and a thermometer, 100 parts by mass of 2-hydroxyethyl acrylate ("BHEA" manufactured by Nippon Shokubai Co., Ltd.), 86 parts by mass of (meth)acrylate compound having a hydroxyl group were charged. 46 parts by mass of hexamethylene diisocyanate (trade name "HDI" manufactured by Nippon Polyurethane Co., Ltd.) as a polyisocyanate compound, 46 parts by mass of stearyl alcohol as a higher alcohol ("Conol 30SS"), the temperature was raised to 100°C, and the temperature was kept for 7 hours to allow the reaction. The result of IR measurement confirmed that the isocyanate group disappeared, and the reaction was terminated.

[Example 23]

Except having changed into the following composition p23, it carried out similarly to Example 21, and produced the release film.

<Composition p23>

17 parts by mass of the non-polymerizable long-chain alkyl group-containing compound (α2-1) (a compound not containing an ethylenically unsaturated group in the molecule) synthesized below, 53 Parts by mass of diperythritol hexaacrylate (trade name "DPHA" manufactured by Daicel-Cytec Co., Ltd.) and 30 parts by mass of urethane acrylate ("UA-306T" manufactured by Kyoeisha Chemical Co., Ltd.) ), 10 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.), heated to 100° C., and mixed for 1 hour to obtain an active energy ray-curable composition. This composition was prepared with a mixed solvent of toluene and isopropanol (IPA) (toluene:IPA=3:1 (mass ratio)) so that the solid content concentration was 4% by mass.

<Synthesis of non-polymerizable long-chain alkyl group-containing compound (α2-1)>

In a 4-necked flask equipped with a stirrer, a nitrogen introduction pipe, a cooling pipe, and a rubber septum, 70 parts by mass of stearyl methacrylate, 25 parts by mass of butyl acrylate, 5 parts by mass of acrylic acid and 150 parts by mass of of toluene, nitrogen replacement will be carried out in the system. Therein, under nitrogen flow, 0.4 parts by mass of 2,2-azobisisobutyronitrile was added, heated to 60° C., and polymerized for 24 hours to obtain a viscous solution of an acrylic polymer. This acrylic polymer is a random copolymer of octadecyl methacrylate, butyl acrylate and acrylic acid. It has octadecyl in the side chain as a long-chain alkyl group and a carboxyl group as a functional group. The number average molecular weight is 96,000.

[Example 24]

Except having changed the base film into the polyester film 4, it carried out similarly to Example 21, and produced the release film.

[Example 25]

A release film was produced in the same manner as in Example 21 except that it was changed to the following composition p24 and the thickness of the release layer was changed to 500 nm.

<Composition p24>

Add 25 parts by mass of the polymerizable long-chain alkyl-containing compound (α1-1) synthesized above, and 75 parts by mass of diperythritol hexaacrylate (Daicel-Cytec Co., Ltd.) as the polymerizable compound (β). ) product name "DPHA"), 10 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.), heated to 100°C, and mixed for 1 hour, followed by mixing melamine‧silica composite particles ( "Optbeads (registered trademark)" manufactured by Nissan Chemical Industry Co., Ltd. 2000M; average particle size 2.0μm, 10% compressive strength 58MPa) was added so as to become 10% by mass relative to 100% by mass of the total solid content of the composition, An active energy ray curable composition was obtained. This composition was prepared with a mixed solvent of toluene and isopropanol (IPA) (toluene:IPA=3:1 (mass ratio)) so that the solid content concentration was 4% by mass.

[Example 26]

A release film was produced in the same manner as in Example 21 except that it was changed to the following composition p25 and the thickness of the release layer was changed to 500 nm.

<Composition p25>

25 parts by mass of the polymerizable long-chain alkyl-containing compound (α1-1) synthesized above, and 75 parts by mass of dipenteoerythritol hexaacrylate (Daicel-Cytec ( Co., Ltd. (trade name "DPHA"), 10 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.), heated to 100°C, mixed for 1 hour, and then mixed with melamine‧silica composite particles (Nissan Chemical Industry Co., Ltd. "Optbeads (registered trademark)" 2000M; average particle size 2.0μm, 10% compressive strength 58MPa) Added so that it becomes 20% by mass relative to 100% by mass of the total solid content of the composition to obtain an active energy ray curable composition. This composition was prepared with a mixed solvent of toluene and isopropanol (IPA) (toluene:IPA=3:1 (mass ratio)) so that the solid content concentration was 4% by mass.

[Example 27]

A release film was produced in the same manner as in Example 21 except that it was changed to the following composition p26 and the thickness of the release layer was changed to 500 nm.

<Composition p26>

25 parts by mass of the polymerizable long-chain alkyl-containing compound (α1-1) synthesized above, and 75 parts by mass of dipenteoerythritol hexaacrylate (Daicel-Cytec ( Co., Ltd. (trade name "DPHA"), 10 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.), heated to 100°C, mixed for 1 hour, and then mixed with melamine‧silica composite particles ("Optbeads (registered trademark)" manufactured by Nissan Chemical Industry Co., Ltd. 2000M; average particle size 2.0μm, 10% compressive strength 58MPa) Added so that it becomes 40% by mass relative to 100% by mass of the total solid content of the composition to obtain an active energy ray curable composition. This composition was prepared with a mixed solvent of toluene and isopropanol (IPA) (toluene:IPA=3:1 (mass ratio)) so that the solid content concentration was 4% by mass.

[evaluate]

The release films of the examples and comparative examples prepared above were evaluated in accordance with the above-mentioned measurement method and evaluation method. Table 1 and Table 2 show the results.

[Embodiment of application example 2]

This embodiment relates to an embodiment of a release film used for a support film or a protective film, which is used to form a ceramic layer, an adhesive layer or a photosensitive resin layer.

The measurement method and evaluation method are shown below.

(1) Determination of haze value of release film and substrate film

Based on JIS K 7136 (2000), the haze value of the release film was measured using a turbidity meter "NDH-4000" manufactured by Nippon Denshoku Industries Co., Ltd. At the time of measurement, it arrange|positions so that light may be incident on the surface of the release layer of a release film.

In addition, the haze value of the base film was also measured using a nephelometer "NDH-4000" manufactured by Nippon Denshoku Kogyo Co., Ltd. based on JIS K 7136 (2000).

(2) Determination of the surface free energy of the release layer

It is the same as the measurement method in the embodiment of application example 1.

(3) Evaluation of solvent resistance

As an organic solvent, methyl ethyl ketone (MEK), toluene, and ethyl acetate were used, and the solvent resistance to each organic solvent was evaluated by the following procedure.

The surface of the release layer of the release film was wiped back and forth five times with a cotton swab soaked in the organic solvent, the state of the release layer was visually observed, and the following criteria were used for evaluation.

A: There is no change in the release layer in any of the above three solvents

B: Among the above three solvents, there may be a solvent that whitens the release layer

C: Among the above three solvents, there may be a solvent that makes the release layer disappear

(4) Defect inspection

From Toray Co., Ltd.'s polyester film ("Lumirror (registered trademark)" S10), foreign matter defects (fish eyes) with a maximum length of 300 μm were marked. Next, use 3M's acrylic adhesive sheet ("OCA (registered trademark)" 8146-2; thickness 50 μm) to attach the part marked with foreign matter defects and the release surface of the release film to prepare a test piece. Next, this test piece was placed on the stand with the release film facing upward, and was visually observed under a 40W three-wavelength fluorescent light installed at a position 50 cm high from the laminate, and evaluated by the following criteria .

A: A foreign matter defect can be easily visually recognized.

B: A foreign matter defect can be barely recognized visually.

C: A foreign matter defect cannot be visually recognized.

(5) Recognition of release film

The separator on one side of the 3M (stock) acrylic adhesive sheet ("OCA (registered trademark)" 8146-2) was peeled off, and the release film produced in the examples and comparative examples was attached to prepare a test piece. Next, this test piece was placed on the stand with the release film on top, and was visually observed under a 40W three-wavelength fluorescent light installed at a height of 50 cm from the test piece, and evaluated according to the following criteria .

A: The release film can be easily recognized.

B: The release film can be barely recognized.

C: The release film cannot be recognized.

[Preparation of substrate film]

As the base film, the following polyester film was prepared.

<Mylar 11>

Toray's polyester film ("Lumirror (registered trademark)" R75X) was prepared. This polyester film has a thickness of 25 μm and a haze value of 4.7%.

<Mylar 12>

Toray's polyester film ("Lumirror (registered trademark)" R60) was prepared. This polyester film has a thickness of 38 μm and a haze value of 9.4%.

<Mylar 13>

Toray's polyester film ("Lumirror (registered trademark)" FB40) was prepared. This polyester film has a thickness of 25 μm and a haze value of 0.6%.

<Mylar 14>

A polyester film having a three-layer structure of A layer/B layer/A layer was produced in the following manner.

Raw materials for layer A: In polyethylene terephthalate (PET) with an intrinsic viscosity of 0.60, during polymerization, add 0.08% by mass of agglomerated silica with an average particle diameter of 1.1 μm, and dry until the moisture content reaches 200ppm .

Raw materials for layer B: In polyethylene terephthalate (PET) with an intrinsic viscosity of 0.58, during polymerization, add 0.02% by mass of agglomerated silica with an average particle diameter of 1.0 μm, and dry until the moisture content reaches 200ppm .

The above raw materials were extruded at 290°C into a 3-layer laminated sheet comprising A layer/B layer/A layer, which was rapidly cooled and solidified on a cooling roll whose surface temperature was controlled at 30°C. This unstretched laminated sheet was stretched in the longitudinal direction at a stretching temperature of 115°C and a stretching ratio of 3.8 times, then stretched in the width direction at a stretching temperature of 120°C and a stretching ratio of 3.7 times, and then stretched at 215°C with a relaxation rate of 5.0. % heat treatment to obtain a biaxially aligned laminated polyester film with a total thickness of 20 μm with a thickness of A layer/B layer/A layer of 1/18/1 (μm). The haze value of this polyester film is 2.7%.

<Mylar 15>

In addition to changing the addition amount of agglomerated silica in the A-layer raw material to 0.07% by mass and changing the addition amount of agglomerated silica in the B-layer raw material to 0.01% by mass in the manufacture of the polyester film 14, the poly The ester film 14 is produced in the same manner. The haze value of this polyester film is 2.1%.

<Mylar 16>

In addition to changing the addition amount of agglomerated silica in the A-layer raw material to 0.09% by mass and changing the addition amount of agglomerated silica in the B-layer raw material to 0.03% by mass in the manufacture of the polyester film 14, the poly The ester film 14 is produced in the same manner. The haze value of this polyester film is 3.8%.

<Mylar 17>

In addition to changing the addition amount of agglomerated silica in the A-layer raw material to 0.04% by mass and changing the addition amount of agglomerated silica in the B-layer raw material to 0.004% by mass in the manufacture of the polyester film 14, the poly The ester film 14 is produced in the same manner. The haze value of this polyester film was 1.2%.

<Mylar 18>

A polyester film having a three-layer structure of A layer/B layer/A layer was produced in the following manner.

(manufacture of calcium carbonate particles)

The crushed and screened limestone containing 70ppm Fe ₂ O ₃ as the iron element is used as the crude raw material, and after the production of lime milk, the CO ₂ gas is conducted to complete the carbonation reaction, while the obtained average particle size is 0.05μm Milk of lime was added to calcium carbonate seed particles (a 10% by mass aqueous dispersion) and aged to a particle diameter of 1.2 μm, followed by dehydration and drying. The iron element content of the calcium carbonate particles was 70 ppm. Then, polyacrylic acid ammonium salt (manufactured by Toagosei Co., Ltd.: A-30SL) was added so as to become 1.0% by mass relative to calcium carbonate, slurried with ethylene glycol, and wet pulverized to obtain an average 50% by mass ethylene glycol slurry of calcite-type synthetic calcium carbonate particles with a particle size of 1.1 μm. Then, it was diluted with ethylene glycol to a concentration of 35% by mass, and the slurry was supplied with a ball rotation speed of 4000 rpm, a back drive rotation speed of 1800 rpm, and a supply speed of 0.4 m ³ /hr using a Super-D-Canter (P-3000 manufactured by TOMOE). The material temperature was 35°C, wet classification was carried out, and finally diluted with ethylene glycol to a concentration of 10% by mass, and filtered with a 10 μm filter before use.

(Manufacture of polyester composition 1)

The slurry of terephthalic acid and ethylene glycol (ethylene glycol /Terephthalic acid molar ratio is 1.15). During the supply of the slurry, a pressure of 0.1 MPa was applied in the esterification reaction device, and the esterification reaction was carried out at 250°C. The direct polymerization oligomer with an esterification reaction rate of 98.0% was obtained in a reaction time of 4 hours. Move the charged part of the esterification reactant to the polycondensation reaction tank. The average degree of polymerization of the low polymer system of this esterification reaction product was 7.0. To this low polymer, 0.23 moles of ethylene glycol was first added under normal pressure, and 5 minutes later, the concentration was 230 ppm for antimony, 65 ppm for magnesium, and 65 ppm for lithium. Add antimony trioxide/magnesium acetate‧4hydrate/lithium acetate‧2hydrate at 2ppm, add 0.23 moles of ethylene glycol after 5 minutes, and make it 45ppm after 5 minutes Trimethyl phosphate (((1/2)A+M)/P=1.94) was added, and after 5 minutes again, it was added so that the total molar ratio became 1.85 (the total amount of added ethylene glycol added in three times 0.7 mol) was added 0.24 mol of ethylene glycol. The average degree of polymerization of the low polymer is 2.1. Then, the 10% by mass ethylene glycol slurry of the calcium carbonate particles prepared above was added to oligomerization under normal pressure at 250° C. in things. After stirring for 10 minutes, the reaction system was slowly lowered from normal pressure to 100 Pa, and the temperature was raised to 290°C to complete the polycondensation reaction, and polyester composition 1 was obtained.

(Manufacture of polyester composition 2)

Polyester composition 2 containing only calcium carbonate particles was produced in the same manner as polyester composition 1 above.

(Manufacture of polyester film 18)

From the recycled raw materials of the film described below and the polyester composition 1, the B layer (26 μm) blended at 50% by weight, and the polyester composition 1 and the polyester composition 2 are 0.5 in terms of calcium carbonate particles. The layer A (2 μm) was blended in the weight % to obtain a polyester film (total thickness 30 μm) with a 3-layer laminate structure of layer A (2 μm)/layer B (26 μm)/layer A (2 μm).

Specifically, recycled polyester compositions 1 and 2 and films were blended, dried under reduced pressure at 160°C for 8 hours, supplied to an extruder, melt-extruded at 275°C, and filtered with high precision to obtain 3 layers of buildup. Then, through a slit die maintained at 285°C, static electricity was applied to a cooling roll, wound on a casting drum with a surface temperature of 25°C, cooled and solidified to obtain an unstretched laminated film. The unstretched laminated film was stretched 3.6 times in the length direction and 4.1 times in the width direction at 95°C by a linear motor-type simultaneous biaxial stretching machine, for a total of 14.8 times, and then stretched again at 180°C at Stretch 1.05 times in the width direction, and heat-treat at 220°C for 3 seconds at a fixed length to obtain a polyester film with a total thickness of 30 μm. The haze value of this polyester film was 7.0%.

<Mylar 19>

It manufactured similarly to the polyester film 18 except having changed the average particle diameter of calcium carbonate into 0.3 micrometers. The haze value of this polyester film is 6.0%.

<polyester film 20>

It manufactured similarly to the polyester film 18 except having changed the average particle diameter of calcium carbonate into 1.7 micrometers. The haze value of this polyester film is 10.5%.

[Example 31]

On one side of the polyester film 11, the composition p21 of Example 21 was coated as the composition (II) with a gravure coater, and after drying at 100°C, it was irradiated with 300mJ/ ^cm2 of ultraviolet rays to harden it to form a release layer And make release film. The thickness of the release layer is 200nm.

[Example 32]

Except having changed into the composition p22 of Example 22, it carried out similarly to Example 31, and produced the release film.

[Example 33]

Except having changed into the following composition p31, it carried out similarly to Example 31, and produced the release film.

<Composition p31>

10 parts by mass of the non-polymerizable long-chain alkyl group-containing compound (α2-2) synthesized below, 66 parts by mass of urethane acrylate as the polymerizable compound (β) (Kyoeisha Chemical Co., Ltd. "UA-306T" manufactured by Ciba Specialty Chemicals Co., Ltd.), 33 parts by mass of tricyclodecane dimethanol acrylate, 3 parts by mass of photopolymerization initiator (Irgacure 184 produced by Ciba Specialty Chemicals Co., Ltd.), mixed with toluene and isopropanol The solvent (toluene:IPA=3:1 (mass ratio)) was prepared so that the solid content concentration would be 4% by mass.

<Synthesis of non-polymerizable long-chain alkyl group-containing compound (α2-2)>

In a 4-neck flask equipped with a stirrer, nitrogen introduction pipe, cooling pipe, and rubber septum, add 50 parts by weight of octadecyl acrylate, and further add 1.2 parts by weight of 2,2'-bipyridine to replace nitrogen in the system . Under nitrogen flow, add 0.5 parts by mass of copper bromide, heat the reaction system to 90°C, add 0.6 parts by mass of polymerization initiator (ethyl 2-bromoisobutyrate) to start polymerization, without solvent, in nitrogen Polymerization was carried out at 90°C for 10 hours under flow. After confirming that the polymerization rate was 85% by weight or more, 33 parts by mass of 2-ethylhexyl acrylate was added from the rubber separator, and heated at 110° C. for 20 hours.

In this way, an A-B type diblock polymer of stearyl acrylate polymer block and 2-ethylhexyl acrylate polymer block was obtained. This was heated to 60° C., centrifuged at a centrifugal force of 8,000 g for 30 minutes, and a supernatant polymer was obtained. Add 10 parts by mass of sulfonic acid ion exchange resin to 50 parts by mass of this polymer, stir at 100°C for 1 hour, filter off the ion exchange resin, and obtain a long-chain alkyl compound (polymer) with a number average molecular weight of 25,000 .

[Example 34]

Except having changed into the polyester film 14, it carried out similarly to Example 31, and produced the release film.

[Example 35]

Except having changed into the polyester film 15, it carried out similarly to Example 31, and produced the release film.

[Example 36]

Except having changed into the polyester film 16, it carried out similarly to Example 31, and produced the release film.

[Example 37]

Except having changed into the polyester film 18, it carried out similarly to Example 31, and produced the release film.

[Example 38]

Except having changed into the polyester film 19, it carried out similarly to Example 31, and produced the release film.

[Example 39]

On one side of the polyester film 11, the following composition p32 was coated as the composition (I) with a gravure coater, pre-dried at 100° C., and then heated and dried at 170° C. to form a release layer, and a release film was produced. The thickness of the release layer is 120nm.

<Composition p32>

‧Long-chain alkyl group-containing compound (a): 10 parts by mass of long-chain alkyl group-containing polyethylene resin ("Piroiru" 1050 of LION SPECIALTY CHEMICALS Co., Ltd.) in terms of solid content

‧Crosslinking agent (b): 25 parts by mass of melamine-based crosslinking agent in terms of solid content ("U-VAN" 28-60 of Mitsui Chemicals Co., Ltd.)

‧Acid catalyst (c): 1.8 parts by mass of p-toluenesulfonic acid in terms of solid content ("TAYCACURE" AC-707 of TAYCA Co., Ltd.)

‧Solvent: Adjust to a solid content concentration of 2.0% by mass with a mixed solvent (toluene:methyl ethyl ketone:cyclohexanone=45:45:10 (mass ratio)).

[Example 40]

Except having changed into the following composition p33, it carried out similarly to Example 39, and produced the release film.

<Composition p33>

‧Long-chain alkyl group-containing compound (a): 10 parts by mass of long-chain alkyl group-containing polyethylene resin ("Piroiru" 1050 of LION SPECIALTY CHEMICALS Co., Ltd.) in terms of solid content

‧Crosslinking agent: Melamine-based crosslinking agent ("U-VAN" 28-60 of Mitsui Chemicals Co., Ltd., 90 parts by mass in terms of solid content)

‧Acid catalyst (c): 6.3 parts by mass of p-toluenesulfonic acid in terms of solid content ("TAYCACURE" AC-707 of TAYCA Co., Ltd.)

‧Solvent: Adjust to a solid content concentration of 2.0% by mass with a mixed solvent (toluene:methyl ethyl ketone:cyclohexanone=45:45:10 (mass ratio)).

[Example 41]

Except having changed into the following composition p34, it carried out similarly to Example 39, and produced the release film.

<Composition p34>

‧Long-chain alkyl group-containing compound (a): 10 parts by mass of long-chain alkyl group-containing polyethylene resin ("Piroiru" 1050 of LION SPECIALTY CHEMICALS Co., Ltd.) in terms of solid content

‧Crosslinking agent (b): 190 parts by mass of melamine-based crosslinking agent in terms of solid content ("U-VAN" 28-60 of Mitsui Chemicals Co., Ltd.)

‧Acid catalyst (c): 13.3 parts by mass of p-toluenesulfonic acid in terms of solid content ("TAYCACURE" AC-707 of TAYCA Co., Ltd.)

‧Solvent: Adjust to a solid content concentration of 2.0% by mass with a mixed solvent (toluene:methyl ethyl ketone:cyclohexanone=45:45:10 (mass ratio)).

[Comparative Example 31]

On one side of the polyester film 11, the following composition p35 was coated with a gravure coater, pre-dried at 100° C., and then heat-dried at 170° C. to form a release layer, thereby producing a release film. The thickness of the release layer is 120nm.

<Composition p35>

The long-chain alkyl group-containing compound (a) ("ASHIO RESIN (registered trademark)" RA-95H of ASHIO-SANGYO Co., Ltd.) was 10 parts by mass in terms of solid content, and 1.3 parts by mass in terms of solid content. One part acid catalyst (p-toluenesulfonic acid ("TAYCACURE" AC-700 of TAYCA Co., Ltd.)) was dissolved in toluene to prepare a coating liquid having a solid content concentration of 2.0% by mass.

[Comparative Example 32]

Except having changed into the polyester film 12, it carried out similarly to the comparative example 31, and produced the release film.

[Comparative Example 33]

Except having changed into the polyester film 13, it carried out similarly to the comparative example 31, and produced the release film.

[Comparative Example 34]

Except having changed into the polyester film 17, it carried out similarly to the comparative example 31, and produced the release film.

[Comparative Example 35]

Except having changed into the polyester film 20, it carried out similarly to the comparative example 31, and produced the release film.

[evaluate]

The release films of the examples and comparative examples prepared above were evaluated in accordance with the above-mentioned measurement method and evaluation method. The results are shown in Table 3.

1‧‧‧Semiconductor components (chips)

2‧‧‧substrate

3‧‧‧Sealing material

4‧‧‧Release film

10‧‧‧Lower mold

20‧‧‧upper mold

Claims (15)

A release film, which is a release film with a release layer on at least one side of a substrate film, wherein the release layer is a hardened layer of composition (I) or composition (II), and the surface of the release layer The free energy is 20~35mJ/m ² , the centerline average roughness Ra of the surface of the release layer is more than 200nm, and the haze value of the release film is 1.5~8.0%; composition (I): a thermosetting composition, It contains a compound (a) containing an alkyl group having 8 or more carbon atoms and a crosslinking agent (b); Composition (II): an active energy ray curable composition containing a compound containing an alkyl group having 8 or more carbon atoms ( a). As the release film of claim 1, wherein the crosslinking agent (b) in the composition (I) is a melamine-based crosslinking agent. Such as the release film of claim 1, wherein the compound (a) containing an alkyl group with 8 or more carbons in the composition (I) is a polyethylene resin containing an alkyl group with 8 or more carbons or a compound (a) containing an alkyl group with 8 or more carbons Alkyl alkyd resin. The release film according to claim 1, wherein the compound (α) containing an alkyl group with 8 or more carbon atoms in the composition (II) is a polymer containing an ethylenically unsaturated group and an alkyl group with 8 or more carbon atoms in the molecule A compound (α1) containing a long-chain alkyl group. The release film according to claim 1, wherein the composition (II) further contains a polymerizable compound (β) which contains an ethylenically unsaturated group in its molecule and does not contain an alkyl group having 8 or more carbon atoms. The release film of any one of claims 1 to 5, wherein the substrate film is 3 Laminated layer construction. The release film according to any one of Claims 1 to 5, wherein the base film has a 3-layer laminate structure including A layer/B layer/A layer. The release film according to any one of claims 1 to 5, wherein the centerline average roughness Ra of the surface of the laminated release layer of the base film is 100 nm or more. The release film according to any one of claims 1 to 5, wherein the centerline average roughness Ra of the release film on the side opposite to the laminated release layer is 20 nm or more. The release film according to any one of claims 1 to 5, wherein the centerline average roughness Ra of both sides of the base film is 100 nm or more. The release film according to any one of Claims 1 to 5, wherein the stresses of the base film at 150°C in the longitudinal direction (MD direction) and width direction (TD direction) of 100% elongation are each 60 MPa or less. A compression molding method, which is a compression molding method in which a release film, a sealing material, and a semiconductor element according to any one of claims 1 to 11 are sequentially arranged in a mold and heated and pressurized, wherein the release film The release film is arranged such that the release layer of the film faces the sealing material. A manufacturing method of a semiconductor package, which uses the compression molding method as claimed in claim 12. A laminated film, which is on the release layer of the release film according to any one of claims 1 to 11, and is laminated with any transfer film selected from the group consisting of a ceramic layer, an adhesive layer and a photosensitive resin layer. printing layer. A laminated film which is laminated on a support film with any transfer printing selected from the group consisting of a ceramic layer, an adhesive layer and a photosensitive resin layer layer, further laminated on the transfer layer with the release layer facing the transfer layer, such as the release film of any one of Claims 1 to 11.

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