WO2019082966A1 - 保護膜形成用フィルム、保護膜形成用複合シート、及び半導体チップの製造方法 - Google Patents

保護膜形成用フィルム、保護膜形成用複合シート、及び半導体チップの製造方法

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Publication number
WO2019082966A1
WO2019082966A1 PCT/JP2018/039660 JP2018039660W WO2019082966A1 WO 2019082966 A1 WO2019082966 A1 WO 2019082966A1 JP 2018039660 W JP2018039660 W JP 2018039660W WO 2019082966 A1 WO2019082966 A1 WO 2019082966A1
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WO
WIPO (PCT)
Prior art keywords
protective film
film
forming
meth
sensitive adhesive
Prior art date
Application number
PCT/JP2018/039660
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
力也 小橋
洋一 稲男
Original Assignee
リンテック株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to CN201880069262.XA priority Critical patent/CN111279468B/zh
Priority to JP2019551240A priority patent/JP7086986B2/ja
Priority to KR1020207011563A priority patent/KR102448152B1/ko
Publication of WO2019082966A1 publication Critical patent/WO2019082966A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/52—Mounting semiconductor bodies in containers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation

Definitions

  • the present invention relates to a protective film-forming film, a protective film-forming composite sheet, and a method of manufacturing a semiconductor chip.
  • semiconductor devices have been manufactured to which a mounting method called a so-called face down method is applied.
  • a mounting method called a so-called face down method
  • a semiconductor chip having electrodes such as bumps on a circuit surface is used, and the electrodes are bonded to a substrate. Therefore, the back surface of the semiconductor chip opposite to the circuit surface may be exposed.
  • a resin film containing an organic material is formed as a protective film on the back surface of the exposed semiconductor chip, and may be taken into a semiconductor device as a semiconductor chip with a protective film.
  • the protective film is used to prevent the occurrence of cracks in the semiconductor chip after the dicing process or packaging.
  • a composite sheet for forming a protective film comprising a protective film-forming film for forming a protective film on a support sheet.
  • the film for protective film formation can form a protective film by hardening.
  • the support sheet can be used to fix the semiconductor wafer when dividing a semiconductor wafer provided with a protective film-forming film or a protective film on the back surface into semiconductor chips.
  • the support sheet can also be used as a dicing sheet, and the composite sheet for protective film formation can also be used as an integrated film of the protective film formation film and the dicing sheet.
  • thermosetting protective film-forming film that forms a protective film by curing by heating
  • heat curing of a thermosetting protective film-forming film usually requires a long time of about several hours, shortening of the curing time is desired.
  • a film for forming a protective film that is curable by energy ray
  • energy rays such as ultraviolet rays
  • Patent Document 1 discloses an energy ray-curable film for chip protection that is attached to the back surface of a circuit formation surface of a wafer.
  • the energy ray-curable film for chip protection has a peeling film and an energy ray-curable protective film forming layer formed on the peeling film.
  • the energy ray-curable protective film-forming layer contains, in addition to the energy ray-curable component, a non-energy ray-curable component as a binder polymer component.
  • the semiconductor chip on which the protective film is formed using the energy ray-curable film for chip protection described in Patent Document 1 is bonded to a desired device by heating.
  • a component having a relatively low molecular weight may segregate on the surface of the protective film and the surface gloss of the protective film may be significantly reduced.
  • the design of the protective film is reduced and the visibility when printed on the surface of the protective film is reduced.
  • the protective film can suppress the reduction of the surface gloss of the protective film. It is an object of the present invention to provide a film for forming, a composite sheet for forming a protective film including the film for forming a protective film, and a method for manufacturing a semiconductor chip using the film for forming a protective film or the composite sheet for forming a protective film. Do.
  • the present invention is a film for forming an energy ray-curable protective film, wherein the film for forming a protective film is attached to a semiconductor wafer, and the gloss value measured after irradiating the energy ray is The protective film-forming film is attached to a semiconductor wafer, irradiated with energy rays, and further heated at 260 ° C. for 5 minutes to provide a protective film-forming film having a reduction rate of the gloss value of 30% or less.
  • the present invention provides a composite sheet for protective film formation, which comprises a support sheet, and the protective film-forming film is provided on the support sheet.
  • a step of sticking the film for forming a protective film or the film for forming a protective film in the composite sheet for forming a protective film on a semiconductor wafer, and the film for forming the protective film after being stuck to the semiconductor wafer Irradiating the substrate with ultraviolet light to form a protective film, and cutting the semiconductor wafer together with the protective film or the film for forming a protective film to divide the semiconductor wafer to obtain a plurality of semiconductor chips. And providing a method of manufacturing a semiconductor chip.
  • the film for protective film formation of the present invention has a decrease in surface gloss of the protective film even when the semiconductor chip provided with the protective film which is a cured product of the film for protective film formation on the back surface is heated for the purpose of bonding. It can be suppressed. Further, according to the present invention, there is provided a composite sheet for forming a protective film provided with the film for forming a protective film, and a method of manufacturing a semiconductor chip using the film for forming a protective film or the composite sheet for forming a protective film. .
  • a protective film-forming film according to an embodiment of the present invention is an energy ray-curable protective film-forming film, and the protective film-forming film is attached to a semiconductor wafer to form an energy ray.
  • the film for forming a protective film is attached to a semiconductor wafer with respect to the gloss value measured after the irradiation, and the decrease rate of the gloss value measured after irradiating the energy beam for 5 minutes at 260 ° C. is 30% or less And preferably 25% or less, more preferably 20% or less.
  • the reduction rate of the gloss value is equal to or less than the upper limit, A reduction in surface gloss can be suppressed.
  • the reduction rate of the gloss value is most preferably 0%, but even when the semiconductor chip provided with a protective film which is a cured product of a film for protective film formation on the back surface is heated for the purpose of bonding etc.
  • the reduction rate may be low enough to sufficiently suppress the reduction in surface gloss of the protective film. From this viewpoint, the reduction rate of the gloss value may be 1% or more, or 2% or more.
  • the gloss value can be measured with a gloss meter (for example, “VG7000” manufactured by Nippon Denshoku Kogyo Co., Ltd.) under the condition of an incident angle of 60 °.
  • VG7000 manufactured by Nippon Denshoku Kogyo Co., Ltd.
  • the reduction rate of the gloss value can be obtained by dividing the difference between the gloss value before heating and the gloss value after heating by the gloss value before heating.
  • a composite sheet for forming a protective film can be configured by providing the film for forming a protective film on a support sheet.
  • the film for protective film formation is cured by irradiation of energy rays to be a protective film.
  • the protective film protects the back surface (surface opposite to the electrode formation surface) of the semiconductor wafer or the semiconductor chip.
  • the protective film-forming film is soft and can be easily attached to an object to be attached. Since the film for protective film formation is energy ray curable, the protective film can be formed by curing in a shorter time than the thermosetting film for protective film formation.
  • the “protective film-forming film” means one before curing, and the “protective film” means one obtained by curing the protective film-forming film.
  • the protective film-forming film contains at least an energy ray curable component.
  • the energy ray curable component energy ray polymerization obtained by reacting a non-energy ray curable acrylic polymer with a compound containing an energy ray polymerizable group, wherein the energy ray curable group is introduced into the acrylic polymer It is preferable to contain an acrylic acrylic polymer (hereinafter, also referred to as "adduct type acrylic polymer").
  • the energy ray-curable component is preferably uncured, preferably has tackiness, and more preferably is uncured and tacky.
  • the term "energy beam” means an electromagnetic wave or charged particle beam having an energy quantum, and examples thereof include ultraviolet light, radiation, electron beam and the like.
  • the ultraviolet light can be irradiated, for example, by using a high pressure mercury lamp, a fusion H lamp, a xenon lamp, a black light or an LED lamp as an ultraviolet light source.
  • the electron beam can irradiate what was generated by the electron beam accelerator or the like.
  • energy ray curing property means the property of curing by irradiation with energy rays
  • non energy ray curing property means the property of not curing even by irradiation of energy rays. .
  • the film for protective film formation may be only one layer (single layer), or two or more layers, and in the case of multiple layers, these multiple layers may be the same or different from one another.
  • the combination is not particularly limited.
  • "a plurality of layers may be the same as or different from each other” means “all layers may be the same or all layers are It may be different, meaning that only some of the layers may be the same.
  • “a plurality of layers are different from each other” means “at least one of the constituent material and thickness of each layer is different from each other” It means that.
  • the thickness of the protective film-forming film is preferably 1 to 100 ⁇ m, more preferably 3 to 75 ⁇ m, and particularly preferably 5 to 50 ⁇ m.
  • a protective film with higher protective ability can be formed.
  • the thickness of the film for protective film formation being below the said upper limit, it is suppressed that a protective film becomes excessive thickness.
  • the thickness of the film for protective film formation means the thickness of the whole film for protective film formation, for example, the thickness of the film for protective film formation which consists of multiple layers is a film for protective film formation. Means the total thickness of all the layers that make up.
  • the curing conditions for curing the protective film-forming film to form a protective film are not particularly limited as long as the protective film has a curing degree sufficient to exhibit its function, and the type of protective film-forming film Depending on the situation, it may be selected appropriately.
  • the illuminance of the energy ray is preferably 4 to 280 mW / cm 2 at the time of curing of the protective film-forming film.
  • the light quantity of the energy ray at the time of curing is preferably 3 to 1000 mJ / cm 2 .
  • FIG. 1 is a cross-sectional view schematically showing a protective film-forming film according to an embodiment of the present invention.
  • the main parts may be enlarged for convenience for the sake of easy understanding of the features of the present invention, and the dimensional ratio of each component is the same as the actual one. Not necessarily.
  • the film 13 for protective film formation shown here is provided with the 1st peeling film 151 on one surface (it may be called a "1st surface” in this specification) 13a, and the said 1st surface 13a
  • a second release film 152 is provided on the other surface (which may be referred to herein as the “second surface”) 13b of the opposite side.
  • Such a protective film-forming film 13 is suitable, for example, for storage as a roll.
  • the film 13 for protective film formation can be formed using the composition for protective film formation mentioned later.
  • the protective film-forming film 13 is energy ray curable.
  • Both the first release film 151 and the second release film 152 may be known ones.
  • the first release film 151 and the second release film 152 may be identical to each other, or may be different from each other, for example, the release forces necessary for releasing from the protective film-forming film 13 may be different from each other. May be
  • one of the first release film 151 and the second release film 152 is removed, and the back surface of the semiconductor wafer (not shown) is attached to the resulting exposed surface. And the other of the remaining of the 1st exfoliation film 151 and the 2nd exfoliation film 152 is removed, and the generated exposed side turns into the sticking side of a support sheet.
  • the film for protective film formation can be formed using the composition for protective film formation containing the constituent material.
  • the composition for protective film formation may be coated on the formation target surface of the film for protective film formation, and dried as needed, so that the film for protective film formation can be formed on the target site.
  • the ratio of the content of components which do not vaporize at normal temperature in the composition for forming a protective film is usually the same as the ratio of the content of the components of the film for forming a protective film.
  • “normal temperature” means a temperature which is not particularly cooled or heated, ie, a normal temperature, and includes, for example, a temperature of 15 to 25 ° C. and the like.
  • Coating of the composition for forming a protective film may be performed by a known method, for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, Examples include methods using various coaters such as a screen coater, a Mayer bar coater, and a kiss coater.
  • composition for protective film formation contains the solvent mentioned below, it is preferred to carry out heat drying.
  • the composition for forming a protective film containing a solvent is preferably dried, for example, at 70 to 130 ° C. for 10 seconds to 5 minutes.
  • composition for forming protective film (IV-1) includes a composition for forming a protective film (IV-1) containing at least the energy ray curable component (a).
  • the energy ray curable component (a) is a component which is cured by irradiation of energy rays, and is also a component for imparting film forming property, flexibility and the like to the protective film forming film.
  • the energy ray curable component (a) includes, for example, an energy ray curable group, a polymer (a1) having a weight average molecular weight of 80000 to 2,000,000, and an energy ray curable group, and a molecular weight of 100 to 80,000.
  • the compound (a2) of At least a part of the polymer (a1) may or may not be crosslinked by a crosslinking agent (f) described later.
  • the weight average molecular weight means a polystyrene equivalent value measured by gel permeation chromatography (GPC) unless otherwise specified.
  • Examples of the polymer (a1) having a weight average molecular weight of 80000 to 2000000 and having an energy ray curable group include the above-mentioned adduct type acrylic polymer (a1-1).
  • the adduct type acrylic polymer (a1-1) comprises an acrylic polymer (a11) having a functional group capable of reacting with a group possessed by another compound, a group reactive with the functional group, and an energy ray-curable double polymer. It can be obtained by reacting an energy ray-curable compound (a12) having an energy ray-curable group such as bonding.
  • Examples of the functional group capable of reacting with a group possessed by another compound include, for example, a hydroxyl group, a carboxy group, an amino group, and a substituted amino group (hereinafter, “substituted amino group” means one or two hydrogens of the amino group) It means a group in which an atom is substituted by a group other than a hydrogen atom), an epoxy group and the like.
  • the functional group is preferably a group other than a carboxy group.
  • the functional group is preferably a hydroxyl group.
  • Acrylic polymers having functional groups (a11) examples include those obtained by copolymerizing an acrylic monomer having the functional group and an acrylic monomer having no functional group. In addition to the monomers, monomers (non-acrylic monomers) other than acrylic monomers may be copolymerized.
  • the acrylic polymer (a11) may be a random copolymer or a block copolymer.
  • a hydroxyl-containing monomer a carboxy-group containing monomer, an amino-group containing monomer, a substituted amino-group containing monomer, an epoxy-group containing monomer etc. are mentioned, for example.
  • hydroxyl group-containing monomer examples include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) Hydroxyalkyl (meth) acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; non (meth) acrylics such as vinyl alcohol and allyl alcohol A saturated alcohol (unsaturated alcohol which does not have a (meth) acryloyl frame) etc. are mentioned.
  • (meth) acrylic acid is a concept including both “acrylic acid” and “methacrylic acid”. The same applies to terms similar to (meth) acrylic acid.
  • carboxy group-containing monomer examples include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth) acrylic acid and crotonic acid; fumaric acid, itaconic acid, maleic acid, citraconic Ethylenically unsaturated dicarboxylic acids such as acids (dicarboxylic acids having an ethylenically unsaturated bond); anhydrides of the above-mentioned ethylenically unsaturated dicarboxylic acids; (meth) acrylic acid carboxyalkyl esters such as 2-carboxyethyl methacrylate and the like Be
  • monocarboxylic acids having an ethylenically unsaturated bond such as (meth) acrylic acid and crotonic acid
  • fumaric acid, itaconic acid, maleic acid, citraconic Ethylenically unsaturated dicarboxylic acids such as acids (dicar
  • the acrylic monomer having a functional group is preferably a hydroxyl group-containing monomer or a carboxy group-containing monomer, and more preferably a hydroxyl group-containing monomer.
  • the acrylic monomer having the functional group constituting the acrylic polymer (a11) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof are optionally It can be selected.
  • acrylic monomer having no functional group examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate and n (meth) acrylate -Butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate ( 2-ethylhexyl acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth) Undecyl acrylate, dodec
  • acrylic monomer having no functional group examples include alkoxyalkyl groups such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate.
  • (meth) acrylic acid ester Containing (meth) acrylic acid ester; (meth) acrylic acid aryl ester such as phenyl (meth) acrylate etc., (meth) acrylic acid ester having an aromatic group; non-crosslinkable (meth) acrylamide and derivatives thereof And (meth) acrylic acid esters having a non-crosslinkable tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate.
  • the acrylic monomer having no functional group constituting the acrylic polymer (a11) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof are arbitrary. Can be selected.
  • non-acrylic monomers examples include olefins such as ethylene and norbornene; vinyl acetate; styrene and the like.
  • the non-acrylic monomer constituting the acrylic polymer (a11) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the ratio (content) of the amount of the structural unit derived from the acrylic monomer having the functional group to the total amount of the structural units constituting the same is 0.1 to 50 mass % Is preferable, 1 to 40% by mass is more preferable, and 3 to 30% by mass is particularly preferable.
  • the content of the energy ray-curable group contained therein can be easily adjusted so that the degree of curing of the protective film falls within a preferred range.
  • the acrylic polymer (a11) constituting the adduct type acrylic polymer (a1-1) may be only one type, or two or more types, and in the case of two or more types, a combination and ratio thereof Is optional.
  • the content of the adduct type acrylic polymer (a1-1) is 1 to 10 parts by mass relative to the total mass of the composition (IV-1) for forming a protective film.
  • the content is preferably 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 10 to 35% by mass.
  • the energy ray curable compound (a12) is one or two selected from the group consisting of an isocyanate group, an epoxy group and a carboxy group as a group capable of reacting with the functional group possessed by the acrylic polymer (a11) What has the above is preferable, and what has an isocyanate group as said group is more preferable.
  • the energy beam curable compound (a12) has, for example, an isocyanate group as the group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.
  • the energy ray curable compound (a12) preferably has 1 to 5, and more preferably 1 to 3 of the energy ray curable groups in one molecule.
  • Examples of the energy ray curable compound (a12) include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, 1,1- (bisacryloyloxymethyl) Ethyl isocyanate; Acryloyl monoisocyanate compounds obtained by the reaction of diisocyanate compounds or polyisocyanate compounds with hydroxyethyl (meth) acrylate; The acryloyl monoisocyanate compound etc.
  • the energy ray curable compound (a12) is preferably 2-methacryloyloxyethyl isocyanate.
  • the energy ray-curable compound (a12) constituting the adduct type acrylic polymer (a1-1) may be only one type, or two or more types, and in the case of two or more types, a combination thereof and The ratio can be selected arbitrarily.
  • an energy ray curable group derived from the energy ray curable compound (a12) relative to the content of the functional group derived from the acrylic polymer (a11) The content ratio of is preferably 1 to 90 mol%, more preferably 5 to 80 mol%, still more preferably 10 to 70 mol%, and preferably 20 to 40 mol%. Is particularly preferred.
  • the adhesive force of the protective film formed by hardening becomes larger because the ratio of the said content is such a range.
  • the upper limit of the content ratio is 100 mol%, but the energy ray In the case where the curable compound (a12) is a polyfunctional compound (having two or more of the groups in one molecule), the upper limit of the content ratio may exceed 100 mol%.
  • the weight average molecular weight (Mw) of the polymer (a1) is preferably 100,000 to 2,000,000, and more preferably 300,000 to 1,500,000.
  • the polymer (a1) When the polymer (a1) is at least a part of which is crosslinked by the crosslinking agent (f), the polymer (a1) has been described as constituting the acrylic polymer (a11) And a monomer which does not correspond to any of the above-mentioned monomers and which has a group reactive with the crosslinking agent (f) may be polymerized and crosslinked in the group reactive with the crosslinking agent (f) The group which reacts with the functional group and is derived from the energy ray curable compound (a12) may be crosslinked.
  • composition (IV-1) for forming a protective film and the polymer (a1) contained in the film for forming a protective film may be only one type, or two or more types, and in the case of two or more types, Combinations and ratios can be selected arbitrarily.
  • Compound (a2) having an energy ray curable group and having a molecular weight of 100 or more and less than 80,000 examples include a group containing an energy ray-curable double bond. Meta) acryloyl group, a vinyl group etc. are mentioned.
  • the compound (a2) is not particularly limited as long as it satisfies the above conditions, but a low molecular weight compound having an energy ray curable group, an epoxy resin having an energy ray curable group, and an energy ray curable group A phenol resin etc. are mentioned.
  • a low molecular weight compound which has an energy ray curable group among the said compounds (a2) a polyfunctional monomer, an oligomer, etc. are mentioned, for example,
  • the acrylate type compound which has a (meth) acryloyl group is preferable.
  • the acrylate compound examples include 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, polyethylene glycol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, and 2,2-bis [4 -((Meth) acryloxypolyethoxy) phenyl] propane, ethoxylated bisphenol A di (meth) acrylate, 2,2-bis [4-((meth) acryloxydiethoxy) phenyl] propane, 9,9-bis [4- (2- (Meth) acryloyloxyethoxy) phenyl] fluorene, 2,2-bis [4-((meth) acryloxypolypropoxy) phenyl] propane, tricyclodecanedimethanol di (meth) acrylate (tri) Cyclodecane dimethylol di (meth) a 1,10-decanediol di (meth) acrylate, 1,6-he
  • an epoxy resin having an energy ray-curable group and a phenol resin having an energy ray-curable group are described, for example, in paragraph 0043 of "JP-A-2013-194102" and the like. The thing can be used.
  • Such a resin also corresponds to a resin constituting a thermosetting component (h) described later, but in the present invention, it is handled as the compound (a2).
  • the molecular weight of the compound (a2) is preferably 100 to 30,000, and more preferably 300 to 10,000.
  • the molecular weight can be calculated from its formula weight.
  • the molecular weight means a weight average molecular weight.
  • composition for forming a protective film (IV-1) and the compound (a2) contained in the film for forming a protective film may be only one type, or two or more types, and in the case of two or more types, a combination thereof And the ratio can be selected arbitrarily.
  • the protective film-forming film contains the energy ray-curable component (a)
  • the energy ray-curable group is irradiated with ultraviolet rays to turn the protective film-forming film into a protective film.
  • the linear curable component (a) polymerizing and the low molecular weight polymer being hardly contained in the protective film, the low molecular weight polymer is less likely to be segregated on the surface of the protective film even if the protective film is heated.
  • the film for protective film formation contains the energy ray-curable component (a), the film for protective film formation is stuck on a semiconductor wafer, and the gloss measured after irradiating with an energy ray With respect to the value, the film for forming a protective film is attached to a semiconductor wafer, irradiated with energy rays, and further heated at 260 ° C. for 5 minutes, and the reduction rate of the gloss value measured is 30% or less.
  • composition for forming a protective film (IV-1) and the film for forming a protective film may contain a polymer (b) having no energy ray curable group.
  • the polymer (b) may be at least a part of which is crosslinked by a crosslinking agent (f) described later, or may not be crosslinked.
  • polymer (b) which does not have an energy ray curable group for example, an acrylic polymer, phenoxy resin, urethane resin, polyester, rubber resin, acrylic urethane resin, polyvinyl alcohol (PVA), butyral resin, polyester urethane Resin etc. are mentioned.
  • the polymer (b) is preferably an acrylic polymer (hereinafter sometimes abbreviated as “acrylic polymer (b-1)”).
  • the acrylic polymer (b-1) may be a known one, for example, may be a homopolymer of one acrylic monomer, or a copolymer of two or more acrylic monomers, It may also be a copolymer of one or more acrylic monomers and a monomer (non-acrylic monomer) other than one or more acrylic monomers.
  • acrylic monomer constituting the acrylic polymer (b-1) examples include (meth) acrylic acid alkyl ester, (meth) acrylic acid ester having a cyclic skeleton, glycidyl group-containing (meth) acrylic acid ester, Examples thereof include hydroxyl group-containing (meth) acrylic acid esters and substituted amino group-containing (meth) acrylic acid esters.
  • substituted amino group is as described above.
  • Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n- (meth) acrylate Butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, (meth) acrylate ) 2-ethylhexyl acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth
  • Examples of the (meth) acrylic acid ester having a cyclic skeleton include (meth) acrylic acid cycloalkyl esters such as (meth) acrylic acid isobornyl and (meth) acrylic acid dicyclopentanyl; (Meth) acrylic acid aralkyl esters such as benzyl (meth) acrylate; (Meth) acrylic acid cycloalkenyl esters such as (meth) acrylic acid dicyclopentenyl ester; Examples include (meth) acrylic acid cycloalkenyloxyalkyl esters such as (meth) acrylic acid dicyclopentenyl oxyethyl ester and the like.
  • glycidyl group containing (meth) acrylic acid ester glycidyl (meth) acrylate etc.
  • hydroxyl group-containing (meth) acrylic acid ester examples include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxy (meth) acrylate Propyl, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like can be mentioned.
  • substituted amino group-containing (meth) acrylic acid ester examples include N-methylaminoethyl (meth) acrylate and the like.
  • non-acrylic monomer constituting the acrylic polymer (b-1) examples include olefins such as ethylene and norbornene; vinyl acetate; styrene and the like.
  • the reactive functional group in the polymer (b) is a crosslinking agent (f What reacted with) is mentioned.
  • the reactive functional group may be appropriately selected depending on the type of the crosslinking agent (f) and the like, and is not particularly limited.
  • the crosslinking agent (f) is a polyisocyanate compound
  • examples of the reactive functional group include a hydroxyl group, a carboxy group, an amino group and the like, and among these, a hydroxyl group having high reactivity with the isocyanate group. Is preferred.
  • the crosslinking agent (f) is an epoxy compound
  • examples of the reactive functional group include a carboxy group, an amino group, an amido group and the like, among which a carboxy group having high reactivity with the epoxy group is preferable.
  • the reactive functional group is a group other than a carboxy group in terms of preventing corrosion of the circuit of the semiconductor wafer or the semiconductor chip.
  • a polymer (b) which does not have an energy ray curable group which has the said reactive functional group the thing obtained by polymerizing the monomer which has at least the said reactive functional group is mentioned, for example.
  • the acrylic polymer (b-1) those having the reactive functional group as one or both of the acrylic monomer and the non-acrylic monomer mentioned as the monomer constituting the polymer It may be used.
  • said polymer (b) which has a hydroxyl group as a reactive functional group what was obtained by polymerizing a hydroxyl-containing (meth) acrylic acid ester is mentioned, for example, In addition to this, the said acrylics mentioned above What is obtained by polymerizing a monomer in which one or more hydrogen atoms are substituted by the reactive functional group among the system monomer or the non-acrylic monomer is mentioned.
  • the ratio (content) of the amount of the structural unit derived from the monomer having the reactive functional group to the total amount of the constituent units constituting the polymer is 1 to 25
  • the content is preferably in the range of 2% by mass to 20% by mass.
  • the semiconductor chip provided with the protective film which is a cured product of the protective film forming film is bonded or the like
  • the surface gloss of the protective film is reduced when heated for the purpose of
  • the weight average molecular weight (Mw) of the polymer (b) having no energy ray curable group is preferably 200,000 or more, more preferably 250000 or more, and still more preferably 300,000 or more. If the weight average molecular weight of the polymer (b) having no energy ray curable group is not less than the lower limit value, a semiconductor chip provided with a protective film which is a cured product of a film for protective film formation on the back surface is heated by bonding or the like. In this case also, the gloss on the surface of the protective film does not easily decrease.
  • the upper limit value of the weight average molecular weight of the polymer (b) having no energy ray curable group is not particularly limited, but from the viewpoint of easy production of the composite sheet for forming a protective film, a weight having no energy ray curable group
  • the weight-average molecular weight of the combined (b) is preferably 2,000,000 or less.
  • the weight average molecular weight of the polymer (b) having no energy ray-curable group is 2,000,000 or less, the dispersibility in the protective film-forming composition (IV-1) is improved.
  • As a combination of the upper limit value and the lower limit value 200000 or more and 2000000 or less, 250,000 or more and 2000000 or less, and 300000 or more and 2000000 or less can be mentioned.
  • the polymer (b) having no energy ray curable group is used as an adduct and the energy ray It is preferable to introduce an energy ray curable group such as a curable double bond.
  • the adduct of the polymer (b) having no energy ray curable group is a polymer (b) having no energy ray curable group having a functional group capable of reacting with a group possessed by another compound And a group capable of reacting with the functional group and an energy ray curable compound having an energy ray curable group such as an energy ray curable double bond.
  • an adduct can be obtained by the same method as the adduct type acrylic polymer (a1-1) described above.
  • the film for forming a protective film is attached to a semiconductor wafer to obtain energy
  • the film for protective film formation is attached to a semiconductor wafer with respect to the gloss value measured after irradiating a line, the energy beam is irradiated, and the reduction rate of the gloss value measured after heating for 5 minutes at 260 ° C. is 30% or less This is a low value.
  • composition for forming a protective film (IV-1) and the film for forming a protective film may contain only one type of polymer (b) having no energy ray-curable group, or two or more types of polymers (2) When it is species or more, their combination and ratio can be arbitrarily selected.
  • the protective film-forming composition (IV-1) preferably contains the compound (a2) and the polymer (a1).
  • the composition for forming a protective film (IV-1) contains the polymer (a1) and the compound (a2) and does not contain a polymer (b) having no energy ray curable group. Is also preferred.
  • the composition for forming a protective film (IV-1) may contain the polymer (a1) without containing the compound (a2).
  • the polymer (a1) is preferably an adduct type acrylic polymer (a1-1).
  • composition (IV-1) for protective film formation contains the said polymer (a1) and said compound (a2)
  • composition (IV-1) for protective film formation containing of the said compound (a2)
  • the amount is preferably 10 to 400 parts by mass, more preferably 30 to 350 parts by mass with respect to 100 parts by mass of the total content of the polymer (a1).
  • the content of the energy ray curable component (a) is preferably 12 to 90% by mass, based on the total content of the components other than the solvent, It is more preferably 80% by mass, particularly preferably 20 to 70% by mass, and may be, for example, any of 25 to 60% by mass and 30 to 50% by mass.
  • the energy ray curability of the film for protective film formation becomes more favorable because the said content is such a range.
  • the weight of the composition for forming a protective film (IV-1) and the film for forming a protective film is preferably 30 to 100 parts by mass, more preferably 50 to 95 parts by mass, with respect to 100 parts by mass of the energy ray curable component (a). Preferably, 70 to 90 parts by mass is particularly preferred.
  • the content of the polymer (a1-1) is in such a range, the energy ray curability of the film for protective film formation becomes better.
  • the composition for forming a protective film (IV-1) is a photopolymerization initiator (c) other than the energy ray curable component (a) and the polymer (b) having no energy ray curable group according to the purpose.
  • Filler (d), coupling agent (e), crosslinking agent (f), colorant (g), thermosetting component (h), curing accelerator (i), and general purpose additive (z) You may contain 1 type, or 2 or more types selected from a group.
  • the film for protective film formation formed by using the composition (IV-1) for protective film formation containing the said energy beam curable component (a) and the thermosetting component (h) is heated by heating
  • the adhesion to the adherend is improved, and the strength of the protective film formed from the protective film-forming film is also improved.
  • Photopolymerization initiator (c) examples include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, benzoin dimethyl ketal; acetophenone, 2 Acetophenone compounds such as 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one; bis (2,4,6-trimethylbenzoyl) phenyl Acyl phosphine oxide compounds such as phosphine oxide and 2,4,6-trimethyl benzoyl diphenyl phosphine oxide; sulfides such as benzyl phenyl sulfide and tetramethylthiuram monosulfide Compounds; ⁇ -ketol compounds such as 1-
  • composition (IV-1) for forming a protective film may contain only one type of photoinitiator, or two or more types, and in the case of two or more types, the combination and ratio thereof are arbitrary. Can be selected.
  • the content of the photopolymerization initiator (c) in the composition for forming a protective film (IV-1) is 100 parts by mass of the energy ray curable compound (a)
  • the amount is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 15 parts by mass, and particularly preferably 0.05 to 10 parts by mass.
  • filler (d) When the film for protective film formation contains a filler (d), adjustment of a thermal expansion coefficient of the protective film obtained by hardening the film for protective film formation becomes easy. And the reliability of the package obtained using the composite sheet for protective film formation improves more by optimizing this thermal expansion coefficient with respect to the formation object of a protective film.
  • the film for protective film formation contains a filler (d) When the film for protective film formation contains a filler (d), the moisture absorption rate of a protective film can be reduced and heat dissipation can also be improved.
  • a filler (d) what consists of heat conductive materials is mentioned, for example.
  • the filler (d) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.
  • Preferred inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium white, bengala, silicon carbide, boron nitride, etc .; spherical beads of these inorganic fillers; surface modification of these inorganic fillers Articles: single crystal fibers of these inorganic fillers; glass fibers and the like.
  • the inorganic filler is preferably silica or alumina.
  • the average particle size of the filler (d) is not particularly limited, but is preferably 0.01 to 20 ⁇ m, more preferably 0.1 to 15 ⁇ m, and particularly preferably 0.3 to 10 ⁇ m. .
  • average particle size means the value of particle size (D 50 ) at an integrated value of 50% in a particle size distribution curve determined by a laser diffraction scattering method, unless otherwise specified.
  • composition (IV-1) for forming a protective film and the filler (d) contained in the film for forming a protective film may be only one type, or two or more types, and in the case of two or more types, a combination thereof And the ratio can be selected arbitrarily.
  • the content of the filler (d) in the film is preferably 10 to 85% by mass, more preferably 20 to 80% by mass, and particularly preferably 30 to 75% by mass, for example, It may be 40 to 70% by mass, and 45 to 65% by mass.
  • Coupleling agent (e) By using a coupling agent (e) having a functional group capable of reacting with an inorganic compound or an organic compound, the adhesion and adhesiveness of the protective film-forming film to the adherend can be improved. By using the coupling agent (e), the protective film obtained by curing the protective film-forming film is improved in water resistance without impairing the heat resistance.
  • the coupling agent (e) is preferably a compound having a functional group capable of reacting with the functional group of the energy ray curable component (a), the polymer (b) having no energy ray curable group, etc. It is more preferable that it is a silane coupling agent.
  • silane coupling agent examples include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2- (3,4-Epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-amino) Ethylamino) propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyl Trimethoxysi
  • composition (IV-1) for forming a protective film and the coupling agent (e) contained in the film for forming a protective film may be only one type, or two or more types, and in the case of two or more types, Combinations and ratios can be selected arbitrarily.
  • the content of the coupling agent (e) in the composition for forming a protective film (IV-1) and the film for forming a protective film is the content of the energy ray curable component (a)
  • the amount is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass with respect to 100 parts by mass.
  • the content of the coupling agent (e) is at least the lower limit value, the dispersibility of the filler (d) in the resin is improved, and the adhesion of the film for protective film formation to the adherend is improved.
  • the effect of using the coupling agent (e) can be obtained more remarkably. Moreover, generation
  • Crosslinking agent (f) By crosslinking the energy beam curable component (a) described above and the polymer (b) having no energy beam curable group using the crosslinking agent (f), the initial adhesion and cohesion of the film for protective film formation You can adjust the power.
  • crosslinking agent (f) examples include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate type crosslinking agents (crosslinking agents having a metal chelate structure), aziridine type crosslinking agents (crosslinking agents having an aziridinyl group), etc. Can be mentioned.
  • organic polyvalent isocyanate compound for example, an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds are collectively referred to as “aromatic polyvalent isocyanate compound etc.” Abbreviated in some cases); trimers such as the above-mentioned aromatic polyvalent isocyanate compounds, isocyanurates and adducts; terminal isocyanate urethane prepolymers obtained by reacting the above-mentioned aromatic polyvalent isocyanate compounds and the like with a polyol compound Etc.
  • aromatic polyvalent isocyanate compound etc Abbreviated in some cases
  • trimers such as the above-mentioned aromatic polyvalent isocyanate compounds, isocyanurates and adducts
  • terminal isocyanate urethane prepolymers obtained by reacting the above-mentioned aromatic polyvalent isocyanate compounds and the like with a polyol compound Et
  • the “adduct” includes the above-mentioned aromatic polyvalent isocyanate compound, aliphatic polyvalent isocyanate compound or alicyclic polyvalent isocyanate compound, and low contents such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil It means a reactant with a molecule active hydrogen-containing compound.
  • Examples of the adduct include xylylene diisocyanate adduct of trimethylolpropane as described later, and the like.
  • “Terminal isocyanate urethane prepolymer” means a prepolymer having a urethane bond and having an isocyanate group at the end of the molecule.
  • organic polyvalent isocyanate compound for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4 Diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; trimethylol Any one of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate in the hydroxyl groups of all or part of a polyol such as propane Or two or more compounds are added; lysine diisocyanate.
  • a polyol such as propane Or two or
  • organic polyhydric imine compound examples include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane-tri- ⁇ -aziridinyl propionate, and tetramethylolmethane.
  • an organic polyvalent isocyanate compound as the crosslinking agent (f)
  • the crosslinking agent (f) has an isocyanate group and the energy ray-curable component (a) or the energy ray-curable group-free polymer (b) has a hydroxyl group
  • the crosslinking agent (f) and energy ray-curable A crosslinked structure can be simply introduced into the protective film-forming film by the reaction with the component (a) or the polymer (b) having no energy ray-curable group.
  • composition for forming a protective film (IV-1) and the crosslinking agent (f) contained in the film for forming a protective film may be only one type, or two or more types, and in the case of two or more types, a combination thereof And the ratio can be selected arbitrarily.
  • the content of the crosslinking agent (f) in the composition for forming a protective film (IV-1) is a weight having no energy ray curable component (a) and no energy ray curable group
  • the amount is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and further preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the total content of the combined (b). Being particularly preferred.
  • the content of the crosslinking agent (f) is equal to or more than the lower limit value, the effect of using the crosslinking agent (f) can be more remarkably obtained.
  • the said content of a crosslinking agent (f) being below the said upper limit, the excess use of a crosslinking agent (f) is suppressed.
  • Colorant (g) examples include known pigments such as inorganic pigments, organic pigments, and organic dyes.
  • organic pigments and organic dyes examples include aminium dyes, cyanine dyes, merocyanine dyes, croconium dyes, squalium dyes, azulenium dyes, polymethine dyes, naphthoquinone dyes, pyrilium dyes, and phthalocyanines.
  • the inorganic pigment examples include carbon black, cobalt dyes, iron dyes, chromium dyes, titanium dyes, vanadium dyes, zirconium dyes, molybdenum dyes, ruthenium dyes, platinum dyes, ITO ( Indium tin oxide) dyes, ATO (antimony tin oxide) dyes and the like can be mentioned.
  • composition (IV-1) for forming a protective film and the colorant (g) contained in the film for forming a protective film may be only one type, or two or more types, and in the case of two or more types, a combination thereof And the ratio can be selected arbitrarily.
  • the content of the colorant (g) in the composition for forming a protective film (IV-1) and the film for forming a protective film may be appropriately adjusted according to the purpose.
  • the composition (IV-1) for forming a protective film may be other than the solvent.
  • the ratio of the content of the colorant (g) to the total content of all the components is preferably 0.1 to 10% by mass It is more preferably 0.4 to 7.5% by mass, and particularly preferably 0.8 to 5% by mass.
  • the effect by using a coloring agent (g) is acquired more notably by the said content of a coloring agent (g) being more than the said lower limit.
  • a coloring agent (g) is less than or equal to the upper limit value, excessive use of the colorant (g) is suppressed.
  • thermosetting component (h) The composition (IV-1) for forming a protective film and the thermosetting component (h) contained in the film for forming a protective film may be only one type, or two or more types, and in the case of two or more types, The combination and ratio of can be selected arbitrarily.
  • thermosetting component (h) an epoxy-type thermosetting resin, a thermosetting polyimide, polyurethane, unsaturated polyester, a silicone resin etc. are mentioned, for example, An epoxy-type thermosetting resin is preferable.
  • the epoxy-based thermosetting resin comprises an epoxy resin (h1) and a thermosetting agent (h2).
  • the composition for forming a protective film (IV-1) and the epoxy thermosetting resin contained in the film for forming a protective film may be only one type, or two or more types, in the case of two or more types, Combinations and ratios can be selected arbitrarily.
  • Epoxy resin (h1) As an epoxy resin (h1), a well-known thing is mentioned, for example, a polyfunctional epoxy resin, a biphenyl compound, bisphenol A diglycidyl ether and its hydrogenated substance, an ortho cresol novolak epoxy resin, a dicyclopentadiene type epoxy resin, The bifunctional or more epoxy compound such as biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, etc. may be mentioned.
  • an epoxy resin having an unsaturated hydrocarbon group may be used as the epoxy resin (h1).
  • An epoxy resin having an unsaturated hydrocarbon group has higher compatibility with an acrylic resin than an epoxy resin having no unsaturated hydrocarbon group. Therefore, the reliability of the package obtained using the composite sheet for protective film formation improves by using the epoxy resin which has an unsaturated hydrocarbon group.
  • an epoxy resin which has an unsaturated hydrocarbon group the compound formed by converting a part of epoxy group of polyfunctional epoxy resin into the group which has an unsaturated hydrocarbon group is mentioned, for example.
  • a compound can be obtained, for example, by addition reaction of (meth) acrylic acid or a derivative thereof to an epoxy group.
  • an epoxy resin which has an unsaturated hydrocarbon group the compound etc. which the group which has an unsaturated hydrocarbon group directly couple
  • the unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include ethenyl group (also referred to as vinyl group), 2-propenyl group (also referred to as allyl group) and (meth) acryloyl group And (meth) acrylamide group etc. is mentioned, and an acryloyl group is preferable.
  • the number average molecular weight of the epoxy resin (h1) is not particularly limited, but is preferably 300 to 30000, and is 400 to 10000, from the viewpoint of the curability of the film for protective film formation and the strength and heat resistance of the protective film. And more preferably 500 to 3,000.
  • “number average molecular weight” means, unless otherwise specified, a number average molecular weight represented by a value in terms of standard polystyrene measured by gel permeation chromatography (GPC).
  • the epoxy equivalent of the epoxy resin (h1) is preferably 100 to 1000 g / eq, and more preferably 150 to 800 g / eq.
  • epoxy equivalent means the number of grams of epoxy compound containing 1 gram equivalent of epoxy group (g / eq) and can be measured according to the method of JIS K 7236: 2001.
  • epoxy resin (h1) one type may be used alone, or two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be optionally selected.
  • Heat curing agent (h2) functions as a curing agent for the epoxy resin (h1).
  • a thermosetting agent (h2) the compound which has 2 or more of functional groups which can react with an epoxy group in 1 molecule is mentioned, for example.
  • the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, and a group in which an acid group is anhydrated, and the phenolic hydroxyl group, an amino group, or an acid group is anhydrated. It is preferably a group, more preferably a phenolic hydroxyl group or an amino group.
  • thermosetting agents (h2) as a phenol-based curing agent having a phenolic hydroxyl group, for example, polyfunctional phenol resin, biphenol, novolak-type phenol resin, dicyclopentadiene-based phenol resin, aralkyl phenol resin and the like can be mentioned.
  • thermosetting agents (h2) examples of amine-based curing agents having an amino group include dicyandiamide.
  • the thermosetting agent (h2) may have an unsaturated hydrocarbon group.
  • the thermosetting agent (h2) having an unsaturated hydrocarbon group for example, a compound obtained by substituting a part of hydroxyl groups of a phenol resin with a group having an unsaturated hydrocarbon group, an aromatic ring of a phenol resin, The compound etc. which a group which has a saturated hydrocarbon group directly couple
  • bonds are mentioned.
  • the unsaturated hydrocarbon group in the thermosetting agent (h2) is the same as the unsaturated hydrocarbon group in the epoxy resin having an unsaturated hydrocarbon group described above.
  • the heat-curing agent (h2) When a phenol-based curing agent is used as the heat-curing agent (h2), the heat-curing agent (h2) preferably has a high softening point or glass transition temperature, from the viewpoint that the removability of the protective film from the support sheet is improved.
  • the "glass transition temperature” refers to the temperature of the inflection point of the obtained DSC curve by measuring the DSC curve of a sample using a differential scanning calorimeter.
  • thermosetting agents (h2) for example, the number average molecular weight of resin components such as polyfunctional phenol resin, novolak type phenol resin, dicyclopentadiene type phenol resin, aralkyl phenol resin and the like is preferably 300 to 30,000, It is more preferably 400 to 10,000, and particularly preferably 500 to 3,000.
  • the molecular weight of the non-resin component such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, for example.
  • thermosetting agent (h2) may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combination and ratio can be selected arbitrarily.
  • the content of the thermosetting agent (h2) in the composition for forming a protective film (IV-1) and the film for forming a protective film is the content of the epoxy resin (h1) 100
  • the amount is preferably 0.01 to 20 parts by mass with respect to the parts by mass.
  • thermosetting component (h) when used, the content of the thermosetting component (h) (for example, epoxy resin (h1) and heat) in the composition for forming a protective film (IV-1) and the film for forming a protective film
  • the total content of the curing agent (h2) is preferably 1 to 500 parts by mass with respect to 100 parts by mass of the polymer (b) having no energy ray curable group.
  • a hardening accelerator (i) is a component for adjusting the hardening speed of the film for protective film formation.
  • Preferred curing accelerators (i) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol and tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole Imidazoles such as 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole; tributylphosphine, diphenylphosphine, triphenylphosphine and the like Organic phosphines; tetraphenylboronium salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate
  • the curing accelerator (i) one type may be used alone, or two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be optionally selected.
  • the content of the protective film-forming composition (IV-1) and the content of the curing accelerator (i) of the protective film-forming film are not particularly limited, and it depends on the components used in combination. It may be selected as appropriate.
  • the general-purpose additive (z) may be a known one, can be selected arbitrarily according to the purpose, and is not particularly limited. Preferred examples thereof include a plasticizer, an antistatic agent, an antioxidant, a gettering agent, etc. Can be mentioned.
  • composition (IV-1) for forming a protective film and the general-purpose additive (z) contained in the film for forming a protective film may be only one type, or two or more types, and in the case of two or more types, Combinations and ratios can be selected arbitrarily.
  • the content of the protective film-forming composition (IV-1) and the content of the general-purpose additive (z) of the protective film-forming film are not particularly limited, and may be appropriately selected depending on the purpose. do it.
  • the composition for forming a protective film (IV-1) preferably further contains a solvent.
  • the composition for forming a protective film (IV-1) containing a solvent has good handleability.
  • the solvent is not particularly limited, but preferred examples thereof include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutyl alcohol (also referred to as 2-methylpropan-1-ol), 1-butanol and the like Alcohols such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; and amides (compounds having an amide bond) such as dimethylformamide and N-methyl pyrrolidone.
  • the solvent contained in the composition for forming a protective film (IV-1) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • composition (IV-1) for forming a protective film is methyl ethyl ketone, toluene, ethyl acetate or the like in that the components contained in composition (IV-1) for forming a protective film can be mixed more uniformly. Is preferred.
  • the film for forming a protective film comprises an adduct type acrylic polymer (a1-1) as the total mass of the film for forming a protective film as the polymer (a1) having an energy ray curable group.
  • the adduct type acrylic polymer (a1-1) is an acrylic polymer (a11) obtained by copolymerizing methyl acrylate and 2-hydroxyethyl acrylate and 2 as an energy curable compound (a12). It is preferably obtained by reacting with -methacryloyloxyethyl isocyanate. Furthermore, the ratio of the content of the energy ray curable group derived from the energy curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) is 5 to 50 mol% Is preferably 20 to 40 mol%. In addition, the ratio may be 2 to 15 mol%.
  • the said film for protective film formation does not contain the polymer (b) which does not have an energy ray curable group.
  • the polymer (b) which does not have an energy ray curable group 25 to 40 parts by mass of a phthalocyanine blue dye, 10 to 25 parts by mass of an isoindolinone yellow dye, and 40 to 60 parts by mass of an anthraquinone red dye as coloring agents (g)
  • composition for forming a protective film such as the composition for forming a protective film (IV-1) can be obtained by blending the respective components for constituting the composition. There is no particular limitation on the order of addition of each component at the time of blending, and two or more components may be added simultaneously.
  • a solvent it may be used by mixing the solvent with any compounding component other than the solvent and diluting this compounding component in advance, or by previously diluting any compounding component other than the solvent A solvent may be used by mixing with these compounding ingredients without storage.
  • the method of mixing each component at the time of compounding is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade, etc .; a method of mixing using a mixer; a method of adding ultrasonic waves and mixing, etc. It may be selected as appropriate.
  • the temperature and time of addition and mixing of the respective components are not particularly limited as long as the respective blended components do not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.
  • the protective film-forming film can be produced by coating the protective film-forming composition on a release film (preferably the release-treated surface thereof) and drying it as required. .
  • the manufacturing method at this time is as described above.
  • the film for protective film formation is normally stored in the state in which the peeling film was bonded together by the both surfaces.
  • a release film (preferably a release-treated surface) is preferably formed on the exposed surface (surface opposite to the side provided with the release film) of the protective film-forming film formed on the release film as described above. You just need to paste
  • the protective film-forming film can be formed on a support sheet to form a protective film-forming composite sheet.
  • the composite sheet for protective film formation is stuck on the back surface (surface on the opposite side to the electrode formation surface) of the semiconductor wafer by the protective film formation film. Thereafter, from this state, the target semiconductor chip and semiconductor device can be manufactured by the manufacturing method described later.
  • the protective film-forming film may be provided first on the back surface of the semiconductor wafer, not on the support sheet.
  • a protective film-forming film is attached to the back surface of the semiconductor wafer, and a supporting sheet is attached to the exposed surface of the protective film-forming film (the surface opposite to the side attached to the semiconductor wafer)
  • the film for forming a protective film in the attached state is irradiated with energy rays to be cured to form a protective film, and then the exposed surface of this protective film (the surface on the opposite side to the side attached to the semiconductor wafer)
  • the support sheet is pasted together to make a composite sheet for forming a protective film. Thereafter, from this state, the target semiconductor chip and semiconductor device can be manufactured by the manufacturing method described later.
  • the composite sheet for forming a protective film according to an embodiment of the present invention includes a support sheet, and the film for forming a protective film is provided on the support sheet.
  • the thickness of the semiconductor wafer to be used for the composite sheet for protective film formation of the present invention is not particularly limited, but is preferably 30 to 1000 ⁇ m from the viewpoint of easier division into semiconductor chips described later. More preferably, it is 100 to 400 ⁇ m.
  • the configuration of the protective film-forming composite sheet will be described in detail.
  • the support sheet may be formed of a single layer (single layer), or may be formed of two or more layers.
  • the plurality of layers may be identical to or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.
  • a substrate is provided, and an adhesive layer is directly laminated on the substrate and laminated (a substrate and an adhesive layer are laminated in direct contact in this order)
  • FIG. 2 is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention.
  • FIG. 2 is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention.
  • the same components as shown in the already described drawings are given the same reference numerals as in the case of the already described drawings, and the detailed description thereof is omitted.
  • the composite sheet 1A for protective film formation shown here is provided with the base material 11, the adhesive layer 12 is provided on the base material 11, and the protective film formation film 13 is provided on the adhesive layer 12.
  • the support sheet 10 is a laminate of the base 11 and the pressure-sensitive adhesive layer 12, and the composite sheet 1A for protective film formation is, in other words, one surface of the support sheet 10 (in the present specification, "first surface” And a protective film-forming film 13 is laminated on the substrate 10a).
  • the protective film-forming composite sheet 1A further includes a peeling film 15 on the protective film-forming film 13.
  • the pressure-sensitive adhesive layer 12 is laminated on one surface (sometimes referred to as a “first surface” in the present specification) 11a of the substrate 11.
  • the film 13 for protective film formation is laminated on the entire surface of one surface (sometimes referred to as “first surface” in the present specification) 12 a, and a part of the first surface 13 a of the film 13 for protective film formation That is, the jig adhesive layer 16 is laminated in a region near the peripheral portion, and the surface of the first surface 13 a of the protective film-forming film 13 on which the jig adhesive layer 16 is not laminated, and the jig A release film 15 is laminated on the surface 16 a (upper surface and side surface) of the adhesive layer 16.
  • the protective film-forming film 13 contains an energy ray-curable component (a), and the above-mentioned adduct-type acrylic polymer (a1-1) is the above-mentioned (a). Is preferred.
  • the jig adhesive layer 16 may have, for example, a single layer structure containing an adhesive component, or a plurality of layers in which layers containing the adhesive component are laminated on both sides of a sheet to be a core material. It may be of a structure.
  • the composite sheet 1A for protective film formation shown in FIG. 2 has the back surface of a semiconductor wafer (not shown) attached to the first surface 13a of the protective film formation film 13 with the release film 15 removed.
  • the upper surface of the surface 16 a of the tool adhesive layer 16 is used by being attached to a jig such as a ring frame.
  • FIG. 3 is a cross-sectional view schematically showing a composite sheet for protective film formation according to another embodiment of the present invention.
  • the composite sheet 1B for protective film formation shown here is the same as the composite sheet 1A for protective film formation shown in FIG. 2 except that the jig adhesive layer 16 is not provided. That is, in the protective film-forming composite sheet 1B, the pressure-sensitive adhesive layer 12 is laminated on the first surface 11a of the substrate 11, and the protective film-forming film 13 is laminated on the entire first surface 12a of the pressure-sensitive adhesive layer 12 The release film 15 is laminated on the entire surface of the first surface 13 a of the protective film-forming film 13.
  • the protective film-forming film 13 contains an energy ray-curable component (a), and the above-mentioned adduct-type acrylic polymer (a1-1) is the above-mentioned (a). Is preferred.
  • the composite sheet 1B for protective film formation shown in FIG. 3 is a semiconductor wafer (not shown) on the central region of the first surface 13a of the protective film formation film 13 with the release film 15 removed. And the area in the vicinity of the peripheral portion is used by being attached to a jig such as a ring frame.
  • FIG. 4 is a cross-sectional view schematically showing a composite sheet for protective film formation according to still another embodiment of the present invention.
  • the composite sheet 1C for protective film formation shown here is the same as the composite sheet 1A for protective film formation shown in FIG. 2 except that the adhesive layer 12 is not provided. That is, in the composite sheet 1C for protective film formation, the support sheet 10 consists only of the base material 11.
  • the protective film-forming film 13 is laminated on the first surface 11 a of the substrate 11 (the first surface 10 a of the support sheet 10), and a part of the first surface 13 a of the protective film-forming film 13, that is, the peripheral portion
  • the jig adhesive layer 16 is laminated in the vicinity area, and the area where the jig adhesive layer 16 is not laminated in the first surface 13a of the protective film forming film 13, and the jig adhesive layer A release film 15 is laminated on the sixteen surfaces 16a (upper and side surfaces).
  • the protective film-forming film 13 contains an energy ray-curable component (a), and the above-mentioned adduct-type acrylic polymer (a1-1) is the above-mentioned (a). Is preferred.
  • the composite sheet 1C for protective film formation shown in FIG. 4 is on the first surface 13a of the film 13 for protective film formation with the release film 15 removed.
  • the back surface of the semiconductor wafer (not shown) is attached, and the upper surface of the surface 16a of the adhesive layer 16 for jig is used by being adhered to a jig such as a ring frame.
  • FIG. 5 is a cross-sectional view schematically showing a composite sheet for protective film formation according to still another embodiment of the present invention.
  • the composite sheet for protective film formation 1D shown here is the same as the composite sheet for protective film formation 1C shown in FIG. 4 except that the jig adhesive layer 16 is not provided. That is, in the protective film-forming composite sheet 1D, the protective film-forming film 13 is laminated on the first surface 11a of the substrate 11, and the release film 15 is laminated on the entire first surface 13a of the protective film-forming film 13. It is done.
  • the protective film-forming film 13 contains an energy ray curable component (a), and the above-mentioned adduct type acrylic polymer (a1-1) is the above-mentioned (a). Is preferred.
  • the composite sheet 1D for protective film formation shown in FIG. 5 is the same as the composite sheet 1B for protective film formation shown in FIG. 3 with the release film 15 removed, on the first surface 13a of the film 13 for protective film formation.
  • the back surface of a semiconductor wafer (not shown) is attached to a partial region on the center side, and the region in the vicinity of the peripheral portion is attached to a jig such as a ring frame and used.
  • FIG. 6 is a cross-sectional view schematically showing a composite sheet for protective film formation according to still another embodiment of the present invention.
  • the composite sheet 1E for protective film formation shown here is the same as the composite sheet 1B for protective film formation shown in FIG. 3 except that the shape of the film for protective film formation is different. That is, the composite sheet 1E for protective film formation is provided with the base material 11, the adhesive layer 12 is provided on the base material 11, and the protective film formation film 23 is provided on the adhesive layer 12.
  • the support sheet 10 is a laminate of the base 11 and the pressure-sensitive adhesive layer 12, and in other words, the protective film-forming film 23 is laminated on the first surface 10 a of the support sheet 10. Have the following configuration.
  • the protective film-forming composite sheet 1E further includes a release film 15 on the protective film-forming film 23.
  • the pressure-sensitive adhesive layer 12 is laminated on the first surface 11a of the substrate 11, and a protective film is formed on a part of the first surface 12a of the pressure-sensitive adhesive layer 12, ie, the central region.
  • Film 23 is laminated.
  • the release film 15 is formed on the region of the first surface 12 a of the adhesive layer 12 where the protective film-forming film 23 is not laminated and the surface 23 a (upper surface and side surface) of the protective film-forming film 23. It is stacked.
  • the protective film-forming film 23 When the protective film-forming composite sheet 1E is viewed from above from above and planarly viewed, the protective film-forming film 23 has a smaller surface area than the pressure-sensitive adhesive layer 12, and has, for example, a circular shape.
  • the protective film-forming film 23 contains an energy ray-curable component (a), and the above-mentioned adduct-type acrylic polymer (a1-1) is the above-mentioned (a). Is preferred.
  • the composite sheet 1E for protective film formation shown in FIG. 6 has the back surface of a semiconductor wafer (not shown) attached to the surface 23a of the protective film formation film 23 in a state where the release film 15 is removed.
  • stacked among 12 1st surface 12a is stuck on jigs, such as a ring frame, and is used.
  • composite sheet 1E for protective film formation shown in FIG. 6 in the area
  • a jig adhesive layer may be laminated on the substrate (not shown). Similar to the composite sheet for protective film formation shown in FIGS. 2 and 4, the composite sheet 1E for protective film formation provided with such an adhesive layer for jigs has a ring frame for the surface of the adhesive layer for jigs. It is stuck on a jig etc. and used.
  • the composite sheet for protective film formation may be provided with the adhesive layer for jigs, regardless of the form of the support sheet and the film for protective film formation.
  • the adhesive layer for jigs regardless of the form of the support sheet and the film for protective film formation.
  • FIGS. 2 and 4 as a composite sheet for protective film formation provided with a jig adhesive layer, one provided with a jig adhesive layer on a protective film formation film Is preferred.
  • the composite sheet for protective film formation which concerns on one Embodiment of this invention is not limited to what is shown in FIGS. 2-6, A part of what is shown in FIGS. 2-6 in the range which does not impair the effect of this invention
  • the configuration of the above may be changed or deleted, or another configuration may be added to those described above.
  • an intermediate layer may be provided between the substrate 11 and the protective film formation film 13.
  • the intermediate layer can be selected arbitrarily according to the purpose.
  • an intermediate layer may be provided between the substrate 11 and the pressure-sensitive adhesive layer 12. That is, in the composite sheet for protective film formation of the present invention, the support sheet may be formed by laminating the base material, the intermediate layer and the pressure-sensitive adhesive layer in this order in the thickness direction.
  • the intermediate layer is the same as the intermediate layer which may be provided in the composite sheet for protective film formation shown in FIGS. 4 and 5.
  • layers other than the intermediate layer may be provided at arbitrary places.
  • a partial gap may be generated between the release film and the layer in direct contact with the release film.
  • the size and shape of each layer can be arbitrarily adjusted according to the purpose.
  • the layer such as the pressure-sensitive adhesive layer which is in direct contact with the protective film-forming film of the support sheet be non-energy ray curable. .
  • Such a composite sheet for protective film formation enables easier pickup of the semiconductor chip with a protective film.
  • the support sheet may be transparent or opaque, and may be colored according to the purpose. Among them, in the present invention in which the protective film-forming film has energy ray curability, it is preferable that the support sheet transmits energy rays.
  • the transmittance of light having a wavelength of 375 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more.
  • the light transmittance is in such a range, when the protective film-forming film is irradiated with energy rays (ultraviolet light) through the support sheet, the degree of curing of the protective film-forming film is further improved.
  • the upper limit of the transmittance of light with a wavelength of 375 nm is not particularly limited.
  • the light transmittance may be 95% or less.
  • the transmittance of light having a wavelength of 532 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more.
  • the transmittance of light is in such a range, the protective film-forming film or the protective film is irradiated with a laser beam through the support sheet, and printing can be performed more clearly.
  • the upper limit of the transmittance of light of wavelength 532 nm is not particularly limited.
  • the light transmittance may be 95% or less.
  • the transmittance of light having a wavelength of 1064 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more.
  • the transmittance of light is in such a range, the protective film-forming film or the protective film is irradiated with a laser beam through the support sheet, and printing can be performed more clearly.
  • the upper limit value of the transmittance of light with a wavelength of 1064 nm is not particularly limited.
  • the light transmittance may be 95% or less.
  • the transmittance of light with a wavelength of 1342 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more.
  • the semiconductor wafer is irradiated with laser light through the support sheet and the protective film-forming film or protective film, and the modified layer is formed on the semiconductor wafer. It can be easily formed.
  • the upper limit of the transmittance of light with a wavelength of 1342 nm is not particularly limited.
  • the light transmittance may be 95% or less.
  • the base material is in the form of a sheet or a film, and examples of the constituent material thereof include various resins.
  • the resin include polyethylenes such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE); polyethylene other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene and norbornene resin Polyolefins; Ethylene copolymers such as ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-norbornene copolymer (ethylene as monomer Copolymers obtained by using a vinyl chloride resin such as polyvinyl chloride and vinyl chloride copolymer (resin obtained by using vinyl chloride as a monomer), polystyrene, polycycloolefin, polyethylene terephthalate, polyethylene Nafta
  • the polymer alloy of the polyester and the other resin is preferably one in which the amount of the resin other than the polyester is relatively small.
  • the resin for example, a crosslinked resin obtained by crosslinking one or more of the above-described resins exemplified so far; a modified resin such as an ionomer using one or more of the above-described resins exemplified so far It can be mentioned.
  • the resin constituting the substrate may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the base material may consist of one layer (a single layer), or may consist of a plurality of layers of two or more layers, and in the case of a plurality of layers, these plural layers may be the same or different from each other, and these plural
  • the combination of layers is not particularly limited.
  • the thickness of the substrate is preferably 50 to 300 ⁇ m, and more preferably 60 to 100 ⁇ m.
  • the thickness of the substrate means the thickness of the entire substrate, for example, the thickness of the substrate comprising a plurality of layers means the total thickness of all the layers constituting the substrate means.
  • thickness is a value measured by measuring any five places of an object with a contact-type thickness meter and expressing the average.
  • the substrate is preferably a substrate having high thickness accuracy, that is, a substrate in which the thickness variation is suppressed regardless of the part.
  • a substrate having high thickness accuracy for example, polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer, etc. Can be mentioned.
  • the base contains, in addition to the main constituent materials such as the resin, known additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and a softener (plasticizer). May be
  • the optical properties of the substrate are preferably such as to satisfy the optical properties of the support sheet described above.
  • the substrate may be transparent or opaque, or may be colored according to the purpose, or other layers may be deposited.
  • the base material is preferably one which transmits energy rays.
  • the substrate is roughened by sand blasting, solvent treatment, etc., corona discharge treatment, electron beam irradiation treatment, plasma treatment, etc., in order to improve the adhesion to other layers such as the pressure-sensitive adhesive layer provided thereon.
  • the surface may be subjected to oxidation treatment such as ozone / ultraviolet radiation treatment, flame treatment, chromic acid treatment, hot air treatment or the like.
  • the substrate may have a surface subjected to primer treatment.
  • the base material is an antistatic coating layer; a layer for preventing the base material from adhering to another sheet or the base material from adhering to the adsorption table when the composite sheet for protective film formation is superposed and stored. It may have the
  • the substrate can be produced by a known method.
  • the base material containing resin can be manufactured by shape
  • the pressure-sensitive adhesive layer is in the form of a sheet or a film, and contains a pressure-sensitive adhesive.
  • the pressure-sensitive adhesive include pressure-sensitive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins. Acrylic resins are preferable. .
  • tacky resin is a concept including both a resin having tackiness and a resin having adhesiveness, and, for example, not only those in which the resin itself has tackiness, but also additives It also includes a resin that exhibits adhesiveness when used in combination with other components such as, and a resin that exhibits adhesion due to the presence of a trigger such as heat or water.
  • the pressure-sensitive adhesive layer may be formed of one layer (single layer) or may be formed of two or more layers, and in the case of two or more layers, these layers may be the same or different from one another.
  • the combination of multiple layers is not particularly limited.
  • the thickness of the pressure-sensitive adhesive layer is preferably 1 to 100 ⁇ m, more preferably 1 to 60 ⁇ m, and particularly preferably 1 to 30 ⁇ m.
  • the thickness of the pressure-sensitive adhesive layer means the thickness of the entire pressure-sensitive adhesive layer, and for example, the thickness of the pressure-sensitive adhesive layer composed of a plurality of layers means the total of all layers constituting the pressure-sensitive adhesive layer. Means the thickness of.
  • the optical properties of the pressure-sensitive adhesive layer preferably satisfy the optical properties of the support sheet described above.
  • the pressure-sensitive adhesive layer may be transparent or opaque, or may be colored according to the purpose.
  • the pressure-sensitive adhesive layer preferably transmits energy rays.
  • the pressure-sensitive adhesive layer may be formed using an energy ray-curable pressure-sensitive adhesive, or may be formed using a non-energy ray-curable pressure-sensitive adhesive.
  • the pressure-sensitive adhesive layer formed using the energy ray-curable pressure-sensitive adhesive can easily adjust physical properties before and after curing.
  • the pressure-sensitive adhesive layer can be formed using a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive.
  • the pressure-sensitive adhesive layer can be formed on a target site by coating the pressure-sensitive adhesive composition on the surface to be formed of the pressure-sensitive adhesive layer and drying it as necessary.
  • the more specific formation method of an adhesive layer is demonstrated in detail later with the formation method of another layer.
  • the ratio of the contents of the components which do not vaporize at normal temperature in the pressure-sensitive adhesive composition is usually the same as the ratio of the contents of the components of the pressure-sensitive adhesive layer.
  • the application of the pressure-sensitive adhesive composition may be performed by a known method, for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, a screen coater And methods using various coaters such as a Mayer bar coater and a kiss coater.
  • the drying conditions of the pressure-sensitive adhesive composition are not particularly limited, but when the pressure-sensitive adhesive composition contains a solvent described later, it is preferable to heat and dry.
  • the solvent-containing pressure-sensitive adhesive composition is preferably dried, for example, at 70 to 130 ° C. for 10 seconds to 5 minutes.
  • a pressure-sensitive adhesive composition containing an energy ray-curable pressure-sensitive adhesive that is, an energy ray-curable pressure-sensitive adhesive composition
  • an energy ray-curable pressure-sensitive adhesive composition for example, non-energy ray-curable tackiness
  • Pressure-sensitive adhesive composition (I-1) containing resin (I-1a) hereinafter sometimes abbreviated as “adhesive resin (I-1a)” and an energy ray-curable compound
  • non-energy Energy ray curable adhesive resin (I-2a) hereinafter referred to as “adhesive resin (I-2a)
  • pressure-sensitive adhesive composition (I-3) containing the adhesive resin (I-2a) and an energy ray-curable compound, etc.
  • the pressure-sensitive adhesive composition (I-1) contains a non-energy ray-curable adhesive resin (I-1a) and an energy ray-curable compound.
  • the adhesive resin (I-1a) is preferably an acrylic resin.
  • the acrylic resin the acrylic polymer which has a structural unit derived from the (meth) acrylic-acid alkylester at least is mentioned, for example.
  • the structural unit which the said acrylic resin has may be only 1 type, may be 2 or more types, and when it is 2 or more types, those combination and ratio can be selected arbitrarily.
  • Examples of the (meth) acrylic acid alkyl ester include ones in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms, and the alkyl group is linear or branched. Is preferred. More specifically, as (meth) acrylic acid alkyl ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid n-Butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octy
  • the said acryl-type polymer has a structural unit derived from the (meth) acrylic-acid alkylester whose carbon number of the said alkyl group is 4 or more from the point which the adhesive force of an adhesive layer improves.
  • the carbon number of the alkyl group is preferably 4 to 12, and more preferably 4 to 8, from the viewpoint of further improving the adhesive strength of the pressure-sensitive adhesive layer.
  • the (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group is preferably a methacrylic acid alkyl ester.
  • the acrylic polymer preferably further has a structural unit derived from a functional group-containing monomer, in addition to the structural unit derived from the (meth) acrylic acid alkyl ester.
  • a functional group-containing monomer for example, reaction of the functional group with a crosslinking agent described later becomes a crosslinking origin, or the functional group reacts with an unsaturated group in an unsaturated group-containing compound described later And those which make it possible to introduce an unsaturated group into the side chain of the acrylic polymer.
  • a hydroxyl group, a carboxy group, an amino group, an epoxy group etc. are mentioned, for example. That is, as a functional group containing monomer, a hydroxyl group containing monomer, a carboxy group containing monomer, an amino group containing monomer, an epoxy group containing monomer etc. are mentioned, for example.
  • hydroxyl group-containing monomer examples include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) Hydroxyalkyl (meth) acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; non (meth) acrylics such as vinyl alcohol and allyl alcohol A saturated alcohol (unsaturated alcohol which does not have a (meth) acryloyl frame) etc. are mentioned.
  • carboxy group-containing monomer examples include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth) acrylic acid and crotonic acid; fumaric acid, itaconic acid, maleic acid, citraconic Ethylenically unsaturated dicarboxylic acids such as acids (dicarboxylic acids having an ethylenically unsaturated bond); anhydrides of the above-mentioned ethylenically unsaturated dicarboxylic acids; (meth) acrylic acid carboxyalkyl esters such as 2-carboxyethyl methacrylate and the like Be
  • monocarboxylic acids having an ethylenically unsaturated bond such as (meth) acrylic acid and crotonic acid
  • fumaric acid, itaconic acid, maleic acid, citraconic Ethylenically unsaturated dicarboxylic acids such as acids (dicar
  • the functional group-containing monomer is preferably a hydroxyl group-containing monomer or a carboxy group-containing monomer, and more preferably a hydroxyl group-containing monomer.
  • the functional group-containing monomer constituting the acrylic polymer may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the constituent unit derived from the functional group-containing monomer is preferably 1 to 35% by mass, and more preferably 2 to 32% by mass, with respect to the total mass of the constituent unit. Preferably, it is 3 to 30% by mass.
  • the acrylic polymer may further have a structural unit derived from another monomer in addition to the structural unit derived from the (meth) acrylic acid alkyl ester and the structural unit derived from the functional group-containing monomer.
  • the other monomer is not particularly limited as long as it is copolymerizable with (meth) acrylic acid alkyl ester and the like.
  • Examples of the other monomers include styrene, ⁇ -methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide and the like.
  • the other monomer constituting the acrylic polymer may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the acrylic polymer can be used as the above-mentioned non-energy ray curable tackifying resin (I-1a).
  • the unsaturated group-containing compound having an energy ray polymerizable unsaturated group (energy ray polymerizable group) is reacted with the functional group in the acrylic polymer have the above-mentioned energy ray curable tackiness It can be used as a resin (I-2a).
  • the adhesive resin (I-1a) contained in the adhesive composition (I-1) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof are optionally It can be selected.
  • the content of the adhesive resin (I-1a) is 5 to 99% by mass with respect to the total mass of the pressure-sensitive adhesive composition (I-1).
  • the content is preferably 10 to 95% by mass, and particularly preferably 15 to 90% by mass.
  • Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) include monomers or oligomers which have an energy ray-polymerizable unsaturated group and can be cured by irradiation of energy rays.
  • the energy ray-curable compounds as a monomer, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4 -Multivalent (meth) acrylates such as -butylene glycol di (meth) acrylate and 1,6-hexanediol (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylate; polyether (meth) acrylate; epoxy ( Meta) acrylate etc. are mentioned.
  • examples of the oligomers include oligomers formed by polymerization of the monomers exemplified above.
  • the energy ray-curable compound is preferably a urethane (meth) acrylate or a urethane (meth) acrylate oligomer in that the molecular weight is relatively large and the storage elastic modulus of the pressure-sensitive adhesive layer is hardly reduced.
  • the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected. .
  • the content of the energy ray-curable compound is preferably 1 to 95% by mass with respect to the total mass of the pressure-sensitive adhesive composition (I-1). It is more preferably 5 to 90% by mass, and particularly preferably 10 to 85% by mass.
  • crosslinking agent reacts with the functional group to crosslink the adhesive resin (I-1a).
  • Crosslinking agents include, for example, tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isocyanate-based crosslinking agents such as adducts of these diisocyanates (crosslinking agents having an isocyanate group); epoxy-based crosslinking agents such as ethylene glycol glycidyl ether ( Crosslinking agent having glycidyl group); Aziridine type crosslinking agent such as hexa [1- (2-methyl) -aziridinyl] triphosphatriazine (crosslinking agent having aziridinyl group); Metal chelate type crosslinking agent such as aluminum chelate (metal chelate Crosslinking agent having a structure); isocyanurate crosslinking agent (crosslinking agent having an isocyanuric acid skeleton) and the like.
  • the cross-linking agent
  • the crosslinking agent contained in the pressure-sensitive adhesive composition (I-1) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be optionally selected.
  • the content of the crosslinking agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the content of the adhesive resin (I-1a), The amount is more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass.
  • the pressure-sensitive adhesive composition (I-1) may further contain a photopolymerization initiator.
  • the pressure-sensitive adhesive composition (I-1) containing a photopolymerization initiator sufficiently proceeds curing reaction even when irradiated with energy rays of relatively low energy such as ultraviolet rays.
  • photopolymerization initiator examples include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate and benzoin dimethyl ketal; acetophenone, 2-hydroxy Acetophenone compounds such as -2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6-trimethylbenzoyl) phenyl phosphine Oxides, acyl phosphine oxide compounds such as 2,4,6-trimethyl benzoyl diphenyl phosphine oxide; sulfides such as benzyl phenyl sulfide and tetramethylthiuram monosulfide Substances; ⁇ -ketol compounds such as 1-hydroxycyclohexyl phenyl
  • the photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-1) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the content of the energy ray-curable compound, and 0
  • the content is more preferably in the range of 03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.
  • the pressure-sensitive adhesive composition (I-1) may contain other additives which do not correspond to any of the components described above, as long as the effects of the present invention are not impaired.
  • the other additives include antistatic agent, antioxidant, softener (plasticizer), filler (filler), rust inhibitor, coloring agent (pigment, dye), sensitizer, tackifier
  • Well-known additives, such as a reaction retarder, a crosslinking accelerator (catalyst), etc. are mentioned.
  • the reaction retarder for example, an unintended crosslinking reaction proceeds in the pressure-sensitive adhesive composition (I-1) during storage by the action of a catalyst mixed in the pressure-sensitive adhesive composition (I-1). Restrain
  • the other additives contained in the pressure-sensitive adhesive composition (I-1) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the other additive is not particularly limited, and may be appropriately selected depending on the type.
  • the pressure-sensitive adhesive composition (I-1) may contain a solvent.
  • the pressure-sensitive adhesive composition (I-1) contains a solvent, whereby the coating suitability to the surface to be coated is improved.
  • the solvent is preferably an organic solvent
  • examples of the organic solvent include ketones such as methyl ethyl ketone and acetone; esters such as ethyl acetate (carboxylic acid esters); ethers such as tetrahydrofuran and dioxane; cyclohexane, n-hexane, etc.
  • ketones such as methyl ethyl ketone and acetone
  • esters such as ethyl acetate (carboxylic acid esters)
  • ethers such as tetrahydrofuran and dioxane
  • Aliphatic hydrocarbons aromatic hydrocarbons such as toluene and xylene
  • alcohols such as 1-propanol and 2-propanol.
  • the solvent for example, one used in the production of the adhesive resin (I-1a) may be used as it is in the adhesive composition (I-1) without removing it from the adhesive resin (I-1a)
  • the same or a different type of solvent as that used in the production of the adhesive resin (I-1a) may be separately added in the production of the pressure-sensitive adhesive composition (I-1).
  • the solvent contained in the pressure-sensitive adhesive composition (I-1) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the solvent is not particularly limited, and may be appropriately adjusted.
  • the pressure-sensitive adhesive composition (I-2) is, as described above, an energy ray-curable adhesive resin in which an unsaturated group is introduced into the side chain of the non-energy ray-curable adhesive resin (I-1a). (I-2a) is contained.
  • the adhesive resin (I-2a) can be obtained, for example, by reacting a functional group in the adhesive resin (I-1a) with an unsaturated group-containing compound having an energy beam polymerizable unsaturated group.
  • the unsaturated group-containing compound can be bonded to the adhesive resin (I-1a) by further reacting with the functional group in the adhesive resin (I-1a) in addition to the energy beam polymerizable unsaturated group It is a compound having a group.
  • the energy ray polymerizable unsaturated group include (meth) acryloyl group, vinyl group (also referred to as ethenyl group), allyl group (also referred to as 2-propenyl group), etc., and (meth) acryloyl group is preferable. .
  • Examples of the group capable of binding to a functional group in the adhesive resin (I-1a) include, for example, an isocyanate group and a glycidyl group capable of binding to a hydroxyl group or an amino group, and a hydroxy group and amino group capable of binding to a carboxy group or an epoxy group. Etc.
  • Examples of the unsaturated group-containing compound include (meth) acryloyloxyethyl isocyanate, (meth) acryloyl isocyanate, glycidyl (meth) acrylate and the like.
  • the adhesive resin (I-2a) contained in the adhesive composition (I-2) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof are optionally It can be selected.
  • the content of the adhesive resin (I-2a) is 5 to 99% by mass with respect to the total mass of the pressure-sensitive adhesive composition (I-2).
  • the content is preferably 10 to 95% by mass, and particularly preferably 10 to 90% by mass.
  • Examples of the crosslinking agent in the pressure-sensitive adhesive composition (I-2) include the same as the crosslinking agent in the pressure-sensitive adhesive composition (I-1).
  • the crosslinking agent contained in the pressure-sensitive adhesive composition (I-2) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be optionally selected.
  • the content of the crosslinking agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the content of the adhesive resin (I-2a), The amount is more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass.
  • the pressure-sensitive adhesive composition (I-2) may further contain a photopolymerization initiator.
  • the pressure-sensitive adhesive composition (I-2) containing a photopolymerization initiator sufficiently proceeds a curing reaction even when irradiated with energy rays of relatively low energy such as ultraviolet rays.
  • the photopolymerization initiator in the pressure-sensitive adhesive composition (I-2) may be the same as the photopolymerization initiator in the pressure-sensitive adhesive composition (I-1).
  • the photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-2) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the content of the adhesive resin (I-2a)
  • the amount is more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.
  • the pressure-sensitive adhesive composition (I-2) may contain other additives which do not correspond to any of the components described above, as long as the effects of the present invention are not impaired.
  • Examples of the other additives in the pressure-sensitive adhesive composition (I-2) include the same as the other additives in the pressure-sensitive adhesive composition (I-1).
  • the other additives contained in the pressure-sensitive adhesive composition (I-2) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be optionally selected.
  • the content of the other additives is not particularly limited, and may be appropriately selected according to the type.
  • the pressure-sensitive adhesive composition (I-2) may contain a solvent for the same purpose as the pressure-sensitive adhesive composition (I-1).
  • the solvent in the pressure-sensitive adhesive composition (I-2) may be the same as the solvent in the pressure-sensitive adhesive composition (I-1).
  • the solvent contained in the pressure-sensitive adhesive composition (I-2) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the solvent is not particularly limited, and may be appropriately adjusted.
  • the pressure-sensitive adhesive composition (I-3) contains, as described above, the pressure-sensitive adhesive resin (I-2a) and an energy ray-curable compound.
  • the content of the adhesive resin (I-2a) is 5 to 99% by mass with respect to the total mass of the pressure-sensitive adhesive composition (I-3).
  • the content is preferably 10 to 95% by mass, and particularly preferably 15 to 90% by mass.
  • Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) include monomers and oligomers which have an energy ray-polymerizable unsaturated group and can be cured by irradiation of energy rays, and the pressure-sensitive adhesive composition The same as the energy ray-curable compound contained in the compound (I-1) can be mentioned.
  • the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected. .
  • the content of the energy ray-curable compound is 0.01 to 300 parts by mass with respect to 100 parts by mass of the content of the adhesive resin (I-2a) Is more preferably 0.03 to 200 parts by mass, and particularly preferably 0.05 to 100 parts by mass.
  • the pressure-sensitive adhesive composition (I-3) may further contain a photopolymerization initiator.
  • the pressure-sensitive adhesive composition (I-3) containing a photopolymerization initiator sufficiently proceeds curing reaction even when irradiated with energy rays of relatively low energy such as ultraviolet rays.
  • the photopolymerization initiator in the pressure-sensitive adhesive composition (I-3) may be the same as the photopolymerization initiator in the pressure-sensitive adhesive composition (I-1).
  • the photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-3) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the photopolymerization initiator is 0.01 to 100 parts by mass relative to the total content of the adhesive resin (I-2a) and the energy ray-curable compound.
  • the amount is preferably 20 parts by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.
  • the pressure-sensitive adhesive composition (I-3) may contain other additives which do not correspond to any of the components described above, as long as the effects of the present invention are not impaired.
  • Examples of the other additives include the same as the other additives in the pressure-sensitive adhesive composition (I-1).
  • the other additives contained in the pressure-sensitive adhesive composition (I-3) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be optionally selected.
  • the content of the other additives is not particularly limited, and may be appropriately selected depending on the type.
  • the pressure-sensitive adhesive composition (I-3) may contain a solvent for the same purpose as the pressure-sensitive adhesive composition (I-1).
  • the solvent in the pressure-sensitive adhesive composition (I-3) may be the same as the solvent in the pressure-sensitive adhesive composition (I-1).
  • the solvent contained in the pressure-sensitive adhesive composition (I-3) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the solvent is not particularly limited, and may be appropriately adjusted.
  • Adhesive Composition Other than Adhesive Composition (I-1) to (I-3)>
  • the pressure-sensitive adhesive composition (I-1), the pressure-sensitive adhesive composition (I-2) and the pressure-sensitive adhesive composition (I-3) have been mainly described, but those described as the components thereof are General pressure-sensitive adhesive compositions other than these three pressure-sensitive adhesive compositions (herein referred to as "pressure-sensitive adhesive compositions other than pressure-sensitive adhesive compositions (I-1) to (I-3)") But it can be used as well.
  • non-energy ray-curable pressure-sensitive adhesive compositions in addition to the energy ray-curable pressure-sensitive adhesive composition, non-energy ray-curable pressure-sensitive adhesive compositions can also be mentioned.
  • a non-energy ray curable pressure-sensitive adhesive composition for example, non-energy ray curing such as acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, ester resin, etc.
  • the pressure-sensitive adhesive composition (I-4) containing the adhesive resin (I-1a), and those containing an acrylic resin are preferable.
  • the pressure-sensitive adhesive composition other than the pressure-sensitive adhesive compositions (I-1) to (I-3) preferably contains one or more crosslinking agents, and the content thereof is the pressure-sensitive adhesive composition described above The same can be applied to the case of (I-1) and the like.
  • Preferred examples of the pressure-sensitive adhesive composition (I-4) include those containing the above-mentioned adhesive resin (I-1a) and a crosslinking agent.
  • Adhesive resin (I-1a) examples of the adhesive resin (I-1a) in the adhesive composition (I-4) include the same ones as the adhesive resin (I-1a) in the adhesive composition (I-1).
  • the adhesive resin (I-1a) contained in the adhesive composition (I-4) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof are optionally It can be selected.
  • the content of the adhesive resin (I-1a) is 5 to 99% by mass with respect to the total mass of the pressure-sensitive adhesive composition (I-4).
  • the content is preferably 10 to 95% by mass, and particularly preferably 15 to 90% by mass.
  • crosslinking agent in the pressure-sensitive adhesive composition (I-4) examples include the same as the crosslinking agents in the pressure-sensitive adhesive composition (I-1).
  • the crosslinking agent contained in the pressure-sensitive adhesive composition (I-4) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be optionally selected.
  • the content of the crosslinking agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the content of the adhesive resin (I-1a), The amount is more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass.
  • the pressure-sensitive adhesive composition (I-4) may contain other additives which do not correspond to any of the components described above, as long as the effects of the present invention are not impaired.
  • Examples of the other additives include the same as the other additives in the pressure-sensitive adhesive composition (I-1).
  • the other additives contained in the pressure-sensitive adhesive composition (I-4) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be optionally selected.
  • the content of the other additives is not particularly limited, and may be appropriately selected depending on the type.
  • the pressure-sensitive adhesive composition (I-4) may contain a solvent for the same purpose as the pressure-sensitive adhesive composition (I-1).
  • the solvent in the pressure-sensitive adhesive composition (I-4) may be the same as the solvent in the pressure-sensitive adhesive composition (I-1).
  • the solvent contained in the pressure-sensitive adhesive composition (I-4) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the content of the solvent is not particularly limited, and may be appropriately adjusted.
  • the pressure-sensitive adhesive layer is preferably non-energy ray curable. This is because when the pressure-sensitive adhesive layer is energy beam curable, when the film for forming a protective film is cured by irradiation with energy rays, it may not be possible to simultaneously cure the pressure-sensitive adhesive layer. When the pressure-sensitive adhesive layer is cured simultaneously with the protective film-forming film, the cured protective film-forming film and the pressure-sensitive adhesive layer may stick to such an extent that they can not be peeled off at these interfaces.
  • the effect when the pressure-sensitive adhesive layer is non-energy ray curable has been described, but even if the layer in direct contact with the protective film-forming film of the support sheet is a layer other than the pressure-sensitive adhesive layer, If the layer is non-energy radiation curable, the same effect can be obtained.
  • Pressure-sensitive adhesive compositions other than pressure-sensitive adhesive compositions (I-1) to (I-3) and pressure-sensitive adhesive compositions (I-1) to (I-3) such as pressure-sensitive adhesive composition (I-4) It is obtained by blending the pressure-sensitive adhesive and, if necessary, each component for constituting the pressure-sensitive adhesive composition, such as components other than the pressure-sensitive adhesive. There is no particular limitation on the order of addition of each component at the time of blending, and two or more components may be added simultaneously.
  • a solvent When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting this compounding component in advance, or by previously diluting any compounding component other than the solvent A solvent may be used by mixing with these compounding ingredients without storage.
  • the method of mixing each component at the time of compounding is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade, etc .; a method of mixing using a mixer; a method of adding ultrasonic waves and mixing, etc. It may be selected as appropriate.
  • the temperature and time of addition and mixing of the respective components are not particularly limited as long as the respective blended components do not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.
  • the protective film-forming composite sheet can be produced by laminating the above-described respective layers so as to have a corresponding positional relationship.
  • the method of forming each layer is as described above.
  • the above-mentioned pressure-sensitive adhesive composition may be coated on the substrate and dried as necessary.
  • the composition for protective film formation is coated on the pressure-sensitive adhesive layer to form a protective film. It is possible to form the forming film directly. Layers other than the protective film-forming film can be laminated on the pressure-sensitive adhesive layer in the same manner using the composition for forming this layer. As described above, in the case of forming a continuous two-layer laminated structure using any of the compositions, the composition is further coated on the layer formed of the composition to form a new layer.
  • the layer to be laminated later is formed in advance using the composition on another release film, and the side of the formed layer in contact with the release film is It is preferable to form a continuous two-layered laminated structure by bonding the opposite exposed surface to the exposed surface of the remaining layer that has already been formed.
  • the composition is preferably applied to the release-treated surface of the release film.
  • the release film may be removed as necessary after the formation of the laminated structure.
  • a composite sheet for protective film formation in which a pressure-sensitive adhesive layer is laminated on a substrate and a protective film-forming film is laminated on the pressure-sensitive adhesive layer (the support sheet is a laminate of the substrate and the pressure-sensitive adhesive layer)
  • the pressure-sensitive adhesive composition is coated on a base material, and dried as needed to laminate the pressure-sensitive adhesive layer on the base material separately.
  • the protective film-forming film is formed on the release film by applying the composition for forming a protective film on the release film and drying it as necessary. Then, the exposed surface of the protective film-forming film is attached to the exposed surface of the pressure-sensitive adhesive layer laminated on the substrate, and the protective film-forming film is laminated on the pressure-sensitive adhesive layer to form a protective film.
  • Composite sheet is obtained.
  • the pressure-sensitive adhesive composition is applied on the release film instead of the method of applying the pressure-sensitive adhesive composition on the substrate, and necessary
  • the pressure-sensitive adhesive layer is formed on the release film, and the exposed surface of this layer is laminated to one surface of the substrate to laminate the pressure-sensitive adhesive layer on the substrate.
  • the release film may be removed at any timing after formation of the intended laminated structure.
  • any layers other than the base material constituting the composite sheet for forming a protective film can be formed in advance on the peelable film and laminated on the surface of the intended layer, as required.
  • a layer adopting such a process may be appropriately selected to manufacture a composite sheet for forming a protective film.
  • the composite sheet for protective film formation is usually stored in a state in which a release film is attached to the surface of the outermost layer (for example, a film for protective film formation) opposite to the support sheet. Therefore, a composition for forming a layer constituting the outermost layer, such as a composition for forming a protective film, is coated on the release film (preferably, the release-treated surface thereof), and dried as necessary. Then, the layer constituting the outermost layer is formed on the release film, and the remaining layers are laminated by any of the methods described above on the exposed surface of the layer opposite to the side in contact with the release film.
  • the composite film for forming a protective film can also be obtained by leaving the release film in place without removing it.
  • the film for forming a protective film and the composite sheet for forming a protective film can be used for manufacturing a semiconductor chip.
  • a film for forming a protective film which does not constitute the composite sheet for forming a protective film, or a film for forming a protective film in the composite sheet for forming a protective film is used as a semiconductor wafer.
  • a step of forming a protective film by irradiating the film for forming a protective film after being attached to the semiconductor wafer with ultraviolet rays hereinafter, referred to as a step of forming a protective film).
  • a process for forming a plurality of semiconductor chips (hereinafter referred to as “division,” abbreviated as “protective film forming process”), and dividing the semiconductor wafer together with the protective film or a film for protective film formation And the like, which may be abbreviated as “process”.
  • FIG. 7 is a cross-sectional view for schematically describing one embodiment of a method of manufacturing a semiconductor chip in the case of using a protective film-forming film which does not constitute a protective film-forming composite sheet.
  • FIG. 8 is a cross-sectional view for schematically describing one embodiment of a method of manufacturing a semiconductor chip in the case of using a composite sheet for forming a protective film in which a film for forming a protective film is previously integrated with a support sheet. .
  • the protective film forming film 13 is attached to the back surface (surface opposite to the electrode forming surface) 9b of the semiconductor wafer 9.
  • the case where the first release film 151 is removed from the protective film formation film 13 and the first surface 13a of the protective film formation film 13 is bonded to the back surface 9b of the semiconductor wafer 9 is shown.
  • illustration of bumps and the like on the circuit surface of the semiconductor wafer 9 is omitted.
  • the protective film-forming film 13 after being stuck to the semiconductor wafer 9 is irradiated with ultraviolet light, as shown in FIG.
  • a protective film 13 ′ is formed on the wafer 9. The irradiation of the ultraviolet light may be performed after removing the second release film 152 from the film 13 for forming a protective film.
  • the surface of the protective film 13 ′ on the side to which the semiconductor wafer 9 is attached (this specification , The support sheet 10 is attached to the surface 13b 'opposite to the "first surface” 13a' (sometimes referred to herein as the "second surface”). .
  • the support sheet 10 is shown in FIG. 2 and the like, and is attached to the protective film 13 ′ by the pressure-sensitive adhesive layer 12.
  • the semiconductor wafer 9 is divided by dicing or the like together with the protective film 13 ′ to divide the semiconductor wafer 9, and as shown in FIG. A semiconductor chip 9 'is obtained.
  • the protective film 13 ' is cut (divided) at a position along the periphery of the semiconductor chip 9'.
  • the protective film 13 'after this cutting is indicated by reference numeral 130'.
  • FIG. 7 after performing a protective film formation process, it shows about the case where the support sheet 10 is stuck on protective film 13 '.
  • the protective film forming step may be performed after the support sheet 10 is attached to the protective film forming film 13.
  • the dividing step is performed after the protective film forming step.
  • the dividing step is performed without the protective film forming step, and the protective film is performed after the dividing step. You may perform a formation process.
  • the film 13 for forming a protective film in the composite sheet 1A for forming a protective film is attached to the back surface 9b of the semiconductor wafer 9.
  • the protective film-forming composite sheet 1A is used after removing the release film 15.
  • the protective film-forming film 13 after being stuck to the semiconductor wafer 9 is irradiated with ultraviolet light, as shown in FIG. A protective film 13 ′ is formed on the wafer 9.
  • ultraviolet rays are applied to the protective film-forming film 13 through the support sheet 10.
  • the composite sheet for protective film formation after the film 13 for protective film formation becomes protective film 13 'is shown with code
  • the semiconductor wafer 9 is divided by cutting the semiconductor wafer 9 together with the protective film 13 'by dicing or the like in the division step of the manufacturing method (2), as shown in FIG. As shown in FIG. 5, a plurality of semiconductor chips 9 'are obtained.
  • the protective film 13 ' is cut (divided) at a position along the peripheral portion of the semiconductor chip 9' to form a protective film 130 '.
  • the target semiconductor chip 9 ' is obtained as a semiconductor chip with a protective film.
  • the dividing step is performed after the protective film forming step, but in the manufacturing method of the semiconductor chip according to the present embodiment, the dividing step is performed without the protective film forming step, and the protective film is performed after the dividing step. You may perform a formation process.
  • the method of manufacturing a semiconductor chip has been described using the film 13 for forming a protective film shown in FIG. 1, the support sheet 10 shown in FIG. 2, and the composite sheet 1A for forming a protective film shown in FIG.
  • the manufacturing method of the semiconductor chip of the present invention is not limited to these.
  • composite sheets 1B to 1E for protective film formation shown in FIGS. 3 to 6 a composite sheet for protective film formation further including the intermediate layer, etc.
  • a semiconductor chip can be manufactured similarly even if it uses things other than composite sheet 1A for protective film formation shown.
  • the semiconductor chip is manufactured similarly even when using a support sheet other than the support sheet 10 shown in FIG.
  • the semiconductor chip is supported as it is with the protective film after division (ie, as a semiconductor chip with a protective film). Pull away from and pick up (not shown).
  • the semiconductor chip of the semiconductor chip with a protective film obtained is disposed on the circuit surface of the substrate by face-down method, and flip chip connection is carried out by heating the surface of the semiconductor chip on which the protective film is formed at 100 to 280 ° C. , And a semiconductor package. Then, the target semiconductor device may be manufactured using this semiconductor package (not shown).
  • Adduct-type acrylic polymer (weight-average molecular weight 350000, glass transition temperature) obtained by reacting an amount of 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko) corresponding to 1 6 ° C).
  • [Energy ray curable component (a2)] (A2) -1: ⁇ -caprolactone modified tris- (2-acryloxyethyl) isocyanurate (“A-93001 CL” manufactured by Shin-Nakamura Chemical Co., Ltd., a trifunctional ultraviolet-curable compound).
  • [Polymer having no energy ray curable group (b)] (B) -1: An acrylic polymer obtained by copolymerizing methyl acrylate (85 parts by mass) and HEA (15 parts by mass) (weight average molecular weight 350000, glass transition temperature 6 ° C.).
  • the weight average molecular weights of the adduct type acrylic polymers (a1-1) -1 and (a1-1) -2 and the polymer (b) -1 having no energy ray curable group are obtained by the following method.
  • Example 1 Manufacture of composite sheet for protective film formation> (Production of composition for forming a protective film (IV-1)) 10 parts by mass of the energy ray curable component (a2) -1, 28 parts by mass of the adduct type acrylic polymer (a1-1) -1 and 100 parts by mass of the solid content, and a photopolymerization initiator (c) -1 0.6 parts by mass, 57 parts by mass of filler (d) -1, 0.4 parts by mass of coupling agent (e) -1, and 3 parts by mass of colorant (g) -1.
  • a composition for forming a protective film (IV-1) having a solid content concentration of 50% by mass was prepared.
  • the pressure-sensitive adhesive composition (I-4) obtained above was applied to the release-treated surface of a release film ("SP-PET 381031" manufactured by Lintec Corporation, 38 ⁇ m thick) whose release treatment was performed on one side of a polyethylene terephthalate film by silicone treatment. C.) and heat-dried at 120.degree. C. for 2 minutes to form a 10 .mu.m thick non-energy ray curable pressure-sensitive adhesive layer. Then, a base material, an adhesive layer and a release film are laminated in this order in the thickness direction by laminating a polypropylene film (80 ⁇ m in thickness) as a substrate on the exposed surface of the adhesive layer. Support sheet was obtained.
  • the protective film obtained above is formed on the release-treated surface of a release film (second release film, "SP-PET 382150" manufactured by Lintec Corporation, thickness 38 ⁇ m) in which one surface of a polyethylene terephthalate film is release-treated by silicone treatment.
  • the composition for preparation (IV-1) was applied and dried at 100 ° C. for 2 minutes to produce a 25 ⁇ m-thick energy ray-curable protective film-forming film.
  • the exfoliation process of the exfoliation film (the 1st exfoliation film, the lintec "SP-PET 38 1031", 38 micrometers in thickness) is carried out to the exposure side of the side which does not equip the 2nd exfoliation film of the film for protective film formation obtained
  • a laminated film provided with a first peelable film on one surface of the protective film-forming film and a second peelable film on the other surface was obtained.
  • the release film was removed from the pressure-sensitive adhesive layer of the support sheet obtained above.
  • the first release film was removed from the laminated film obtained above.
  • a base material and adhesion are obtained by sticking together the exposed surface of the pressure-sensitive adhesive layer produced by removing the above-mentioned release film and the exposed surface of the film for protective film formation produced by removing the above-mentioned first release film.
  • the composite sheet for protective film formation in which an agent layer, the film for protective film formation, and the 2nd exfoliation film are laminated in this thickness direction in this order was produced.
  • a film for protective film formation is cured to form a protective film.
  • the gloss value (gloss value before heating) of the formed protective film surface was measured using a gloss meter (“VG7000” manufactured by Nippon Denshoku Kogyo Co., Ltd.) under the condition of an incident angle of 60 °.
  • the measured gloss values (gloss values before heating) are shown in Table 1.
  • the silicon wafer on which the protective film was formed was heated at 260 ° C. for 5 minutes using an oven. Thereafter, the gloss value (gloss value after heating) of the protective film surface was measured under the same conditions as the measurement of the gloss value before heating. It was judged that the case where the decreasing rate of the gloss value after heating from the gloss value before heating was 30% or less was good.
  • the measured gloss value before heating, the gloss value after heating, and the reduction rate of the gloss value after heating are shown in Table 1.
  • Example 2 Example except that the adduct type acrylic polymer (a1-1) -1 was changed to the adduct type acrylic polymer (a1-1) -2 at the time of production of the composition (IV-1) for forming a protective film
  • the film for protective film formation and the composite sheet for protective film formation were manufactured by the same method as 1, and the protective film was evaluated. The results are shown in Table 1.
  • Comparative Example 1 The adduct type acrylic polymer (a1-1) -1 at the time of producing the composition (IV-1) for forming a protective film was changed to a polymer (b) -1 having no energy ray curable group, The film for protective film formation and the composite sheet for protective film formation were manufactured by the same method as Example 1, and the protective film was evaluated. The results are shown in Table 1.
  • Example 1 both the gloss value before heating and the gloss value after heating of the protective film surface are as high as 80 and 65, and the reduction rate of the gloss value after heating is also 19%. It was low.
  • Example 2 both the gloss value before heating and the gloss value after heating of the protective film surface were as high as 80 and 72, and the decreasing rate of the gloss value after heating was also as low as 10%. This is because the adduct type acrylic polymer is polymerized by ultraviolet irradiation, so the low molecular weight polymer is hardly contained in the protective film, and the low molecular weight polymer segregates on the surface of the protective film even if the protective film is heated. It is thought that it was not.
  • Comparative Example 1 the gloss value before heating of the surface of the protective film was as high as 80, while the gloss value after heating was reduced to 9. This is because the protective film contains a large amount of the polymer (b) having no low-molecular-weight energy ray-curable group in the protective film as compared with the cases of Examples 1 and 2, and the protective film is heated. It is considered that the gloss value is lowered because the low molecular weight polymer is segregated on the surface of the protective film.
  • the present invention is applicable to the manufacture of semiconductor devices.

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JP2021125514A (ja) * 2020-02-03 2021-08-30 リンテック株式会社 保護膜形成フィルム、保護膜形成用複合シートおよび装置の製造方法
KR20220135157A (ko) 2021-03-29 2022-10-06 린텍 가부시키가이샤 지지 시트, 수지막 형성용 복합 시트, 키트, 및 수지막이 형성된 칩의 제조 방법

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JP2007084722A (ja) * 2005-09-22 2007-04-05 Nitto Denko Corp 粘着シートとその製造方法、及び、製品の加工方法
WO2014148496A1 (ja) * 2013-03-19 2014-09-25 リンテック株式会社 保護膜形成用フィルム
JP2017092122A (ja) * 2015-11-04 2017-05-25 リンテック株式会社 硬化性樹脂フィルム及び第１保護膜形成用シート
WO2017163971A1 (ja) * 2016-03-24 2017-09-28 リンテック株式会社 支持シート及び保護膜形成用複合シート

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JP2021125514A (ja) * 2020-02-03 2021-08-30 リンテック株式会社 保護膜形成フィルム、保護膜形成用複合シートおよび装置の製造方法
JP7457513B2 (ja) 2020-02-03 2024-03-28 リンテック株式会社 保護膜形成フィルム、保護膜形成用複合シートおよび装置の製造方法
KR20220135157A (ko) 2021-03-29 2022-10-06 린텍 가부시키가이샤 지지 시트, 수지막 형성용 복합 시트, 키트, 및 수지막이 형성된 칩의 제조 방법

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