CN108701640A - Protective film formation film and protective film formation composite sheet - Google Patents

Protective film formation film and protective film formation composite sheet Download PDF

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Publication number
CN108701640A
CN108701640A CN201780011923.9A CN201780011923A CN108701640A CN 108701640 A CN108701640 A CN 108701640A CN 201780011923 A CN201780011923 A CN 201780011923A CN 108701640 A CN108701640 A CN 108701640A
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protective film
film formation
methyl
curable
energy ray
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Granted
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CN201780011923.9A
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CN108701640B (en
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稻男洋
稻男洋一
小桥力也
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Lintec Corp
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Lintec Corp
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    • 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 at least one potential-jump barrier or surface barrier, e.g. 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
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • 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
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • 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
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/72—Cured, e.g. vulcanised, cross-linked
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51—Elastic
    • 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
    • B32B2310/00—Treatment by energy or chemical effects
    • B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
    • B32B2310/0806—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation
    • B32B2310/0831—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation using UV radiation
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/14—Semiconductor wafers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/6834—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used to protect an active side of a device or wafer

Abstract

The present invention provides a kind of can form protective film and protective layer with high elastic modulus, the protective film formation film of energy ray-curable at the back side of semiconductor crystal wafer or semiconductor chip.The protective film formation film 13 of the present invention is the protective film formation film of energy ray-curable, and the protective film formation is 30MPa or more with the tensile modulus of elasticity of film 13.

Description

Protective film formation film and protective film formation composite sheet
Technical field
The present invention relates to protective film formation film and protective film formation composite sheets
The Japanese Patent Application 2016-092031 claims priorities that the application is filed an application based on April 28th, 2016 in Japan Power, and its content is applied at this.
Background technology
In recent years, it is carrying out applying partly leading for the so-called Method for Installation referred to as upside-down mounting (face down) mode The manufacture of body device.In upside-down mounting mode, using the semiconductor chip with the electrodes such as convex block in circuit face, the electrode with Substrate engages.Therefore, the back side with the circuit face opposite side of semiconductor chip is exposed sometimes.
It is formed with the resin film containing organic material as protective film at the back side of the semiconductor chip of the exposing, sometimes Semiconductor device is packed into as the semiconductor chip with protective film.
It cracks to utilize protective film on a semiconductor die after cutting action or encapsulation in order to prevent.
In order to form such protective film, such as use a kind of protective film for having on support chip and being used to form protective film The protective film formation composite sheet of formation film.In protective film formation composite sheet, protective film formation film can pass through solidification And protective film is formed, support chip can be also used as to cutting sheet, can be made into protective film formation film and the integrated protection of cutting sheet Film formation composite sheet.
As such protective film formation composite sheet, such as mainly uses to have so far and carried out by heating Cure and be consequently formed the protective film formation composite sheet of the protective film formation film of the Thermocurable of protective film.At this point, for example Protective film formation is attached at the back side of semiconductor crystal wafer (with electrode with composite sheet with film using the protective film formation of Thermocurable The face of forming face opposite side) after, make the solidification of protective film formation film to which protective film be made by heating, will partly be led by cutting Body wafer divides that semiconductor chip is made together with protective film.Then, the state for being pasted with the protective film is kept, will partly be led Body chip is detached and is picked up from support chip.In addition, also carrying out protective film with sequence contrary to the above sometimes forms use The solidification and cutting of film.
However, being heating and curing for the protective film formation film of Thermocurable usually requires the long-time of hours or so, because This it is expected to shorten hardening time.In this regard, studying can be by the cured protective film of the irradiation of the energy-rays such as ultraviolet light Formation is used for the formation of protective film with film.For example, having been disclosed for being formed in the energy ray-curable protective film on stripping film (referring to patent document 1) and high rigidity can be formed and to the energy-ray of the excellent protective film of the adherence of semiconductor chip Cure cake core protection with film (with reference to patent document 2).
Existing technical literature
Patent document
Patent document 1:No. 5144433 bulletin of Japan's patent
Patent document 2:Japanese Unexamined Patent Publication 2010-031183 bulletins
Invention content
The technical problem to be solved in the present invention
However, using in energy ray-curable protective film formation film disclosed in Patent Document 1 or patent document 2 Disclosed energy ray-curable chip protection film, and after dicing irradiation ultraviolet light etc. energy-rays and make film solidification to When protective film is made, in cutting process, there is technical issues that lead to that blade occurs because of the chip of film.
Therefore, the present invention provides a kind of can form protective film and can at the back side of semiconductor crystal wafer or semiconductor chip Inhibit the protective film formation film of the energy ray-curable of the blocking of cutting blade.
Solve the technological means of technical problem
In order to solve the above technical problem, the present invention provides a kind of protective film formation films, are energy ray-curable Protective film formation film, the tensile modulus of elasticity of the protective film formation film is 30MPa or more.
It is preferred that the protective film formation composite sheet of the present invention on support chip by having the protective film formation film At.
It is preferred that in the protective film formation composite sheet of the present invention, the support chip has adhering agent layer, the protective film Formation is in direct contact with film and the adhering agent layer.
It is preferred that the adhering agent layer of the protective film formation composite sheet of the present invention is non-energy ray-curable.
Invention effect
According to the present invention, it is possible to provide a kind of to form protective film and energy at the back side of semiconductor crystal wafer or semiconductor chip Enough inhibit the protective film formation film of the energy ray-curable of the blocking of cutting blade.
Description of the drawings
Fig. 1 is the sectional view for an embodiment for schematically showing the protective film formation piece of the present invention.
Fig. 2 is the sectional view for an embodiment for schematically showing the protective film formation composite sheet of the present invention.
Fig. 3 is the sectional view for the another embodiment for schematically showing the protective film formation composite sheet of the present invention.
Fig. 4 is the sectional view for the another embodiment for schematically showing the protective film formation composite sheet of the present invention.
Fig. 5 is the sectional view for the another embodiment for schematically showing the protective film formation composite sheet of the present invention.
Fig. 6 is the sectional view for the another embodiment for schematically showing the protective film formation composite sheet of the present invention.
Specific implementation mode
◇ protective film formation films
The protective film formation protective film formation film that film is energy ray-curable of the present invention, the protective film are formed It is 30MPa or more with the tensile modulus of elasticity of film.
In addition, in the present specification, " protective film formation film " refers to film before curing, and " protective film " is to instigate protective film Film made of formation is cured with film.
The protective film formation film is cured by the irradiation of energy-ray, becomes protective film.The protective film is for protecting Protect the back side (face with electrode forming surface opposite side) of semiconductor crystal wafer or semiconductor chip.Protective film formation film be it is soft, It can be simply attached to attach object.Moreover, by make the tensile modulus of elasticity of protective film formation film be 30MPa with On, such as the semiconductor core as target can be cut before curing protective film formation film by the irradiation of energy-ray When piece, inhibit the blocking of the blade caused by the chip of film.
The tensile modulus of elasticity of protective film formation film of the present invention is preferably 30MPa or more, more preferably 100MPa with On, further preferably 140MPa or more.
By making tensile modulus of elasticity be 30MPa or more, even if being if protective film formation film before energy ray curing High elastic modulus can inhibit bonding of the protective film formation film to blade, therefore can inhibit the blocking of blade, can keep Higher production efficiency.
On the other hand, the upper limit value of the tensile modulus of elasticity of protective film formation film is not particularly limited, such as can be Any one in 1000MPa, 900MPa, 800MPa etc..But these are an example.
In the present specification, the tensile modulus of elasticity of protective film formation film can utilize the measurement side described in embodiment Method is measured.
In the present invention, " energy-ray " refers to the ray with the quantum of energy in electromagnetic wave or charged particle beam, as it Example can enumerate ultraviolet light, radioactive ray, electron beam etc..
Ultraviolet light for example can be by using high-pressure sodium lamp, fusion H lamps (fusion H lamp), xenon lamp, black light lamp or LED Lamp etc. is irradiated as ultraviolet source.Electron beam can irradiate the electron beam using generations such as electron-beam accelerators.
In the present invention, " energy ray-curable " refers to carrying out cured property by irradiation energy ray, " non-energy Amount ray-curable " refers to irradiation energy ray without cured property.
The tensile modulus of elasticity of above-mentioned protective film formation film can be by containing such as protective film formation film Type and amount of ingredient etc. are adjusted, to suitably adjust.
For example, the type containing ingredient and amount of protective film formation film can pass through aftermentioned protective film formation composition The type containing ingredient and amount be adjusted.Moreover, by protective film formation composition containing in ingredient, for example The type and content of energy ray-curable ingredient (a) is adjusted, and can more easily adjust protective film formation film Tensile modulus of elasticity.
Protective film formation has energy ray-curable with film, such as can enumerate containing energy ray-curable ingredient (a) protective film formation film.
Preferred energy ray-curable ingredient (a) is uncured, preferably its with adherence, more preferably its is uncured and has Adherence and elasticity.
Protective film formation film can be one layer (single layer), or two layers or more of multiple layers, when being multiple layers, this A little multiple layers mutually the same can also be different, these multiple layers combinations are not particularly limited.
The thickness of protective film formation film is preferably 1~100 μm, more preferably 5~75 μm, particularly preferably 5~50 μm. Thickness by making protective film formation film is the lower limiting value or more, can form the higher protective film of protective capability.In addition, Become excessive thickness hereinafter, can inhibit thickness by making the thickness of protective film formation film be the upper limit value.
Herein, " thickness of protective film formation film " refers to the thickness of protective film formation film entirety, such as by multiple layers The thickness of the protective film formation film of composition refers to the thickness of the total for all layers for constituting protective film formation film.In addition, The assay method of thickness as protective film formation film, such as can enumerate using contact thickness gauge in arbitrary five positions Measurement thickness is set, and calculates the average method etc. of measured value.
As long as protective film become fully play its function degree curing degree, then make protective film formation film solidification from And condition of cure when forming protective film is not particularly limited, and according to the type of protective film formation film suitably select i.e. It can.
For example, the illumination of energy-ray when solidification protective film formation film is preferably 4~280mW/cm2.Moreover, described The light quantity of energy-ray when solidification is preferably 3~1000mJ/cm2。
< < protective films, which are formed, uses composition > >
Protective film formation film can be used the protective film formation composition containing its constituent material and be formed.For example, logical It crosses and protective film formation is coated in the formation object surface of protective film formation film and is dried as needed, energy with composition It is enough to form protective film formation film in target site.Ingredient in protective film formation composition, not gasifying under room temperature is each other Content than usually with the mutual content of the ingredient of protective film formation film than identical.In addition, in the present specification, " often Temperature " refers to the temperature for especially not cooled down or being heated, i.e. usual temperature, such as can enumerate 15~25 DEG C of temperature Deng.
The coating of protective film formation composition is carried out using well known method, such as can be enumerated and be applied using air knife Cloth machine, scraping blade coating machine, bar coater, gravure coater, roll coater, roller knife coating machine, curtain coater, die coating machine, knife type coater, The method of the various coating machines such as silk screen coating machine (screen coater), Meyer rod coater, kiss painting machine (kiss coater).
The drying condition of protective film formation composition is not particularly limited, but after protective film formation composition contains It when the solvent stated, is preferably thermally dried, at this point, for example preferably being done with the condition of 70~130 DEG C, 10 seconds~5 minutes It is dry.
< protective films, which are formed, uses composition (IV-1) >
As protective film formation composition, such as the guarantor containing the energy ray-curable ingredient (a) can be enumerated Cuticula is formed with composition (IV-1) etc..
&#91;Energy ray-curable ingredient (a) &#93;
Energy ray-curable ingredient (a) be by the cured ingredient of the irradiation of energy-ray, and for protection Film formation film assigns the ingredient for making film property, pliability etc..
As energy ray-curable ingredient (a), for example, can enumerate it is with energy ray-curable group, divide equally again Polymer (a1) that son amount is 80000~2000000 and with energy ray-curable group, molecular weight be 100~ 80000 compound (a2).The polymer (a1) can be made of its at least part is crosslinked by aftermentioned crosslinking agent (f) Substance, or uncrosslinked substance.
In addition, in the present specification, unless otherwise indicated, weight average molecular weight refers to utilizing gel permeation chromatography (GPC) method The polystyrene scaled value of measurement.
(polymer (a1) that with energy ray-curable group, weight average molecular weight is 80000~2000000)
The polymer (a1) for being 80000~2000000 as with energy ray-curable group, weight average molecular weight, Such as can enumerate with can with the acrylic polymer (a11) for the functional group that group react possessed by other compounds and Energy-ray with group and the energy ray-curables group such as energy ray-curable double bond with the functional group reactions The acrylic resin (a1-1) that curability compound (a12) is polymerized.
As the functional group that can be reacted with group possessed by other compounds, for example, can enumerate hydroxyl, carboxyl, Amino, substituted-amino (group made of one or two hydrogen atom of amino is replaced by the group in addition to hydrogen atom), epoxy Base etc..Wherein, from the point of the corrosion for the circuit for preventing semiconductor crystal wafer or semiconductor chip etc., the preferably described functional group is Group in addition to carboxyl.
Wherein, the preferably described functional group is hydroxyl.
Acrylic polymer (a11) with functional group
As the acrylic polymer (a11) with functional group, such as can enumerate with the functional group Acrylic monomer and polymer made of the acrylic monomer copolymerization without the functional group, or remove these lists Further copolymerization has the polymer of the monomer (non-acrylic monomer) in addition to acrylic monomer other than body.
In addition, the acrylic polymer (a11) can be random copolymer, or block copolymer.
As the acrylic monomer with the functional group, such as hydroxyl monomer can be enumerated, carboxyl group-containing monomer, contained Amino monomers, monomer containing substituted-amino, containing epoxy based monomers etc..
As the hydroxyl monomer, such as (methyl) acrylate, (methyl) acrylic acid 2- hydroxyls can be enumerated Ethyl ester, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 3- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxybutyls, (first Base) (methyl) hydroxyalkyl acrylates such as acrylic acid 3- hydroxybutyls, (methyl) acrylic acid 4- hydroxybutyls;Vinyl alcohol, alkene Non- (methyl) acrylic compounds unsaturated alcohol such as propyl alcohol (unsaturated alcohol for not having (methyl) acryloyl group skeleton) etc..
As the carboxyl group-containing monomer, such as the olefinics unsaturation unitary carboxylic such as can enumerate (methyl) acrylic acid, crotonic acid Acid (monocarboxylic acid with ethylenic unsaturated bond);The ethylenically unsaturated dicarboxylics such as fumaric acid, itaconic acid, maleic acid, citraconic acid (dicarboxylic acids with ethylenic unsaturated bond);The acid anhydrides of the ethylenically unsaturated dicarboxylic;Methacrylic acid 2- carboxyethyls etc. (methyl) acrylic acid carboxyalkyl ester etc..
In addition, in the present specification, " (methyl) acrylic acid " be comprising " acrylic acid " and " methacrylic acid " both Concept.It is also identical as term as (methyl) acrylic compounds.
It is preferred that the acrylic monomer with the functional group is hydroxyl monomer or carboxyl group-containing monomer, more preferably contain hydroxyl Base monomer.
Constitute the acrylic polymer (a11), the acrylic monomer with the functional group can be only one Kind, or two or more, when being two or more, combination thereof and ratio can be selected arbitrarily.
As the acrylic monomer without the functional group, such as (methyl) methyl acrylate, (first can be enumerated Base) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) Isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) third The own ester of olefin(e) acid, (methyl) heptylacrylate, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) third Olefin(e) acid n-octyl, the positive nonyl ester of (methyl) acrylic acid, the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate, (methyl) propylene Sour hendecane base ester, (methyl) dodecylacrylate ((methyl) lauryl acrylate), (methyl) acrylic acid tridecyl Ester, (methyl) acrylic acid tetradecane base ester ((methyl) myristyl ester), (methyl) acrylic acid pentadecane base ester, (methyl) Aliphatic acrylate ((methyl) acrylic acid palm ester), (methyl) acrylic acid heptadecane base ester, (methyl) acrylic acid 18 Arrcostab ((methyl) stearyl acrylate acid esters) etc., composition Arrcostab alkyl is the chain structure that carbon atom number is 1~18 (methyl) alkyl acrylate etc..
In addition, as the acrylic monomer without the functional group, such as can also enumerate (methyl) acrylic acid first Oxygroup methyl esters, (methyl) methoxyethyl acrylate, (methyl) ethioxy methyl esters, (methyl) ethoxyethyl acrylate Deng (methyl) acrylate containing alkoxyalkyl;Including (methyl) phenyl acrylate etc. (methyl) benzyl acrylate etc., (methyl) acrylate with aromatic group;(methyl) acrylamide and its derivative of non-crosslinked property;(methyl) propylene Sour N, N- dimethylamino ethyl ester, (methyl) acrylic acid N, N- dimethylamino propyl ester etc. have the tertiary amino of non-crosslinked property (methyl) acrylate etc..
Constitute the acrylic polymer (a11), the acrylic monomer without the functional group can be only It is a kind of, or two or more, when being two or more, combination thereof and ratio can be selected arbitrarily.
As the non-acrylic monomer, such as the alkene such as ethylene, norbornene can be enumerated;Vinyl acetate;Benzene Ethylene etc..
The non-acrylic monomer for constituting the acrylic polymer (a11) can be only one kind, or Two or more, when being two or more, combination thereof and ratio can be selected arbitrarily.
In the acrylic polymer (a11), relative to the total amount for the structural unit for constituting the polymer, by having The ratio (content) of the amount of structural unit derived from the acrylic monomer of the functional group is preferably 0.1~50 mass %, more Preferably 1~40 mass %, particularly preferably 3~30 mass %.By making the ratio be such range, pass through described third Alkene acids polymers (a11) and the acrylic compounds tree obtained from the copolymerization of the energy ray-curable compound (a12) The curing degree of protective film easily can be adjusted to preferred model by the content of the energy ray-curable group in fat (a1-1) It encloses.
The acrylic polymer (a11) for constituting the acrylic resin (a1-1) can be only one kind, also may be used Think it is two or more, for it is two or more when, combination thereof and ratio can be selected arbitrarily.
In protective film formation in composition (IV-1), relative to the protective film formation gross mass of composition (IV-1), The content of acrylic resin (a1-1) is preferably 1~40 mass %, more preferably 2~30 mass %, and particularly preferably 3~20 Quality %.
Energy ray-curable compound (a12)
It is preferred that the energy ray-curable compound (a12), which has, selects free isocyanate group, epoxy group and carboxyl group At one or more of group as can be with the base of functional group reactions possessed by the acrylic polymer (a11) Group more preferably has isocyanate group as the group.For example, when the energy ray-curable compound (a12) has When isocyanate group is as the group, which is easy and has acrylic polymer of the hydroxyl as the functional group The hydroxyl for closing object (a11) is reacted.
It is preferred that the energy ray-curable compound (a12) is described energy ray curing with 1~5 in 1 molecule Property group, more preferably have 1~3 energy ray-curable group.
As the energy ray-curable compound (a12), such as 2- methylacryoyloxyethyl isocyanides can be enumerated Acid esters, isopropenyl-bis (alpha, alpha-dimethylbenzyl) based isocyanate, methacryloyl isocyanate, allyl iso cyanurate, 1, 1- (double acryloyloxymethyls) ethyl isocyanate;
By diisocyanate cpd or polyisocyanate compounds are with (methyl) reacting for Hydroxyethyl Acrylate Obtained acryloyl group monoisocyanate compound;
Pass through diisocyanate cpd or polyisocyanate compounds, polyol compound and (methyl) dihydroxypropyl Acryloyl group monoisocyanate compound etc. obtained from the reaction of ethyl ester.
The energy ray-curable compound (a12) for constituting the acrylic resin (a1-1) can be only one Kind, or two or more, when being two or more, combination thereof and ratio can be selected arbitrarily.
In the acrylic resin (a1-1), the energy from the energy ray-curable compound (a12) is penetrated The content of line curative group is excellent relative to the ratio of the content of the functional group from the acrylic polymer (a11) It is selected as 20~120 moles of %, more preferably 35~100 moles of %, particularly preferably 50~100 moles of %.By making described contain The ratio of amount is such range, is become much larger by the bonding force for the protective film being solidified to form.In addition, when the energy is penetrated When line curability compound (a12) is simple function (having 1 group in 1 molecule) compound, the ratio of the content Upper limit value be 100 moles of %, and when the energy ray-curable compound (a12) be it is multifunctional (in 1 molecule have 2 A above group) compound when, the upper limit value of the ratio of the content is sometimes more than 100 moles of %.
The weight average molecular weight (Mw) of the polymer (a1) is preferably 100000~2000000, more preferably 300000~ 1500000。
When the polymer (a1) is that its at least part is crosslinked substance made of agent (f) crosslinking, the polymer (a1) can be any for being not belonging in the above-mentioned monomer illustrated as the monomer for constituting the acrylic polymer (a11) It person and is copolymerized with the monomer of group reacted with crosslinking agent (f), and at the group reacted with the crosslinking agent (f) Polymer made of being crosslinked can also be in from the energy ray-curable compound (a12) and the function Polymer made of being crosslinked at the group of group's reaction.
The polymer (a1) contained by protective film formation composition (IV-1) and protective film formation film can be only For one kind, or two or more, when being two or more, combination thereof and ratio can be selected arbitrarily.
(compound (a2) that with energy ray-curable group, molecular weight is 100~80000)
Energy possessed by the compound (a2) for being 100~80000 as with energy ray-curable group, molecular weight Ray-curable group is measured, the group for including energy ray-curable double bond can be enumerated, as preferred group, can be enumerated (methyl) acryloyl group, vinyl etc..
The compound (a2) is not particularly limited as long as meeting above-mentioned condition, can enumerate with energy ray curing The low molecular weight compound of property group, the epoxy resin with energy ray-curable group, with energy ray-curable base The phenol resin etc. of group.
As the low molecular weight compound with energy ray-curable group in the compound (a2), such as can arrange Enumerate polyfunctional monomer or oligomer etc., the preferably acrylic ester compound with (methyl) acryloyl group.
As the acrylic ester compound, such as 2- hydroxyls -3- (methyl) acryloxypropyl first can be enumerated Base acrylate, polyethylene glycol two (methyl) acrylate, propoxylation Ethoxylated bisphenol A bis- (methyl) acrylate, 2, The bis- &#91 of 2-;4- ((methyl) acryloxy polyethoxy) Ben Ji &#93;Propane, Ethoxylated bisphenol A bis- (methyl) acrylate, 2,2- Shuan &#91;4- ((methyl) acryloxy diethoxy) Ben Ji &#93;The bis- &#91 of propane, 9,9-;4- (2- (methyl) acryloyloxyethoxy) Ben Ji &#93;The bis- &#91 of fluorenes, 2,2-;4- (the poly- propoxyl group of (methyl) acryloxy) Ben Ji &#93;Propane, Tricyclodecane Dimethanol two (methyl) third Olefin(e) acid ester (tristane dihydroxymethyl two (methyl) acrylate), 1,10- decanediols two (methyl) acrylate, 1,6- oneself two Alcohol two (methyl) acrylate, 1,9- nonanediols two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, 3 the third two Alcohol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, polytetramethylene glycol two (methyl) acrylate, ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, the bis- &#91 of 2,2-;4- ((methyl) acryloyloxyethoxy) Ben Ji &#93;Propane, neopentyl glycol two (methyl) acrylate, ethoxylated polypropylene glycol two Difunctionalities (methyl) acrylate such as (methyl) acrylate, 2- hydroxyls -1,3- two (methyl) acryloxy propane;
Three (2- (methyl) acrylyl oxy-ethyl) isocyanuric acid esters, 6-caprolactone are modified three (2- (methyl) acryloyl-oxy second Base) isocyanuric acid ester, ethoxylated glycerol three (methyl) acrylate, pentaerythrite three (methyl) acrylate, trihydroxy methyl Propane three (methyl) acrylate, two trimethylolpropane four (methyl) acrylate, ethoxylation pentaerythrite four (methyl) Poly- (methyl) acrylate of acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol, six (first of dipentaerythritol Base) multifunctional (methyl) acrylates such as acrylate;
Multifunctional (methyl) acrylates oligomer such as carbamate (methyl) acrylate oligomer etc..
Wherein, the preferably described compound (a2) is (methyl) acrylate of tristane dihydroxymethyl two or 6-caprolactone Modified three (2- (methyl) acrylyl oxy-ethyl) isocyanuric acid esters.
As the epoxy resin with energy ray-curable group, solid with energy-ray in the compound (a2) Described in phenol resin, such as paragraph 0043 that " Japanese Unexamined Patent Publication 2013-194102 bulletins " can be used of the property changed group etc. Resin.Such resin also corresponds to constitute the resin of aftermentioned thermosetting component (h), but describedization is regarded as in the present invention Close object (a2).
The weight average molecular weight of the compound (a2) is preferably 100~30000, and more preferably 300~10000.
The compound (a2) contained by protective film formation composition (IV-1) and protective film formation film can be only For one kind, or two or more, when being two or more, combination thereof and ratio can be selected arbitrarily.
&#91;Polymer (b) &#93 without energy ray-curable group;
When protective film formation composition (IV-1) and protective film formation use film to contain the compound (a2) described in When energy ray-curable ingredient (a), preferably further also contain the polymer (b) without energy ray-curable group.
The polymer (b) can be that at least part is crosslinked substance made of agent (f) crosslinking, or uncrosslinked Substance.
As the polymer (b) without energy ray-curable group, such as acrylic polymer, benzene can be enumerated Oxygroup resin, carbamate resins, polyester, rubber resin, propenoic methyl carbamate resin, polyvinyl alcohol (PVA), fourth Urea formaldehyde, polyester urethane resin etc..
Wherein, the preferably described polymer (b) is acrylic polymer (hereinafter, writing a Chinese character in simplified form work " acrylic polymer sometimes (b-1)")。
Acrylic polymer (b-1) can be well known acrylic polymer, such as can be a kind of acrylic compounds The homopolymer of monomer, or the copolymer of two or more acrylic monomers can also be one or more kinds of The copolymerization of acrylic monomer and one or more kinds of monomers (non-acrylic monomer) in addition to acrylic monomer Object.
As the acrylic monomer of composition acrylic polymer (b-1), such as (methyl) propylene can be enumerated Acid alkyl ester, (methyl) acrylate with cyclic skeleton, (methyl) acrylate containing glycidyl, hydroxyl (methyl) acrylate, (methyl) acrylate etc. containing substituted-amino.Herein, " substituted-amino " and the phase being illustrated above Together.
As (methyl) alkyl acrylate, such as (methyl) methyl acrylate, (methyl) acrylic acid can be enumerated Ethyl ester, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid are different Butyl ester, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid are just pungent Ester, the positive nonyl ester of (methyl) acrylic acid, the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate, (methyl) acrylic acid hendecane Base ester, (methyl) dodecylacrylate ((methyl) lauryl acrylate), (methyl) tridecyl acrylate, (methyl) Acrylic acid tetradecane base ester ((methyl) myristyl ester), (methyl) acrylic acid pentadecane base ester, (methyl) acrylic acid ten Six Arrcostabs ((methyl) acrylic acid palm ester), (methyl) acrylic acid heptadecane base ester, (methyl) octadecyl acrylate ((methyl) stearyl acrylate acid esters) etc., constitute Arrcostab alkyl be the chain structure that carbon atom number is 1~18 (first Base) alkyl acrylate etc..
As described (methyl) acrylate with cyclic skeleton, such as (methyl) isobomyl acrylate can be enumerated (methyl) the acrylate base esters such as ester, (methyl) acrylic acid bicyclopentyl ester;
(methyl) benzyl acrylate etc. (methyl) acrylic acid aralkyl ester;
(methyl) acrylic acid cyclenes base ester such as (methyl) acrylic acid dicyclopentenyl base ester;
(methyl) acrylic acid cycloalkenyl oxy Arrcostab such as (methyl) acrylic acid dicyclopentenyl oxygroup ethyl ester etc..
As described (methyl) acrylate containing glycidyl, such as (methyl) glycidyl can be enumerated Ester etc..
As (methyl) acrylate of the hydroxyl, such as (methyl) acrylate, (methyl) can be enumerated Acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 3- hydroxy propyl esters, (methyl) acrylic acid 2- Hydroxybutyl, (methyl) acrylic acid 3- hydroxybutyls, (methyl) acrylic acid 4- hydroxybutyls etc..
As described (methyl) acrylate containing substituted-amino, such as (methyl) acrylic acid N- methylaminos can be enumerated Ethyl ester etc..
As the non-acrylic monomer of composition acrylic polymer (b-1), such as ethylene, drop ice can be enumerated The alkene such as piece alkene;Vinyl acetate;Styrene etc..
As being crosslinked at least partially, agent (f) is crosslinked, the polymer without energy ray-curable group (b), for example, the reactive functional groups that can enumerate in the polymer (b) reacted with crosslinking agent (f) obtained from polymer.
The reactive functional groups are suitably selected according to progress such as the types of crosslinking agent (f), are not particularly limited.Example Such as, when crosslinking agent (f) is polyisocyanate compounds, as the reactive functional groups, hydroxyl, carboxyl, ammonia can be enumerated Base etc., wherein preferably with the hydroxyl with high reactivity of isocyanate group.In addition, when crosslinking agent (f) is epoxy compounds, As the reactive functional groups, carboxyl, amino, amide groups etc. can be enumerated, wherein preferably with high reactivity with epoxy group Carboxyl.However, from the point of the corrosion for the circuit for preventing semiconductor crystal wafer or semiconductor chip, the preferably described functional group be except Group other than carboxyl.
As the polymer (b) with the reactive functional groups and without energy ray-curable group, such as can Enumerate polymer obtained from at least monomer polymerization with the reactive functional groups of sening as an envoy to.For acrylic polymer (b-1) it when, is arranged using the monomer with the reactive functional groups as the monomer for constituting the acrylic polymer (b-1) It is lifting, in the acrylic monomer and non-acrylic monomer any one or both.For example, as with hydroxyl As the polymer (b) of reactive functional groups, such as it can enumerate (methyl) acrylic ester polymerization of hydroxyl and obtain The polymer arrived can enumerate the acrylic monomer that will hereinbefore enumerate or non-acrylic monomer in addition to this One or two of more than hydrogen atom be substituted by polymer obtained from monomer polymerization made of the reactive functional groups.
In the polymer (b) with reactive functional groups, by the knot of the monomer derived with reactive functional groups The amount of structure unit is preferably 1~25 mass % relative to the ratio (content) of the total amount for the structural unit for constituting the polymer (b), More preferably 2~20 mass %.By make the ratio be such range, in the polymer (b), crosslinked degree at For preferred range.
The more good point of film property is made from protective film formation composition (IV-1), is not had energy ray curing The weight average molecular weight (Mw) of the polymer (b) of property group is preferably 10000~2000000, more preferably 100000~ 1500000。
Protective film formed it is with composition (IV-1) and contained by protective film is formationed film, without energy ray-curable The polymer (b) of group can be only one kind, or two or more, when being two or more, combination thereof and ratio can Arbitrarily to select.
As protective film formation with composition (IV-1), can enumerate containing the polymer (a1) and the compound (a2) in any one or both protective film formation composition.Moreover, when containing the compound (a2), preferably protect Cuticula is formed further contains the polymer (b) without energy ray-curable group with composition (IV-1), at this point, also excellent Choosing further contains (a1).In addition, protective film formation composition (IV-1) can not also contain the compound (a2) And contain the polymer (a1) and the polymer (b) without energy ray-curable group simultaneously.
When protective film formation composition (IV-1) containing the polymer (a1), the compound (a2) and does not have energy When measuring the polymer (b) of ray-curable group, in protective film formation in composition (IV-1), relative to the polymer (a1) and 100 mass parts of the total content of the polymer (b) without energy ray-curable group, compound (a2's) contains Amount is preferably 40~1500 mass parts, more preferably 45~1000 mass parts.
In protective film formation in composition (IV-1), the energy ray-curable ingredient (a) and penetrated without energy Total content of the polymer (b) of line curative group is (that is, the energy ray-curable ingredient of protective film formation film (a) and total content of the polymer (b) without energy ray-curable group) relative to the total of the ingredient in addition to solvent The ratio of content is preferably 5~90 mass %, more preferably 10~80 mass %, particularly preferably 15~70 mass %.Pass through It is such range to make the ratio of total content, and the energy ray-curable of protective film formation film becomes more good.
When protective film formation contains the energy ray-curable ingredient (a) with composition (IV-1) and is penetrated without energy When the polymer (b) of line curative group, in protective film formation composition (IV-1) and protective film formation film, relative to The content of 100 mass parts of content of energy ray-curable ingredient (a), the polymer (b) is preferably 5~300 mass parts, more Preferably 8~250 mass parts.By making the content of the polymer (b) be such range, protective film formation film Energy ray-curable becomes more good.
In addition to contain energy ray-curable ingredient (a) and polymer (b) without energy ray-curable group with Outside, protective film formation composition (IV-1) can also be according to purpose and containing selected from by Photoepolymerizationinitiater initiater (c), packing material (d), coupling agent (e), crosslinking agent (f), colorant (g), Thermocurable ingredient (h), curing accelerator (i) and universal additive (z) one or more of the group formed.For example, by using the energy ray-curable ingredient (a) and heat is contained The protective film of curability composition (h), which is formed, uses composition (IV-1), is formed by bonding of the protective film formation film to adherend Power is improved because of heating, and the protection film strength formed with film by the protective film formation is also improved.
&#91;Photoepolymerizationinitiater initiater (c) &#93;
As Photoepolymerizationinitiater initiater (c), such as can to enumerate benzoin, benzoin methylether, benzoin ethyl ether, benzoin different The benzoins chemical combination such as propyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin dimethyl ketal Object;The benzene such as acetophenone, 2- hydroxy-2-methyl -1- phenyl-propan -1- ketone, 2,2- dimethoxy -1,2- diphenylethane -1- ketone Ethanone compounds;Bis- (2,4,6- trimethylbenzoyls) phosphine oxides of phenyl, the oxidation of 2,4,6- trimethyl benzoyl diphenyl bases The acylphosphine oxides compound such as phosphine;The sulphur compounds such as benzyl phenyl thioether, tetramethylthiuram monosulfide;1- hydroxy-cyclohexyls The α -one alcoholic compounds such as phenyl ketone;The azo-compounds such as azodiisobutyronitrile;The titanocenes compound such as titanocenes;The thiophenes such as thioxanthones Ton ketone compound;Benzophenone, 2- (dimethylamino) -1- (4- morpholinyl phenyls) -2- benzyl -1- butanone, 1-&#91;9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- Jis &#93;The benzophenone cpds such as ethyl ketone 1- (O- acetyl oxime);Peroxide chemical combination Object;The dione compounds such as biacetyl;Benzyl;Dibenzyl;2,4- diethyl thioxanthones;1,2- diphenyl methanes;2- hydroxyl -2- first Base -1-&#91;4- (1- methyl ethylenes) Ben Ji &#93;Acetone;2- chloroanthraquinones etc..
In addition, as Photoepolymerizationinitiater initiater (c), such as the naphtoquinone compounds such as 1- chloroanthraquinones also can be used;Photosensitizers such as amine etc..
Photoepolymerizationinitiater initiater (c) contained by protective film formation composition (IV-1) can be only one kind, or Two or more, when being two or more, combination thereof and ratio can be selected arbitrarily.
When using Photoepolymerizationinitiater initiater (c), in protective film formation in composition (IV-1), relative to energy ray curing 100 mass parts of content of property ingredient (a), the content of Photoepolymerizationinitiater initiater (c) is preferably 0.01~20 mass parts, more preferably 0.03~15 mass parts, particularly preferably 0.05~10 mass parts.
&#91;Packing material (d) &#93;
By making protective film formation film contain packing material (d), protective film formation is cured with film and is protected obtained from The adjustment of the coefficient of thermal expansion of cuticula becomes easy, by keeping the coefficient of thermal expansion most suitable relative to the formation object of protective film Change, the reliability encapsulated obtained from composite sheet using protective film formation is further enhanced.In addition, by making protective film Formation film contains packing material (d), can reduce the hydroscopicity of protective film, or can improve thermal diffusivity.
As packing material (d), such as the packing material being made of Heat Conduction Material can be enumerated.
Packing material (d) can be any one of organic filler material and inorganic filling material, preferably inorganic fill Material.
As preferred inorganic filling material, for example, can enumerate silica, aluminium oxide, talcum, calcium carbonate, titanium white, The powder such as colcother, silicon carbide, boron nitride;By pearl made of these inorganic filling material spheroidizations;These inorganic filling materials Surface be modified product;The mono-crystlling fibre of these inorganic filling materials;Glass fibre etc..
Wherein, preferably inorganic filling material is silica or aluminium oxide.
The average grain diameter of packing material (d) is not particularly limited, preferably 0.01~20 μm, more preferably 0.1~15 μm, Particularly preferably 0.3~10 μm.Crossing makes the average grain diameter of packing material (d) be such range, is able to maintain that protective film It forms the adhesiveness of object and inhibits the reduction of the transmitance of the light of protective film simultaneously.
In addition, unless otherwise indicated, " average grain diameter " in this specification refers to being acquired using laser diffraction scattering method In size distribution curve, accumulated value is the grain size (D at 50%50) value.
Packing material (d) contained by protective film formation composition (IV-1) and protective film formation film can be only one Kind, or two or more, when being two or more, combination thereof and ratio can be selected arbitrarily.
When using packing material (d), in protective film formation in composition (IV-1), the content of packing material (d) (is protected The content of the packing material (d) of cuticula formation film) relative to the total content of all the components in addition to solvent ratio it is preferred For 5~83 mass %, more preferably 7~78 mass %.It is above-mentioned by making the content of packing material (d) be such range The adjustment of coefficient of thermal expansion becomes easier to.
&#91;Coupling agent (e) &#93;
By using with can be with the substance of the functional group of inorganic compound or organic compound reaction as coupling agent (e), adhesiveness and adherence of the protective film formation film to adherend can be improved.In addition, by using coupling agent (e), it will Protective film improves water resistance in the state of not damaging heat resistance obtained from protective film formation is cured with film.
Coupling agent (e) preferably have can with energy ray-curable ingredient (a), do not have energy ray-curable group Polymer (b) etc. possessed by functional group reactions functional group compound, more preferably silane coupling agent.
As the preferred silane coupling agent, such as 3- glycydoxy trimethoxy silicon can be enumerated Alkane, 3- glycydoxies methyldiethoxysilane, 3- glycidyl ether oxypropyltriethoxysilanes, 3- contractings Water glycerin ether oxygroup methyldiethoxysilane, 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane, 3- methacryls Oxygroup propyl trimethoxy silicane, 3- TSL 8330s, 3- (2- aminoethylaminos) propyl trimethoxy silicon Alkane, 3- (2- aminoethylaminos) hydroxypropyl methyl diethoxy silane, 3- (phenyl amino) propyl trimethoxy silicane, 3- aniline Base propyl trimethoxy silicane, 3- ureas propyl-triethoxysilicane, 3- mercaptopropyl trimethoxysilanes, 3- mercapto hydroxypropyl methyl diformazans Oxysilane, bis- (3- triethoxy silicon substrates propyl) tetrasulfides, methyltrimethoxysilane, methyltriethoxysilane, second Alkenyl trimethoxy silane, vinyltriacetoxy silane, imidizole silane etc..
Coupling agent (e) contained by protective film formation composition (IV-1) and protective film formation film can be only one Kind, or two or more, when being two or more, combination thereof and ratio can be selected arbitrarily.
When using coupling agent (e), in protective film formation composition (IV-1) and protective film formation film, relative to energy 100 mass parts of total content of ray-curable ingredient (a) and the polymer (b) without energy ray-curable group are measured, it is even The content for joining agent (e) is preferably 0.03~20 mass parts, more preferably 0.05~10 mass parts, particularly preferably 0.1~5 mass Part.The content by making coupling agent (e) is the lower limiting value or more, can significantly more obtain packing material (d) in resin In the raising of dispersibility, protective film formation film and adherend the raising of adhesiveness etc., produced by using coupling agent (e) Raw effect.In addition, by make the content of coupling agent (e) be the upper limit value hereinafter, the production of degassing can be further suppressed It is raw.
&#91;Crosslinking agent (f) &#93;
Above-mentioned energy ray-curable ingredient (a) is crosslinked by using crosslinking agent (f) or without energy ray curing The polymer (b) of property group, can adjust the initial bond power and cohesiveness of protective film formation film.
As crosslinking agent (f), such as organic polyisocyanate compound, organic multicomponent group with imine moiety, gold can be enumerated Belong to chelates crosslinking agent (crosslinking agent with metallo-chelate structure), (friendship with '-aziridino of aziridines crosslinking agent Join agent) etc..
As the organic polyisocyanate compound, such as aromatic polyisocyanate compound, fat can be enumerated Race's polyisocyanate compound and alicyclic polyisocyanates compound by these compounds (hereinafter, uniformly write a Chinese character in simplified form work " virtue sometimes Fragrant race's polyisocyanate compound etc. ");The tripolymer of the aromatic polyisocyanate compound etc., isocyanuric acid ester body and Addition product;Terminal isocyanate ammonia obtained from making described aromatic polyisocyanate compound etc. be reacted with polyol compound Carbamate prepolymer etc.." addition product " refers to the aromatic polyisocyanate compound, aliphatic polyisocyante Compound or alicyclic polyisocyanates compound and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil etc. The reactant of low molecule active hydrogen-contg compound can enumerate the benzene two of trimethylolpropane as described later as its example Methylene diisocyanate addition product etc..In addition, " terminal isocyanate carbamate prepolymer " refers to carbamic acid Ester bond and the terminal part of molecule have isocyanate group prepolymer.
As the organic polyisocyanate compound, more specifically, such as 2,4- toluene diisocynates can be enumerated Ester;2,6- toluene di-isocyanate(TDI)s;1,3- benzene dimethylene diisocyanate;1,4- benzene dimethylene diisocyanate;Hexichol Methylmethane -4,4 '-diisocyanate;Diphenyl methane -2,4 '-diisocyanate;3- Dimethyl diphenylmethane diisocyanate; Hexamethylene diisocyanate;Isophorone diisocyanate;Dicyclohexyl methyl hydride -4,4 '-diisocyanate;Dicyclohexyl first Alkane -2,4 '-diisocyanate;Addition has toluene diisocyanate on all or part of hydroxyl of the polyalcohols such as trimethylolpropane In acid esters, hexamethylene diisocyanate and benzene dimethylene diisocyanate any one or it is two or more made of chemical combination Object;Lysine diisocyanate etc..
As the organic multicomponent group with imine moiety, such as N can be enumerated, diphenyl methane -4 N ' -, 4 '-bis- (1- nitrogen third Pyridine formamide) ,-three-β of trimethylolpropane-'-aziridino propionic ester ,-three-β of tetramethylol methane-'-aziridino propionic ester, N, N '-Toluene-2,4-diisocyanate, bis- (1- aziridine formamide) triethylenemelanins of 4- etc..
When using organic polyisocyanate compound as crosslinking agent (f), as energy ray-curable ingredient (a) or not Polymer (b) with energy ray-curable group, it is preferable to use hydroxyl polymer.When crosslinking agent (f) has isocyanide When perester radical, energy ray-curable ingredient (a) or the polymer (b) without energy ray-curable group have hydroxyl, By crosslinking agent (f) with energy ray-curable ingredient (a) or the polymer (b) without energy ray-curable group it is anti- It answers, can cross-linked structure simply be imported into protective film formation film.
Crosslinking agent (f) contained by protective film formation composition (IV-1) and protective film formation film can be only one Kind, or two or more, when being two or more, combination thereof and ratio can be selected arbitrarily.
When using crosslinking agent (f), in protective film formation in composition (IV-1), relative to energy ray-curable ingredient (a) and 100 mass parts of the total content of the polymer (b) without energy ray-curable group, the content of crosslinking agent (f) are preferred For 0.01~20 mass parts, more preferably 0.1~10 mass parts, particularly preferably 0.5~5 mass parts.By making crosslinking agent (f) The content be the lower limiting value or more, can significantly more obtain by using crosslinking agent (f) and the effect that generates.In addition, By make crosslinking agent (f) the content be the upper limit value hereinafter, can inhibit being excessively used for crosslinking agent (f).
&#91;Colorant (g) &#93;
As colorant (g), such as well known to inorganic pigment, organic pigment, organic dyestuff being enumerated etc. Toner.
As the organic pigment and organic dyestuff, such as amine can be enumerated(aminium) class pigment, cyanine class Pigment, merocyanine class pigment, crocic acid (croconium) class pigment, sour cyanines (squarylium) the class pigment in side, azulene (azulenium) class pigment, polymethine class pigment, naphthalene Quinone Pigments, pyransClass pigment, phthalocyanines pigment, naphthalene cyanines class pigment, Naphthalene lactim (naphtholactam) class pigment, azo pigment, condensation azo pigment, indigoid type pigment, purple cyclic ketones (perinone) class pigment, class pigment, dioxazines pigment, quinacridine ketone pigment, isoindoline ketone pigment, quinophthalone Class pigment, pyroles pigment, thioindigo class pigment, metal complex species pigment (metal complex salt dyestuff), dithiol metal complexing Species pigment, indoles phenol sulfonate, triallyl methane class pigment, anthraquinone pigments, aphthols pigment, azomethine class pigment, Benzimidazole ketone pigment, pyranthrone pigment and intellectual circle (threne) class pigment etc..
As the inorganic pigment, such as carbon black, cobalt class pigment, iron class pigment, chromium class pigment, titanium class color can be enumerated Element, vanadium class pigment, zirconium class pigment, molybdenum class pigment, ruthenium class pigment, platinum class pigment, ITO (tin indium oxide) classes pigment, ATO (oxidations Antimony tin) class pigment etc..
Colorant (g) contained by protective film formation composition (IV-1) and protective film formation film can be only one Kind, or two or more, when being two or more, combination thereof and ratio can be selected arbitrarily.
When using colorant (g), the content that protective film forms the colorant (g) of film according to purpose suitably adjust i.e. It can.For example, protective film is subjected to lettering sometimes through laser irradiation, pass through containing for the colorant (g) to protective film formation film Amount is adjusted and the translucency of protective film is adjusted, and thus, it is possible to adjust lettering visuality.At this point, being formed in protective film With in composition (IV-1), the content (i.e. the content of the colorant (g) of protective film formation film) of colorant (g) is relative to except molten The ratio of the total content of all the components other than agent is preferably 0.1~10 mass %, more preferably 0.4~7.5 mass %, especially Preferably 0.8~5 mass %.The content by making colorant (g) is the lower limiting value or more, can significantly more be obtained logical Cross the effect generated using colorant (g).In addition, by make colorant (g) the content be the upper limit value hereinafter, can Inhibit being excessively used for colorant (g).
&#91;Thermocurable ingredient (h) &#93;
Thermocurable ingredient (h) contained by protective film formation composition (IV-1) and protective film formation film can be only For one kind, or two or more, when being two or more, combination thereof and ratio can be selected arbitrarily.
As Thermocurable ingredient (h), for example, can enumerate epoxies heat-curing resin, Thermocurable polyimides, Polyurethane, unsaturated polyester (UP), organic siliconresin etc., preferably epoxies heat-curing resin.
(epoxies heat-curing resin)
Epoxies heat-curing resin is made of epoxy resin (h1) and thermal curing agents (h2).
Epoxies heat-curing resin contained by protective film formation composition (IV-1) and protective film formation film can To be only one kind, or two or more, when being two or more, combination thereof and ratio can be selected arbitrarily.
Epoxy resin (h1)
As epoxy resin (h1), well known epoxy resin can be enumerated, for example, can enumerate multifunctional based epoxy resin, Biphenol compound, bisphenol A diglycidyl ether and its hydride, o-cresol phenolic resin varnish, dicyclopentadiene type ring Oxygen resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenylene matrix type epoxy resin etc. Epoxide more than difunctionality.
As epoxy resin (h1), the epoxy resin with unsaturated alkyl can be used.With without unsaturated alkyl Epoxy resin is compared, and the compatibility of epoxy resin and acrylic resin with unsaturated alkyl is high.Therefore, by using tool The epoxy resin for having unsaturated alkyl, the reliability encapsulated obtained from composite sheet using protective film formation are improved.
As the epoxy resin with unsaturated alkyl, for example, can enumerate multifunctional based epoxy resin epoxy group one Partial Transformation is at compound made of the group with unsaturated alkyl.Such compound for example can be by making (methyl) propylene Acid or derivatives thereof carries out addition reaction with epoxy group and obtains.
In addition, as the epoxy resin with unsaturated alkyl, such as can enumerate in the aromatic rings for constituting epoxy resin There is the compound etc. of the group with unsaturated alkyl Deng upper Direct Bonding.
Unsaturated alkyl is the unsaturated group with polymerism can enumerate ethylidine (ethylene as its concrete example Base), 2- acrylic (allyl), (methyl) acryloyl group, (methyl) acrylamido etc., preferably acryloyl group.
The number-average molecular weight of epoxy resin (h1) is not particularly limited, curability, Yi Jibao from protective film formation film The point of shield film strength and heat resistance sets out, preferably 300~30000, more preferably 400~10000, particularly preferably 500 ~3000.
In the present specification, unless otherwise indicated, " number-average molecular weight " refers to be surveyed using gel permeation chromatography (GPC) method Fixed standard polystyren scaled value and the number-average molecular weight indicated.
The epoxide equivalent of epoxy resin (h1) is preferably 100~1000g/eq, more preferably 150~800g/eq.
In the present specification, " epoxide equivalent " refers to the grams (g/ of the epoxide comprising 1 gram equivalent of epoxy group It eq), can be according to JIS K 7236:2001 method is measured.
Epoxy resin (h1) can be used alone, can also use simultaneously it is two or more, while using two or more When, combination thereof and ratio can be selected arbitrarily.
Thermal curing agents (h2)
Thermal curing agents (h2) play a role as the curing agent for epoxy resin (h1).
As thermal curing agents (h2), such as can enumerate has two or more can be with the official of epoxy reaction in 1 molecule The compound that can be rolled into a ball.As the functional group, such as phenolic hydroxyl group, alcohol hydroxyl group, amino, carboxyl, acidic group acid anhydrides can be enumerated Group made of group made of change etc., preferably phenolic hydroxyl group, amino or acidic group acid anhydrides, more preferably phenolic hydroxyl group or Amino.
As the phenols curing agent with phenolic hydroxyl group in thermal curing agents (h2), such as multifunctional phenol tree can be enumerated Fat, '-biphenyl diphenol, novolak type phenol resin, bicyclopentadiene class phenol resin, aralkyl-phenol resin etc..
As the amine curing agent with amino in thermal curing agents (h2), such as dicyandiamide can be enumerated (hereinafter, sometimes Write a Chinese character in simplified form work " DICY ") etc..
Thermal curing agents (h2) can have unsaturated alkyl.
As the thermal curing agents (h2) with unsaturated alkyl, for example, can enumerate phenol resin hydroxyl a part through tool Compound made of having the group of unsaturated alkyl to replace, Direct Bonding has unsaturated alkyl on the aromatic rings of phenol resin Compound obtained from group etc..
In the unsaturated alkyl and the above-mentioned epoxy resin with unsaturated alkyl in thermal curing agents (h2) not Saturated hydrocarbyl is identical.
When using phenols curing agent as thermal curing agents (h2), the pointing out from the fissility of support chip from raising protective film Hair, thermal curing agents (h2) are preferably softening point or the high thermal curing agents of glass transition temperature.
Phenol resin in thermal curing agents (h2), for example multifunctional, novolak type phenol resin, bicyclopentadiene class phenol tree The number-average molecular weight of the resin components such as fat, aralkyl-phenol resin is preferably 300~30000, and more preferably 400~10000, especially Preferably 500~3000.
In thermal curing agents (h2), the molecular weight of non-resin ingredient such as '-biphenyl diphenol, dicyandiamide is not particularly limited, Such as preferably 60~500.
Thermal curing agents (h2) can be used alone, can also use simultaneously it is two or more, while using two or more When, combination thereof and ratio can be selected arbitrarily.
When using Thermocurable ingredient (h), in protective film formation composition (IV-1) and protective film formation film, phase For 100 mass parts of content of epoxy resin (h1), the content of thermal curing agents (h2) is preferably 0.01~20 mass parts.
When using Thermocurable ingredient (h), in protective film formation composition (IV-1) and protective film formation film, phase For 100 mass parts of content of the polymer (b) without energy ray-curable group, the content of Thermocurable ingredient (h) (for example, total content of epoxy resin (h1) and thermal curing agents (h2)) is preferably 1~500 mass parts.
&#91;Curing accelerator (i) &#93;
Curing accelerator (i) is the ingredient of the curing rate for adjusting protective film formation film.
As preferred curing accelerator (i), such as triethylene diamine, benzyl dimethylamine, triethanolamine, two can be enumerated The tertiary amines such as methylaminoethanol, three (dimethylaminomethyl) phenol;2-methylimidazole, 2- phenylimidazoles, 2- phenyl -4- methyl The imidazoles such as imidazoles, 2 pheny1 4,5 dihydroxymethyl imidazole, 2 phenyl 4 methyl 5 hydroxy methylimidazole;Tributylphosphine, hexichol Organic phosphine such as base phosphine, triphenylphosphine;Tetraphenyl borates such as tetraphenylphosphoniphenolate tetraphenyl borate, triphenyl phosphonium tetraphenyl borate etc..
Curing accelerator (i) can be used alone, can also use simultaneously it is two or more, while using two or more When, combination thereof and ratio can be selected arbitrarily.
When using curing accelerator (i), protective film is formed to be promoted with the solidification of composition (IV-1) and protective film formation film Content into agent (i) is not particularly limited, and according to ingredient used at the same time suitably select.
&#91;Universal additive (z) &#93;
Universal additive (z) can be well known additive, can arbitrarily be selected, be not particularly limited according to purpose, as Preferred additive, such as plasticizer, antistatic agent, antioxidant, capturing agent (gettering agent) can be enumerated etc..
Universal additive (z) contained by protective film formation composition (IV-1) and protective film formation film can be only It is a kind of, or two or more, when being two or more, combination thereof and ratio can be selected arbitrarily.
When using universal additive (z), general the adding of protective film formation composition (IV-1) and protective film formation film Add the content of agent (z) to be not particularly limited, according to purpose suitably select.
&#91;Rong Ji &#93;
Protective film formation composition (IV-1) preferably further contains solvent.Protective film formation combination containing solvent The operability of object (IV-1) becomes good.
The solvent is not particularly limited, and as preferred solvent, such as can enumerate the hydrocarbon such as toluene, dimethylbenzene;Methanol, The alcohol such as ethyl alcohol, 2- propyl alcohol, isobutanol (2- methylpropane -1- alcohol), n-butyl alcohol;The esters such as ethyl acetate;Acetone, methyl ethyl ketone etc. Ketone;The ethers such as tetrahydrofuran;Amides such as dimethylformamide, N-Methyl pyrrolidone (compound with amido bond) etc..
Solvent contained by protective film formation composition (IV-1) can be only one kind, or and it is two or more, be When two or more, combination thereof and ratio can be selected arbitrarily.
From can by the point that containing ingredient more uniformly mixes of the protective film formation in composition (IV-1), protect It is preferably methyl ethyl ketone, toluene or ethyl acetate etc. that film, which is formed with the solvent contained by composition (IV-1),.
The preparation method > > of < < protective film formation compositions
The protective films formation such as protective film formation composition (IV-1) composition can be by blending for constituting its Each ingredient and obtain.
Order of addition when blending each ingredient is not particularly limited, and can also add two or more ingredients simultaneously.
It, can be pre- by the blending ingredient by mixing solvent with the arbitrary blending ingredient in addition to solvent when using solvent Dilution, can not also be by the arbitrary blending ingredient pre-dilution in addition to solvent and by by solvent and these to be used Ingredient mixing is blended to be used.
The method that each ingredient is mixed when blending is not particularly limited, and is suitably selected from following well known methods:Make Blender or stirring blade etc. rotate and mixed method;The method mixed using blender;Apply ultrasonic wave and Mixed method etc..
As long as respectively blending ingredient not deteriorate, then the temperature and time when adding and mix each ingredient are not particularly limited, Suitably adjust, preferable temperature is 15~30 DEG C.
◇ protective film formation pieces
The protective film formation piece of the present invention has the protective film formation film, the two of the protective film formation film The surface of side has stripping film.
" stripping film " is the film with stripping function, refers to specifically being attached at semiconductor crystal wafer or support to protect Protective film formation film before piece and the film for being attached at the surface of the both sides of protective film formation film, peeled in operation and It is used.
As stripping film, such as polyethylene film, polypropylene screen, polybutene film, polybutadiene film, polymethylpentene can be used Film, polychloroethylene film, vinyl chloride copolymer film, polyethylene terephthalate film, poly (ethylene naphthalate) film, poly- pair Benzene dicarboxylic acid butanediol ester film, polyurethane film, vinyl-vinyl acetate copolymer film, ionomer resin film, ethylene-(methyl) Acrylic copolymer film, ethylene-(methyl) acrylate copolymer film, polystyrene film, polycarbonate membrane, polyimide film, The hyaline membranes such as fluororesin film.Further, it is also possible to use their cross linking membrane.Further or their stacked film.In addition, Film, the opaque coating etc. for colouring them can be used.As remover, such as organic silicon can be enumerated, fluorine class, contain long-chain The removers such as the carbamate of alkyl.
The thickness of stripping film is usually 10 μm or more, 500 μm hereinafter, preferably 15 μm or more, 300 μm hereinafter, especially excellent It is selected as 20 μm or more, 250 μm or less Zuo You.
In the protective film formation piece of the present invention, by making the tensile modulus of elasticity of the protective film formation film be 30MPa or more, such as half as target can be cut before curing protective film formation film using the irradiation of energy-ray When conductor chip, inhibit the blocking of blade.
The protective film formation of the present invention can be provided with piece in the form of the strip film being rolled into a roll.
As not had using the semiconductor crystal wafer of object or the thickness of semiconductor chip for protective film formation piece of the invention It is particularly limited to, due to can get the effect of the more significant present invention, so preferably 30~1000 μm, more preferably 100~ 300μm。
Fig. 1 is the sectional view for an embodiment for schematically showing the protective film formation piece of the present invention.In Fig. 1, It is sequentially laminated with stripping film 15, protective film formation film 13 and stripping film 15.
In protective film formation in piece 100, protective film formation is 30MPa or more with the tensile modulus of elasticity of film 13.
Protective film formation shown in FIG. 1 is used in the following manner with piece 100:In the state for eliminating stripping film 15 Under, semiconductor crystal wafer is attached on a part of region of the center side in surface 13a of the protective film formation with film 13 (saves sketch map Show) the back side will and in the state that it is stripping film 15 of opposite side to eliminate with the surface 13a of protective film formation film 13 Support chip apposition is in the surface 13b of protective film formation film 13, further near the peripheral part in protective film formation with film 13 Region attaches the fixtures such as annular frame.
The present invention protective film formation in piece 100, can be protective film formation film 13 surface 13a be attached at The surface at the back side (that is, being the surface of opposite side with circuit face) of semiconductor crystal wafer, and protective film forms the surface 13b with film 13 For with surface that the surface at the back side for being attached at semiconductor crystal wafer is opposite side;It can also be the surface of protective film formation film 13 13b is the surface at the back side (that is, being the surface of opposite side with circuit face) for being attached at semiconductor crystal wafer, and protective film formation film The surface that 13 surface 13a is with the surface at the back side for being attached at semiconductor crystal wafer is opposite side.
In the form of the present invention, protective film formation of the invention has the protective film shape containing following component with piece At with film:Tristane dihydroxymethyl diacrylate as energy ray-curable ingredient (a2) is (10~30 mass parts, excellent It is selected as 20 mass parts);Acrylic resin (1~3 mass as the polymer (b) without energy ray-curable group Part, preferably 2 mass parts), wherein the acrylic resin is by butyl acrylate (8~12 mass parts, preferably 10 mass Part), methyl acrylate (60~80 mass parts, preferably 70 mass parts), glycidyl methacrylate (3~7 mass parts, Preferably 5 mass parts) and acrylic acid 2- hydroxy methacrylates (13~17 mass parts, preferably 15 mass parts) be copolymerized;As light 2- (dimethylamino) -1- (4- the morpholinyl phenyls) -2- benzyl -1- butanone of polymerization initiator (c) is (0.1~0.5 mass parts, excellent It is selected as 0.3 mass parts) and 1-&#91;9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- Jis &#93;Ethyl ketone 1- (O- acetyl oxime) (0.1~0.5 mass parts, preferably 0.3 mass parts);Vitreous silica filler (8 μm of average grain diameter) as packing material (d) (71~81 mass parts, preferably 76 mass parts);3- methacryloxypropyl trimethoxy silanes as coupling agent (e) (0.1~0.7 mass parts, preferably 0.4 mass parts);As colorant (g), be generally used to protect film formation film it is known Pigment (1~3 mass parts, preferably 2 mass parts), more specifically by phthalocyanines blue pigment (Pigment Blue 15:3) 32 mass parts, isoindoline ketone xanthein (Pigment Yellow 139) 18 mass parts and anthraquinone type of red color Plain (Pigment Red 177) 50 mass parts mixing and so that three kinds of pigments total amount/styrene acrylic resin amount The mode of=1/3 (mass ratio) carries out pigment obtained from pigmentation (1~3 mass parts, preferably 2 mass parts).
The manufacturing method of ◇ protective film formation pieces
Can by make above-mentioned each layer as corresponding position relationship in a manner of stack gradually above-mentioned each layer and make Make the protective film formation piece of the present invention.The forming method of each layer is identical as what is be illustrated above.
For example, by the way that the protective film formation is coated on composition on the lift-off processing face of stripping film to form guarantor Cuticula formation film, thus, it is possible to manufacture protective film formation piece.Further, by the way that stripping film is fitted in established protection In the exposed surface for the side opposite side of film formation film contacted with the stripping film, has stripping on two sides it is possible thereby to manufacture The protective film formation piece of film.
The application method of ◇ protective film formation pieces
The protective film formation of the present invention can for example be used with piece using method as shown below.
That is, the protective film formation piece for the stripping film for eliminating side is made to be attached at half with film by its protective film formation The back side (face with electrode forming surface opposite side) of semiconductor wafer.Then, remove remaining stripping film, be attached to semiconductor Support chip is attached on the face of the protective film formation film of face opposite side on wafer.The layer of the support chip and protective film formation film Folded object is equivalent to aftermentioned protective film formation composite sheet.Then, by cutting semiconductor crystal wafer and protective film formation film Divide together and semiconductor chip is made.Then, to protective film formation film irradiation energy ray, keep protective film formation film solid Change and protective film is made.Then, it will partly be led using the state (that is, as semiconductor chip with protective film) for being pasted with the protective film Body chip is detached and is picked up from support chip.
Later, using method identical with previous method, by the semiconductor of the obtained semiconductor chip with protective film After flip-chip is connected in the circuit face of substrate, semiconductor package body is made.Then, it using the semiconductor package body, makes Target semiconductor device.
◇ protective film formation composite sheets
The protective film formation of the present invention is formed by having the protective film formation on support chip with film with composite sheet.
In the protective film formation composite sheet of the present invention, by the tensile modulus of elasticity for making the protective film formation film For 30MPa or more, such as can be cut as target before being cured protective film formation film using the irradiation of energy-ray When semiconductor chip, inhibit the blocking of blade.
In addition, for the protective film formation composite sheet of the present invention, by making the protective film formation with film be that energy is penetrated Line curability, can the protective film formation film than having Thermocurable previous protective film formation composite sheet it is shorter Cured to form protective film in time.
The semiconductor crystal wafer of object or the thickness of semiconductor chip are used as protective film formation composite sheet of the invention Degree is not particularly limited, due to can get the effect of the more significant present invention, so preferably 30~1000 μm, more preferably 100~300 μm.
Hereinafter, being described in detail to the composition of the present invention.
◎ support chips
The support chip can be made of a layer (single layer), can also be made of two layers or more of multiple layers.Support chip When being made of multiple layers, these multiple layers constituent materials and thickness mutually the same can also be different, as long as not damaging this The effect of invention, then these multiple layers combinations are not particularly limited.
In addition, in the present specification, the case where being not limited only to support chip, " multiple layers mutually the same can also be different " Refer to " layer that can be all is identical, and layer that can also be all is different, can be identical with the layer of only a part ", in addition, " multiple layers It is different from each other " refer to " constituent material of each layer and thickness at least one different from each other ".
As preferred support chip, such as the support that adhering agent layer is in direct contact and is laminated with base material can be enumerated Support chip and the support chip etc. being only made of base material made of piece, adhering agent layer are laminated via middle layer on base material.
The protective film of the present invention is formed with compound hereinafter, accordinging to the type of such support chip while with reference to attached drawing The example of piece illustrates.In addition, in order to which the feature of the present invention is more readily understood, for conveniently, will make in following explanation sometimes The pith of figure expands display, and dimensional ratios of each integral part etc. are not necessarily identical as reality.
Fig. 2 is the sectional view for an embodiment for schematically showing the protective film formation composite sheet of the present invention.
Protective film formation composite sheet 1A shown here has adhering agent layer 12 on base material 11, on adhering agent layer 12 Has protective film formation film 13.Support chip 10 is the laminated body of base material 11 and adhering agent layer 12, and in other words, protective film is formed There is the composition that protective film formation film 13 is laminated on the surface 10a of the side of support chip 10 with composite sheet 1A.In addition, protecting Cuticula formation with composite sheet 1A in protective film formation with being further equipped with stripping film 15 on film 13.
In protective film formation in composite sheet 1A, it is laminated with adhering agent layer 12 on the surface 11a of the side of base material 11, Protective film formation film 13 is laminated in the entire surface of the surface 12a of adhering agent layer 12, on the protective film formation surface of film 13 A part of 13a, the region i.e. near peripheral part are laminated with fixture adhesive phase 16, on the protective film formation surface of film 13 The surface 16a (upper surface and side) on the surface that fixture adhesive phase 16 is not laminated and fixture adhesive phase 16 in 13a On be laminated with stripping film 15.
In protective film formation in composite sheet 1A, protective film formation is 30MPa or more with the tensile modulus of elasticity of film 13.
Fixture adhesive phase 16 for example can be the single layer structure containing adhesive ingredients, or as core material Sheet material two sides on stacking the layer containing adhesive ingredients made of multilayered structure.
Protective film formation shown in Fig. 2 is used in the following manner with composite sheet 1A:In the shape for eliminating stripping film 15 Under state, the back side of semiconductor crystal wafer (illustration omitted) is attached on surface 13a of the protective film formation with film 13, further makes fixture It is attached on the fixtures such as annular frame with the upper surface in the surface 16a of adhesive phase 16.
Fig. 3 is the sectional view for the another embodiment for schematically showing the protective film formation composite sheet of the present invention. In addition, in the figure after Fig. 3, for inscape identical with the inscape shown in figure being explained, Label reference numeral identical with the figure that this is explained, and description is omitted.
Protective film formation composite sheet 1B shown here is not other than having 16 this point of fixture adhesive phase, with figure Protective film shown in 2 forms identical with composite sheet 1A.That is, in protective film formation in composite sheet 1B, in the side of base material 11 It is laminated with adhering agent layer 12 on the 11a of surface, protective film formation film is laminated in the entire surface of the surface 12a of adhering agent layer 12 13, it is laminated with stripping film 15 in the entire surface of the surface 13a of protective film formation film 13.
Protective film formation shown in Fig. 3 is used in the following manner with composite sheet 1B:In the shape for eliminating stripping film 15 Semiconductor crystal wafer, which is attached, under state, on a part of region of the center side in surface 13a of the protective film formation with film 13 (saves sketch map Show) the back side, so that protective film formation is attached on the fixtures such as annular frame with the region near the peripheral part of film 13.
Fig. 4 is the sectional view for the another embodiment for schematically showing the protective film formation composite sheet of the present invention.
Protective film formation composite sheet 1C shown here is not other than having 12 this point of adhering agent layer, with Fig. 2 institutes The protective film formation composite sheet 1A shown is identical.That is, in protective film formation in composite sheet 1C, support chip 10 is only by 11 structure of base material At.It is used moreover, being laminated with protective film on the surface 11a (the surface 10a of the side of support chip 10) of the side of base material 11 and being formed Film 13 is laminated with fixture bonding on the region near a part of the surface 13a of protective film formation film 13, i.e. peripheral part Oxidant layer 16, the surface that fixture adhesive phase 16 is not laminated in surface 13a of the protective film formation with film 13 are used viscous with fixture It is laminated with stripping film 15 on the surface 16a (upper surface and side) of mixture layer 16.
In protective film formation in composite sheet 1C, protective film formation is 30MPa or more with the tensile modulus of elasticity of film 13.
Identical with composite sheet 1A as protective film formation shown in Fig. 2, protective film shown in Fig. 4, which is formed, uses composite sheet 1C or less The mode of stating is used:In the state of eliminating stripping film 15, attaches on surface 13a of the protective film formation with film 13 and partly lead The back side of body wafer (illustration omitted) further makes the upper surface in the surface 16a of fixture adhesive phase 16 be attached to annular On the fixtures such as frame.
Fig. 5 is the sectional view for the another embodiment for schematically showing the protective film formation composite sheet of the present invention.
Protective film formation composite sheet 1D shown here is not other than having 16 this point of fixture adhesive phase, with figure Protective film shown in 4 forms identical with composite sheet 1C.That is, in protective film formation in composite sheet 1D, in the side of base material 11 It is laminated with protective film formation film 13 on the 11a of surface, stripping is laminated in the entire surface of the surface 13a of protective film formation film 13 From film 15.
Protective film as shown in figure 3 forms, shown in fig. 5 protective film formation composite sheet 1D or less identical with composite sheet 1B The mode of stating is used:In the state of eliminating stripping film 15, the center side in surface 13a of the protective film formation with film 13 A part of region on attach semiconductor crystal wafer (illustration omitted) the back side, further make the peripheral part of protective film formation film 13 Neighbouring region is attached on the fixtures such as annular frame.
Fig. 6 is the sectional view for the another embodiment for schematically showing the protective film formation composite sheet of the present invention.
Protective film formation shown here with composite sheet 1E other than the shape difference this point of protective film formation film, It is identical with composite sheet 1A as protective film formation shown in Fig. 2.That is, protective film formation composite sheet 1E has adhesion on base material 11 Oxidant layer 12 has protective film formation film 23 on adhering agent layer 12.Support chip 10 is the stacking of base material 11 and adhering agent layer 12 Body, in other words, protective film formation has with composite sheet 1E is laminated with protective film shape on the surface 10a of the side of support chip 10 At the composition with film 23.In addition, protective film formation is further equipped with stripping film in protective film formation with composite sheet 1E on film 23 15。
In protective film formation in composite sheet 1E, it is laminated with adhering agent layer 12 on the surface 11a of the side of base material 11, A part of the surface 12a of adhering agent layer 12 is laminated with protective film formation film 23 on the region of center side.Moreover, The surface on the surface that protective film formation film 23 is not laminated and protective film formation film 23 in the surface 12a of adhering agent layer 12 23a is laminated with stripping film 15 on (upper surface and side).
When overlooking protective film formation down from above with composite sheet 1E, protective film forms the surface area ratio sticker with film 23 Layer 12 is small, has the shape such as circle.
In protective film formation in composite sheet 1E, protective film formation is 30MPa or more with the tensile modulus of elasticity of film 23.
Protective film formation shown in fig. 6 is used in the following manner with composite sheet 1E:In the shape for eliminating stripping film 15 Under state, the back side of semiconductor crystal wafer (illustration omitted) is attached on surface 23a of the protective film formation with film 23, further makes adhesion The protective film formation that is not laminated in the surface 12a of oxidant layer 12 is attached to the surface of film 23 on the fixtures such as annular frame.
It is used in composite sheet 1E in addition, protective film shown in Fig. 6 is formed, it can be in a manner of identical with shown in Fig. 2 and Fig. 4 Not being laminated on the surface of protective film formation film 23 in the surface 12a of adhering agent layer 12 is laminated fixture adhesive phase and (saves Sketch map shows).It is identical as Fig. 2 and protective film formation composite sheet shown in Fig. 4, have the protection of such fixture adhesive phase Film formation is used with composite sheet 1E in a manner of so that the surface of fixture adhesive phase is attached on the fixtures such as annular frame.
As described previously for the protective film formation composite sheet of the present invention, no matter support chip and protective film formation are with film What kind of form can have fixture adhesive phase.Wherein, usually as shown in Figures 2 and 4, has fixture adhesive The protective film formation composite sheet of the present invention of layer, preferably in protective film formation with having fixture adhesive phase on film.
The present invention protective film formation with composite sheet be not limited to Fig. 2~6 shown in composite sheet, do not damaging the present invention In the range of effect, what can be constituted to change or deleting a part for protective film formation composite sheet shown in Fig. 2~6 answers It closes piece or may be to have added the compound of other compositions on the basis of the protective film formation composite sheet that is illustrated above Piece.
For example, in Fig. 4 and protective film formation composite sheet shown in fig. 5, it can be in base material 11 and protective film formation film Middle layer is set between 13.As middle layer, arbitrary middle layer can be selected according to purpose.
In addition, in Fig. 2, Fig. 3 and protective film formation composite sheet shown in fig. 6, it can be in base material 11 and adhering agent layer 12 Between middle layer is set.That is, in the protective film formation composite sheet of the present invention, support chip can stack gradually base material, centre Layer and adhering agent layer form.Herein, middle layer refers to and can be arranged in Fig. 4 and protective film formation composite sheet shown in fig. 5 The identical middle layer of middle layer.
In addition, protective film formation composite sheet shown in Fig. 2~6 can be arranged on arbitrary position remove the middle layer with Outer layer.
In addition, in the protective film formation composite sheet of the present invention, can stripping film with and the stripping film be in direct contact A part of gap is generated between layer.
In addition, in the protective film formation composite sheet of the present invention, the size of each layer can be arbitrarily adjusted according to purpose And shape.
The present invention protective film formation composite sheet in, as described below, it is preferably adhering agent layer etc., support chip with Protective film formation is non-energy ray-curable with the layer that film is in direct contact.Such protective film formation composite sheet can more be held It changes places and picks up the semiconductor chip that the back side has protective film.
Support chip can be transparent, can not also be transparent, can also be coloured according to purpose.
Wherein, in protective film formation has the present invention of energy ray-curable with film, preferably support chip penetrates energy Ray.
For example, in support chip, the transmitance of the light of wavelength 375nm is preferably 30% or more, more preferably 50% or more, Particularly preferably 70% or more.By making the transmitance of the light be such range, protective film is formed through support chip and is used When film irradiation energy ray (ultraviolet light), the curing degree of protective film formation film is further enhanced.
On the other hand, in support chip, the upper limit value of the transmitance of the light of wavelength 375nm is not particularly limited, such as can To be set as 95%.
In addition, in support chip, the transmitance of the light of wavelength 532nm is preferably 30% or more, more preferably 50% or more, Particularly preferably 70% or more.By making the transmitance of the light be such range, protective film is formed through support chip and is used It, being capable of more clearly lettering when film or protective film irradiation laser to it so that carry out lettering.
On the other hand, in support chip, the upper limit value of the transmitance of the light of wavelength 532nm is not particularly limited, such as can To be set as 95%.
In addition, in support chip, the transmitance of the light of wavelength 1064nm is preferably 30% or more, more preferably 50% with On, particularly preferably 70% or more.Transmitance by making the light is such range, is formed to protective film through support chip It, being capable of more clearly lettering when with film or protective film irradiation laser to carry out lettering to it.
On the other hand, in support chip, the upper limit value of the transmitance of the light of wavelength 1064nm is not particularly limited, such as can To be set as 95%.
Then, further each layer for constituting support chip is described in detail.
Zero base material
The base material is sheet or membranaceous, as its constituent material, such as can enumerate various resins.
As the resin, for example, can enumerate low density polyethylene (LDPE) (LDPE), straight-chain low density polyethylene (LLDPE), The polyethylene such as high density polyethylene (HDPE) (HDPE);Polypropylene, polybutene, polybutadiene, polymethylpentene, norbornene resin etc. remove Polyolefin other than polyethylene;Vinyl-vinyl acetate copolymer, ethylene-(methyl) acrylic copolymer, ethylene-(methyl) The ethene copolymers such as acrylate copolymer, ethylene-norbornene copolymer (are copolymerized using ethylene as obtained from monomer Object);The vinyl chloride resins such as polyvinyl chloride, vinyl chloride copolymer (use vinyl chloride as resin obtained from monomer);Polyphenyl Ethylene;Polycyclic alkene;Polyethylene terephthalate, polybutylene terephthalate (PBT), gathers at polyethylene naphthalate Ethylene isophthalate, poly- 2,6- (ethylene naphthalate)s, all structural units have the complete of aromatic series cyclic group The polyester such as aromatic polyester;The copolymer of the two or more polyester;Poly- (methyl) acrylate;Polyurethane;Polyurethane third Olefin(e) acid ester;Polyimides;Polyamide;Makrolon;Fluororesin;Polyacetals;Noryl;Polyphenylene sulfide;Polysulfones;Polyether-ketone Deng.
In addition, as the resin, such as can also enumerate the polyester and gather with the mixture of resin etc. in addition to it Close object alloy.It is preferred that the amount of the polyester and the resin in addition to polyester in the polymer alloy of resin in addition to it be compared with On a small quantity.
In addition, as the resin, such as can also enumerate the one or more of the resin above illustrated Crosslinked resin made of crosslinking;The modified tree such as one or more kinds of ionomers of the resin above illustrated is used Fat.
Constitute base material resin can be only one kind, or it is two or more, for it is two or more when, combination thereof and Ratio can be selected arbitrarily.
Base material can be made of a layer (single layer), can also be made of two layers or more of multiple layers, be made of multiple layers When, these multiple layers mutually the same can also be different, these multiple layers combinations are not particularly limited.
The thickness of base material is preferably 50~300 μm, more preferably 60~100 μm.By making the thickness of base material be such Range, the pliability of the protective film formation composite sheet and to the adhesion of semiconductor crystal wafer or semiconductor chip obtain into One step improves.
Herein, " thickness of base material " refers to the thickness of base material entirety, such as the thickness for the base material being made of multiple layers refers to Constitute the thickness of the total of all layers of base material.In addition, the assay method of the thickness as base material, such as use can be enumerated Contact thickness gauge calculates the average method etc. of measured value in arbitrary five position finding thickness.
Preferred substrates be thickness base material with high accuracy, i.e. no matter what part thickness the base that is inhibited of deviation Material.As it is in above-mentioned constituent material, can be used as constituting the material of the high base material of such thickness and precision, such as can enumerate poly- Ethylene, the polyolefin in addition to polyethylene, polyethylene terephthalate, vinyl-vinyl acetate copolymer etc..
Base material can also contain packing material, colorant, anti-quiet other than containing the main compositions material such as described resin Various additives well known to electric agent, antioxidant, organic lubricant, catalyst, softening agent (plasticizer) etc..
As long as the optical characteristics of base material meets the optical characteristics of support chip described above.That is, base material can be saturating It is bright, can not also be transparent, it can also be coloured according to purpose, other layers can also be deposited.
Moreover, in protective film formation has the present invention of energy ray-curable with film, preferred substrates are penetrated through energy Line.
In order to improve and be set to the adherence of other layers of adhering agent layer on it etc., base material can be to implement to surface At further provided for contouring processing, Corona discharge Treatment, electron beam treatment with irradiation, plasma based on blasting treatment, solvent processing etc. The base material of the oxidation processes such as reason, the processing of ozone-ultraviolet line treatment with irradiation, flame treatment, chromic acid, hot wind processing etc..
In addition, base material can also be base material of the surface through prime treatment.
In addition, overlapping antistatic coating, protective film formation composite sheet and when being preserved, base material can also have and prevent Base material bonds or prevents the layer etc. that base material is bonded with suction unit with other sheet materials.
Wherein, the point of the generation of the part of base material caused by the friction of knife when inhibiting by cutting, particularly preferably Base material is the base material that surface implements electron beam treatment with irradiation.
Base material can utilize well known method to manufacture.For example, the base material containing resin can be by that will contain the resin Resin combination molding and manufacture.
Zero adhering agent layer
The adhering agent layer is sheet or membranaceous, and contains sticker.
As the sticker, for example, can enumerate acrylic resin, urethane based resin, rubber resin, The adherences resin such as organic silicon resin, epoxylite, polyvinylether, makrolon, esters resin, preferably acrylic compounds tree Fat.
In addition, in the present invention, " adherence resin " be comprising with adherence resin and with the resin of adhesiveness Both concept, for example, include not only the resin that resin itself has adherence, also include by with additive etc. other at Point while use and show adherence resin or by heat or the triggers (trigger) such as water there are by show bonding The resin etc. of property.
Adhering agent layer can be made of a layer (single layer), can also be made of two layers or more of multiple layers, by multiple layers When composition, these multiple layers mutually the same can also be different, these multiple layers combinations are not particularly limited.
The thickness of adhering agent layer is preferably 1~100 μm, more preferably 1~60 μm, particularly preferably 1~30 μm.
Herein, " thickness of adhering agent layer " refers to the thickness of adhering agent layer entirety, such as the sticker being made of multiple layers The thickness of layer refers to the thickness of the total for all layers for constituting adhering agent layer.In addition, the measurement of the thickness as adhering agent layer Method, such as can enumerate using contact thickness gauge in arbitrary five position finding thickness, and calculate being averaged for measured value Method etc..
As long as the optical characteristics of adhering agent layer meets the optical characteristics of support chip described above.That is, sticker Layer can be transparent, can not also be transparent, can also be coloured according to purpose.
Moreover, in protective film formation has the present invention of energy ray-curable with film, preferably adhering agent layer penetrates energy Measure ray.
Adhering agent layer can be formed using energy ray-curable sticker, can also use non-energy ray-curable Sticker and formed.The adhering agent layer formed using the sticker of energy ray-curable can easily adjust solidification before and Physical property after solidification.
< < adhesion agent composition > >
The adhesion agent composition containing sticker can be used to form adhering agent layer.For example, by by adhesion agent composition It is coated in the formation object surface of adhering agent layer and is dried as needed, adhering agent layer can be formed in target site.It is viscous The more specific forming method of oxidant layer will below be described in detail together with other layers of forming method.Sticker group In object, the mutual content of ingredient that does not gasify under room temperature is closed than usually comparing phase with the mutual content of the ingredient of adhering agent layer Together.Herein, " room temperature " is identical as what is be illustrated above.
Using well known method carry out adhesion agent composition coating, such as can enumerate using Kohler coater, Scraping blade coating machine, bar coater, gravure coater, roll coater, roller knife coating machine, curtain coater, die coating machine, knife type coater, silk screen The method of the various coating machines such as coating machine, Meyer rod coater, kiss painting machine.
The drying condition of adhesion agent composition is not particularly limited, but when adhesion agent composition contains aftermentioned solvent, It is preferred that being thermally dried, at this point, being for example preferably dried with the condition of 70~130 DEG C, 10 seconds~5 minutes.
When adhering agent layer is energy ray-curable, as the sticker combination containing energy ray-curable sticker The adhesion agent composition of object, i.e. energy ray-curable, such as the adherence tree containing non-energy ray-curable can be enumerated Fat (I-1a) (hereinafter, writing a Chinese character in simplified form work " adherence resin (I-1a) " sometimes) is combined with the sticker of energy ray-curable compound Object (I-1);Side chain containing the adherence resin (I-1a) in non-energy ray-curable is imported with the energy of unsaturated group The adhesion agent composition of the adherence resin (I-2a) (hereinafter, writing a Chinese character in simplified form work " adherence resin (I-2a) " sometimes) of ray-curable (I-2);Adhesion agent composition (I-3) etc. containing the adherence resin (I-2a) Yu energy ray-curable compound.
< adhesion agent compositions (I-1) >
As described above, adherence resin (I-1a) of the adhesion agent composition (I-1) containing non-energy ray-curable With energy ray-curable compound.
&#91;Adherence resin (I-1a)s &#93;
It is preferred that the adherence resin (I-1a) is acrylic resin.
As the acrylic resin, such as the structure at least having and coming from (methyl) alkyl acrylate can be enumerated The acrylic polymer of unit.
Structural unit possessed by acrylic resin can be only one kind, or and it is two or more, it is two or more When, combination thereof and ratio can be selected arbitrarily.
As (methyl) alkyl acrylate, such as it is 1 that can enumerate the carbon atom number for the alkyl for constituting Arrcostab ~20 (methyl) alkyl acrylate, the preferably described alkyl are straight-chain or branched.
As (methyl) alkyl acrylate, more specifically, (methyl) methyl acrylate, (methyl) propylene can be enumerated Acetoacetic ester, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid Isobutyl ester, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) acrylic acid oneself Ester, (methyl) heptylacrylate, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid are just Monooctyl ester, the positive nonyl ester of (methyl) acrylic acid, the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate, (methyl) acrylic acid 11 Arrcostab, (methyl) dodecylacrylate ((methyl) lauryl acrylate), (methyl) tridecyl acrylate, (first Base) acrylic acid tetradecane base ester ((methyl) myristyl ester), (methyl) acrylic acid pentadecane base ester, (methyl) acrylic acid Cetyl ester ((methyl) acrylic acid palm ester), (methyl) acrylic acid heptadecane base ester, (methyl) octadecyl acrylate ((methyl) stearyl acrylate acid esters), (methyl) acrylic acid nonadecane base ester, (methyl) acrylic acid eicosane base ester etc..
From the point for the adhesion strength for improving adhering agent layer, the preferably described acrylic polymer, which has, comes from the alkyl Carbon atom number be 4 or more (methyl) alkyl acrylate structural unit.Moreover, from the viscous of adhering agent layer is further increased The point puted forth effort sets out, and the carbon atom number of the alkyl is preferably 4~12, and more preferably 4~8.Furthermore it is preferred that the carbon of the alkyl (methyl) alkyl acrylate that atomicity is 4 or more is alkyl acrylate.
The acrylic polymer in addition to have come from (methyl) alkyl acrylate structural unit other than, preferably into One step has the structural unit for carrying out self-contained monomer.
Contain monomer as described, such as can enumerate by the functional group is with aftermentioned reacting for crosslinking agent Generate crosslinked starting point or can be by the unsaturated group in the functional group and the aftermentioned compound containing unsaturated group Group reaction and the side chain of acrylic polymer import unsaturated group contain monomer.
As containing the functional group in monomer, such as hydroxyl, carboxyl, amino, epoxy group can be enumerated etc..
That is, as containing monomer, such as hydroxyl monomer can be enumerated, carboxyl group-containing monomer, emulsion stability, contain ring Oxygroup monomer etc..
As the hydroxyl monomer, such as (methyl) acrylate, (methyl) acrylic acid 2- hydroxyls can be enumerated Ethyl ester, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 3- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxybutyls, (first Base) (methyl) hydroxyalkyl acrylates such as acrylic acid 3- hydroxybutyls, (methyl) acrylic acid 4- hydroxybutyls;Vinyl alcohol, alkene Non- (methyl) acrylic compounds unsaturated alcohol such as propyl alcohol (unsaturated alcohol for not having (methyl) acryloyl group skeleton) etc..
As the carboxyl group-containing monomer, such as the olefinics unsaturation unitary carboxylic such as can enumerate (methyl) acrylic acid, crotonic acid Acid (monocarboxylic acid with ethylenic unsaturated bond);The ethylenically unsaturated dicarboxylics such as fumaric acid, itaconic acid, maleic acid, citraconic acid (dicarboxylic acids with ethylenic unsaturated bond);The acid anhydrides of the ethylenically unsaturated dicarboxylic;Methacrylic acid 2- carboxyethyls etc. (methyl) acrylic acid carboxyalkyl ester etc..
It is preferred that being hydroxyl monomer, carboxyl group-containing monomer, more preferably hydroxyl monomer containing monomer.
Constitute the acrylic polymer can be only one kind containing monomer, or and it is two or more, be When two or more, combination thereof and ratio can be selected arbitrarily.
In the acrylic polymer, relative to the total amount of structural unit, carry out the structure list of self-contained monomer The content of member is preferably 1~35 mass %, more preferably 2~32 mass %, particularly preferably 3~30 mass %.
The acrylic polymer is in addition to having the structural unit for coming from (methyl) alkyl acrylate and coming self-contained Other than the structural unit of monomer, can further have the structural unit from other monomers.
As long as the other monomers can be not particularly limited with copolymerization such as (methyl) alkyl acrylates.
As the other monomers, such as styrene, α-methylstyrene, vinyltoluene, vinyl formate can be enumerated Ester, vinyl acetate, acrylonitrile, acrylamide etc..
The other monomers for constituting the acrylic polymer can be only one kind, or and it is two or more, be When two or more, combination thereof and ratio can be selected arbitrarily.
The acrylic polymer can be used as the adherence resin (I-1a) of above-mentioned non-energy ray-curable.
On the other hand, make to have energy-ray polymerism unsaturated group (energy-ray polymerizable group) contains insatiable hunger With the compound of group and the functional group reactions in the acrylic polymer and the substance that generates, above-mentioned energy can be used as Measure the adherence resin (I-2a) of ray-curable.
Adherence resin (I-1a) contained by adhesion agent composition (I-1) can be only one kind, or two kinds with On, when being two or more, combination thereof and ratio can be selected arbitrarily.
In adhesion agent composition (I-1), relative to the gross mass of adhesion agent composition (I-1), adherence resin (I- Content 1a) is preferably 5~99 mass %, more preferably 10~95 mass %, particularly preferably 15~90 mass %.
&#91;Energy ray-curable Hua Hewu &#93;
The energy ray-curable compound contained by as adhesion agent composition (I-1), can enumerate with energy It measures ray polymerization unsaturated group and the cured monomer of the irradiation of energy-ray or oligomer can be passed through.
As the monomer in energy ray-curable compound, such as trimethylolpropane tris (methyl) propylene can be enumerated Acid esters, pentaerythrite (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylic acid Polynary (methyl) acrylate such as ester, 1,4- butanediols two (methyl) acrylate, 1,6-HD (methyl) acrylate;Ammonia Carbamate (methyl) acrylate;Polyester (methyl) acrylate;Polyethers (methyl) acrylate;Epoxy (methyl) acrylic acid Ester etc..
As the oligomer in energy ray-curable compound, for example, the monomer polymerization above illustrated can be enumerated and At oligomer etc..
Storage modulus larger with regard to molecular weight, adhering agent layer is not easy for reducing this point, energy ray-curable chemical combination Object is preferably carbamate (methyl) acrylate or carbamate (methyl) acrylate oligomer.
The energy ray-curable compound contained by adhesion agent composition (I-1) can be only one kind, can also It is two or more, when being two or more, combination thereof and ratio can be selected arbitrarily.
In the adhesion agent composition (I-1), relative to the gross mass of adhesion agent composition (I-1), the energy is penetrated The content of line curability compound is preferably 1~95 mass %, more preferably 5~90 mass %, particularly preferably 10~85 matter Measure %.
&#91;Jiao Lianji &#93;
It will be other than there is the structural unit for coming from (methyl) alkyl acrylate, further with next self-contained functional group When the acrylic polymer of the structural unit of monomer is used as adherence resin (I-1a), preferred adhesive compositions (I- 1) further contain crosslinking agent.
The crosslinking agent with the functional group for example by reacting adherence resin (I-1a) being cross-linked to each other.
As crosslinking agent, such as toluene di-isocyanate(TDI), hexamethylene diisocyanate, phenylenedimethylidyne two can be enumerated The isocyanates crosslinking agent such as addition product (crosslinking agent with isocyanate group) of isocyanates, these diisocyanate;Second The epoxies such as glycol glycidyl ether crosslinking agent (crosslinking agent with glycidyl);Liu &#91;1- (2- methyl) Dan Bingdingji &#93; Triphosphoric acid triazine (Hexa&#91;1-(2-methyl)-aziridinyl&#93;Triazines cross-linkings agent (the tool such as triphosphatriazine) There is the crosslinking agent of '-aziridino);The metal-chelatings species such as aluminium chelate compound crosslinking agent (crosslinking agent with metallo-chelate structure); Isocyanuric acid esters crosslinking agent (crosslinking agent with isocyanuric acid skeleton) etc..
From the cohesiveness for improving sticker to improve the point of the adhesion strength of adhering agent layer and be pointed out from what is be easy to get etc. Hair, preferably crosslinking agent are isocyanates crosslinking agent.
Crosslinking agent contained by adhesion agent composition (I-1) can be only one kind, or it is two or more, be two kinds with When upper, combination thereof and ratio can be selected arbitrarily.
In the adhesion agent composition (I-1), relative to 100 mass parts of content of adherence resin (I-1a), crosslinking The content of agent is preferably 0.01~50 mass parts, more preferably 0.1~20 mass parts, particularly preferably 0.3~15 mass parts.
&#91;Guang Juheyinfaji &#93;
Adhesion agent composition (I-1) can also further contain Photoepolymerizationinitiater initiater.Even if to containing Photoepolymerizationinitiater initiater Adhesion agent composition (I-1) irradiation ultraviolet light etc. compared with the energy-ray of low energy, be also sufficiently carried out curing reaction.
As the Photoepolymerizationinitiater initiater, such as benzoin, benzoin methylether, benzoin ethyl ether, benzoin can be enumerated The benzoins such as isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin dimethyl ketal Close object;Acetophenone, 2- hydroxy-2-methyl -1- phenyl-propan -1- ketone, 2,2- dimethoxy -1,2- diphenylethane -1- ketone etc. Acetophenone compound;Bis- (2,4,6- trimethylbenzoyls) phosphine oxides of phenyl, 2,4,6- trimethyl benzoyl diphenyl base oxygen Change the acylphosphine oxides compounds such as phosphine;The sulphur compounds such as benzyl phenyl thioether, tetramethylthiuram monosulfide;1- hydroxy cyclohexylphenyls The α -one alcoholic compounds such as base phenyl ketone;The azo-compounds such as azodiisobutyronitrile;The titanocenes compound such as titanocenes;Thioxanthones etc. Thioxanthone compounds;Peroxide compound;The dione compounds such as biacetyl;Benzyl;Dibenzyl;Benzophenone;2,4- diethyls Base thioxanthones;1,2- diphenyl methanes;2- hydroxy-2-methyls -1-&#91;4- (1- methyl ethylenes) Ben Ji &#93;Acetone;2- chloroanthraquinones Deng.
In addition, as the Photoepolymerizationinitiater initiater, such as the naphtoquinone compounds such as 1- chloroanthraquinones also can be used;The photosensitizers such as amine Deng.
Photoepolymerizationinitiater initiater contained by adhesion agent composition (I-1) can be only one kind, or and it is two or more, be When two or more, combination thereof and ratio can be selected arbitrarily.
In adhesion agent composition (I-1), relative to 100 mass parts of content of the energy ray-curable compound, The content of Photoepolymerizationinitiater initiater is preferably 0.01~20 mass parts, more preferably 0.03~10 mass parts, particularly preferably 0.05 ~5 mass parts.
&#91;Other Tian Jiajis &#93;
Within the scope of the effect of the invention, adhesion agent composition (I-1) can also be above-mentioned containing not corresponding to Other additives of any ingredient.
As other described additives, such as antistatic agent, antioxidant, softening agent (plasticizer), filling can be enumerated Material (filler), antirust agent, colorant (pigment, dyestuff), sensitizer, tackifier, response delay agent, crosslinking accelerator (catalysis Agent) etc. well known to additive.
In addition, response delay agent refers to, such as pass through the effect of mixed catalyst in adhesion agent composition (I-1), suppression The additive of the progress of the cross-linking reaction of the non-purpose in adhesion agent composition (I-1) in system preservation.As response delay Agent, such as can enumerate and form chelate complex (chelate complex) using chelate corresponding with catalyst Response delay agent more specifically can enumerate the response delay in 1 molecule with more than two carbonyls (- C (=O) -) Agent.
Other additives contained by adhesion agent composition (I-1) can be only one kind, or and it is two or more, it is two Kind or more when, combination thereof and ratio can be selected arbitrarily.
In adhesion agent composition (I-1), the content of other additives is not particularly limited, and it is appropriate to be carried out according to its type Selection.
&#91;Rong Ji &#93;
Adhesion agent composition (I-1) can contain solvent.Adhesion agent composition (I-1) is improved by containing solvent to applying The coating adaptive of cloth subject surface.
It is preferred that the solvent is organic solvent, as the organic solvent, such as methyl ethyl ketone, acetone can be enumerated etc. Ketone;The esters such as ethyl acetate (carboxylate);The ethers such as tetrahydrofuran, dioxanes;The aliphatic hydrocarbons such as hexamethylene, n-hexane;Toluene, diformazan The aromatic hydrocarbons such as benzene;Alcohol such as 1- propyl alcohol, 2- propyl alcohol etc..
As the solvent, for example, when can not will manufacture adherence resin (I-1a) solvent that uses from adherence resin (I-1a) it is removed in and is directly used in adhesion agent composition (I-1), can also in addition added when manufacturing adhesion agent composition (I-1) Add the solvent with the identical or different type of solvent used when manufacture adherence resin (I-1a).
Solvent contained by adhesion agent composition (I-1) can be only one kind, or and it is two or more, it is two or more When, combination thereof and ratio can be selected arbitrarily.
In adhesion agent composition (I-1), the content of solvent is not particularly limited, and can suitably be adjusted.
< adhesion agent compositions (I-2) >
As described above, the adhesion agent composition (I-2) contains the adherence resin (I- in non-energy ray-curable Side chain 1a) is imported with the adherence resin (I-2a) of the energy ray-curable of unsaturated group.
&#91;Adherence resin (I-2a)s &#93;
The adherence resin (I-2a) for example contains insatiable hunger by make to have energy-ray polymerism unsaturated group It is obtained with the functional group reactions in adherence resin (I-1a) with the compound of group.
The compound containing unsaturated group be other than with the energy-ray polymerism unsaturated group, Further have and can be bonded with adherence resin (I-1a) by being reacted with the functional group in adherence resin (I-1a) Group compound.
As the energy-ray polymerism unsaturated group, such as can to enumerate (methyl) acryloyl group, vinyl (secondary Ethyl), allyl (2- acrylic) etc., preferably (methyl) acryloyl group.
As the group that can be bonded with the functional group in adherence resin (I-1a), such as can enumerate can be with hydroxyl or ammonia The isocyanate group and glycidyl and the hydroxyl that can be bonded with carboxyl or epoxy group and amino etc. of base bonding.
As the compound containing unsaturated group, such as (methyl) acryloyl-oxyethyl isocyanic acid can be enumerated Ester, (methyl) propenoyl isocyanate, (methyl) glycidyl acrylate etc..
Adherence resin (I-2a) contained by adhesion agent composition (I-2) can be only one kind, or two kinds with On, when being two or more, combination thereof and ratio can be selected arbitrarily.
In adhesion agent composition (I-2), relative to the gross mass of adhesion agent composition (I-2), adherence resin (I- Content 2a) is preferably 5~99 mass %, more preferably 10~95 mass %, particularly preferably 10~90 mass %.
&#91;Jiao Lianji &#93;
For example, will be identical with adherence resin (I-1a), with the structural unit for carrying out self-contained monomer When the acrylic polymer is used as adherence resin (I-2a), preferred adhesive compositions (I-2) further contain crosslinking Agent.
As the crosslinking agent in adhesion agent composition (I-2), can enumerate and the friendship in adhesion agent composition (I-1) Join the identical crosslinking agent of agent.
Crosslinking agent contained by adhesion agent composition (I-2) can be only one kind, or it is two or more, be two kinds with When upper, combination thereof and ratio can be selected arbitrarily.
In the adhesion agent composition (I-2), relative to 100 mass parts of content of adherence resin (I-2a), crosslinking The content of agent is preferably 0.01~50 mass parts, more preferably 0.1~20 mass parts, particularly preferably 0.3~15 mass parts.
&#91;Guang Juheyinfaji &#93;
Adhesion agent composition (I-2) can also further contain Photoepolymerizationinitiater initiater.Even if to containing Photoepolymerizationinitiater initiater Adhesion agent composition (I-2) irradiation ultraviolet light etc. compared with the energy-ray of low energy, be also sufficiently carried out curing reaction.
As the Photoepolymerizationinitiater initiater in adhesion agent composition (I-2), can enumerate and adhesion agent composition (I-1) In the identical Photoepolymerizationinitiater initiater of Photoepolymerizationinitiater initiater.
Photoepolymerizationinitiater initiater contained by adhesion agent composition (I-2) can be only one kind, or and it is two or more, be When two or more, combination thereof and ratio can be selected arbitrarily.
In adhesion agent composition (I-2), relative to 100 mass parts of content of adherence resin (I-2a), photopolymerization is drawn The content for sending out agent is preferably 0.01~20 mass parts, more preferably 0.03~10 mass parts, particularly preferably 0.05~5 mass Part.
&#91;Other Tian Jiajis &#93;
Within the scope of the effect of the invention, adhesion agent composition (I-2) can also be above-mentioned containing not corresponding to Other additives of any ingredient.
As other described additives in adhesion agent composition (I-2), can enumerate with adhesion agent composition (I-1) in Other identical additives of other additives.
Other additives contained by adhesion agent composition (I-2) can be only one kind, or and it is two or more, it is two Kind or more when, combination thereof and ratio can be selected arbitrarily.
In adhesion agent composition (I-2), the content of other additives is not particularly limited, and it is appropriate to be carried out according to its type Selection.
&#91;Rong Ji &#93;
The case where for adhesion agent composition (I-1) identical purpose, adhesion agent composition (I-2) can also contain molten Agent.
As the solvent in adhesion agent composition (I-2), can enumerate and the solvent in adhesion agent composition (I-1) Identical solvent.
Solvent contained by adhesion agent composition (I-2) can be only one kind, or and it is two or more, it is two or more When, combination thereof and ratio can be selected arbitrarily.
In adhesion agent composition (I-2), the content of solvent is not particularly limited, and can suitably be adjusted.
< adhesion agent compositions (I-3) >
As described above, the adhesion agent composition (I-3) containing the adherence resin (I-2a) with it is energy ray curing Property compound.
In adhesion agent composition (I-3), relative to the gross mass of adhesion agent composition (I-3), adherence resin (I- Content 2a) is preferably 5~99 mass %, more preferably 10~95 mass %, particularly preferably 15~90 mass %.
&#91;Energy ray-curable Hua Hewu &#93;
The energy ray-curable compound contained by as adhesion agent composition (I-3), can enumerate with energy It measures ray polymerization unsaturated group and can be enumerated by the cured monomer of the irradiation of energy-ray or oligomer Energy ray-curable compound identical with the energy ray-curable compound contained by adhesion agent composition (I-1).
The energy ray-curable compound contained by adhesion agent composition (I-3) can be only one kind, can also It is two or more, when being two or more, combination thereof and ratio can be selected arbitrarily.
It is described relative to 100 mass parts of content of adherence resin (I-2a) in the adhesion agent composition (I-3) The content of energy ray-curable compound is preferably 0.01~300 mass parts, more preferably 0.03~200 mass parts, especially Preferably 0.05~100 mass parts.
&#91;Guang Juheyinfaji &#93;
Adhesion agent composition (I-3) can also further contain Photoepolymerizationinitiater initiater.Even if to containing Photoepolymerizationinitiater initiater Adhesion agent composition (I-3) irradiation ultraviolet light etc. compared with the energy-ray of low energy, be also sufficiently carried out curing reaction.
As the Photoepolymerizationinitiater initiater in adhesion agent composition (I-3), can enumerate and adhesion agent composition (I-1) In the identical Photoepolymerizationinitiater initiater of Photoepolymerizationinitiater initiater.
Photoepolymerizationinitiater initiater contained by adhesion agent composition (I-3) can be only one kind, or and it is two or more, be When two or more, combination thereof and ratio can be selected arbitrarily.
In adhesion agent composition (I-3), relative to adherence resin (I-2a) and the energy ray-curable chemical combination The content of 100 mass parts of total content of object, Photoepolymerizationinitiater initiater is preferably 0.01~20 mass parts, more preferably 0.03~10 matter Measure part, particularly preferably 0.05~5 mass parts.
&#91;Other Tian Jiajis &#93;
Within the scope of the effect of the invention, adhesion agent composition (I-3) can also be above-mentioned containing not corresponding to Other additives of any ingredient.
As other described additives, can enumerate it is identical with other additives in adhesion agent composition (I-1) its His additive.
Other additives contained by adhesion agent composition (I-3) can be only one kind, or and it is two or more, it is two Kind or more when, combination thereof and ratio can be selected arbitrarily.
In adhesion agent composition (I-3), the content of other additives is not particularly limited, and it is appropriate to be carried out according to its type Selection.
&#91;Rong Ji &#93;
The case where for adhesion agent composition (I-1) identical purpose, adhesion agent composition (I-3) can also contain molten Agent.
As the solvent in adhesion agent composition (I-3), can enumerate and the solvent in adhesion agent composition (I-1) Identical solvent.
Solvent contained by adhesion agent composition (I-3) can be only one kind, or and it is two or more, it is two or more When, combination thereof and ratio can be selected arbitrarily.
In adhesion agent composition (I-3), the content of solvent is not particularly limited, and can suitably be adjusted.
Adhesion agent composition >s of the < in addition to adhesion agent composition (I-1)~(I-3)
So far, mainly to adhesion agent composition (I-1), adhesion agent composition (I-2) and adhesion agent composition (I-3) It is illustrated, can be equally used for combining except these three stickers as their substance being illustrated containing ingredient All adhesion agent compositions other than object are (in the present specification, referred to as " in addition to adhesion agent composition (I-1)~(I-3) Adhesion agent composition ") in.
As the adhesion agent composition in addition to adhesion agent composition (I-1)~(I-3), in addition to energy ray-curable Other than adhesion agent composition, the adhesion agent composition of non-energy ray-curable can be also enumerated.
As the adhesion agent composition of non-energy ray-curable, such as can enumerate containing acrylic resin, amino Formate ester resin, rubber resin, organic silicon resin, epoxylite, polyvinylether, makrolon, esters resin etc. The adhesion agent composition (I-4) of the adherence resin (I-1a) of non-energy ray-curable, preferably comprises acrylic resin The adhesion agent composition of non-energy ray-curable.
It is preferred that the adhesion agent composition in addition to adhesion agent composition (I-1)~(I-3) contains one or more Crosslinking agent, can be by the setting of its content identical as the situation of above-mentioned adhesion agent composition (I-1) etc..
< adhesion agent compositions (I-4) >
As preferred adhesion agent composition (I-4), such as can enumerate containing the adherence resin (I-1a) and friendship Join the adhesion agent composition of agent.
&#91;Adherence resin (I-1a)s &#93;
As the adherence resin (I-1a) in adhesion agent composition (I-4), can enumerate and adhesion agent composition (I-1) In the identical adherence resin (I-1a) of adherence resin (I-1a).
Adherence resin (I-1a) contained by adhesion agent composition (I-4) can be only one kind, or two kinds with On, when being two or more, combination thereof and ratio can be selected arbitrarily.
In adhesion agent composition (I-4), relative to the gross mass of adhesion agent composition (I-4), adherence resin (I- Content 1a) is preferably 5~99 mass %, more preferably 10~95 mass %, particularly preferably 15~90 mass %.
&#91;Jiao Lianji &#93;
It will be other than there is the structural unit for coming from (methyl) alkyl acrylate, further with next self-contained functional group When the acrylic polymer of the structural unit of monomer is used as adherence resin (I-1a), preferred adhesive compositions (I- 4) further contain crosslinking agent.
As the crosslinking agent in adhesion agent composition (I-4), can enumerate and the crosslinking agent in adhesion agent composition (I-1) Identical crosslinking agent.
Crosslinking agent contained by adhesion agent composition (I-4) can be only one kind, or it is two or more, be two kinds with When upper, combination thereof and ratio can be selected arbitrarily.
In the adhesion agent composition (I-4), relative to 100 mass parts of content of adherence resin (I-1a), crosslinking The content of agent is preferably 0.01~50 mass parts, more preferably 0.1~20 mass parts, particularly preferably 0.3~15 mass parts.
&#91;Other Tian Jiajis &#93;
Within the scope of the effect of the invention, adhesion agent composition (I-4) can also be above-mentioned containing not corresponding to Other additives of any ingredient.
As other described additives, can enumerate it is identical with other additives in adhesion agent composition (I-1) its His additive.
Other additives contained by adhesion agent composition (I-4) can be only one kind, or and it is two or more, it is two Kind or more when, combination thereof and ratio can be selected arbitrarily.
In adhesion agent composition (I-4), the content of other additives is not particularly limited, and it is appropriate to be carried out according to its type Selection.
&#91;Rong Ji &#93;
The case where for adhesion agent composition (I-1) identical purpose, adhesion agent composition (I-4) can also contain molten Agent.
As the solvent in adhesion agent composition (I-4), can enumerate and the solvent in adhesion agent composition (I-1) Identical solvent.
Solvent contained by adhesion agent composition (I-4) can be only one kind, or and it is two or more, it is two or more When, combination thereof and ratio can be selected arbitrarily.
In adhesion agent composition (I-4), the content of solvent is not particularly limited, and can suitably be adjusted.
In the protective film formation composite sheet of the present invention, preferably adhering agent layer is non-energy ray-curable.This be by In, if adhering agent layer is energy ray-curable, when the irradiation by energy-ray makes protective film formation film cure, nothing Method inhibits to cure while adhering agent layer.If adhering agent layer cures simultaneously with protective film formation film, after solidification can be caused The attaching for the degree that cannot be removed occurs on their interface for protective film formation film and adhering agent layer.At this time, it is difficult to By the back side have solidification after protective film formation film, i.e. protective film semiconductor chip (in the present specification, sometimes referred to as " semiconductor chip with protective film ") it is removed from the support chip for having the adhering agent layer after curing, lead to not normally pick up Semiconductor chip with protective film.It can by making adhering agent layer be non-energy ray-curable for the support chip of the present invention Definitely avoid such undesirable condition, is capable of the semiconductor chip of more easily pick-up tape protective film.
Herein, to adhering agent layer be non-energy ray-curable when effect be illustrated, even if support chip with The protective film formation layer that the layer that film is in direct contact is in addition to adhering agent layer, as long as the layer is non-energy ray-curable, then Play same effect.
The preparation method > > of < < adhesion agent compositions
Adhesion agent composition (I-1)~(I-3) or adhesion agent composition (I-4) etc. except adhesion agent composition (I-1)~ (I-3) adhesion agent composition other than can be by blending the sticker and the ingredient in addition to the sticker as needed It is obtained Deng for constituting each ingredient of adhesion agent composition.
Order of addition when blending each ingredient is not particularly limited, and can also add two or more ingredients simultaneously.
It, can be pre- by the blending ingredient by mixing solvent with the arbitrary blending ingredient in addition to solvent when using solvent Dilution, can not also be by the arbitrary blending ingredient pre-dilution in addition to solvent and by by solvent and these to be used Ingredient mixing is blended to be used.
The method that each ingredient is mixed when blending is not particularly limited, and is suitably selected from following well known methods:Make Blender or stirring blade etc. rotate and mixed method;The method mixed using blender;Apply ultrasonic wave and Mixed method etc..
As long as respectively blending ingredient not deteriorate, then the temperature and time when adding and mix each ingredient are not particularly limited, Suitably adjust, preferable temperature is 15~30 DEG C.
In the form of the present invention, protective film formation of the invention has protective film formation film with composite sheet, should Protective film formation with film contain in said protection film formation substance identical with the substance illustrated in piece.
In addition, in the form of the present invention, protective film formation composite sheet of the invention, which has, contains following component Protective film formation film:It is different that 6-caprolactone as energy ray-curable ingredient (a2) is modified three (2- acrylyl oxy-ethyls) Cyanurate (8~12 mass parts, preferably 10 mass parts);As the polymer (b) without energy ray-curable group Acrylic resin (19~25 mass parts, preferably 22 mass parts), wherein the acrylic resin is by butyl acrylate (8~12 mass parts, preferably 10 mass parts), methyl acrylate (60~80 mass parts, preferably 70 mass parts), metering system Acid glycidyl ester (3~7 mass parts, preferably 5 mass parts) and acrylic acid 2- hydroxy methacrylates (13~17 mass parts, preferably 15 mass parts) it is copolymerized;2- (dimethylamino) -1- (4- morpholinyl phenyls) -2- benzyls-as Photoepolymerizationinitiater initiater (c) 1- butanone (0.1~0.5 mass parts, preferably 0.3 mass parts) and 1-&#91;9- ethyls -6- (2- methyl benzoyls) -9H- clicks Azoles -3- Jis &#93;Ethyl ketone 1- (O- acetyl oxime) (0.1~0.5 mass parts, preferably 0.3 mass parts);As the molten of packing material (d) Fused silica filler (8 μm of average grain diameter) (51~61 mass parts, preferably 56 mass parts);3- methyl-props as coupling agent (e) Alkene acryloxypropylethoxysilane trimethoxy silane (0.1~0.7 mass parts, preferably 0.4 mass parts);As colorant (g), usual For the well known pigment (1~3 mass parts, preferably 2 mass parts) of protective film formation film, more specifically by phthalocyanines Blue pigment (Pigment Blue 15:3) 32 mass parts, isoindoline ketone xanthein (Pigment Yellow 139) 18 mass parts and Anthraquinones red pigments (Pigment Red 177) 50 mass parts mixing and so that three kinds of pigments conjunction The mode of metering/styrene acrylic resin amount=1/3 (mass ratio) carry out pigment obtained from pigmentation (1~3 mass parts, Preferably 2 mass parts);Toluene di-isocyanate(TDI) class crosslinking agent (0.1~0.5 mass parts, preferably 0.3 as crosslinking agent (f) Mass parts).
The manufacturing method of ◇ protective film formation composite sheets
Can by make above-mentioned each layer as corresponding position relationship in a manner of stack gradually above-mentioned each layer and make Make the protective film formation composite sheet of the present invention.The forming method of each layer is identical as what is be illustrated above.
For example, when manufacture support chip, when adhering agent layer is laminated on base material, above-mentioned adhesion agent composition is coated on base It is dried on material and as needed.
On the other hand, such as when protective film formation film is further laminated on adhering agent layer on base material has been laminated, Protective film formation can be coated on composition on adhering agent layer and directly form protective film formation film.For removing protective film shape At with the layer other than film, same method can be also utilized, is laminated on adhering agent layer using the composition for being used to form this layer The layer.It like this, can be in the layer formed by the composition when forming continuous two layers of stepped construction using arbitrary composition Upper further coating composition is to form new layer.Wherein, it is preferable to use the composition advance shape on other stripping films At the layer of the rear stacking in above-mentioned two layers, and by with the side contacted with the stripping film being opposite by the established layer The exposed surface of side and the fitting of the exposed surface of another layer formed, form continuous two layers of stepped construction.At this point, it is preferred that will The composition is coated on the lift-off processing face of stripping film.After forming stepped construction, stripping film is removed as needed.
For example, manufacture on base material be laminated adhering agent layer and on the adhering agent layer be laminated protective film formation film and Obtained protective film formation is with composite sheet (support chip is the protective film formation composite sheet of the sandwich of base material and adhering agent layer) When, by the way that adhesion agent composition is coated on base material and is dried as needed, sticker is thus laminated on base material Thus layer, is in addition being removed by being coated on protective film formation on stripping film with composition and being dried as needed again Protective film formation film is formed on film.Then, by by the exposed surface of the protective film formation film be laminated it is on base material The exposed surface of adhering agent layer is bonded, and protective film formation is stacked in film layer on adhering agent layer, and protective film can be obtained and formed with multiple Close piece.
In addition, when adhering agent layer is laminated on base material, as described above, on base material instead of adhesion agent composition to be coated with Adhesion agent composition is coated on stripping film and is dried as needed, thus forms sticker on stripping film by method Layer, and the exposed surface of this layer is bonded with the surface of the side of base material, thus adhering agent layer can be layered on base material.
In arbitrary method, the arbitrary opportunity after forming target stepped construction removes stripping film.
As noted previously, as stripping can be previously formed in by constituting the layer in addition to base material of protective film formation composite sheet It on film, and is laminated in the method for being fitted in the surface of destination layer, therefore appropriate selection uses such process as needed Layer manufacture protective film formation composite sheet.
In addition, protective film formation with composite sheet usually with the most surface layer of its support chip opposite side (such as protective film shape At with film) surface be fitted with the state of stripping film and taken care of.Therefore, even if by protective film formation composition etc., use It is coated on stripping film (preferably its lift-off processing face) in the composition for forming the layer for constituting most surface layer, and carries out as needed It is dry, the layer for constituting most surface layer is thus formed on stripping film, and using above-mentioned arbitrary method in this layer and same stripping film The side of contact is the other each layers of stacking in the exposed surface of opposite side, when holding does not remove and is bonded the state of stripping film, Protective film formation composite sheet can be obtained.
The application method of ◇ protective film formation composite sheets
The protective film formation of the present invention can for example be used with composite sheet using method as shown below.
That is, protective film formation composite sheet is made to pass through its protective film formation film to be attached at the back side of semiconductor crystal wafer (face with electrode forming surface opposite side).Then, by cutting, semiconductor crystal wafer is divided together with protective film, is made and partly leads Body chip.Then, to protective film formation film irradiation energy ray, make protective film formation film solidification to which protective film be made. Then, to be pasted with the state (that is, as semiconductor chip with protective film) of the protective film, by semiconductor chip from support chip Upper separation is simultaneously picked up.
Later, using method identical with previous method, by the semiconductor of the obtained semiconductor chip with protective film After flip-chip is connected to the circuit face of substrate, semiconductor package body is made.Then, using the semiconductor package body, mesh is made Mark semiconductor device.
Embodiment
Hereinafter, according to specific embodiment, the present invention will be described in more detail.But the present invention is not limited to Embodiment described below.
The ingredient used in the manufacture of protective film formation composition described below.
Energy ray-curable ingredient
(a2)-1:Tristane dihydroxymethyl diacrylate be (Nippon Kayaku Co., Ltd. manufactures " KAYARAD R-684 ", the ultra-violet solidified compound of difunctionality, molecular weight 304)
(a2)-2:6-caprolactone is modified three (2- acrylyl oxy-ethyls) isocyanuric acid ester (SHIN-NAKAMURA " A-9300-1CL " of CHEMICAL CO., LTD. manufactures, the ultra-violet solidified compound of trifunctional)
Polymer without energy ray-curable group
(b)-1:By butyl acrylate (hereinafter, writing a Chinese character in simplified form work " BA ") (10 mass parts), methyl acrylate (hereinafter, writing a Chinese character in simplified form work " MA ") (70 mass parts), glycidyl methacrylate (hereinafter, writing a Chinese character in simplified form work " GMA ") (5 mass parts) and acrylic acid 2- hydroxyls Acrylic resin (weight average molecular weight 300000, glass made of ethyl ester (hereinafter, writing a Chinese character in simplified form work " HEA ") (15 mass parts) copolymerization Change -1 DEG C of transition temperature).
Photoepolymerizationinitiater initiater
(c)-1:2- (dimethylamino) -1- (4- morpholinyl phenyls) -2- benzyl -1- butanone be (BASF AG's manufacture " Irgacure (registered trademark) 369 ")
(c)-2:1-&#91;9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- Jis &#93;Ethyl ketone 1- (O- acetyl oxime) (BASF " Irgacure (registered trademark) OXE02 " of company's manufacture)
Packing material
(d)-1:Silica filler (vitreous silica filler, 8 μm of average grain diameter)
Coupling agent
(e)-1:3- methacryloxypropyl trimethoxy silanes (Shin-Etsu Chemical Co., Ltd. systems " KBM-503 " made, silane coupling agent)
Crosslinking agent
(f)-1:Toluene di-isocyanate(TDI) class crosslinking agent (Nippon Polyurethane Industry Co., Ltd. systems " the CORONATE L " made)
Colorant
(g)-1:By phthalocyanines blue pigment (Pigment Blue 15:3) 32 mass parts, isoindoline ketone yellow color Plain (Pigment Yellow 139) 18 mass parts and the mixing of Anthraquinones red pigments (Pigment Red 177) 50 mass parts, So that the mode of the total amount of three kinds of pigments/styrene acrylic resin amount=1/3 (mass ratio) carries out pigmentation and obtains The pigment arrived.
&#91;Embodiment 1&#93;
The manufacture > of < protective film formation composite sheets
(protective film forms the preparation with composition (IV-1))
So that energy ray-curable ingredient (a2) -1, polymer (b) -1, Photoepolymerizationinitiater initiater (c) -1, photopolymerization initiation Agent (c) -2, packing material (d) -1, coupling agent (e) -1 and colorant (g) -1 content (solid content, mass parts) become table The mode being worth shown in 1 is dissolved or dispersed in methyl ethyl ketone, and is stirred in 23 DEG C, and it is dense to be thus prepared for solid constituent Degree is the protective film formation composition (IV-1) of 50 mass %.In addition, the record of the "-" in the column containing ingredient in table 1 Refer to that protective film formation composition (IV-1) does not contain the ingredient.
(preparation of adhesion agent composition (I-4))
It is prepared for containing acrylic polymer (100 mass parts, solid constituent) and two isocyanide of trifunctional phenylenedimethylidyne Esters of gallic acid crosslinking agent " the TAKENATE D110N " of manufacture (three fields Jing Wu chemical companies) (10.7 mass parts, solid constituent), simultaneously Further contain methyl ethyl ketone as solvent, solid component concentration be 30 mass % non-energy ray-curable adhesion Agent composition (I-4).The acrylic polymer is by 2-EHA (hereinafter, writing a Chinese character in simplified form work " 2EHA ") (36 matter Measure part), BA (59 mass parts) and HEA (5 mass parts) copolymerization made of weight average molecular weight be 600000 acrylic Object.
(manufacture of support chip)
Adhesion agent composition obtained above (I-4) is coated on using silicone-treated to polyethylene terephthalate The single side of film has carried out stripping film (" SP-PET381031 " of Lintec Corporation. manufactures, the thickness of lift-off processing 38 μm) the lift-off processing face on, and in 120 DEG C of heat dryings 2 minutes, thus form the non-energy ray of 10 μm of thickness The adhering agent layer of curability.
It then, will be as the polypropylene film of base material (Mitsubishi Plastics, Inc. manufactures, 80 μm of thickness) patch It closes in the exposed surface of the adhering agent layer, results in and have the adhering agent layer on the surface of the side of the base material Support chip (10) -1.
(manufacture of protective film formation composite sheet)
Protective film formation obtained above is coated on composition (IV-1) using knife type coater and utilizes silicone-treated (the Lintec Corporation. systems of stripping film 1 of lift-off processing have been carried out to the single side of polyethylene terephthalate film " SP-PET381031 " made, 38 μm of thickness) the lift-off processing face on, and in 100 DEG C of heat dryings 2 minutes, thus make The protective film formation film (13) -1 of the energy ray-curable of 25 μm of thickness is made.
Then, stripping film is removed from the adhering agent layer of support chip (10) -1 obtained above, by guarantor obtained above Cuticula formation is fitted in the exposed surface of film (13) -1 in the exposed surface of the adhering agent layer, has been made base material, adhering agent layer, guarantor Cuticula formed film (13) -1 and stripping film along their thickness direction stack gradually made of protective film shown in fig. 6 form use Composite sheet.The composition of obtained protective film formation composite sheet is shown in table 2.
The evaluation > of < protective film formation composite sheets
(measurement of the tensile modulus of elasticity of protective film formation film)
By protective film formation composite sheet severing to make test film, according to JIS K7161:1994 pairs 23 DEG C described The tensile modulus of elasticity (Young's modulus) of test film is determined.At this point, width when the measurement of the test film be 15mm, Distance is 100mm between fixture.
(blocking of blade)
So that protective film formation composite sheet obtained above is passed through its protective film formation film (13) -1 and is attached to 6 inches of silicon On the #2000 abradant surfaces of wafer (200 μm of thickness), further formed via the protective film that is not laminated in the surface of adhering agent layer With the face of film, which is fixed on ring-shaped frame, and has stood 30 minutes.
Then, using cutting blade, Silicon Wafer is sliced with protective film formation together with film, the silicon of 5mm × 5mm has been obtained Chip.It at this point, whether visual confirmation blade blocks, will be determined as "○" the case where blocking completely, will on a small quantity be blocked up even having The case where plug, is determined as "×", is evaluated.Show the result in table 2." blocking of blade " column in table 2 is recorded as corresponding to Result.
&#91;Embodiment 2&#93;
The manufacture > of < protective film formation pieces
(protective film forms the preparation with composition (IV-1))
The protective film formation composition (IV-1) obtained in embodiment 1 is used
(manufacture of protective film formation piece)
Using method same as Example 1, the protective film for having made the energy ray-curable of 25 μm of thickness forms use Film (13) -1.
Then, protective film formation obtained above is fitted in through silicone-treated with the exposed surface of film (13) -1 to poly- pair The single side of ethylene terephthalate film carried out lift-off processing stripping film 2 (Lintec Corporation. manufacture " PET382150 ", 38 μm of thickness) the lift-off processing face on, made stripping film 1, protective film formation film (13) -1 and Stripping film 2 along their thickness direction stack gradually made of protective film formation piece.By obtained protective film formation piece Composition is shown in table 2.
The evaluation > of < protective film formation pieces
(tensile modulus of elasticity of protective film formation film)
By protective film formation piece severing to make test film, according to JIS K7161:1994 pairs 23 DEG C of the experiment The tensile modulus of elasticity (Young's modulus) of piece is determined.At this point, the width when measurement of the test film is 15mm, fixture Between distance be 100mm.
(manufacture of laminated body)
Then, the stripping film 1 of protective film formation piece obtained above is removed, so that protective film obtained above is formed and uses Piece is attached to by its protective film formation film (13) -1 on the #2000 abradant surfaces of 6 inches of Silicon Wafers (200 μm of thickness).
Then, stripping film is removed from the adhering agent layer of the support chip (10) -1 obtained in embodiment 1, is obtained above-mentioned The exposed surface for eliminating stripping film 2 of protective film formation film (13) -1 be bonded with the exposed surface of the adhering agent layer, make Base material, adhering agent layer, protective film formed film (13) -1 and Silicon Wafer along their thickness direction stack gradually made of be laminated Body.Further, via the face for not being laminated with protective film formation film in the surface of adhering agent layer, which is fixed on ring Shape frame, and stood 30 minutes.
(blocking of blade)
Then, using cutting blade, Silicon Wafer is sliced with protective film formation together with film, the silicon of 5mm × 5mm has been obtained Chip.At this point, visual confirmation has the blocking for blade caused by the chip of film of having no way of, will be determined as the case where blocking completely "○", will be even there is the case where a small amount of blocking to be determined as "×", is evaluated.Show the result in table 2.In table 2 " blade Blocking " column is recorded as corresponding result.
&#91;Embodiment 3&#93;
The manufacture > of < protective film formation composite sheets
(protective film forms the preparation with composition (IV-1))
As shown in table 1, in addition to being changed to 20 mass parts of content (blended amount) of energy ray-curable ingredient (a2) -2 10 mass parts of content (blended amount) of energy ray-curable ingredient (a2) -2,2 matter of content (blended amount) by polymer (b) -1 Amount part is changed to 22 mass parts, 76 mass parts of content (blended amount) of packing material (d) -1 is changed to 56 mass parts and are added Other than the crosslinking agent (h) -1 of 0.3 mass parts, protective film formation composition is prepared for using method same as Example 1 (IV-1)。
(manufacture of protective film formation composite sheet)
Other than using protective film formation composition (IV-1) this point obtained above, using with 1 phase of embodiment Same method, has made the protective film formation film (13) -2 of the energy ray-curable of 25 μm of thickness.
In addition, in addition to use the protective film formation film (13) -2 replace (13) -1 this point of protective film formation film with Outside, using method same as Example 1, protective film formation composite sheet shown in fig. 6 has been manufactured.The protective film shape that will be obtained It is shown in table 2 at the composition of composite sheet.
The evaluation > of < protective film formation composite sheets
For protective film formation composite sheet obtained above, evaluated using method same as Example 1.It will As a result it is shown in table 2.
&#91;Comparative example 1&#93;
The manufacture > of < protective film formation composite sheets
(protective film forms the preparation with composition (IV-1))
As shown in table 1, in addition to 20 mass parts of content (blended amount) of energy ray-curable ingredient (a2) -1 are changed to 2 76 mass parts of content (blended amount) of packing material (d) -1 are changed to other than 56 mass parts by mass parts, using with embodiment 1 Identical method is prepared for protective film formation composition (IV-1).
(manufacture of protective film formation composite sheet)
Other than using protective film formation composition (IV-1) this point obtained above, using with 1 phase of embodiment Same method, has made the protective film formation film (13) -3 of the energy ray-curable of 25 μm of thickness.
In addition, in addition to use the protective film formation film (13) -3 replace (13) -1 this point of protective film formation film with Outside, using method same as Example 1, protective film formation composite sheet shown in fig. 6 has been manufactured.The protective film shape that will be obtained It is shown in table 2 at the composition of composite sheet.
The evaluation > of < protective film formation composite sheets
For protective film formation composite sheet obtained above, evaluated using method same as Example 1.It will As a result it is shown in table 2.
&#91;Comparative example 2&#93;
The manufacture > of < protective film formation pieces
(protective film forms the preparation with composition (IV-1))
The protective film formation composition (IV-1) obtained in comparative example 1 is used.
(manufacture of protective film formation piece)
Other than using protective film formation composition (IV-1) this point obtained in comparative example 1, using with implementation 1 identical method of example has made the protective film formation film (13) -3 of the energy ray-curable of 25 μm of thickness.
Then, protective film formation obtained above is fitted in through silicone-treated with the exposed surface of film (13) -3 to poly- pair The single side of ethylene terephthalate film carried out lift-off processing stripping film 2 (Lintec Corporation. manufacture " PET382150 ", 38 μm of thickness) the lift-off processing face on, made stripping film 1, protective film formation film (13) -3 and Stripping film 2 along their thickness direction stack gradually made of protective film formation piece.By obtained protective film formation piece Composition is shown in table 2.
The evaluation > of < protective film formation pieces
For protective film formation piece obtained above, evaluated using method same as Example 2.By result It is shown in table 2.
&#91;Table 1&#93;
&#91;Table 2&#93;
According to the above results it is found that using Examples 1 to 3 protective film formation composite sheet or protective film formation piece When, the tensile modulus of elasticity of protective film formation film can inhibit the blocking of blade, do not observe in the range of 30MPa or more Other unfavorable conditions, cutting adaptive are excellent.
When in contrast, using the protective film formation composite sheet of Comparative Examples 1 and 2 or protective film formation piece, protective film shape At in the range of less than 30MPa, the tensile modulus of elasticity is small with the tensile modulus of elasticity of film, knife can not be inhibited in cutting The blocking of piece, cutting adaptive are poor.It is presumably due to be formed using the protective film formation composite sheet or protective film of Comparative Examples 1 and 2 and use When piece, the tensile modulus of elasticity of protective film formation film is low, therefore in cutting because the chip of protective film formation film results in Blade blocks.
Industrial applicibility
The present invention can be used for the manufacture of semiconductor device.
Reference sign
1A,1B,1C,1D,1E:Protective film formation composite sheet;10:Support chip;10a:The surface of support chip;11:Base material; 11a:The surface of base material;12:Adhering agent layer;12a:The surface of adhering agent layer;13,23:Protective film formation film;13a,23a:It protects The surface of cuticula formation film;13b:With the surface for the protective film formation film that 13a is opposite side;15:Stripping film;16:Fixture Use adhesive phase;16a:The surface of fixture adhesive phase;100:Protective film formation piece.

Claims (4)

1. a kind of protective film formation film is the protective film formation film of energy ray-curable,
The tensile modulus of elasticity of the protective film formation film is 30MPa or more.
2. a kind of protective film formation composite sheet forms use by having protective film described in claim 1 on support chip Film forms.
3. protective film formation composite sheet according to claim 2, wherein the support chip has adhering agent layer, described Protective film formation is in direct contact with film and the adhering agent layer.
4. protective film formation composite sheet according to claim 3, wherein the adhering agent layer is non-energy actinic radiation-curable Property.
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