WO2021235389A1

WO2021235389A1 - Adhesive laminated film and method for manufacturing electronic device

Info

Publication number: WO2021235389A1
Application number: PCT/JP2021/018599
Authority: WO
Inventors: 崇畦▲崎▼; 喬士甲斐; 貴信室伏; 仁木下
Original assignee: 三井化学東セロ株式会社
Priority date: 2020-05-22
Filing date: 2021-05-17
Publication date: 2021-11-25
Also published as: TW202144519A; JP7464706B2; KR20220152328A; JPWO2021235389A1; CN115605556B; CN115605556A

Abstract

Provided is an adhesive laminated film (50) used to protect circuit-forming surfaces of electronic components, the adhesive laminated film (50) comprising a base layer (20), a concave-convex absorbent resin layer (30), and an adhesive resin layer (40) in this order, wherein the concave-convex absorbent resin layer (30) contains an ethylene-based copolymer having a melting point of 40-80°C and a crosslinking agent, and the content of the crosslinking agent in the concave-convex absorbent resin layer (30) is 0.06-0.60 parts by mass with respect to 100 parts by mass of the ethylene-based copolymer.

Description

Manufacturing method of adhesive laminated film and electronic device

The present invention relates to a method for manufacturing an adhesive laminated film and an electronic device.

In the manufacturing process of an electronic device (for example, a semiconductor device), a thermosetting protective film is attached to the non-circuit forming surface (back surface) of the electronic component (for example, a semiconductor wafer) from the viewpoint of protecting the non-circuit forming surface (back surface). The process of attaching may be performed.
Examples of the technique relating to such a thermosetting protective film include those described in Patent Document 1 (Japanese Unexamined Patent Publication No. 2017-1188).

Patent Document 1 describes a protective film for a semiconductor including a protective layer made of a non-conductive inorganic material and an adhesive layer provided on one surface of the protective layer.

Japanese Unexamined Patent Publication No. 2017-1188

As a recent trend, the thickness of electronic components is becoming thinner. According to the study by the present inventors, as the thickness of the electronic component becomes thinner, the thermosetting protective film is attached to the non-circuit-forming surface of the electronic component in the conventional manufacturing method of the electronic component, and then the protective film is applied. It has become clear that electronic components tend to warp during thermosetting and after the backgrinding process. In particular, when the sealing resin and the semiconductor are integrated like a wafer level CSP and the thickness of the sealing resin is relatively thick, warpage tends to occur easily. If the electronic component is warped, it becomes difficult to handle the electronic component or the electrode may be cracked.

The present invention has been made in view of the above circumstances, and provides a method for manufacturing an adhesive laminated film and an electronic device capable of suppressing warpage of an electronic component and suppressing contamination of the electronic component and peripheral devices. It is something to do.

The present inventors have made extensive studies in order to achieve the above-mentioned problems. As a result, as a surface protective film for protecting the circuit forming surface of the electronic component, an uneven absorption resin layer containing a base material layer, an ethylene-based copolymer having a melting point in a specific range, and a cross-linking agent, and adhesion. By using an adhesive laminated film having a sex resin layer in this order and having a cross-linking agent content in a specific range, warpage of the electronic component is suppressed, and electronic components and peripheral devices associated with the adhesive film are used. The present invention has been completed by finding that the contamination of the adhesive (particularly the exudation of the resin constituting the adhesive laminated film) can be suppressed.

According to the present invention, the following methods for manufacturing an adhesive laminated film and an electronic device are provided.

[1]
An adhesive laminated film provided with a base material layer, a concave-convex absorbent resin layer, and an adhesive resin layer in this order, and used to protect a circuit-forming surface of an electronic component.
The uneven absorbing resin layer contains an ethylene-based copolymer having a melting point of 40 ° C. or higher and 80 ° C. or lower, and a cross-linking agent.
An adhesive laminated film in which the content of the cross-linking agent in the uneven absorbing resin layer is 0.06 parts by mass or more and 0.60 parts by mass or less with respect to 100 parts by mass of the ethylene-based copolymer.
[2]
In the adhesive laminated film according to the above [1],
An adhesive laminated film containing at least one of the above ethylene-based copolymers selected from the group consisting of ethylene / α-olefin copolymers and ethylene / vinyl ester copolymers.
[3]
In the adhesive laminated film according to the above [2],
An adhesive laminated film in which the above ethylene / vinyl ester copolymer contains an ethylene / vinyl acetate copolymer.
[4]
In the adhesive laminated film according to any one of the above [1] to [3],
A pressure-sensitive laminated film containing at least one of the cross-linking agents selected from the group consisting of photo-crosslinking initiators and organic peroxides.
[5]
In the adhesive laminated film according to any one of the above [1] to [4],
Adhesive laminated film that is a back grind tape.
[6]
In the adhesive laminated film according to any one of the above [1] to [5],
An adhesive laminated film in which the uneven absorbent resin layer further contains a cross-linking aid.
[7]
In the adhesive laminated film according to the above [6],
An adhesive laminated film containing one or more selected from the group consisting of a divinyl aromatic compound, a cyanurate compound, a diallyl compound, an acrylate compound, a triallyl compound, an oxime compound and a maleimide compound.
[8]
In the adhesive laminated film according to any one of the above [1] to [7],
An adhesive laminated film containing one or more selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, and polyimide as the resin constituting the base material layer.
[9]
In the adhesive laminated film according to any one of the above [1] to [7],
An adhesive laminated film in which the resin constituting the base material layer contains polyethylene naphthalate.
[10]
In the adhesive laminated film according to any one of the above [1] to [9],
An adhesive laminated film having a thickness of 10 μm or more and 1000 μm or less of the uneven absorbent resin layer.
[11]
In the adhesive laminated film according to any one of the above [1] to [10],
Adhesives constituting the adhesive resin layer include one or more selected from (meth) acrylic adhesives, silicone adhesives, urethane adhesives, olefin adhesives and styrene adhesives. Sex laminated film.
[12]
An electronic component having a circuit forming surface, an adhesive laminated film attached to the circuit forming surface side of the electronic component, and heat curing attached to a surface of the electronic component opposite to the circuit forming surface. Sex protection film and
Preparation step (A) for preparing a structure comprising
The thermosetting step (B) of thermosetting the thermosetting protective film by heating the structure, and
The method for manufacturing an electronic device according to the above, wherein the adhesive laminated film is the adhesive laminated film according to any one of the above [1] to [11].
[13]
In the method for manufacturing an electronic device according to the above [12],
The above preparation step (A) is
A curing step of thermosetting or ultraviolet curing the unevenness-absorbing resin layer in the adhesive laminated film with the adhesive laminated film attached to the circuit forming surface of the electronic component.
The process of attaching the thermosetting protective film to the surface of the electronic component opposite to the circuit forming surface, and
A method of manufacturing an electronic device including.
[14]
In the method for manufacturing an electronic device according to the above [13],
A method for manufacturing an electronic device in which the heating temperature in the step of attaching the thermosetting protective film to the surface of the electronic component opposite to the circuit forming surface is 50 ° C. or higher and 90 ° C. or lower.
[15]
In the method for manufacturing an electronic device according to the above [13] or [14].
In the preparation step (A), before the curing step, the adhesive laminated film is attached to the circuit forming surface of the electronic component, and the side of the electronic component is opposite to the circuit forming surface. A method of manufacturing an electronic device that includes a backgrinding process for backgrinding a surface.
[16]
In the method for manufacturing an electronic device according to any one of the above [12] to [15].
A method for manufacturing an electronic device in which the heating temperature in the thermosetting step (B) is 120 ° C. or higher and 170 ° C. or lower.
[17]
In the method for manufacturing an electronic device according to any one of the above [12] to [16].
The circuit forming surface of the electronic component is a method for manufacturing an electronic device including a bump electrode.
[18]
In the method for manufacturing an electronic device according to the above [17],
A method for manufacturing an electronic device in which H / d is 0.01 or more and 1 or less when the height of the bump electrode is H [μm] and the thickness of the uneven absorbing resin layer is d [μm].

According to the present invention, it is possible to provide a method for manufacturing an adhesive laminated film and an electronic device capable of suppressing the warpage of an electronic component and suppressing contamination of the electronic component and peripheral devices.

It is sectional drawing which shows typically the example of the adhesive laminated film of embodiment which concerns on this invention. It is sectional drawing which shows typically an example of the manufacturing method of the electronic apparatus of embodiment which concerns on this invention.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, similar components are designated by a common reference numeral, and the description thereof will be omitted as appropriate. Further, the figure is a schematic view and does not match the actual dimensional ratio. Further, "A to B" in the numerical range represent A or more and B or less unless otherwise specified. Further, in the present embodiment, "(meth) acrylic" means acrylic, methacryl or both acrylic and methacrylic.

1. 1. Adhesive Laminated Film FIG. 1 is a cross-sectional view schematically showing an example of the adhesive laminated film 50 according to the embodiment of the present invention.
The adhesive laminated film 50 according to the present embodiment includes a base material layer 20, an unevenness absorbing resin layer 30, and an adhesive resin layer 40 in this order, in order to protect the circuit forming surface of the electronic component. In the adhesive laminated film 50 used, the unevenness-absorbing resin layer 30 contains an ethylene-based copolymer having a melting point of 40 ° C. or higher and 80 ° C. or lower, and a cross-linking agent, and is contained in the unevenness-absorbing resin layer 30. The content of the cross-linking agent is 0.06 parts by mass or more and 0.60 parts by mass or less with respect to 100 parts by mass of the ethylene-based copolymer.
The melting point of the ethylene-based copolymer is measured by a differential scanning calorimeter (DSC).

As described above, according to the study by the present inventors, as the thickness of the electronic component becomes thinner, the thermosetting protective film is attached to the non-circuit forming surface of the electronic component in the conventional manufacturing method of the electronic device. Later, it became clear that the electronic components tend to be warped when the protective film is thermoset or after the backgrinding process. In particular, when the resin and the semiconductor are integrated like a wafer level CSP and the thickness of the resin is relatively thick, warpage tends to occur easily. If the electronic component is warped, it becomes difficult to handle the electronic component or the electrode may be cracked.
The present inventors have made extensive studies to achieve the above-mentioned problems. As a result, as a surface protective film for protecting the circuit-forming surface of the electronic component, the substrate layer 20, the ethylene-based copolymer having a melting point of 40 ° C. or higher and 80 ° C. or lower, and a cross-linking agent are contained as an uneven absorption property. By using the adhesive laminated film 50 having the resin layer 30 and the adhesive resin layer 40 in this order and having the content of the cross-linking agent in the above range, the adhesive film can be formed while suppressing the warp of the electronic parts. It has been found that the accompanying contamination of electronic parts and peripheral devices (particularly the exudation of the resin constituting the adhesive laminated film) can be suppressed.
As described above, according to the adhesive laminated film 50 according to the present embodiment, it is possible to suppress the warp of electronic components.

The adhesive laminated film 50 according to the present embodiment is used for protecting the surface of an electronic component and fixing the electronic component in the manufacturing process of the electronic device, and more specifically, in the manufacturing process of the electronic device. It is suitably used as a back grind tape used for protecting a circuit forming surface (that is, a circuit surface including a circuit pattern) of an electronic component in a process of grinding an electronic component (also referred to as a back grind process), which is one of the above. Specifically, it is used in a step of attaching an adhesive laminated film 50 to a circuit forming surface of an electronic component to protect it and grinding a surface opposite to the circuit forming surface. When the bump electrode is provided on the circuit forming surface, the adhesive laminated film 50 according to the present embodiment provided with the unevenness absorbing resin layer 30 can be suitably applied.
Further, the adhesive laminated film 50 according to the present embodiment is an adhesive film used for protecting or holding electronic components (for example, semiconductor wafers, encapsulating wafers, etc.) having surface irregularities in, for example, a dicing step or a transfer step. Adhesive film for temporarily fixing electronic components with surface irregularities (eg, semiconductor chips, semiconductor packages, etc.); Dry polish of electronic components (eg, semiconductor wafers, etc.), electronic components (eg, semiconductor wafers, etc.) Heating at 90 ° C or higher, such as attaching / curing a back surface protective member, forming an electromagnetic wave shielding film on an electronic component (for example, a semiconductor package, etc.), forming a metal film on the back surface of an electronic component (for example, a semiconductor wafer, etc.), etc. It can also be used as an adhesive film used in the process.

<Base layer>
The base material layer 20 is a layer provided for the purpose of improving the handleability, mechanical properties, heat resistance, and other properties of the adhesive laminated film 50.
The base material layer 20 is not particularly limited, and examples thereof include a resin film.
Examples of the resin constituting the base material layer 20 include one or more selected from polyethylene terephthalate, polyethylene naphthalate, polyimide and the like.
Among these, at least one selected from polyethylene naphthalate and polyimide is preferable, and polyethylene naphthalate is more preferable, from the viewpoint of further improving heat resistance.

The base material layer 20 may be a single layer or two or more types of layers.
Further, the form of the resin film used for forming the base material layer 20 may be a stretched film or a film stretched in a uniaxial direction or a biaxial direction.

The thickness of the base material layer 20 is preferably 10 μm or more and 500 μm or less, more preferably 20 μm or more and 200 μm or less, and further preferably 25 μm or more and 100 m or less from the viewpoint of obtaining good film characteristics.
The base material layer 20 may be surface-treated in order to improve the adhesiveness with other layers. Specifically, corona treatment, plasma treatment, undercoat treatment, primer coating treatment and the like may be performed.

<Concave and convex absorbent resin layer>
The adhesive laminated film 50 according to the present embodiment has a concave-convex absorbent resin layer 30 between the base material layer 20 and the adhesive resin layer 40.
The unevenness-absorbing resin layer 30 is provided for the purpose of improving the followability of the adhesive laminated film 50 to the circuit forming surface 10A and improving the adhesion between the circuit forming surface 10A and the adhesive laminated film 50. It is a layer. Further, the unevenness absorbing resin layer 30 is a layer provided for the purpose of increasing the heat resistance of the adhesive laminated film 50 by being heat-cured or ultraviolet-cured. As a result, in the step (A2) of attaching the thermosetting protective film 70 to the surface 10C opposite to the circuit forming surface 10A of the electronic component 10 and the thermosetting step (B) of thermosetting the thermosetting protective film 70. Warpage of electronic components can be suppressed. Further, in the step (A2) of attaching the thermosetting protective film 70 to the surface 10C opposite to the circuit forming surface 10A of the electronic component 10 and the thermosetting step (B) of thermosetting the thermosetting protective film 70, unevenness is formed. It is possible to prevent the absorbent resin layer 30 from melting and exuding the resin.

The uneven absorption resin layer 30 contains an ethylene-based copolymer.
As the ethylene-based copolymer according to the present embodiment, at least one selected from the group consisting of an ethylene / α-olefin copolymer and an ethylene / vinyl ester copolymer can be used.

The ethylene / α-olefin copolymer according to the present embodiment is, for example, a copolymer obtained by copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms.
As the α-olefin, for example, one type of α-olefin having 3 to 20 carbon atoms can be used alone or two or more types can be used in combination. Of these, α-olefins having 10 or less carbon atoms are preferable, and α-olefins having 3 to 8 carbon atoms are particularly preferable. Specific examples of such α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, and 4-methyl-1-. Penten, 1-octene, 1-decene, 1-dodecene and the like can be mentioned. Of these, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene and 1-octene are preferable because of their availability. The ethylene / α-olefin copolymer may be a random copolymer or a block copolymer, but a random copolymer is preferable from the viewpoint of flexibility.

Here, examples of the ethylene / α-olefin copolymer include Tuffmer (registered trademark) manufactured by Mitsui Chemicals, ENGAGE (registered trademark) manufactured by DOW, EXACT (registered trademark) manufactured by ExxonMobil, and Japan Polyethylene. A company-made kernel (registered trademark) and the like can be mentioned.

The density of the ethylene / α-olefin copolymer measured according to ASTM D1505 is preferably 850 to 900 kg / m ³ , more preferably 850 to 880 kg / m ³ , still more preferably 850 to 870 kg / m ³ . be.
When the density is equal to or higher than the above lower limit, handling troubles such as blocking can be avoided. Further, when the density is not more than the above upper limit value, the unevenness absorbing resin layer 30 having excellent unevenness absorbing property can be obtained.
The melt flow rate (MFR) of the ethylene / α-olefin copolymer measured at 190 ° C. and a load of 2.16 kg according to ASTM D1238 is preferably 0.1 to 50 g / 10 minutes. , More preferably 1 to 40 g / 10 minutes, still more preferably 3 to 35 g / 10 minutes.
When the MFR is at least the above lower limit value, the fluidity of the ethylene / α-olefin copolymer is improved, and the processability of the uneven absorbing resin layer 30 can be further improved.
Further, when the MFR is not more than the above upper limit value, the unevenness-absorbing resin layer 30 having a more uniform thickness can be obtained, and the exudation of the resin caused by the unevenness-absorbing resin layer during the heating step can be suppressed.

Examples of the ethylene / vinyl ester copolymer according to the present embodiment include an ethylene / vinyl acetate copolymer, an ethylene / vinyl acetate copolymer, an ethylene / vinyl butyrate copolymer, and an ethylene / vinyl stearate copolymer. It is preferable to contain one or more kinds selected from the above, and it is more preferable to contain an ethylene / vinyl acetate copolymer.

The ethylene-vinyl acetate copolymer is a copolymer of ethylene and vinyl acetate, and is, for example, a random copolymer.
The content ratio of the structural unit derived from vinyl acetate in the ethylene-vinyl acetate copolymer is preferably 15% by mass or more and 50% by mass or less, more preferably 20% by mass or more and 45% by mass or less, and further preferably 25% by mass. % Or more and 40% by mass or less. When the content of vinyl acetate is in this range, the balance of flexibility, heat resistance, transparency, and mechanical properties of the uneven absorbing resin layer 30 is further improved. Further, when the unevenness-absorbing resin layer 30 is formed, the film forming property is improved.
The vinyl acetate content can be measured according to JIS K7192: 1999.

The ethylene / vinyl acetate copolymer is preferably a binary copolymer composed of only ethylene and vinyl acetate, but in addition to ethylene and vinyl acetate, for example, vinyl formate, vinyl glycolate, vinyl propionate, vinyl benzoate, etc. Vinyl ester-based monomers such as; acrylic acid, methacrylic acid, etacrilic acid, or acrylic monoweights such as salts thereof or alkyl esters; etc .; one or more selected from the above may be contained as a copolymerization component. .. When the copolymer component other than ethylene and vinyl acetate is contained, the amount of the copolymer component other than ethylene and vinyl acetate in the ethylene / vinyl acetate copolymer may be 0.5% by mass or more and 5% by mass or less. preferable.

The melt flow rate (MFR) of the ethylene-vinyl ester copolymer measured at 190 ° C. and a 2.16 kg load according to JIS K7210: 1999 is preferably 0.1 to 50 g / 10 minutes. Yes, more preferably 1 to 40 g / 10 minutes, still more preferably 3 to 35 g / 10 minutes.
When the MFR is at least the above lower limit value, the fluidity of the ethylene / vinyl ester copolymer is improved, and the molding processability of the uneven absorbing resin layer 30 can be further improved.
Further, when the MFR is not more than the above upper limit value, the molecular weight becomes high, so that the chill roll or the like is less likely to adhere to the roll surface, and the uneven absorption resin layer 30 having a more uniform thickness can be obtained. Occasionally, it is possible to suppress the exudation of the resin due to the uneven absorption resin layer.

The unevenness-absorbing resin layer 30 can be obtained, for example, by dry-blending or melt-kneading each component and then extrusion-molding. Further, if necessary, an antioxidant can be added.

The total content of the ethylene-based copolymer and the cross-linking agent contained in the uneven-absorbing resin layer 30 is preferably 60% by mass or more, more preferably 70, when the entire uneven-absorbing resin layer 30 is 100% by mass. It is by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and particularly preferably 95% by mass or more.

The melting point of the ethylene-based copolymer is 40 ° C. or higher, preferably 45 ° C. or higher, more preferably 50 ° C. or higher, still more preferably 54 ° C. or higher.
When the melting point of the ethylene-based copolymer is at least the above lower limit value, it is possible to suppress the shape change when the adhesive laminated film 50 is transported and stored. Further, when the melting point of the ethylene-based copolymer is at least the above lower limit value, the shape change of the adhesive laminated film 50 in the back grind step can be suppressed, and the back grind of the electronic component can be further promoted. Further, when the melting point of the ethylene-based copolymer is at least the above lower limit value, the processing temperature of the uneven absorbing resin layer 30 can be raised.

The melting point of the ethylene-based copolymer is 80 ° C. or lower, preferably 75 ° C. or lower, more preferably 70 ° C. or lower, still more preferably 65 ° C. or lower.
When the melting point of the ethylene-based copolymer is not more than the above upper limit value, the temperature at which the adhesive laminated film 50 is attached to the electronic component can be lowered. Further, when the melting point of the ethylene-based copolymer is not more than the above upper limit value, the compatibility of the additive with the ethylene-based copolymer can be improved, and as a result, the bleed of the additive contained in the uneven absorbing resin layer 30. Out can be suppressed. Further, when the melting point of the ethylene-based copolymer is not more than the above upper limit value, the handling property of the adhesive laminated film 50 and the stress relaxation property of the adhesive laminated film 50 when the thickness of the adhesive laminated film 50 is increased are improved. Can be improved

When two or more components of an ethylene-based copolymer are contained, two or more melting points may be observed, but at least one melting point may be within the above range. It is preferable that the two or more melting points are all in the above range.

Further, the uneven absorbing resin layer 30 contains a cross-linking agent. Since the unevenness-absorbing resin layer 30 contains a cross-linking agent, the unevenness-absorbing resin layer 30 can be effectively heat-cured or ultraviolet-cured before the step (B), and the heat resistance of the unevenness-absorbing resin layer 30 can be obtained. Can be improved. As a result, in the step (A2) of attaching the thermosetting protective film 70 to the surface 10C opposite to the circuit forming surface 10A of the electronic component 10 and the thermosetting step (B) of thermosetting the thermosetting protective film 70. Warpage of electronic components can be further suppressed. Further, in the step (A2) of attaching the thermosetting protective film 70 to the surface 10C opposite to the circuit forming surface 10A of the electronic component 10 and the thermosetting step (B) of thermosetting the thermosetting protective film 70, unevenness is formed. It is possible to further suppress the melting of the absorbent resin layer 30 and the exudation of the resin.
The cross-linking agent according to the present embodiment is not particularly limited, and for example, at least one selected from the group consisting of a photo-crosslinking initiator and an organic peroxide can be used.
The content of the cross-linking agent in the uneven absorbing resin layer 30 is 0.60 parts by mass or less and 0.55 parts by mass or less with respect to 100 parts by mass of the ethylene-based copolymer from the viewpoint of suppressing warpage. It is preferably 0.50 part by mass or less, and more preferably 0.50 part by mass or less.
Further, the content of the cross-linking agent in the uneven absorbing resin layer 30 is 0.06 part by mass or more with respect to 100 parts by mass of the ethylene-based copolymer from the viewpoint of preventing the resin from seeping out during heating. It is preferably 0.07 parts by mass or more, and more preferably 0.08 parts by mass or more.

Examples of the organic peroxide include dilauroyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, dibenzoyl peroxide, cyclohexanone peroxide, and di-t-butylper. Phtalate, cumene hydroperoxide, t-butyl hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexene, 2,5-dimethyl-2,5-di (t-butylper) Oxy) hexane, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleic acid, 1,1 -Di (t-amylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-amylperoxy) cyclohexane, t-amylperoxyisononanoate, t-amylperoxynormal octate , 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-butylperoxy) cyclohexane, t-butylperoxyisopropylcarbonate, t-butylperoxy -2-Ethylhexyl carbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-amylperoxybenzoate, t-butylperoxyacetate, t-butylperoxyisononanoate, t-butyl Peroxybenzoate, 2,2-di (butylperoxy) butane, n-butyl-4,4-di (t-butylperoxy) petitlate, methylethylketone peroxide, ethyl-3,3-di (t-butyl) Peroxy) Butylate, Dicumyl peroxide, t-butylcumyl peroxide, t-butyl peroxybenzoate, di-t-butyl peroxide, 1,1,3,3-tetramethylbutylhydroperoxide, acetylacetone peroxide One or more selected from the above can be used.

Among these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylperoxy- It is preferable to use one or more selected from 2-ethylhexyl carbonate and t-butylperoxybenzoate.

Examples of the photocrosslinking initiator include benzophenone, benzophenone derivative, thioxanthone, thioxanthone derivative, benzoin, benzoin derivative, α-hydroxyalkylphenone, α-aminoalkylphenol, acylphosphinoxide, and alkylphenylgluoxylate. , Diethoxyacetophenone, oxime esters, titanosen compounds, anthraquinone derivatives, one or more selected from the group. Among them, benzophenone, benzophenone derivative, benzoin, benzoin derivative, α-hydroxyalkylphenone, oxime ester and anthraquinone derivative are preferable in that crosslinkability is better, and benzophenone, benzophenone derivative and anthraquinone derivative are more preferable, benzophenone, Benzophenone derivatives are most preferred because they also have good transparency.
Preferred examples of benzophenones and benzophenone derivatives are benzophenone, 4-phenylbenzophenone, 4-phenoxybenzophenone, 4,4-bis (diethylamino) benzophenone, methyl o-benzoylbenzoate, 4-methylbenzophenone, 2,4,6-trimethyl. Benzophenone and the like can be mentioned.
Preferred examples of the anthraquinone derivative include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butyl anthraquinone, 1-chloroanthraquinone and the like.

Further, the uneven absorbing resin layer 30 preferably further contains a crosslinking aid from the viewpoint of further improving heat resistance.
As the cross-linking aid, for example, one or more selected from the group consisting of divinyl aromatic compounds, cyanurate compounds, diallyl compounds, acrylate compounds, triallyl compounds, oxime compounds and maleimide compounds can be used.
The content of the cross-linking aid in the uneven absorbing resin layer 30 is preferably 5.0 parts by mass or less, and preferably 2.0 parts by mass or less, based on 100 parts by mass of the ethylene-based copolymer. It is more preferably 1.0 part by mass or less, and particularly preferably 1.0 part by mass or less.
The content of the cross-linking aid in the uneven absorbing resin layer 30 is preferably 0.01 part by mass or more, and 0.05 part by mass or more with respect to 100 parts by mass of the ethylene-based copolymer. More preferably, it is more preferably 0.10 part by mass or more.

Examples of the divinyl aromatic compound include divinylbenzene and di-i-propenylbenzene.
Examples of the cyanurate compound include triallyl cyanurate, triallyl isocyanurate and the like.
Examples of the diallyl compound include diallyl phthalate and the like.
Examples of the triallyl compound include pentaerythritol triallyl ether and the like.
Examples of the acrylate compound include diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and tetramethylolmethane. Examples thereof include tetra (meth) acrylate and tetramethylolmethane tetra (meth) acrylate.
Examples of the oxime compound include p-quinone dioxime and pp'-dibenzoyl quinone dioxime.
Examples of the maleimide compound include m-phenylenedi maleimide and the like.
As the cross-linking aid, a compound having a cross-linking unsaturated bond such as a vinyl group having a trifunctional or higher function in one molecule is preferable, and among them, triallyl cyanurate, triallyl isocyanurate, trimethylolpropane tri (meth) acrylate, and dimethylolpropane. Propanetetra (meth) acrylate is preferable because of its good crosslinkability, and trimethylolcyanolate and trimethylolisocyanurate are particularly preferable.

The thickness of the unevenness-absorbing resin layer 30 is not particularly limited as long as it can embed the unevenness of the circuit forming surface 10A of the electronic component 10, but is preferably 10 μm or more and 1000 μm or less, preferably 20 μm. It is more preferably 900 μm or less, further preferably 30 μm or more and 800 μm or less, and particularly preferably 50 μm or more and 700 μm or less.

When the height of the bump electrode existing on the circuit forming surface 10A of the electronic component 10 is H [μm] and the thickness of the uneven absorbing resin layer 30 is d [μm], H / d is 1 or less. It is preferably 0.85 or less, more preferably 0.7 or less. When H / d is not more than the above upper limit value, the thickness of the adhesive laminated film 50 can be made thinner and the unevenness absorption can be made better.
The lower limit of H / d is not particularly limited, but is, for example, 0.01 or more. The height of the bump electrode is generally 2 μm or more and 600 μm or less.

<Adhesive resin layer>
The adhesive resin layer 40 is a layer provided on one surface side of the unevenness absorbing resin layer 30, and is a circuit of the electronic component 10 when the adhesive laminated film 50 is attached to the circuit forming surface 10A of the electronic component 10. It is a layer that comes into contact with and adheres to the forming surface 10A.

Examples of the adhesive constituting the adhesive resin layer 40 include (meth) acrylic adhesive, silicone adhesive, urethane adhesive, olefin adhesive, styrene adhesive and the like. Among these, a (meth) acrylic pressure-sensitive adhesive using a (meth) acrylic polymer as a base polymer is preferable because the adhesive strength can be easily adjusted.

Further, as the pressure-sensitive adhesive constituting the pressure-sensitive adhesive resin layer 40, a radiation cross-linking type pressure-sensitive adhesive whose adhesive strength is reduced by radiation can also be used. Since the adhesive resin layer 40 composed of the radiation-crosslinked adhesive is crosslinked by irradiation with radiation and the adhesive strength is significantly reduced, the step (C) of peeling the electronic component 10 and the adhesive laminated film 50 described later from each other. In, the electronic component 10 can be easily peeled off from the adhesive resin layer 40. Examples of radiation include ultraviolet rays, electron beams, and infrared rays.
As the radiation cross-linking type pressure-sensitive adhesive, an ultraviolet cross-linking type pressure-sensitive adhesive is preferable.

Examples of the (meth) acrylic polymer contained in the (meth) acrylic pressure-sensitive adhesive include a homopolymer of a (meth) acrylic acid ester compound, a copolymer of a (meth) acrylic acid ester compound and a comonomer, and the like. Can be mentioned. Examples of the (meth) acrylic acid ester compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, and hydroxypropyl (meth). Examples thereof include acrylate, dimethylaminoethyl (meth) acrylate, and glycidyl (meth) acrylate. These (meth) acrylic acid ester compounds may be used alone or in combination of two or more.
Examples of the comonomer constituting the (meth) acrylic copolymer include vinyl acetate, (meth) acrylonitrile, styrene, (meth) acrylic acid, itaconic acid, (meth) acrylic amide, and methylol (meth) acrylic. Examples thereof include acrylamide and maleic anhydride. These comonomer may be used alone or in combination of two or more.

The radiation cross-linking type pressure-sensitive adhesive contains, for example, the above-mentioned (meth) acrylic polymer, a cross-linking compound (a component having a carbon-carbon double bond), and a photopolymerization initiator or a thermal polymerization initiator.

Examples of the crosslinkable compound include a monomer, oligomer or polymer having a carbon-carbon double bond in the molecule and which can be crosslinked by radical polymerization. Examples of such crosslinkable compounds include trimethylolpropanetri (meth) acrylate, pentaerythritol tri (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and neo. Esters of (meth) acrylic acids and polyhydric alcohols such as pentylglycol di (meth) acrylates, dipentaerythritol hexa (meth) acrylates, ditrimethylolpropanetetra (meth) acrylates; ester (meth) acrylate oligomers; 2-propenyldi Examples thereof include isocyanurates such as -3-butenyl cyanurate, 2-hydroxyethylbis (2- (meth) acryloxyethyl) isocyanurate, tris (2-methacryloxyethyl) isocyanurate, and isocyanurate compounds.
When the (meth) acrylic polymer is a radiation-crosslinkable polymer having a carbon-carbon double bond in the side chain of the polymer, it is not necessary to add the crosslinkable compound.

The content of the crosslinkable compound is preferably 1 to 900 parts by mass, more preferably 2 to 100 parts by mass, still more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer. When the content of the crosslinkable compound is in the above range, the adhesive strength can be easily adjusted as compared with the case where the content is less than the above range, and the sensitivity to heat and light is too high as compared with the case where the content is more than the above range. As a result, the storage stability is unlikely to deteriorate.

The photopolymerization initiator may be any compound that cleaves to generate a radical by irradiation with radiation, and is, for example, benzoin alkyl ethers such as benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzyl, benzoin, and benzophenone. , Α-Hydroxycyclohexylphenyl ketone and other aromatic ketones; benzyldimethyl ketal and other aromatic ketals; polyvinylbenzophenone; chlorothioxanthone, dodecylthioxanthone, dimethylthioxanthone, diethylthioxanthone and the like and the like.

Examples of the thermal polymerization initiator include organic peroxide derivatives and azo-based polymerization initiators. It is preferably an organic peroxide derivative because it does not generate nitrogen during heating. Examples of the thermal polymerization initiator include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates and the like.

A cross-linking agent may be added to the pressure-sensitive adhesive. Examples of the cross-linking agent include epoxy compounds such as sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaeristol polyglycidyl ether, and diglycerol polyglycidyl ether; tetramethylolmethane-tri-β-aziridinyl propionate. , Trimethylolpropane-tri-β-aziridinyl propionate, N, N'-diphenylmethane-4,4'-bis (1-aziridinecarboxyamide), N, N'-hexamethylene-1,6-bis Examples thereof include aziridin-based compounds such as (1-aziridine carboxylamide); isocyanate-based compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, and polyisocyanate.
The content of the cross-linking agent is 0.1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the (meth) acrylic polymer from the viewpoint of improving the balance between the heat resistance and the adhesive force of the adhesive resin layer 40. Is preferable.

The thickness of the adhesive resin layer 40 is not particularly limited, but is preferably 1 μm or more and 100 μm or less, and more preferably 3 μm or more and 50 μm or less.

The adhesive resin layer 40 can be formed, for example, by applying a pressure-sensitive adhesive coating liquid on the unevenness-absorbing resin layer 30.
As a method for applying the pressure-sensitive adhesive coating liquid, conventionally known coating methods, for example, a roll coater method, a reverse roll coater method, a gravure roll method, a bar coat method, a comma coater method, a die coater method and the like can be adopted. The drying conditions of the applied pressure-sensitive adhesive are not particularly limited, but it is generally preferable to dry the applied pressure-sensitive adhesive in a temperature range of 80 to 200 ° C. for 10 seconds to 10 minutes. More preferably, it is dried at 80 to 170 ° C. for 15 seconds to 5 minutes. In order to sufficiently promote the cross-linking reaction between the cross-linking agent and the pressure-sensitive adhesive, the pressure-sensitive adhesive coating liquid may be heated at 40 to 80 ° C. for about 5 to 300 hours after the drying is completed.

In the adhesive laminated film 50 according to the present embodiment, when the unevenness-absorbing resin layer 30 is ultraviolet-cured or the adhesive resin layer 40 is ultraviolet-crosslinked, the curing or crosslinking hinders the object of the present invention. It is necessary to have a light transmittance to some extent.

The thickness of the entire adhesive laminated film 50 according to the present embodiment is preferably 25 μm or more and 1100 μm or less, more preferably 100 μm or more and 900 μm or less, and further preferably 200 μm or more, from the viewpoint of the balance between mechanical properties and handleability. It is 800 μm or less.

The adhesive laminated film 50 according to the present embodiment may be provided with an adhesive layer (not shown) between the layers. According to this adhesive layer, the adhesiveness between the layers can be improved.

Next, an example of a method for manufacturing the adhesive laminated film 50 according to the present embodiment will be described.
First, the unevenness-absorbing resin layer 30 is extruded and laminated on one surface of the base material layer 20 by a laminating method. Next, the adhesive resin coating liquid is applied onto the unevenness-absorbing resin layer 30 and dried to form the adhesive resin layer 40, and the adhesive laminated film 50 is obtained.
Further, the base material layer 20 and the unevenness absorbing resin layer 30 may be formed by coextrusion molding, or the film-shaped base material layer 20 and the film-shaped unevenness absorbing resin layer 30 are laminated. May be formed.

2. 2. Manufacturing Method of Electronic Device Next, each step of the manufacturing method of the electronic device according to the present embodiment will be described.
FIG. 2 is a cross-sectional view schematically showing an example of a method for manufacturing an electronic device according to an embodiment of the present invention.
The method for manufacturing an electronic device according to the present embodiment includes the following steps (A) and (B).
(A) The electronic component 10 having the circuit forming surface 10A, the adhesive laminated film 50 attached to the circuit forming surface 10A side of the electronic component 10, and the surface 10C opposite to the circuit forming surface 10A of the electronic component 10. Preparation step for preparing the structure 60 provided with the thermosetting protective film 70 attached to (B) The thermosetting step for thermosetting the thermosetting protective film 70 by heating the structure 60. , The circuit forming surface 10A of the electronic component 10 is in contact with the adhesive resin layer 40.

(Step (A))
First, the electronic component 10 having the circuit forming surface 10A, the adhesive laminated film 50 attached to the circuit forming surface 10A side of the electronic component 10, and the surface 10C opposite to the circuit forming surface 10A of the electronic component 10 A structure 60 including the attached heat-curable protective film 70 is prepared.

Such a structure 60 is, for example, heated to the step (A1) of attaching the adhesive laminated film 50 to the circuit forming surface 10A of the electronic component 10 and the surface 10C opposite to the circuit forming surface 10A of the electronic component 10. It can be produced by performing the step (A2) of attaching the curable protective film 70.

The method of attaching the adhesive laminated film 50 to the circuit forming surface 10A of the electronic component 10 is not particularly limited, and the adhesive laminated film 50 can be peeled off by a generally known method. For example, it may be performed manually, or it may be performed by a device called an automatic pasting machine to which a roll-shaped adhesive laminated film 50 is attached.

The method of attaching the thermosetting protective film 70 to the surface 10C opposite to the circuit forming surface 10A of the electronic component 10 is not particularly limited, and can be peeled off by a generally known method. For example, it may be performed manually, or it may be performed by a device called an automatic pasting machine to which a roll-shaped thermosetting protective film 70 is attached.

The step (A2) of attaching the thermosetting protective film 70 to the surface 10C opposite to the circuit forming surface 10A of the electronic component 10 is performed, for example, while heating the thermosetting protective film 70. The heating temperature in the step (A2) is not particularly limited because it is appropriately set depending on the type of the thermosetting protective film 70, but is, for example, 50 ° C. or higher and 90 ° C. or lower, preferably 60 ° C. or higher and 80 ° C. or lower.

The thermosetting protective film 70 is not particularly limited, and for example, a known thermosetting type semiconductor back surface protective film can be used.
The thermosetting protective film 70 may be provided with, for example, a thermosetting adhesive layer, and may further be provided with a protective layer, if necessary.
The adhesive layer is preferably formed of a thermosetting resin, and more preferably formed of a thermosetting resin and a thermoplastic resin.
Examples of the thermosetting resin include epoxy resin, phenol resin, amino resin, unsaturated polyester resin, polyurethane resin, silicone resin, thermosetting polyimide resin and the like. As these thermosetting resins, one kind or two or more kinds can be used. Among these, epoxy resins having a low content of ionic impurities and the like are preferable.
Examples of the thermoplastic resin include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester copolymer, polybutadiene resin, and polycarbonate resin. Examples thereof include thermoplastic polyimide resin, polyamide resin, phenoxy resin, acrylic resin, saturated polyester resin such as polyethylene terephthalate and polybutylene terephthalate, polyamideimide resin, and fluororesin. As these thermoplastic resins, one kind or two or more kinds can be used. Among these, an acrylic resin having a low content of ionic impurities and the like is preferable.

The adhesive layer can contain other additives as needed. Examples of other additives include fillers, flame retardants, silane coupling agents, ion trapping agents, bulking agents, antioxidants, antioxidants, surfactants and the like.

The protective layer is made of, for example, a heat-resistant resin, a metal, or the like.
The heat-resistant resin constituting the protective layer is not particularly limited, and examples thereof include polyphenylene sulfide, polyimide, polyetherimide, polyallylate, polysulfone, polyethersulfone, polyetheretherketone, liquid crystal polymer, and polytetrafluoroethylene. Be done. Among these, polyimide, polyphenylene sulfide, polysulfone, polyetherimide, polyetherketone, polyetheretherketone and the like can be mentioned.
The metal constituting the protective layer is not particularly limited, and examples thereof include aluminum, alumite, stainless steel, iron, titanium, tin, and copper.

A commercially available film may be used as the thermosetting protective film 70. Examples of commercially available films include chip back surface protective tapes (product name: "LC tape" series) manufactured by Lintec Corporation.

The electronic component 10 is not particularly limited as long as it is an electronic component 10 having a circuit forming surface 10A, and examples thereof include a semiconductor wafer, a sapphire substrate, a lithium tantalate substrate, a molded wafer, a mold panel, a mold array package, and a semiconductor substrate. Will be.
Examples of the semiconductor substrate include a silicon substrate, a germanium substrate, a germanium-arsenic substrate, a gallium-phosphosphide substrate, a gallium-arsenide-aluminum substrate, a gallium-arsenide substrate, and the like.

Further, the electronic component 10 may be an electronic component for any purpose, but for example, an electronic component for logic (for example, for communication, high frequency signal processing, etc.), memory, sensor, power supply, etc. Can be mentioned. These may be used alone or in combination of two or more.

The circuit forming surface 10A of the electronic component 10 has an uneven structure, for example, by having an electrode 10B.
Further, when the electronic device is mounted on the mounting surface, the electrode 10B is bonded to the electrode formed on the mounting surface and is electrically connected between the electronic device and the mounting surface (mounting surface such as a printed substrate). It forms a connection.
Examples of the electrode 10B include bump electrodes such as ball bumps, printed bumps, stud bumps, plated bumps, and pillar bumps. That is, the electrode 10B is usually a convex electrode. These bump electrodes may be used alone or in combination of two or more.
The metal species constituting the bump electrode is not particularly limited, and examples thereof include silver, gold, copper, tin, lead, bismuth, and alloys thereof. These metal species may be used alone or in combination of two or more.

In the method for manufacturing an electronic device according to the present embodiment, in a state where the adhesive laminated film 50 is attached to the circuit forming surface 10A of the electronic component 10, the unevenness absorbing resin layer 30 in the adhesive laminated film 50 is thermally cured or It is preferable to perform a curing step (A3) for curing with ultraviolet rays. This makes it possible to improve the heat resistance of the adhesive laminated film 50. By doing so, a step (A2) of attaching the thermosetting protective film 70 to the surface 10C opposite to the circuit forming surface 10A of the electronic component 10 and a thermosetting step (B) of thermosetting the thermosetting protective film 70. ), The warp of the electronic component 10 can be suppressed. Further, in the step (A2) of attaching the thermosetting protective film 70 to the surface 10C opposite to the circuit forming surface 10A of the electronic component 10 and the thermosetting step (B) of thermosetting the thermosetting protective film 70, unevenness is formed. It is possible to prevent the absorbent resin layer 30 from melting and exuding the resin. The curing step (A3) is not particularly limited, but is preferably performed before the step (A2) of attaching the thermosetting protective film 70 to the surface 10C opposite to the circuit forming surface 10A of the electronic component 10.

The method for thermally curing the uneven absorbing resin layer 30 is not particularly limited as long as it can thermally cure the ethylene-based copolymer, and examples thereof include thermal cross-linking with a radical polymerization initiator.
For the thermal crosslinking by the radical polymerization initiator, the radical polymerization initiator used for the crosslinking of the ethylene-based copolymer can be used. As the radical polymerization initiator, a known thermal radical polymerization initiator can be used.

Further, by irradiating the unevenness-absorbing resin layer 30 with ultraviolet rays, the unevenness-absorbing resin layer 30 can be crosslinked and cured.
The ultraviolet rays are emitted from, for example, the surface of the adhesive laminated film 50 on the base material layer 20 side.
Further, in any of the cross-linking methods, a cross-linking aid may be blended with the uneven-absorbing resin layer 30 to carry out the cross-linking of the uneven-absorbing resin layer 30.

In the method for manufacturing an electronic device according to the present embodiment, in a state where the adhesive laminated film 50 is attached to the circuit forming surface 10A of the electronic component 10, the surface 10C opposite to the circuit forming surface 10A of the electronic component 10 is formed. The back grind step (A4) for back grind may be performed. That is, the adhesive laminated film 50 according to the present embodiment may be used as the back grind tape. Here, if the curing step (A3) is performed before the back grind step (A4), the adhesive strength of the adhesive laminated film 50 is lowered, so that the adhesive laminated film 50 is peeled off in the back grind step (A4). There is a concern that it will end up. Therefore, it is preferable to perform the back grind step (A4) before the curing step (A3).

In the back grind step (A4), the surface 10C opposite to the circuit forming surface 10A of the electronic component 10 is back grinded in a state of being attached to the adhesive laminated film 50.
Here, backgrinding means that the electronic component 10 is thinned to a predetermined thickness without being cracked or damaged.
The backgrinding of the electronic component 10 can be performed by a known method. For example, a method of fixing the electronic component 10 to a chuck table or the like of a grinder and grinding the surface 10C of the electronic component 10 opposite to the circuit forming surface 10A can be mentioned.

The back surface grinding method is not particularly limited, but for example, a known grinding method such as a through feed method or an in-feed method can be adopted. Each grinding can be performed while cooling water by applying it to the electronic component 10 and the grindstone.

(Step (B))
Next, the thermosetting protective film 70 is thermally cured by heating the structure 60.

The heating temperature in the step (B) of thermally curing the thermosetting protective film 70 is not particularly limited because it is appropriately set depending on the type of the thermosetting protective film 70, but is, for example, 120 ° C. or higher and 170 ° C. or lower, preferably 120 ° C. or higher. It is 130 ° C. or higher and 160 ° C. or lower.

(Process (C))
Further, in the method for manufacturing an electronic device according to the present embodiment, a step (C) for peeling off the electronic component 10 and the adhesive laminated film 50 may be further performed after the step (B). By performing this step (C), the electronic component 10 can be peeled off from the adhesive laminated film 50. The peeling temperature is, for example, 20 to 100 ° C.
The peeling of the electronic component 10 and the adhesive laminated film 50 can be performed by a known method.

(Other processes)
The method for manufacturing an electronic device according to the present embodiment may include other steps other than the above. As another step, a step known in the method for manufacturing an electronic device can be used.

For example, it is generally performed in the manufacturing process of electronic parts such as metal film forming process, annealing process, dicing process, die bonding process, wire bonding process, flip chip connection process, cure heating test process, sealing process, reflow process, etc. Any of the above steps may be further performed.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted.

The present invention is not limited to the above-described embodiment, and modifications, improvements, and the like to the extent that the object of the present invention can be achieved are included in the present invention.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
Details regarding the production of the adhesive film are as follows.

<Base layer>
Base material layer 1: Polyethylene naphthalate film (Product name: Theonex Q81, manufactured by Toyobo Film Solution Co., Ltd., Thickness: 50 μm)
Base material layer 2: Polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., product name: E7180, thickness: 50 μm)

<Resin for forming a concave-convex absorbent resin layer>
Resin 1: Ethylene-vinyl acetate copolymer (Product name: Evaflex EV150, manufactured by Mitsui Dow Polychemical Co., Ltd., melting point: 61 ° C)
Resin 2: Ethylene / propylene copolymer (Product name: Toughmer A35070S, manufactured by Mitsui Chemicals, Inc., melting point: 55 ° C)
Resin 3: Ethylene / propylene copolymer (Product name: Toughmer A4070, manufactured by Mitsui Chemicals, Inc., melting point: 55 ° C)

<Adhesive polymer (acrylic resin)>
77 parts by mass of n-butyl acrylate, 16 parts by mass of methyl methacrylate, 16 parts by mass of 2-hydroxyethyl acrylate, and 0.3 parts by mass of t-butylperoxy-2-ethylhexanoate as a polymerization initiator are toluene. The reaction was carried out with 20 parts by mass and 80 parts by mass of ethyl acetate for 10 hours. After completion of the reaction, this solution is cooled, and 30 parts by mass of toluene, 7 parts by mass of methacryloyloxyethyl isocyanate (manufactured by Showa Denko KK, product name: Karens MOI), and 0.05 part by mass of dibutyltin dilaurylate are added to the solution. In addition, the reaction was carried out at 85 ° C. for 12 hours while blowing air to obtain a pressure-sensitive adhesive polymer solution.

<Adhesive coating liquid for adhesive resin layer>
8 parts by mass of benzyl dimethyl ketal (manufactured by BASF, trade name: Irgacure 651) as a photoinitiator, and an isocyanate-based cross-linking agent (manufactured by Mitsui Chemicals, trade name: ole) with respect to 100 parts by mass of the pressure-sensitive adhesive polymer (solid content). Star P49-75S) 2.33 parts by mass and 6 parts by mass of ditrimethylolpropane tetraacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name: AD-TMP) were added to obtain a pressure-sensitive adhesive coating liquid.

[Example 1]
Resin 1 (100 parts by mass), triallyl isocyanurate (manufactured by Mitsubishi Chemical Corporation, trade name: Tyke) 0.44 parts by mass and cross-linking agent t-butylperoxy-2-ethylhexyl carbonate (Alchema) A composition obtained by dry-blending 0.32 parts by mass of (trade name: Luperox TBEC) manufactured by Yoshitomi Co., Ltd. was obtained. Next, the composition obtained by melt-kneading with a laboplast mill was formed into a thickness of 500 μm with a hot press machine to obtain an uneven absorption resin layer. Next, a laminated film was produced by laminating the base material layer 1 to the unevenness absorbing resin layer.

Next, the pressure-sensitive adhesive coating liquid for the pressure-sensitive adhesive resin layer was applied to a polyethylene terephthalate film (38 μm) that had been subjected to a silicone mold release treatment, and dried to form a pressure-sensitive adhesive resin layer having a thickness of 20 μm. Next, the obtained adhesive resin layer was bonded to the unevenness-absorbing resin layer side of the above-mentioned laminated film to obtain an adhesive film. The obtained adhesive film was evaluated as follows. The results obtained are shown in Table 1.

<Evaluation>
(1) Melting point of ethylene-based copolymer The melting point of the ethylene-based copolymer was measured by a differential scanning calorimeter (manufactured by SII, product name: X-DSC7000) according to a differential scanning calorimeter (DSC). .. About 10 mg of the sample was placed in an aluminum pan, heated from 30 ° C. to 230 ° C. at 10 ° C./min (1st heating), and then held for 5 minutes. Then, the mixture was cooled to −100 ° C. at 10 ° C./min, held for 5 minutes, and then heated again to 230 ° C. at 10 ° C./min (2nd heating). The melting point was obtained from the endothermic peak in the graph at the time of 2nd heating when the temperature was taken on the horizontal axis and the DSC was taken on the vertical axis.

(2) Silicon test piece Warpage evaluation A test piece was prepared in which silicon wafers ground to 75 um were separated into 5 cm x 2.5 cm pieces. Peel off the silicone release-treated polyethylene terephthalate film on the adhesive resin layer side of the adhesive film, attach it on a hot plate heated to 70 ° C, and then cut the adhesive film according to the size of the test piece. , An adhesive film / silicon test piece laminate was prepared. Then, the laminate was placed in a heating oven with the silicon test piece side facing down and placed on the mold release surface of the silicone mold-released polyethylene terephthalate, and heated at 150 ° C. for 2 hours and 30 minutes. After that, the taken-out laminate is allowed to stand for 10 minutes and allowed to cool, and then the silicon test piece side of the laminate sample is turned down and the center of one short side (2.5 cm width) of the laminate sample is touched from above with a finger. The height from the bottom of the midpoint of the short side of the other sample that was lifted at that time was measured with a ruler, and the value was taken as the warp.
Warpage was evaluated according to the following criteria.
⊚: ≦ 2 mm
〇: 2 mm <warp <4 mm
×: ≧ 4 mm

(3) Evaluation of exudation of the unevenness-absorbing resin layer It was visually confirmed whether or not the unevenness-absorbing resin layer was exuded from the end of the test piece after the warp evaluation. In addition, if it had exuded, it was confirmed whether the exuded resin layer was attached to the polyethylene terephthalate film.
The exudation was evaluated according to the following criteria.
◎: No exudation 〇: Exud, but not attached to the silicone mold release treated polyethylene terephthalate ×: Exuded and attached to the silicone mold release treated polyethylene terephthalate

[Examples 2 to 4 and Comparative Examples 1 and 2]
Adhesive films were prepared in the same manner as in Example 1 except that the types of the base material layer and the uneven absorbent resin layer were changed to those shown in Table 1. Moreover, each evaluation was performed in the same manner as in Example 1. The results obtained are shown in Table 1.

[Example 5]
Adhesive films were prepared in the same manner as in Example 1 except that the types of the base material layer and the uneven absorbent resin layer were changed to those shown in Table 1. In the warp evaluation, UV irradiation with an ^{irradiation intensity of 100 mW / cm 2} and 3240 mJ / cm ² was carried out from the adhesive film side at room temperature from the adhesive film side before the adhesive film / silicon test piece laminate was placed in a heating oven. Except for the above, each evaluation was performed in the same manner as in Example 1. The results obtained are shown in Table 1. Here, as the photoinitiator, 4-methylbenzophenone (manufactured by SHUANG-BANG INDUSTRIAL, trade name: SB-PI712) was used.

This application claims priority on the basis of Japanese Application Japanese Patent Application No. 2020-089610 filed on May 22, 2020, and incorporates all of its disclosures herein.

10 Electronic components 10A Circuit forming surface 10B Electrode 10C Surface opposite to the circuit forming surface 20 Base material layer 30 Concavo-convex absorbent resin layer 40 Adhesive resin layer 50 Adhesive laminated film 60 Structure 70 Thermosetting protective film

Claims

An adhesive laminated film provided with a base material layer, a concave-convex absorbent resin layer, and an adhesive resin layer in this order, and used to protect a circuit-forming surface of an electronic component.
The uneven absorbing resin layer contains an ethylene-based copolymer having a melting point of 40 ° C. or higher and 80 ° C. or lower, and a cross-linking agent.
An adhesive laminated film in which the content of the cross-linking agent in the uneven absorbing resin layer is 0.06 parts by mass or more and 0.60 parts by mass or less with respect to 100 parts by mass of the ethylene-based copolymer.
In the adhesive laminated film according to claim 1,
An adhesive laminated film containing at least one of the ethylene-based copolymers selected from the group consisting of ethylene / α-olefin copolymers and ethylene / vinyl ester copolymers.
In the adhesive laminated film according to claim 2,
An adhesive laminated film in which the ethylene-vinyl ester copolymer contains an ethylene-vinyl acetate copolymer.
The adhesive laminated film according to any one of claims 1 to 3.
A pressure-sensitive laminated film containing at least one of the cross-linking agents selected from the group consisting of photo-crosslinking initiators and organic peroxides.
The adhesive laminated film according to any one of claims 1 to 4.
Adhesive laminated film that is a back grind tape.
The adhesive laminated film according to any one of claims 1 to 5.
An adhesive laminated film in which the uneven absorbent resin layer further contains a cross-linking aid.
In the adhesive laminated film according to claim 6,
An adhesive laminated film containing one or more selected from the group consisting of a divinyl aromatic compound, a cyanurate compound, a diallyl compound, an acrylate compound, a triallyl compound, an oxime compound and a maleimide compound.
In the adhesive laminated film according to any one of claims 1 to 7.
An adhesive laminated film containing one or more selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, and polyimide as the resin constituting the base material layer.
In the adhesive laminated film according to any one of claims 1 to 7.
An adhesive laminated film in which the resin constituting the base material layer contains polyethylene naphthalate.
The adhesive laminated film according to any one of claims 1 to 9.
An adhesive laminated film having a thickness of the uneven absorbing resin layer of 10 μm or more and 1000 μm or less.
In the adhesive laminated film according to any one of claims 1 to 10.
Adhesives constituting the adhesive resin layer include one or more selected from (meth) acrylic adhesives, silicone adhesives, urethane adhesives, olefin adhesives and styrene adhesives. Sex laminated film.
An electronic component having a circuit forming surface, an adhesive laminated film attached to the circuit forming surface side of the electronic component, and heat curing attached to a surface of the electronic component opposite to the circuit forming surface. Sex protection film and
Preparation step (A) for preparing a structure comprising
The thermosetting step (B) of thermosetting the thermosetting protective film by heating the structure, and
The method for manufacturing an electronic device according to claim 1, wherein the adhesive laminated film is the adhesive laminated film according to any one of claims 1 to 11.
In the method for manufacturing an electronic device according to claim 12,
The preparation step (A) is
A curing step of thermally curing or UV-curing the unevenness-absorbing resin layer in the adhesive laminated film in a state where the adhesive laminated film is attached to the circuit forming surface of the electronic component.
The step of attaching the thermosetting protective film to the surface of the electronic component opposite to the circuit forming surface, and
A method of manufacturing an electronic device including.
In the method for manufacturing an electronic device according to claim 13,
A method for manufacturing an electronic device in which the heating temperature in the step of attaching the thermosetting protective film to the surface of the electronic component opposite to the circuit forming surface is 50 ° C. or higher and 90 ° C. or lower.
In the method for manufacturing an electronic device according to claim 13 or 14.
In the preparation step (A), before the curing step, the adhesive laminated film is attached to the circuit forming surface of the electronic component, and the side of the electronic component is opposite to the circuit forming surface. A method of manufacturing an electronic device that includes a backgrinding process for backgrinding a surface.
The method for manufacturing an electronic device according to any one of claims 12 to 15.
A method for manufacturing an electronic device in which the heating temperature in the thermosetting step (B) is 120 ° C. or higher and 170 ° C. or lower.
The method for manufacturing an electronic device according to any one of claims 12 to 16.
A method for manufacturing an electronic device in which the circuit forming surface of the electronic component includes a bump electrode.
In the method for manufacturing an electronic device according to claim 17,
A method for manufacturing an electronic device in which H / d is 0.01 or more and 1 or less when the height of the bump electrode is H [μm] and the thickness of the uneven absorbing resin layer is d [μm].