TW202144519A - Adhesive laminated film and production method of electronic device - Google Patents

Abstract

An adhesive laminated film (50) including a substrate layer (20), an uneven absorbent resin layer (30) and an adhesive resin layer (40) in sequence and adapted for protecting a circuit forming surface of electronic parts is provided. The uneven absorbent resin layer (30) contains an ethylene-based copolymer having a melting point of 40°C or more and 80°C or less, and a crosslinking agent. The content of the crosslinking agent in the uneven absorbent resin layer (30) 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.

Description

Adhesive laminated film and method for producing electronic device

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

In the manufacturing steps of electronic devices (eg, semiconductor devices), from the viewpoint of protecting the non-circuit-forming surfaces (back surfaces) of electronic components (eg, semiconductor wafers), heat may be applied to the non-circuit-forming surfaces of electronic components. Steps to harden the protective film. As a technique related to the said thermosetting protective film, the technique described in patent document 1 (Japanese Patent Laid-Open No. 2017-1188) is mentioned, for example.

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. [Prior Art Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2017-1188

[The problem to be solved by the invention]

As a trend in recent years, the thickness of electronic components has gradually become thinner. According to the study by the inventors of the present invention, as the thickness of the electronic component becomes thinner, in the conventional manufacturing method of the electronic device, after attaching the thermosetting protective film to the non-circuit forming surface of the electronic component, the above-mentioned protection is protected. When the film is thermally cured, or after the back grinding step, there is a tendency for electronic parts to be easily warped. In particular, when a sealing resin is integrated with a semiconductor like a wafer-level chip scale package (CSP) and the thickness of the sealing resin is thick, warpage tends to be easily generated. When an electronic component is warped, handling of the electronic component becomes difficult, or a crack occurs in the electrode.

The present invention has been made in view of the above-mentioned circumstances, and provides an adhesive laminated film and a method for producing an electronic device which can suppress the warpage of electronic components and suppress contamination to the electronic components or peripheral devices. [Means of Solving Problems]

The inventors of the present invention have repeatedly conducted intensive studies in order to achieve the above-mentioned problems. As a result, it was found that by using a base material layer, a concavo-convex absorbent resin layer containing an ethylene-based copolymer having a melting point within a specific range and a crosslinking agent in this order, and an adhesive resin layer, the content of the crosslinking agent is within a specific range. The adhesive laminate film serves as a surface protective film for protecting the circuit formation surface of electronic parts, suppresses warpage of electronic parts, and suppresses contamination of electronic parts or peripheral devices associated with the adhesive film (especially the formation of adhesive laminates). exudation of the resin of the film), thereby completing the present invention.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the adhesive laminated film and electronic device shown below can be provided.

[1] An adhesive laminated film, which sequentially includes a base material layer, a concave-convex absorbing resin layer and an adhesive resin layer, is used for protecting the circuit forming surface of electronic parts, The unevenness-absorbing resin layer contains an ethylene-based copolymer having a melting point of 40°C or higher and 80°C or lower, and a crosslinking agent, Content of the said crosslinking agent in the said uneven|corrugated absorbent resin layer is 0.06 mass part or more and 0.60 mass part or less with respect to 100 mass parts of said ethylene type copolymers. [2] The adhesive laminated film according to the above [1], wherein The ethylene-based copolymer includes at least one selected from the group consisting of an ethylene-α-olefin copolymer and an ethylene-vinyl ester copolymer. [3] The adhesive laminated film according to the above [2], wherein The ethylene-vinyl ester copolymer comprises ethylene-vinyl acetate copolymer. [4] The adhesive laminated film according to any one of [1] to [3], wherein The crosslinking agent includes at least one selected from the group consisting of a photocrosslinking initiator and an organic peroxide. [5] The adhesive laminated film according to any one of [1] to [4], Grind tape for the backside. [6] The adhesive laminated film according to any one of [1] to [5], wherein The unevenness absorbent resin layer further contains a crosslinking aid. [7] The adhesive laminated film according to the above [6], wherein The cross-linking assistant is selected from the group consisting of divinyl aromatic compounds, cyanurate compounds, diallyl compounds, acrylate compounds, triallyl compounds, oxime compounds and maleimide compounds one or more of the groups. [8] The adhesive laminated film according to any one of [1] to [7], wherein The resin constituting the base material layer includes one or more selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, and polyimide. [9] The adhesive laminated film according to any one of [1] to [7], wherein The resin constituting the base material layer contains polyethylene naphthalate. [10] The adhesive laminated film according to any one of [1] to [9], wherein The thickness of the unevenness-absorbing resin layer is 10 μm or more and 1000 μm or less. [11] The adhesive laminated film according to any one of [1] to [10], wherein The adhesive constituting the adhesive resin layer comprises one selected from the group consisting of (meth)acrylic adhesives, silicone adhesives, urethane adhesives, olefin adhesives and styrene adhesives or two or more. [12] A method of manufacturing an electronic device, comprising: In the preparation step (A), a structure including electronic parts, an adhesive laminate film and a thermosetting protective film is prepared, The electronic component has a circuit formation surface, the adhesive laminate film is attached to the circuit formation surface side of the electronic component, and the thermosetting protective film is attached to the circuit formation surface of the electronic component. the face is the face on the opposite side; and The thermosetting step (B) is to thermally harden the thermosetting protective film by heating the structure, The adhesive laminated film is the adhesive laminated film according to any one of the above [1] to [11]. [13] The method for manufacturing an electronic device as described in [12], wherein The preparation step (A) includes: a curing step of thermally curing or ultraviolet curing the unevenness absorbing resin layer in the adhesive laminate film in a state where the adhesive laminate film is attached to the circuit forming surface of the electronic component; as well as The step of attaching the thermosetting protective film to the surface opposite to the circuit formation surface of the electronic component. [14] The method for manufacturing an electronic device as described in [13], wherein The heating temperature in the step of attaching the thermosetting protective film to the surface opposite to the circuit formation surface of the electronic component is 50° C. or higher and 90° C. or lower. [15] The method for manufacturing an electronic device according to [13] or [14], wherein The preparation step (A) includes a back grinding step before the hardening step, and the back grinding step is to apply the adhesive laminated film to the circuit formation surface of the electronic component in a state where the adhesive laminate film is attached. The surface on the opposite side to the circuit formation surface of the electronic component is back-polished. [16] The method for manufacturing an electronic device according to any one of [12] to [15], wherein The heating temperature in the thermosetting step (B) is 120° C. or higher and 170° C. or lower. [17] The method for manufacturing an electronic device according to any one of [12] to [16], wherein The circuit formation surface of the electronic component includes bump electrodes. [18] The method for manufacturing an electronic device as described in [17], wherein 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 unevenness absorbing resin layer is d [μm]. [Effect of invention]

ADVANTAGE OF THE INVENTION According to this invention, the warpage of an electronic component can be suppressed, and the manufacturing method of an adhesive laminated film and an electronic device which can suppress the contamination to the said electronic component or a peripheral device can be provided.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In addition, in all drawings, the common code|symbol is attached|subjected to the same component, and description is abbreviate|omitted suitably. In addition, the drawing is a schematic drawing, and does not match the actual size ratio. In addition, "A to B" in the numerical range means A or more and B or less unless otherwise specified. In addition, in this embodiment, "(meth)acrylic acid" means acrylic acid, methacrylic acid, or both of acrylic acid and methacrylic acid.

1. Adhesive laminated film FIG. 1 is a cross-sectional view schematically showing an example of an adhesive laminated film 50 according to an embodiment of the present invention. The adhesive laminated film 50 of the present embodiment includes a base material layer 20, a concavo-convex absorbing resin layer 30, and an adhesive resin layer 40 in this order, and is an adhesive laminated film 50 for protecting the circuit forming surface of an electronic component. The 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 the content of the cross-linking agent in the unevenness absorbent resin layer 30 is 0.06 mass parts relative to 100 parts by mass of the ethylene-based copolymer. part or more and 0.60 mass part or less. The melting point of the ethylene-based copolymer was measured with a differential scanning calorimeter (DSC).

As described above, according to the study by the inventors of the present invention, as the thickness of the electronic component becomes thinner, in the conventional manufacturing method of the electronic device, after attaching the thermosetting protective film to the non-circuit forming surface of the electronic component When thermosetting the protective film or after the back grinding step, there is a tendency for electronic parts to be easily warped. In particular, when the resin and the semiconductor are integrated like a wafer-level CSP, and the thickness of the resin is thick, there is a tendency for warpage to easily occur. When an electronic component is warped, handling of the electronic component becomes difficult, or a crack occurs in the electrode. The inventors of the present invention have repeatedly conducted intensive studies in order to achieve the above-mentioned problems. As a result, it was found that by using the base material layer 20, the unevenness absorbent resin layer 30 containing the ethylene-based copolymer having a melting point of 40° C. or higher and 80° C. or lower and a cross-linking agent in this order, and the adhesive resin layer 40 and the cross-linking agent The content of the adhesive laminated film 50 within the range described above serves as a surface protective film for protecting the circuit formation surface of electronic parts, suppresses warpage of electronic parts, and suppresses damage to electronic parts or peripheral devices accompanying the adhesive film. contamination (especially bleed-out of the resins that make up the adhesive laminate film). As described above, according to the adhesive laminated film 50 of the present embodiment, the warpage of electronic components can be suppressed.

The adhesive laminated film 50 of the present embodiment is used to protect the surface of electronic parts or fix electronic parts in the manufacturing steps of electronic devices, and more specifically, in the step of grinding electronic parts (also known as one of the manufacturing steps of electronic devices) It can be preferably used as a back grinding tape for protecting the circuit-forming surface (ie, the circuit surface including the circuit pattern) of the electronic parts in the so-called back grinding step). Specifically, it can be used for a step of adhering and protecting the adhesive laminated film 50 on the circuit formation surface of an electronic component, and grinding the surface on the opposite side to the circuit formation surface. In the case of having bump electrodes on the circuit formation surface, the adhesive laminated film 50 of the present embodiment including the unevenness absorbing resin layer 30 can be preferably applied. In addition, the adhesive laminated film 50 of the present embodiment can also be used, for example, as an adhesive for protecting or maintaining electronic components having surface irregularities (eg, semiconductor wafers, sealing wafers, etc.) in a dicing step, a transfer step, or the like adhesive films; adhesive films used to temporarily fix electronic parts with uneven surfaces (such as semiconductor chips or semiconductor packages, etc.); dry polishing of electronic parts (such as semiconductor wafers, etc.), electronic parts (such as semiconductor wafers, etc.) 90℃ or higher The adhesive film used in the heating step.

<Substrate 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 . Although the base material layer 20 is not specifically limited, For example, a resin film is mentioned. As a resin which comprises the base material layer 20, 1 type or 2 or more types selected from polyethylene terephthalate, polyethylene naphthalate, polyimide, etc. are mentioned. Among these, from the viewpoint of making heat resistance more favorable, at least one kind selected from polyethylene naphthalate and polyimide is preferred, and polyethylene naphthalate is more preferred.

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

From the viewpoint of obtaining good film properties, 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 still more preferably 25 μm or more and 100 μm or less. In order to improve the adhesiveness with other layers, the base material layer 20 may also be subjected to surface treatment. Specifically, corona treatment, plasma treatment, under coat treatment, primer coat treatment, and the like may be performed.

<Concavo-convex absorbent resin layer> The adhesive laminated film 50 of the present embodiment has the unevenness absorbing resin layer 30 between the base material layer 20 and the adhesive resin layer 40 . The unevenness absorptive resin layer 30 is a layer provided for the purpose of improving the conformability 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 . Furthermore, the unevenness absorbing resin layer 30 is a layer provided for the purpose of improving the heat resistance of the adhesive laminated film 50 by thermal curing or ultraviolet curing. Thereby, 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, or the thermosetting step (B) of thermosetting the thermosetting protective film 70 ), the warpage of electronic parts can be suppressed. Furthermore, the step (A2) of attaching the thermosetting protective film 70 to the surface 10C of the electronic component 10 on the opposite side to the circuit forming surface 10A, or the thermosetting step (B) of thermosetting the thermosetting protective film 70 Among them, it is possible to prevent the unevenness absorbent resin layer 30 from melting and overflowing of the resin.

The unevenness absorbent resin layer 30 contains an ethylene-based copolymer. As the ethylene-based copolymer of 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 of the present embodiment is, for example, a copolymer obtained by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms. As the α-olefin, for example, α-olefin having 3 to 20 carbon atoms can be used alone or in combination of two or more. Among them, α-olefins having 10 or less carbon atoms are preferred, and α-olefins having 3 to 8 carbon atoms are particularly preferred. Specific examples of such α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, and 3,3-dimethyl-1-butene ene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, etc. Among them, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 1-octene are preferable in terms of availability. The ethylene-α-olefin copolymer may be a random copolymer or a block copolymer, and a random copolymer is preferred from the viewpoint of flexibility.

Here, examples of the ethylene-α-olefin copolymer include TAFMER (registered trademark) manufactured by Mitsui Chemicals Corporation, ENGAGE (registered trademark) manufactured by Dow Corporation, EXACT (registered trademark) manufactured by Exxon Mobil Corporation, KERNEL (registered trademark) manufactured by Japan Polyethylene Corporation, etc.

The density of the ethylene-α-olefin copolymer measured in accordance with American Society for Testing Materials (ASTM) D1505 is preferably 850 kg/m ³ to 900 kg/m ³ , more preferably 850 kg/m ³ to 850 kg/m 3 . 880 kg/m ³ , more preferably 850 kg/m ³ to 870 kg/m ³ . When the density is equal to or higher than the lower limit value, processing failures such as sticking can be avoided. Moreover, when the density is below the said upper limit value, the uneven|corrugated absorbent resin layer 30 excellent in the unevenness absorption property can be obtained. According to ASTM D1238, the melt flow rate (MFR) of the ethylene-α-olefin copolymer measured under the conditions of 190°C and a load of 2.16 kg is preferably 0.1 g/10 minutes to 50 g/10 minutes, More preferably, it is 1 g/10 minutes - 40 g/10 minutes, More preferably, it is 3 g/10 minutes - 35 g/10 minutes. When MFR is more than the said lower limit, the fluidity|liquidity of an ethylene-alpha-olefin copolymer improves, and the processability of the uneven|corrugated absorbent resin layer 30 can be made more favorable. Moreover, when MFR is below the said upper limit, the uneven|corrugated absorbent resin layer 30 with a more uniform thickness can be obtained, and the bleed-out of resin by the uneven|corrugated absorbent resin layer at the time of a heating process can be suppressed.

The ethylene-vinyl ester copolymer of the present embodiment preferably contains, for example, an ethylene-vinyl acetate copolymer, an ethylene-vinyl propionate copolymer, an ethylene-vinyl butyrate copolymer, an ethylene-vinyl acetate copolymer, and an ethylene-vinyl acetate copolymer. - One or more of vinyl stearate copolymers, etc., more preferably, ethylene-vinyl acetate copolymers are included.

The ethylene-vinyl acetate copolymer is a copolymer of ethylene and vinyl acetate, such as a random copolymer. The content ratio of the vinyl acetate-derived structural unit 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, More preferably, it is 25 mass % or more and 40 mass % or less. When the content of vinyl acetate is within this range, the unevenness-absorptive resin layer 30 is more excellent in the balance of flexibility, heat resistance, transparency, and mechanical properties. In addition, when forming the unevenness-absorbing resin layer 30 into a film, the film-forming property becomes favorable. The content of vinyl acetate can be measured in accordance with Japanese Industrial Standards (JIS) K7192:1999.

In addition, the ethylene-vinyl acetate copolymer is preferably a binary copolymer containing only ethylene and vinyl acetate, and may contain, for example, vinyl formate and vinyl glycolate in addition to ethylene and vinyl acetate. ester, vinyl propionate, vinyl benzoate and other vinyl ester monomers; acrylic acid, methacrylic acid, ethacrylic acid, or these salts or acrylic monomers such as alkyl esters, etc. One or two or more of them are used as copolymerization components. When containing the copolymerization components other than the said ethylene and vinyl acetate, it is preferable to make the quantity of the copolymerization components other than the said ethylene and vinyl acetate in the ethylene-vinyl acetate copolymer into 0.5 mass % or more and 5 mass % or less.

According to JIS K7210:1999, the melt flow rate (MFR) of the ethylene-vinyl ester copolymer measured at 190°C under a load of 2.16 kg is preferably 0.1 g/10 minutes to 50 g/10 minutes, more preferably It is 1 g/10 minutes - 40 g/10 minutes, more preferably 3 g/10 minutes - 35 g/10 minutes. When MFR is more than the said lower limit, the fluidity|liquidity of an ethylene-vinyl ester copolymer improves, and the shaping|molding processability of the uneven|corrugated absorbent resin layer 30 can be made more favorable. In addition, when the MFR is equal to or less than the above upper limit value, the molecular weight becomes high, so that adhesion to the roll surface such as a cooling roll is less likely to occur, the unevenness-absorbing resin layer 30 having a more uniform thickness can be obtained, and the unevenness absorption during the heating step can be suppressed. Bleeding of resin due to resin layer.

The uneven|corrugated absorbent resin layer 30 can be obtained by extrusion molding after dry mixing or melt-kneading each component, for example. In addition, antioxidants can be added as needed.

The total content of the ethylene-based copolymer and the crosslinking agent contained in the concavo-convex absorbent resin layer 30 is preferably 60% by mass or more, more preferably 70% by mass when the entire concavo-convex absorbent resin layer 30 is 100% by mass. The mass % or more is more preferably 80 mass % or more, still more preferably 90 mass % or more, and still more preferably 95 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, and further preferably 54°C or higher. When the melting point of the ethylene-based copolymer is equal to or higher than the lower limit value, the shape change at the time of transportation and storage of the adhesive laminated film 50 can be suppressed. Furthermore, when the melting point of the ethylene-based copolymer is equal to or higher than the lower limit value, the shape change of the adhesive laminated film 50 in the back grinding step can be suppressed, and the back grinding of electronic components can be more favorably advanced. Furthermore, when the melting point of the ethylene-based copolymer is equal to or higher than the lower limit value, the processing temperature of the unevenness absorbent resin layer 30 can be increased.

The melting point of the ethylene-based copolymer is 80°C or lower, preferably 75°C or lower, more preferably 70°C or lower, and further preferably 65°C or lower. When the melting point of the ethylene-based copolymer is below the upper limit, the temperature at which the adhesive laminated film 50 is attached to the electronic component can be lowered. Furthermore, when the melting point of the ethylene-based copolymer is equal to or less than the upper limit, the compatibility of the additive with the ethylene-based copolymer can be improved, and as a result, leakage of the additive contained in the unevenness absorbent resin layer 30 can be suppressed. . Furthermore, when the melting point of the ethylene-based copolymer is equal to or less than the upper limit, the handleability of the adhesive laminated film 50 when the thickness of the adhesive laminated film 50 is increased, or the stress of the adhesive laminated film 50 can be further improved. Alleviation.

In the case of an ethylene-based copolymer containing two or more components, two or more melting points may be observed, and at least one melting point may be within the above-mentioned range. It is preferable that both of the above-mentioned two or more melting points are within the above-mentioned range.

In addition, the unevenness absorbent resin layer 30 contains a crosslinking agent. By including the crosslinking agent in the unevenness absorbing resin layer 30 , the unevenness absorbing resin layer 30 can be effectively thermally cured or UV cured before step (B), and the heat resistance of the unevenness absorbing resin layer 30 can be further improved. Thereby, 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, or the thermosetting step (B) of thermosetting the thermosetting protective film 70 ), the warpage of electronic parts can be further suppressed. Furthermore, the step (A2) of attaching the thermosetting protective film 70 to the surface 10C of the electronic component 10 on the opposite side to the circuit forming surface 10A, or the thermosetting step (B) of thermosetting the thermosetting protective film 70 Among them, it is possible to further suppress the overflow of resin due to melting of the unevenness absorbent resin layer 30 . Although it does not specifically limit as a crosslinking agent of this embodiment, For example, at least 1 sort(s) chosen from the group which consists of a photocrosslinking initiator and an organic peroxide can be used. From the viewpoint of suppressing warpage, the content of the crosslinking agent in the uneven absorbent resin layer 30 is 0.60 parts by mass or less, preferably 0.55 parts by mass or less, and more preferably 0.50 parts by mass relative to 100 parts by mass of the ethylene-based copolymer. parts by mass or less. In addition, from the viewpoint of preventing bleeding of the resin during heating, the content of the crosslinking agent in the unevenness absorbent resin layer 30 is 0.06 parts by mass or more, preferably 0.07 parts by mass with respect to 100 parts by mass of the ethylene-based copolymer. Above, more preferably 0.08 part by mass or more.

As the organic peroxide, for example, a group selected from the group consisting of dilauryl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, dibenzyl peroxide, Cyclohexanone peroxide, di-tert-butyl perphthalate, cumene hydroperoxide, tert-butyl hydroperoxide, 2,5-dimethyl-2,5-bis(tertiary Butylperoxy)hexene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-amylperoxy-2-ethylhexanoate, tert-butylperoxy Peroxy-2-ethylhexanoate, tert-butylperoxyisobutyrate, tert-butylperoxymaleate, 1,1-bis(tert-amylperoxy)-3, 3,5-trimethylcyclohexane, 1,1-bis(3rd amylperoxy)cyclohexane, 3rd amylperoxyisononanoate, 3rd amylperoxyn-octanoate, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, tert-butylperoxy Isopropyl carbonate, tert-butyl peroxy-2-ethylhexyl carbonate, 2,5-dimethyl-2,5-bis(benzyl peroxy) hexane, tert-amyl peroxy Oxybenzoate, tert-butyl peroxyacetate, tert-butyl peroxy isononanoate, tert-butyl peroxybenzoate, 2,2-di(butylperoxy)butyrate Alkane, n-butyl-4,4-bis(tert-butylperoxy)butyrate, methyl ethyl ketone peroxide, ethyl-3,3-bis(tert-butylperoxy)butyrate , Dicumyl peroxide, tert-butyl cumyl peroxide, tert-butyl peroxybenzoate, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl peroxide One or more of hydrogen oxide, acetone acetone peroxide, etc.

Among these, it is preferable to use a group selected from the group consisting of 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexene, 2,5-dimethyl-2,5-bis(tertiary) One or more of butyl peroxy) hexane, tertiary butyl peroxy-2-ethylhexyl carbonate and tertiary butyl peroxybenzoate.

As the photocrosslinking initiator, for example, benzophenones, benzophenone derivatives, thioxanthones, thioxanthone derivatives, benzoin, benzoin derivatives, α-hydroxyphenalkyl ketones can be used Compounds, α-amino alkylphenols, acylphosphine oxides, alkylphenyl glyoxylates, diethoxyacetophenones, oxime esters, titanocene compounds, anthraquinone derivatives one or more of the groups. Among them, benzophenone, benzophenone derivatives, benzoin, benzoin derivatives, α-hydroxybenzoin alkyl ketones, oxime esters, and anthraquinone derivatives are preferred in terms of better crosslinking properties. more preferably benzophenone, benzophenone derivatives, and anthraquinone derivatives, and benzophenone and benzophenone derivatives are most preferred because of their good transparency. Preferable examples of benzophenone and benzophenone derivatives include benzophenone, 4-phenylbenzophenone, 4-phenoxybenzophenone, 4,4-bis(bis(bis(bis(bis(bis(bis(bis(bis(bis(bis))) ethylamino) benzophenone, methyl o-benzoylbenzoate, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, etc. Preferable examples of anthraquinone derivatives include 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, and the like.

Moreover, it is preferable that the uneven|corrugated-absorptive resin layer 30 further contains a crosslinking adjuvant from the viewpoint of further improving heat resistance. As the crosslinking aid, for example, a divinyl aromatic compound, a cyanurate compound, a diallyl compound, an acrylate compound, a triallyl compound, an oxime compound, and a maleimide compound can be used. One or more of the group formed. The content of the crosslinking aid in the uneven absorbent resin layer 30 is preferably 5.0 parts by mass or less, more preferably 2.0 parts by mass or less, and particularly preferably 1.0 parts by mass or less, relative to 100 parts by mass of the ethylene-based copolymer. The content of the crosslinking aid in the uneven absorbent resin layer 30 is preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, and still more preferably 0.10 part by mass or more with respect to 100 parts by mass of the ethylene-based copolymer.

As a divinyl aromatic compound, divinylbenzene, di-isopropenylbenzene, etc. are mentioned, for example. As a cyanurate compound, triallyl cyanurate, triallyl isocyanurate, etc. are mentioned, for example. As a diallyl compound, diallyl phthalate etc. are mentioned, for example. As a triallyl compound, pentaerythritol triallyl ether etc. are mentioned, for example. As the acrylate compound, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane tri(meth)acrylate, Di-trimethylolpropane tetra(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, and the like. As an oxime compound, p-quinone dioxime, p-p'- dibenzoyl quinone dioxime, etc. are mentioned, for example. As a maleimide compound, isophthalimide etc. are mentioned, for example. As the crosslinking aid, a compound having a crosslinkable unsaturated bond such as a trifunctional or more vinyl group in one molecule is preferable, and among them, triallyl trimer is preferable in terms of good crosslinkability Cyanate ester, triallyl isocyanurate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, especially triallyl cyanurate and triallyl isocyanurate.

The thickness of the concavo-convex absorbing resin layer 30 is not particularly limited as long as it can embed the concavities and convexities of the circuit forming surface 10A of the electronic component 10. For example, it is preferably 10 μm or more and 1000 μm or less, more preferably 20 μm Not less than 900 μm, more preferably not less than 30 μm and not more than 800 μm, particularly preferably not less than 50 μm and not more than 700 μm.

When the height of the bump electrodes present on the circuit forming surface 10A of the electronic component 10 is set to H [μm] and the thickness of the unevenness absorbing resin layer 30 is set to d [μm], H/d is preferably 1 or less , more preferably 0.85 or less, still more preferably 0.7 or less. If H/d is below the said upper limit, the thickness of the adhesive laminated film 50 can be made thinner, and the unevenness|corrugation absorption property can be made more favorable. The lower limit of H/d is not particularly limited, but is, for example, 0.01 or more. The height of the bump electrodes is usually 2 μm or more and 600 μm or less.

<Adhesive resin layer> The adhesive resin layer 40 is a layer provided on one side of the concavo-convex absorbing resin layer 30 , and is used to form a contact with the circuit forming surface of the electronic component 10 when the adhesive laminated film 50 is attached to the circuit forming surface 10A of the electronic component 10 . 10A Contact and stick layers.

As an adhesive which comprises the adhesive resin layer 40, a (meth)acrylic-type adhesive, a silicone-type adhesive, a urethane-type adhesive, an olefin-type adhesive, a styrene-type adhesive, etc. are mentioned. Among these, the (meth)acrylic-type adhesive which uses a (meth)acrylic-type polymer as a base polymer is preferable from the point which can adjust adhesive force easily.

Moreover, as an adhesive which comprises the adhesive resin layer 40, the radiation crosslinking type adhesive whose adhesive force is reduced by radiation can also be used. The adhesive resin layer 40 composed of the radiation cross-linkable adhesive is cross-linked by irradiation with radiation, and the adhesive force is remarkably reduced. Therefore, in the step (C) of peeling the electronic component 10 and the adhesive laminated film 50 to be described later , the electronic component 10 is easily peeled off from the adhesive resin layer 40 . Examples of the radiation include ultraviolet rays, electron beams, infrared rays, and the like. The radiation cross-linked adhesive is preferably an ultraviolet cross-linked adhesive.

The (meth)acrylic polymer contained in the (meth)acrylic pressure-sensitive adhesive includes, for example, a homopolymer of a (meth)acrylate compound and a copolymer of a (meth)acrylate compound and a comonomer. Wait. For example, the (meth)acrylate compound includes methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylate ) hydroxyethyl acrylate, hydroxypropyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, and the like. These (meth)acrylate compounds may be used alone or in combination of two or more. In addition, examples of comonomers constituting the (meth)acrylic copolymer include vinyl acetate, (meth)acrylonitrile, styrene, (meth)acrylic acid, itaconic acid, and (meth)acrylonitrile. Amine, methylol (meth)acrylamide, maleic anhydride, etc. These comonomers may be used alone or in combination of two or more.

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

The crosslinkable compound includes, for example, a monomer, an oligomer, or a polymer that has a carbon-carbon double bond in the molecule and can be crosslinked by radical polymerization. Examples of the crosslinkable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tetraethylene glycol di(meth)acrylate, and 1,6-hexanedi Alcohol di(meth)acrylate, neopentyl glycol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, etc. (methyl) Esters of acrylic acid and polyols; ester (meth)acrylate oligomers; 2-propenyl di-3-butenyl cyanurate, 2-hydroxyethyl bis(2-(meth)acrylamide) oxyethyl) isocyanurate, tris(2-methacryloyloxyethyl) isocyanurate or other isocyanurates, isocyanurate compounds, or the like. In addition, when a (meth)acrylic-type polymer is a radiation crosslinking type polymer which has a carbon-carbon double bond in the side chain of a polymer, a crosslinkable compound may not be added.

The content of the crosslinkable compound is preferably 1 part by mass to 900 parts by mass, more preferably 2 parts by mass to 100 parts by mass, and still more preferably 5 parts by mass to 50 parts by mass relative to 100 parts by mass of the (meth)acrylic polymer. parts by mass. When the content of the crosslinkable compound is in the above range, the adjustment of the adhesive force becomes easier compared with the case where the content is less than the above range, and it is less likely to occur due to heat or heat than when the content exceeds the above range. Deterioration of storage stability due to excessively high light sensitivity.

The photopolymerization initiator may be a compound that is cleaved by irradiation with radiation to generate radicals, and examples thereof include benzoin alkyl ethers such as benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzyl, benzoin, Aromatic ketones such as benzophenone and α-hydroxycyclohexyl phenyl ketone; aromatic ketals such as benzyl dimethyl ketal; polyvinyl benzophenone; chlorothioxanthone, dodecane thioxanthones such as thioxanthone, dimethylthioxanthone, diethylthioxanthone, etc.

As a thermal polymerization initiator, an organic peroxide derivative, an azo type polymerization initiator, etc. are mentioned, for example. In terms of not generating nitrogen during heating, organic peroxide derivatives are preferred. As a thermal polymerization initiator, a ketone peroxide, a peroxyketal, a hydroperoxide, a dialkyl peroxide, a diacyl peroxide, a peroxyester, a peroxydicarbonate, etc. are mentioned, for example.

A crosslinking agent can also be added to the adhesive. Examples of crosslinking agents include epoxy-based compounds such as sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, and diglyceryl polyglycidyl ether; tetramethylolmethane-triglyceride -β-aziridine propionate, trimethylolpropane-tri-β-aziridine propionate, N,N'-diphenylmethane-4,4'-bis(1-aziridine aziridine-based compounds such as pyridinecarboxyamide), N,N'-hexamethylene-1,6-bis(1-aziridinecarboxyamide); tetramethylene diisocyanate, hexamethylene diisocyanate Isocyanate-based compounds such as isocyanates and polyisocyanates, and the like. From the viewpoint of improving the heat resistance of the adhesive resin layer 40 or the balance with the adhesive force, the content of the crosslinking agent is preferably 0.1 part by mass or more and 10 parts by mass relative to 100 parts by mass of the (meth)acrylic polymer. copies or less.

The thickness of the adhesive resin layer 40 is not particularly limited. For example, it 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 by, for example, applying an adhesive coating liquid on the unevenness absorbent resin layer 30 . The method of coating the adhesive coating liquid can adopt the existing known coating methods, such as: roll coater method, reverse roll coater method, gravure roll method, bar coating method, notch wheel coater method, Die coater method, etc. The drying conditions of the applied adhesive are not particularly limited, but generally, drying in a temperature range of 80° C. to 200° C. for 10 seconds to 10 minutes is preferable. More preferably, it is dried for 15 seconds to 5 minutes at 80°C to 170°C. In order to fully promote the crosslinking reaction between the crosslinking agent and the adhesive, after the drying of the adhesive coating liquid is completed, it may be heated at 40°C to 80°C for about 5 hours to 300 hours.

Regarding the adhesive laminated film 50 of the present embodiment, when curing the unevenness absorbing resin layer 30 with ultraviolet rays or crosslinking the adhesive resin layer 40 with ultraviolet rays, it is necessary that the curing or crosslinking does not hinder the object of the present invention The degree of light transmittance.

In terms of balance between mechanical properties and handleability, the overall thickness of the adhesive laminated film 50 of 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 still more preferably 200 μm. Above and below 800 μm.

In the adhesive laminated film 50 of the present embodiment, an adhesive layer (not shown) may be provided between the layers. The adhesiveness between the layers can be improved by the adhesive layer.

Next, an example of the manufacturing method of the adhesive laminated film 50 of this embodiment is demonstrated. First, on one surface of the base material layer 20, the uneven|corrugated absorbent resin layer 30 is formed by the extrusion lamination method. Next, the adhesive resin layer 40 is formed by applying the adhesive coating liquid on the unevenness absorbent resin layer 30 and drying, and the adhesive laminated film 50 is obtained. In addition, the base material layer 20 and the concavo-convex absorbent resin layer 30 may be formed by co-extrusion molding, or may be formed by laminating (laminating) the film-shaped base material layer 20 and the film-shaped concavo-convex absorbent resin layer 30 . form.

2. Manufacturing method of electronic device Next, each step of the manufacturing method of the electronic device of the present embodiment will be described. FIGS. 2(A) and 2(B) are cross-sectional views schematically showing an example of a method of manufacturing an electronic device according to an embodiment of the present invention. The manufacturing method of the electronic device of this embodiment includes the following steps (A) and (B). (A) A preparation step for preparing a structure 60 including an electronic component 10 having a circuit forming surface 10A, an adhesive laminate film 50 and a thermosetting protective film 70 , and the adhesive laminate film 50 is attached to On the circuit forming surface 10A side of the electronic component 10 , the thermosetting protective film 70 is attached to the surface 10C on the opposite side to the circuit forming surface 10A of the electronic component 10 (B) Thermosetting step of thermosetting the thermosetting protective film 70 by heating the structure 60 Here, the circuit formation surface 10A of the electronic component 10 is in contact with the adhesive resin layer 40 .

(step (A)) First, a structure 60 including an electronic component 10 having a circuit forming surface 10A, an adhesive laminate film 50 and a thermosetting protective film 70 is prepared, and the adhesive laminate film 50 is attached to the electronic component 10 . On the circuit formation surface 10A side, the thermosetting protective film 70 is attached to the surface 10C of the electronic component 10 on the opposite side to the circuit formation surface 10A.

The structure 60 can be attached to the surface 10C of the electronic component 10 on the opposite side to the circuit formation surface 10A by, for example, the step (A1) of attaching the adhesive laminate film 50 to the circuit formation surface 10A of the electronic component 10 . The thermosetting protective film 70 is attached to the step (A2) to produce.

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

The method of attaching the thermosetting protective film 70 to the surface 10C of the electronic component 10 on the opposite side to the circuit forming surface 10A is not particularly limited, and it can be peeled off by a generally known method. For example, it may be performed manually, or may be performed by an apparatus called an automatic sticker to which the 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 while heating the thermosetting protective film 70 , for example. The heating temperature in step (A2) is appropriately set according to the type of the thermosetting protective film 70 and is not particularly limited, but is, for example, 50°C or higher and 90°C or lower, preferably 60°C or higher and 80°C or lower.

It does not specifically limit as the thermosetting protective film 70, For example, a well-known thermosetting type semiconductor back surface protection film can be used. The thermosetting protective film 70 includes, for example, a thermosetting adhesive layer, and may further include a protective layer as needed. The adhesive layer is preferably formed of a thermosetting resin, and more preferably formed of a thermosetting resin and a thermoplastic resin. As a thermosetting resin, an epoxy resin, a phenol resin, an amino resin, an unsaturated polyester resin, a polyurethane resin, a silicone resin, a thermosetting polyimide resin, etc. are mentioned, for example. One or two or more of these thermosetting resins can be used. Among these, epoxy resins with a small content of ionic impurities and the like are preferred. Examples of thermoplastic resins include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, polybutylene Diene resin, polycarbonate resin, thermoplastic polyimide resin, polyamide resin, phenoxy resin, acrylic resin, saturated polyester such as polyethylene terephthalate or polybutylene terephthalate Resin, polyamide imide resin, fluororesin, etc. One or two or more of these thermoplastic resins can be used. Among these, acrylic resins with a small content of ionic impurities and the like are preferred.

The adhesive layer may contain other additives as needed. As other additives, a filler, a flame retardant, a silane coupling agent, an ion scavenger, an extender, an antiaging agent, an antioxidant, a surfactant, etc. are mentioned, for example.

The protective layer is made of, for example, a heat-resistant resin, metal, or the like. The heat-resistant resin constituting the protective layer is not particularly limited, and examples thereof include polyphenylene sulfide, polyimide, polyetherimide, polyarylate, polyether, polyetherether, polyetheretherketone, liquid crystal polymer, teflon, etc. Among these, polyimide, polyphenylene sulfide, polysulfide, polyetherimide, polyether ketone, polyether ether ketone, etc. are mentioned. Although it does not specifically limit as a metal which comprises a protective layer, For example, aluminum, alumite, stainless steel, iron, titanium, tin, copper, etc. are mentioned.

A commercially available film can be used for the thermosetting protective film 70 . As a commercially available film, the wafer back surface protection tape (product name: "LC tape" series) by Lintec Corporation, etc. are mentioned, for example.

The electronic component 10 is not particularly limited as long as it has the circuit forming surface 10A, and examples thereof include semiconductor wafers, sapphire substrates, lithium tantalate substrates, die wafers, die panels, die array packages, Semiconductor substrates, etc. Moreover, as a semiconductor substrate, a silicon substrate, a germanium substrate, a gallium-arsenic substrate, a gallium-phosphorus substrate, a gallium-arsenic-aluminum substrate, a gallium-arsenic substrate, etc. are mentioned, for example.

In addition, the electronic component 10 may be an electronic component of any application, for example, an electronic component of logic application (eg, communication application, high-frequency signal processing application, etc.), memory application, sensor application, power supply application, and the like. Only one type of these may be used, or two or more types may be used in combination.

The circuit formation surface 10A of the electronic component 10 has the uneven|corrugated structure by having the electrode 10B, for example. The electrodes 10B are joined to electrodes formed on the mounting surface when the electronic device is mounted on the mounting surface to form an electrical connection between the electronic device and the mounting surface (a mounting surface such as a printed circuit board). Examples of the electrodes 10B include bump electrodes such as ball bumps, printed bumps, bolt bumps, plated bumps, and stud 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. In addition, the metal species constituting the bump electrodes is not particularly limited, and examples thereof include silver, gold, copper, tin, lead, bismuth, alloys thereof, and the like. These metal species may be used alone or in combination of two or more.

In the manufacturing method of the electronic device of the present embodiment, it is preferable to perform the unevenness absorbing resin layer in the adhesive laminate film 50 in a state where the adhesive laminate film 50 is attached to the circuit forming surface 10A of the electronic component 10 . 30 Hardening step (A3) for heat hardening or UV hardening. Thereby, the heat resistance of the adhesive laminated film 50 can be improved. Thereby, 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, or the thermosetting step (B) of thermosetting the thermosetting protective film 70 ), the warpage of the electronic component 10 can be suppressed. Furthermore, the step (A2) of attaching the thermosetting protective film 70 to the surface 10C of the electronic component 10 on the opposite side to the circuit forming surface 10A, or the thermosetting step (B) of thermosetting the thermosetting protective film 70 Among them, it is possible to prevent the unevenness absorbent resin layer 30 from melting and overflowing of 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 of the electronic component 10 on the opposite side to the circuit forming surface 10A.

As a thermosetting method of the uneven|corrugated absorbent resin layer 30, if it is a method which can thermoset an ethylene type copolymer, it will not specifically limit, Thermal crosslinking by a radical polymerization initiator is mentioned. The thermal crosslinking by a radical polymerization initiator can use the radical polymerization initiator used for crosslinking of an ethylene type copolymer. As the radical polymerization initiator, a known thermal radical polymerization initiator can be used.

In addition, by irradiating the unevenness-absorbing resin layer 30 with ultraviolet rays, the unevenness-absorbing resin layer 30 can be bridged and cured. Ultraviolet rays are irradiated, for example, from the surface of the adhesive laminated film 50 on the side of the base material layer 20 . In addition, in any of the crosslinking methods, a crosslinking assistant may be prepared with respect to the unevenness absorptive resin layer 30 to perform crosslinking of the unevenness absorptive resin layer 30 .

In the manufacturing method of the electronic device of the present embodiment, a back grinding step (A4) may be performed in a state where the adhesive laminate film 50 is adhered to the circuit formation surface 10A of the electronic component 10 . , the surface 10C of the electronic component 10 on the opposite side to the circuit formation surface 10A is back-polished. That is, the adhesive laminated film 50 of this embodiment can be used as a back grinding tape. Here, if the hardening step (A3) is performed before the back grinding step (A4), the adhesive force of the adhesive laminated film 50 is lowered, so that the adhesive laminated film 50 may be peeled off in the back grinding step (A4). Therefore, it is preferable to perform the back grinding|polishing process (A4) before the hardening process (A3).

In a back grinding|polishing process (A4), back grinding|polishing is performed with respect to the surface 10C on the opposite side to the circuit formation surface 10A of the electronic component 10 in the state stuck to the adhesive laminated film 50. Here, performing back grinding means performing thinning processing to a predetermined thickness without breaking or breaking the electronic component 10 . Back grinding of the electronic component 10 can be performed by a well-known method. For example, a method of fixing the electronic component 10 on a chuck of a grinding machine, etc., and grinding the surface 10C of the electronic component 10 on the opposite side to the circuit forming surface 10A can be mentioned.

The back surface grinding method is not particularly limited, and for example, a known grinding method such as a through feed method and an in feed method can be adopted. Various grindings are performed while pouring water on the electronic components 10 and the grinding stone to cool.

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

Since the heating temperature in the step (B) of thermosetting the thermosetting protective film 70 is appropriately set according to the type of the thermosetting protective film 70 , it is not particularly limited, but is, for example, 120° C. or higher and 170° C. or lower, preferably 130° C. ℃ or more and 160℃ or less.

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

(other steps) The manufacturing method of the electronic device of the present embodiment may include other steps than those described above. As another step, a known step in a manufacturing method of an electronic device can be used.

For example, the steps of manufacturing electronic parts such as metal film forming step, annealing treatment, dicing step, die bonding step, wire bonding step, flip chip bonding step, hardening heating test step, sealing step, reflow soldering step, etc. may be further performed. Arbitrary steps etc. which are usually performed.

As mentioned above, although embodiment of this invention was described, these are examples of this invention, and various structures other than the above may be employ|adopted.

In addition, this invention is not limited to the said embodiment, The deformation|transformation, improvement, etc. within the range which can achieve the objective of this invention are also included in this invention. [Example]

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

<Substrate layer> Substrate layer 1: polyethylene naphthalate film (product name: Teonex Q81, manufactured by Toyobo Film Solutions, thickness: 50 μm) Base material layer 2: polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., product name: E7180, thickness: 50 μm)

<Resin for concavo-convex absorbent resin layer formation> Resin 1: Ethylene-vinyl acetate copolymer (product name: Evaflex EV150, manufactured by Mitsui Dow Polychemical, melting point: 61°C) Resin 2: Ethylene-propylene copolymer (product name: TAFMER A35070S, manufactured by Mitsui Chemicals, melting point: 55°C) Resin 3: Ethylene-propylene copolymer (product name: TAFMER A4070, manufactured by Mitsui Chemicals, 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 mass parts of tert-butylperoxy-2-ethylhexanoate as a polymerization initiator parts were reacted in 20 parts by mass of toluene and 80 parts by mass of ethyl acetate for 10 hours. After the completion of the reaction, the solution was cooled, and 30 parts by mass of toluene, 7 parts by mass of methacryloyloxyethyl isocyanate (manufactured by Showa Denko Co., Ltd., product name: Karenz MOI) and 7 parts by mass were added. 0.05 mass part of dibutyltin dilaurate was reacted at 85 degreeC for 12 hours, blowing in air, and the adhesive polymer solution was obtained.

<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 was added to 100 parts by mass of the adhesive polymer (solid content) , Isocyanate-based crosslinking agent (manufactured by Mitsui Chemicals, trade name: olester P49-75S) 2.33 parts by mass, di-trimethylolpropane tetraacrylate (manufactured by Shin-Nakamura Chemical Industry, trade name : AD-TMP) 6 parts by mass to obtain an adhesive coating liquid.

[Example 1] Resin 1 (100 parts by mass), triallyl isocyanurate (manufactured by Mitsubishi Chemical Corporation, trade name: TMAIC) 0.44 parts by mass as a cross-linking aid, and 0.44 parts by mass as a cross-linking agent were obtained. The composition after dry mixing of 0.32 parts by mass of tertiary butylperoxy-2-ethylhexyl carbonate (manufactured by Arkema GIFT, trade name: LUPEROX TBEC). Next, the composition obtained by melt-kneading in a laboratory plastic mill (LABO PLASTOMILL) was molded into a thickness of 500 μm by a hot press to obtain a concavo-convex absorbing resin layer. Next, a laminated film is produced by bonding the base material layer 1 to the unevenness absorbing resin layer.

Next, the adhesive coating solution for the adhesive resin layer was coated on the polyethylene terephthalate film (38 μm) after the silicone mold release treatment, and dried to form an adhesive resin with a thickness of 20 μm. Floor. Next, an adhesive film is obtained by bonding the obtained adhesive resin layer to the uneven|corrugated absorbent resin layer side of the said laminated film. The following evaluations were performed on the obtained adhesive film. The obtained results are shown in Table 1.

＜Evaluation＞ (1) Melting point of vinyl 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 calorimetry (DSC). About 10 mg of a sample was put into an aluminum pan, and the temperature was raised from 30°C to 230°C at 10°C/min (first heating), and then kept for 5 minutes. Next, it cooled to -100 degreeC at 10 degreeC/min, after holding for 5 minutes, it heated up again to 230 degreeC at 10 degreeC/min (2nd heating). The melting point was obtained from the endothermic peak in the graph in which the abscissa is the temperature and the ordinate is the DSC at the time of the second heating.

(2) Evaluation of warpage of silicon test piece A test piece of 5 cm x 2.5 cm was prepared by singulating a silicon wafer ground to 75 μm. The polyethylene terephthalate film after the silicone mold release treatment on the adhesive resin layer side of the adhesive film was peeled off, attached to a hot plate heated to 70°C, and then cut according to the size of the test piece. The adhesive film was produced as an adhesive film/silicon test piece laminate. Then, the silicon test piece side of the laminate was placed downward, placed on the mold release surface of the polyethylene terephthalate after the silicone mold release treatment, and placed in a heating furnace, and heated at 150° C. 2 hours 30 minutes. Then, the taken out layered body was left to stand for 10 minutes and left to cool, then the silicon test piece side of the layered sample was placed down, the center of one short side (2.5 cm wide) of the layered sample was pressed from above with a finger, and the value was measured with a ruler. The height of the midpoint of the short side of the other sample lifted from the bottom surface, and this value is set as the warp. The warpage was evaluated according to the following criteria. ◎: ≦ 2 mm ○: 2 mm < warpage < 4 mm ×: ≧4 mm

(3) Evaluation of bleed-out of uneven absorbent resin layer Whether or not the concavo-convex absorbent resin layer bleeds out from the end of the test piece after warpage evaluation was visually confirmed. In addition, it was confirmed whether or not the resin layer exuded during exudation was attached to the polyethylene terephthalate film. Bleeding was evaluated according to the following criteria. ◎: No bleeding ○: Exuded, but not adhered to polyethylene terephthalate after silicone mold release treatment ×: Exudation occurs, and it is adhered to polyethylene terephthalate after silicone mold release treatment

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

[Example 5] Adhesive films were produced in the same manner as in Example 1, except that the types of the base material layer and the unevenness-absorbing resin layer were changed to those shown in Table 1. Further, in the evaluation of warpage before the adhesive film / silicon laminate test piece was placed in a heating furnace of the self-adhesive film side using a high pressure mercury lamp at room temperature at an irradiation intensity of 100 mW / cm ² embodiment 3240 mJ / Each evaluation was performed in the same manner as in Example 1, except for the UV irradiation of cm ^{2 .} The obtained results are shown in Table 1, respectively. Here, as the photoinitiator, 4-methylbenzophenone (manufactured by SHUANG-BANG INDUSTRIAL, trade name: SB-PI712) was used.

[Table 1] Table 1 project unit Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 substrate layer Types of substrate layers - Substrate layer 1 Substrate layer 1 Substrate layer 1 Substrate layer 1 Substrate layer 2 Substrate layer 1 Substrate layer 1 Concavo-convex absorbent resin layer Types of vinyl copolymers ① - Resin 1 Resin 1 Resin 1 Resin 1 Resin 2 Resin 1 Resin 1 Melting point of vinyl copolymer ① °C 61 61 61 61 55 61 61 Amount of ethylene-based copolymer ① parts by mass 100 100 100 100 50 100 100 Types of vinyl copolymers ② - - - - - Resin 3 - - Melting point of vinyl copolymer ② °C - - - - 55 - - Amount of ethylene-based copolymer ② parts by mass 0 0 0 0 50 0 0 Dosage of organic peroxide parts by mass 0.32 0.2 0.16 0.08 0.64 0.04 The dosage of photoinitiator parts by mass 0.5 The dosage of cross-linking aids parts by mass 0.44 0.3 0.22 0.11 0.85 0.88 0.06 Evaluation results Test piece warpage - ○ 3 mm ◎ 2 mm ◎ 2 mm ◎ 1mm ◎ 1mm × 4 mm ◎ 1mm Exudate - ◎ ◎ ◎ ○ ◎ ◎ ×

The present application claims priority based on Japanese Patent Application No. 2020-089610 for which it applied on May 22, 2020, and the entire contents of the disclosure are incorporated in the present application.

10: Electronic Parts 10A: circuit forming surface 10B: Electrodes 10C: Surface on the opposite side to the circuit formation surface 20: Substrate layer 30: Concavo-convex absorbent resin layer 40: Adhesive resin layer 50: Adhesive laminated film 60: Structure 70: Thermosetting protective film

FIG. 1 is a cross-sectional view schematically showing an example of an adhesive laminated film according to an embodiment of the present invention. FIGS. 2(A) and 2(B) are cross-sectional views schematically showing an example of a method of manufacturing an electronic device according to an embodiment of the present invention.

20: Substrate layer

30: Concavo-convex absorbent resin layer

40: Adhesive resin layer

50: Adhesive laminated film

Claims (18)

An adhesive laminated film, which sequentially includes a base material layer, a concave-convex absorbing resin layer and an adhesive resin layer, is used for protecting the circuit forming surface of electronic parts, The unevenness-absorbing resin layer contains an ethylene-based copolymer having a melting point of 40°C or higher and 80°C or lower, and a crosslinking agent, Content of the said crosslinking agent in the said uneven|corrugated absorbent resin layer is 0.06 mass part or more and 0.60 mass part or less with respect to 100 mass parts of said ethylene type copolymers. The adhesive laminated film of claim 1, wherein The ethylene-based copolymer includes at least one selected from the group consisting of an ethylene-α-olefin copolymer and an ethylene-vinyl ester copolymer. The adhesive laminated film of claim 2, wherein The ethylene-vinyl ester copolymer comprises ethylene-vinyl acetate copolymer. The adhesive laminated film of claim 1 or claim 2, wherein The crosslinking agent includes at least one selected from the group consisting of a photocrosslinking initiator and an organic peroxide. The adhesive laminated film according to claim 1 or claim 2, It is a back grinding tape. The adhesive laminated film of claim 1 or claim 2, wherein The unevenness absorbent resin layer further contains a crosslinking aid. The adhesive laminated film of claim 6, wherein The cross-linking assistant is selected from the group consisting of divinyl aromatic compounds, cyanurate compounds, diallyl compounds, acrylate compounds, triallyl compounds, oxime compounds and maleimide compounds one or more of the groups. The adhesive laminated film of claim 1 or claim 2, wherein The resin constituting the base material layer includes one or more selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, and polyimide. The adhesive laminated film of claim 1 or claim 2, wherein The resin constituting the base material layer contains polyethylene naphthalate. The adhesive laminated film of claim 1 or claim 2, wherein The thickness of the unevenness-absorbing resin layer is 10 μm or more and 1000 μm or less. The adhesive laminated film of claim 1 or claim 2, wherein The adhesive constituting the adhesive resin layer comprises one selected from the group consisting of (meth)acrylic adhesives, silicone adhesives, urethane adhesives, olefin adhesives and styrene adhesives or two or more. A method of manufacturing an electronic device, comprising: In the preparation step (A), a structure including electronic parts, an adhesive laminate film and a thermosetting protective film is prepared, The electronic component has a circuit formation surface, the adhesive laminate film is attached to the circuit formation surface side of the electronic component, and the thermosetting protective film is attached to the circuit formation surface of the electronic component. the face is the face on the opposite side; and The thermosetting step (B) is to thermally harden the thermosetting protective film by heating the structure, The adhesive laminated film is the adhesive laminated film according to any one of Claims 1 to 11. The manufacturing method of an electronic device as claimed in claim 12, wherein The preparation step (A) includes: a curing step of thermally curing or ultraviolet curing the unevenness absorbing resin layer in the adhesive laminate film in a state where the adhesive laminate film is attached to the circuit forming surface of the electronic component; as well as The step of attaching the thermosetting protective film to the surface opposite to the circuit formation surface of the electronic component. The method for manufacturing an electronic device as claimed in claim 13, wherein The heating temperature in the step of attaching the thermosetting protective film to the surface opposite to the circuit formation surface of the electronic component is 50° C. or higher and 90° C. or lower. The manufacturing method of an electronic device as claimed in claim 13 or claim 14, wherein The preparation step (A) includes a back grinding step before the hardening step, and the back grinding step is to apply the adhesive laminated film to the circuit formation surface of the electronic component in a state where the adhesive laminate film is attached. The surface on the opposite side to the circuit formation surface of the electronic component is back-polished. The method for manufacturing an electronic device according to claim 12 or claim 13, wherein 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 claim 12 or claim 13, wherein The circuit formation surface of the electronic component includes bump electrodes. The method for manufacturing an electronic device as claimed in claim 17, wherein 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 unevenness absorbing resin layer is d [μm].

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