KR20230076589A - Adhesive film - Google Patents

Abstract

The present invention relates to an adhesive film which comprises: a first substrate layer; a first adhesive layer stacked on the first substrate layer; a second adhesive layer stacked on the first adhesive layer; and a second substrate layer stacked on the second adhesive layer. The first adhesive layer is a cured product layer of a composition for forming the first adhesive layer which comprises a silicone resin, a first hydride silicone compound represented by chemical formula 2, a second hydride silicone compound represented by chemical formula 3, an acrylate-modified silicone resin, and a light-cured initiator. The second adhesive layer is a cured product layer of a composition for forming the second adhesive layer which comprises a silicone resin, the first hydride silicone compound represented by chemical formula 2, and the second hydride silicone compound represented by chemical formula 3. The composition for forming the first adhesive layer comprises, based on 100 parts by weight of silicone resins: 12-18 parts by weight of the first hydride silicone compound; 4-6 parts by weight of the second hydride silicone compound; and 20-40 parts by weight of the acrylate-modified silicone resin. The composition for the second adhesive layer comprises, based on 100 parts by weight of silicone resins: 7-13 parts by weight of the first hydride silicone compound; and 7-10 parts by weight of the second hydride silicone compound. According to the present invention, a processing process can be simplified, and the yields can be improved.

Description

Adhesive film {ADHESIVE FILM}

The present invention relates to an adhesive film, and relates to an adhesive film capable of adjusting the adhesive strength of both sides differently.

For miniaturization of portable electronic devices, thinning of semiconductor chips is required. In order to thin the semiconductor chip, a thin film grinding and dicing process is required for the semiconductor wafer, and an adhesive film is used to protect and/or fix the wafer in the grinding and dicing process. . The adhesive film is adhered to the wafer to protect the wafer during semiconductor wafer processing, and must be removed from the wafer if necessary. Various methods may be used to remove, ie peel, the adhesive film from the wafer.

In relation to this, Korean Patent Registration No. 10-1907010 discloses a wafer processing body in which a support, a temporary adhesive layer, and a wafer are sequentially stacked, but the temporary adhesive layer includes a thermoplastic resin layer, so deformation may occur at high temperature Since it is based on the bonding process after forming the temporary adhesive layer on the support and wafer respectively, the process is complicated and the production rate is lowered, and the residue remains after the removal of the temporary adhesive layer, requiring a separate process to remove it. Performance required as an adhesive film was difficult to satisfy.

Accordingly, there is a need for an adhesive film that does not deform even during wafer processing at a high temperature and can be easily removed from the wafer when necessary by adjusting the adhesive strength of both sides differently.

Republic of Korea Patent Registration No. 10-1907010 (2018.10.04. Registration)

An object of the present invention is to provide an adhesive film for semiconductor wafer processing that is provided in the form of a film rather than the form of a conventional composition in order to simplify the processing process of semiconductor wafers and improve the production rate.

In addition, an object of the present invention is to provide an adhesive film that does not undergo deformation even in a high-temperature process and can be used in a semiconductor wafer processing process having irregularities such as bumps on the surface.

In addition, an object of the present invention is to provide an adhesive film that can be easily removed by adjusting the adhesive strength of both sides of the adhesive film adhered to a semiconductor wafer and does not leave residue even after removal of the adhesive layer.

In order to achieve the above object, the present invention is a first base layer; A first adhesive layer laminated on the first substrate layer; a second adhesive layer laminated on the first adhesive layer; and a second substrate layer stacked on the second adhesive layer, wherein the first adhesive layer includes a silicone resin, a first hydride silicone compound represented by Formula 2, a second hydride silicone compound represented by Formula 3, A cured product layer of a composition for forming a first adhesive layer comprising an acrylic modified silicone resin and a photopolymerization initiator, and the second adhesive layer is a silicone resin, a first hydride silicone compound represented by Formula 2 and a second adhesive layer represented by Formula 3 It is a cured layer of a composition for forming a second adhesive layer containing a hydride silicone compound, and the composition for forming the first adhesive layer is based on 100 parts by weight of the silicone resin, 12 to 18 parts by weight of the first hydride silicone compound, the second The composition for forming the second adhesive layer includes 4 to 6 parts by weight of a hydride silicone compound and 20 to 40 parts by weight of an acrylic-modified silicone resin, based on 100 parts by weight of the silicone resin, 7 to 13 parts by weight of the first hydride silicone compound and An adhesive film containing 7 to 10 parts by weight of the second hydride silicone compound is provided.

Since the adhesive film of the present invention is provided in the form of a film, a separate process of bonding after forming a temporary adhesive layer on each of the semiconductor wafer and the support is not required, thereby simplifying the semiconductor wafer processing process and improving the production rate. have

In addition, since the adhesive film of the present invention includes a two-layer laminated structure composed of a first adhesive layer and a second adhesive layer, it has excellent heat resistance properties such as no deformation even in a high-temperature semiconductor wafer processing process, and It has an effect that can be used suitably for the processing process of a semiconductor wafer with irregularities such as bumps.

In addition, the adhesive film of the present invention can adjust the adhesiveness of both sides differently through predetermined heat treatment and UV irradiation, so that the side adhered to the wafer can be more easily peeled off, and no residue remains after the adhesive layer is removed, so it can be removed. There is an advantage that no separate process is required for this.

1 is a view showing an adhesive film according to the present invention.
2 is a view showing a form in which an adhesive film according to the present invention is bonded to a wafer and a carrier.
3 is a diagram showing a residual evaluation criterion according to an embodiment of the present invention.

The present invention relates to an adhesive film capable of adjusting the adhesive strength of both sides differently, and includes a first substrate layer, a first adhesive layer laminated on the first substrate layer, a second adhesive layer laminated on the first adhesive layer, and It includes a second substrate layer laminated on the second adhesive layer.

Hereinafter, the present invention will be described in detail.

Throughout this specification, when a member is said to be located “on” another member, this includes not only a case where a member is in contact with another member, but also a case where another member exists between the two members.

When it is said that a certain part "includes" a certain component throughout this specification, it means that it may further include other components, not excluding other components unless otherwise stated.

<Adhesive film>

The adhesive film 100 according to the present invention includes a first substrate 110 , a first adhesive layer 120 , a second adhesive layer 130 and a second substrate 140 . At this time, the first adhesive layer 120 and the second adhesive layer 140 are each made of the composition for forming the first adhesive layer and the composition for forming the second adhesive layer of the present invention, which will be described later, through a predetermined process. The substrate 110, the first adhesive layer 120, the second adhesive layer 130, and the second substrate 140 may be sequentially stacked.

First substrate 110 and second substrate 140

The first substrate 110 and the second substrate 140 according to the present invention are used to process semiconductor wafers and are not particularly limited as long as the adhesive layers 120 and 130 can be adhered to, but, for example, PE ( Polyethylene; PP (Polypropylene; Polypropylene), PC (Polycarbonate; Polycarbonate), PET (Polyethylene Terephthalate; Polyethylene Tetraphthalate), TAC (Triacetate Cellulose; Triacetyl Cellulose), PI (Polyimide; Polyimide), PEEK (Poly Ether Ether Ketone; polyether ether ketone), PVC (Polyvinyl Chloride; polyvinyl chloride) and PMMA (Polymethyl methacrylate; polymethyl methacrylate), etc. can be used, and PE (Polyethylene; polyethylene) is preferred. may, but is not limited thereto.

The thickness of the first substrate 110 and the second substrate 140 may be the thickness of the substrate in a conventional adhesive sheet for semiconductor wafer processing, and is preferably 20 to 200 μm, more preferably 35 to 80 μm. μm. When the above thickness range is satisfied, sufficient heat resistance can be secured in the process of manufacturing the adhesive film, and phenomena such as lifting can be prevented when storing roll-shaped products after manufacturing the adhesive sheet. When the thickness of the substrate is high, when stored as a roll-type product, lifting with the adhesive layer may occur, resulting in stains or inflow of foreign substances.

The first substrate 110 and the second substrate 140 may be a single layer or a multi-layer structure in which two or more layers are stacked. In addition, in order to improve adhesion to the surface of the first substrate 110 in contact with the first adhesive layer 120 and the surface of the second substrate 140 in contact with the second adhesive layer 130, corona treatment, priming, etc. surface treatment can be performed.

The first substrate 110 and the second substrate 140 may be release films. For example, when the adhesive film 100 according to the present invention is used for processing a semiconductor wafer, the first substrate 110 and the second substrate 140 are removed from the adhesive film 100, and the first adhesive The layer 120 may be adhered to the surface of the semiconductor wafer, and the second adhesive layer 130 may be adhered to the surface of the carrier.

First adhesive layer (120)

The first adhesive layer 120 according to the present invention is a layer for adhering or adhering the adhesive film 100 to the surface of a semiconductor wafer, and is a cured material layer formed by the composition for forming the first adhesive layer of the present invention described later. , It may be provided on the first substrate 110.

The thickness of the first adhesive layer 120 is not particularly limited, but may be 85 to 150 μm, preferably 90 to 120 μm. When the first adhesive layer 120 satisfies the above thickness range, it is advantageous to control adhesive strength, gel fraction, and thickness deviation, and to secure bump cover performance.

Second adhesive layer (130)

The second adhesive layer 130 according to the present invention is a layer for adhering or adhering the adhesive film 100 to a carrier, and is a cured material layer formed by a composition for forming a second adhesive layer described later, and the first adhesive layer 130 It may be provided on the layer 120 .

The thickness of the second adhesive layer 130 is not particularly limited, but may be 20 to 90 μm, preferably 40 to 85 μm. When the second adhesive layer 130 satisfies the above thickness range, there is an advantage in controlling adhesive strength, gel fraction, and thickness deviation.

Adhesive film (100)

The adhesive film 100 according to the present invention is used for semiconductor wafer processing, and includes a first adhesive layer 120 having a predetermined adhesive force to be attached to the wafer and a second adhesive layer having a predetermined adhesive force to be attached to a carrier. 130, and a first substrate 110 and a second substrate 140 adhered to the first adhesive layer 120 and the second adhesive layer 130, respectively.

During semiconductor wafer processing, the adhesive film 100 may be used to protect and fix the semiconductor wafer, and when the semiconductor wafer processing process is completed, the adhesive film 100 must be separated from the semiconductor wafer. For example, in a back grinding process for thinning a semiconductor wafer, the adhesive film 100 must adhere or adhere to the semiconductor wafer in order to protect the semiconductor wafer during the back grinding process. For example, a wafer may be ground to a thickness of about 100 μm using the adhesive film 100 according to the present embodiment, but is not limited thereto. The adhesive film 100 needs to be prevented from being deformed by vibration or heat generated by grinding the backside of a semiconductor wafer. In addition, when the back grinding process for the semiconductor wafer is completed, the adhesive film 100 must be separated from the semiconductor wafer. In this way, the adhesive film 100 must be peeled off without damaging the semiconductor wafer when peeling the adhesive film 100 while having adhesive strength to effectively adhere or adhere to the semiconductor wafer, if necessary.

The weight change rate of the adhesive film 100 at 250° C. calculated through Equation 1 below may be 1% or less.

[Equation 1]

(250 ℃ weight change rate) = 100 * [(initial weight of adhesive film) - (weight of adhesive film after heating at 250 ℃ for 5 minutes)] / (initial weight of adhesive film)

When the weight change rate of the adhesive film 100 at 250° C. satisfies the above numerical range, deformation does not occur even during wafer processing at high temperatures, which is preferable.

The first adhesive layer of the adhesive film 100 may have an initial adhesive force of 0.03 to 0.06 N/25 mm and an adhesive force of 0.03 to 0.07 N/25 mm after heat treatment at 150° C. for 60 minutes. When the initial adhesive strength of the first adhesive layer and the adhesive strength after heat treatment at 150 ° C. for 60 minutes satisfy the above numerical range, it is preferable because it is advantageous in securing process stability because the adhesive strength is maintained at a certain level even during heat treatment when the above numerical range is satisfied. do.

In addition, the first adhesive layer of the adhesive film 100 may have an adhesive strength of 0.01 N/25 mm or less after being irradiated with ultraviolet rays having a wavelength of 365 nm. When the adhesive strength of the first adhesive layer after irradiation with ultraviolet rays satisfies the above numerical range, it is possible to peel the processing member through ultraviolet irradiation at the necessary time after completion of the processing process, and it is possible to secure a very low peeling force, resulting in damage to the member However, it is preferable because it can suppress the generation of adhesive residue.

The second adhesive layer of the adhesive film 100 may have an initial adhesive force of 0.03 to 0.06 N/25 mm and an adhesive force of 0.15 to 0.2 N/25 mm after heat treatment at 150° C. for 60 minutes. When the initial adhesive force of the second adhesive layer and the adhesive force after heat treatment at 150 ° C. for 60 minutes satisfy the above numerical range, it can play a role in supporting the wafer and the carrier in the grinding process, etc., and the carrier after processing is completed. and the adhesive layer can be peeled together. And it is advantageous to peel the adhesive tape from the carrier after peeling, which is preferable because it allows the carrier material to be reused without damage.

<Composition for forming the first adhesive layer>

Adhesive composition according to the present invention is a silicone resin; a first hydride silicone compound; a second hydride silicone compound; acrylic modified silicone resin; and a photopolymerization initiator, and may further include a metal catalyst, an inhibitor, an accelerator, and/or a solvent, but is not limited thereto.

Each component is described in detail below.

silicone resin

The composition for forming the first adhesive layer may include a silicone resin, wherein the silicone resin includes a first silicone resin including units represented by (i) to (iii) and a second silicone resin represented by Chemical Formula 1. can include

First silicone resin

The composition for forming the first adhesive layer may include a first silicone resin including units represented by the following (i) to (iii). The first silicone resin is a cyclic (reticulated) silicone resin, and as the main resin of the composition for forming an adhesive layer, serves as a skeleton forming the adhesive layer after crosslinking and affects overall physical properties.

(i) T unit: 45 to 99 mol%

(ii) D unit: less than 60 mol%

(iii) M unit: 1 mol% or more and less than 25 mol%

(The above R ¹ to R ⁶ are each independently a hydrogen atom, an amino group, a hydroxyl group, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or a carbon number 3 to 30 It is an acrylic group.)

The weight average molecular weight (Mw) of the first silicone resin may be 270,000 to 1 million, preferably 600,000 to 900,000. When the weight average molecular weight of the first silicone resin satisfies the above range, there is an advantage in securing physical properties such as sufficient tensile strength, tensile elongation, and CTE during film production. However, if the molecular weight is too high, the above range is appropriate because very high viscosity occurs during process application, which makes handling difficult.

Commercially available products of the first silicone resin include VPR-0600N, VPR-0500 (above, Biogen), KR-2506, KR-5230, KR-5234, ES-1001N, ES-1023 (above, Shin-Etsu), etc. Examples include, but are not limited to.

In the composition for forming the first adhesive layer, the first silicone resin may be included in an amount of 45 to 85% by weight, preferably 55 to 65% by weight, based on the total weight of solids in the composition for forming the first adhesive layer. can When the above content range is satisfied, sufficient film properties can be secured. If it is less than 45% by weight, sufficient crosslinking of the adhesive film may be insufficient, and if it exceeds 85% by weight, the viscosity of the composition may increase, making handling difficult, and unreacted components may be generated, which may deteriorate the performance of the adhesive film.

In the present invention, the total weight of the solid content in the composition for forming the first adhesive layer means the total weight of the components other than the solvent in the composition for forming the first adhesive layer.

Second silicone resin

The composition for forming the first adhesive layer includes a second silicone resin represented by Formula 1 below. The second silicone resin is a linear silicone resin and has a low molecular weight and viscosity while participating in a crosslinking reaction, so it serves to secure fluidity and coating properties of the entire composition.

[Formula 1]

(In Formula 1 above,

R ¹¹ to R ²⁰ are each independently an amino group, a hydroxyl group, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a carbon number 3 to 30 acryl groups.

m is an integer from 100 to 700;

n is an integer from 100 to 500.)

The weight average molecular weight (Mw) of the second silicone resin may be 500 to 50,000, preferably 1000 to 30,000. When the weight average molecular weight of the second silicone resin satisfies the above range, it is preferable because it has the advantage of being able to control the coating properties of the composition while ensuring sufficient crosslinking reaction.

Commercially available products of the second silicone resin represented by Formula 1 include RF-VN0100, RF-VN0010 (above, Biogen), KC-89S, KR515, X-40-9246 (above, Shin-Etsu), etc. , but not limited thereto.

In the composition for forming the first adhesive layer, the second silicone resin may be included in an amount of 5 to 10% by weight based on the total solid weight of the composition for forming the first adhesive layer. When the above content range is satisfied, it is preferable because it is possible to secure the fluidity and coating properties of the coating solution without deterioration of physical properties.

In the composition for forming the first adhesive layer, the first silicone resin and the second silicone resin may be included in a weight ratio of 80 to 100:5 to 20. When the first silicone resin and the second silicone resin are included in the above weight ratio range, it is possible to secure necessary physical properties when manufacturing an adhesive film, and when manufacturing a coating solution, it is preferable because necessary fluidity and coating properties can be secured.

First hydride silicone compound

The composition for forming the first adhesive layer includes a first hydride silicone compound represented by Formula 2 below. The first hydride silicone compound is a silicone compound having a reactive hydride at a repeating unit site, and serves to increase strength and elasticity of the adhesive layer and suppress deformation by inducing cross-linking between linear molecules.

[Formula 2]

(In Formula 2 above,

R ²¹ to R ²³ and R ²⁸ to R ³⁰ are each independently an amino group, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an acryl group having 3 to 30 carbon atoms, or It is an epoxy group.

R ²⁴ to R ²⁷ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an epoxy group or an amino group. However, at least one of R ²⁴ to R ²⁷ is a hydrogen atom.

o is an integer from 100 to 700;

p is an integer from 100 to 500.)

The weight average molecular weight (Mw) of the first hydride silicone compound may be 500 to 50,000, preferably 1,000 to 30,000. When the weight average molecular weight of the first hydride silicone compound satisfies the above range, it is preferable because sufficient reactivity can be secured and an appropriate viscosity can be induced during composition mixing.

Examples of commercially available products of the first hydride silicone compound include XL-02 (Biogen), Poly(methylhydrosiloxane) (MERCK), HF2020, HF2050, HF2060 (above, PCC), but are not limited thereto.

In the composition for forming the first adhesive layer, the first hydride silicone compound may be included in an amount of 12 to 18 parts by weight based on 100 parts by weight of the silicone resin. When the first hydride silicone compound satisfies the weight part range, the strength and elasticity of the first adhesive layer can be adjusted within an appropriate range, and a sufficient crosslinking reaction can be exhibited, which is preferable.

Second hydride silicone compound

The composition for forming the first adhesive layer includes a second hydride silicone compound represented by Formula 3 below. The second hydride silicone compound is a silicone compound having a reactive hydride at the terminal portion, and serves as a chain extender that increases the length of the polymer chain and enhances the ductility and tensile properties of the film.

[Formula 3]

(In Formula 3,

R ³¹ to R ³³ and R ³⁸ to R ⁴⁰ are each independently a hydrogen atom, an amino group, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylene group having 2 to 30 carbon atoms, and a carbon atom having 3 to 30 carbon atoms. It is an acrylic group or an epoxy group. However, at least one of R ³¹ to R ³³ and R ³⁸ to R ⁴⁰ is a hydrogen atom.

R ³⁴ to R ³⁷ are each independently an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an epoxy group or an amino group.

s is an integer from 100 to 700.

t is an integer from 100 to 500.)

The weight average molecular weight (Mw) of the second hydride silicone compound may be 500 to 50,000, preferably 1,000 to 30,000. When the weight average molecular weight of the second hydride silicone compound satisfies the above range, it is preferable because it has sufficient reactivity and thus has the advantage of inducing a desired reaction in an appropriate amount.

Examples of commercial products of the second hydride silicone compound include RF-HD (Biogen), MHX-1107 Fluid (Dow), Poly (dimethylsiloxane), hydride terminated (MERCK), HF2030 (PCC), etc. , but not limited thereto.

In the composition for forming the first adhesive layer, the second hydride silicone compound is included in an amount of 4 to 6 parts by weight based on 100 parts by weight of the silicone resin. When the weight part range is satisfied, the bump cover performance of the film can be secured by imparting appropriate ductility to the adhesive film, and the elastic property can be satisfied within a desired range, thereby preventing defects such as tearing of the adhesive film during the process. It is desirable because it exists.

Acrylic modified silicone resin

The composition for forming the first adhesive layer includes an acrylic-modified silicone resin, and reacts with a photopolymerization initiator when irradiated with UV of a specific wavelength to reduce the adhesive strength of the adhesive layer.

Specific examples of the acrylic-modified silicone resin include one or more radically polymerized monomer compounds selected from monofunctional, bifunctional, trifunctional or multifunctional acrylic acid ester or methacrylic acid ester monomers, and derived from the acrylic acid ester or methacrylic acid ester polymerizable compounds modified by introducing one or more acrylic acid ester residues or methacrylic acid ester residues into the molecular chain; silicone compounds containing mono- to tri-functional or higher functional groups having radical addition reactivity; and the like, but are limited thereto. It doesn't work.

The acrylic-modified silicone resin may include a compound represented by Formula 4 below.

[Formula 4]

(In Formula 4 above

R ⁴¹ to R ⁴⁶ are each independently a methyl group, a group represented by the following formula (5), or a group represented by the formula (6).

R ⁴⁷ is a methyl group.

R ⁴⁸ is a methyl group or a phenyl group.

u is an integer from 100 to 1000;

v is an integer from 1 to 800.)

[Formula 5]

[Formula 6]

(In Formula 5 and Formula 6, * represents a bond with a silicon atom.)

In the compound represented by Formula 4, at least one of R ⁴¹ to R ⁴⁶ may be a group represented by Formula 5 or a group represented by Formula 6.

Also, in the compound represented by Formula 4, at least one of R ⁴¹ to R ⁴³ and at least one of R ⁴⁴ to R ⁴⁶ may be a group represented by Formula 5 or a group represented by Formula 6.

In the composition for forming the first adhesive layer, the acrylic-modified silicone resin may be included in an amount of 20 to 40 parts by weight based on 100 parts by weight of the silicone resin. When the acrylic modified silicone resin satisfies the above content range, it is preferable because the adhesive strength of the adhesive layer can be sufficiently reduced through UV irradiation of a specific wavelength.

photopolymerization initiator

The composition for forming the first adhesive layer may include a photopolymerization initiator.

The type of the photopolymerization initiator may be used without particular limitation. In particular, the photopolymerization initiator is an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a biimidazole-based compound, an oxime-based compound, and thiochic acid in terms of polymerization characteristics, initiation efficiency, absorption wavelength, availability, price, etc. It may include one or more compounds selected from the group consisting of tone-based compounds and phosphine oxide compounds.

As said acetophenone type compound, for example, diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, Igacure 184 (1-hydroxycyclohexylphenyl ketone), 2-methyl -1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butane- 1-one, Igacure 379 (2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one), and the like.

Examples of the benzophenone compound include benzophenone, o-methyl benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra ( tert-butyl peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and 1-hydroxycyclohexylphenyl ketone. Commercially available products include OMNIRAD 481 from IGM Resins.

As said triazine type compound, for example, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) - 6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1 ,3,5-triazine etc. are mentioned.

Examples of the biimidazole-based compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole and 2,2'-bis(2,3 -Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1, 2'-biimidazole etc. are mentioned.

Examples of the oxime-based compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one. Commercially available products include BASF's Irgacure® OXE-01 and OXE-02 OXE-03 etc. are mentioned.

Examples of the thioxanthone-based compounds include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like. can be heard

Examples of the phosphine oxide compound include trimethylbenzoyldiphenylphosphine oxide, and commercially available products include Darocur TPO and IRGACURE-819 from BASF.

The photopolymerization initiator included in the adhesive composition of the present invention may be included in an amount of 0.5 to 2.5% by weight based on the total weight of the composition for forming the first adhesive layer.

metal catalyst

The composition for forming the first adhesive layer may include a metal catalyst to promote polymerization of the silicone resin.

The metal catalyst is not particularly limited as long as it can be used for polymerization of a silicone resin, but may include one or more selected from the group consisting of platinum, tin, titanium, aluminum, zinc, cobalt, and manganese, and silicon having a vinyl group. In order to crosslink the polymer and the hydride silicone polymer, a platinum catalyst is suitable, and it is preferable to include a platinum catalyst in that there are almost no decomposition products and it is possible to enhance physical properties such as heat resistance.

In the composition for forming the first adhesive layer, the metal catalyst may be included in an amount of 0.01 to 1.0% by weight based on the total weight of the composition for forming the first adhesive layer. When the metal catalyst satisfies the above content range, it is preferable because sufficient reactivity can be induced.

inhibitor

When the composition for forming the first adhesive layer includes a metal catalyst or the like, it may be difficult to properly control the curing reaction in a desired process due to rapid reactivity. Therefore, if necessary, an inhibitor is added to lower the reactivity and the curing reaction in a desired process can be performed. can induce

The inhibitor is not particularly limited, but IHP (4-Hydroxy-TEMPO SFR), IOP (4-Oxo-TEMPO SFR), IBP (2-Sec-butyl-4,6-Dinitrophenol), DNOC (4,6-Dinitro -o-cresol), DNPC (2,6-Dinitro-p-cresol), ISP (p-Nitrosophenol), PTZ (Phenothiazine), MEHQ (Hydroquinone Monomethyl Ether) and ECH (1-Ethynylcyclohexanol) It may include one or more, and is not particularly limited.

In the composition for forming the first adhesive layer, the inhibitor may be included in an amount of 0.002 to 0.5% by weight based on the total weight of the composition for forming the first adhesive layer. When the inhibitor satisfies the above content range, it is preferable because the curing reaction can be induced in a desired process by lowering the reactivity.

accelerant

The composition for forming the first adhesive layer may include an accelerator, if necessary, in order to induce faster reactivity.

The accelerator is not particularly limited, but an accelerator composed of an amine-based compound is mainly formed. In order to reduce odor and obtain a higher degree of curing, an aminobenzoate derivative is preferred, so Darocure EHA (2-ethylhexyl-4- dimethylaminobenzoate).

In the composition for forming the first adhesive layer, the accelerator may be included in an amount of 0.01 to 0.5% by weight based on the total weight of the composition for forming the first adhesive layer. When the accelerator satisfies the above content range, it is preferable because it can induce a curing reaction in a desired process by increasing the reactivity.

solvent

The composition for forming the first adhesive layer may include a solvent for mixing and viscosity control of the respective components.

Specific examples of the solvent may include at least one selected from the group consisting of ethers, aromatic hydrocarbons, ketones, alcohols, esters and amides, and specifically, propylene glycol monomethyl ether acetate, ethylene glycol Monomethyl ether, ethylene glycol monoethyl ether, propylene glycol methyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, toluene, xylene, mesitylene, acetone, methyl amyl ketone, methyl ethyl ketone (MEK) , isobutyl ketone, cyclohexanone, butanol, hexanol, cyclohexanol and ethyl 3-ethoxypropionate, 1,3-butylene glycol diacetate, ethyl-3-ethoxypropionate, propylene glycol diacetate, 1 to 2 selected from the group consisting of ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, methoxybutyl acetate, ethylene glycol and γ-butyrolactone, methylpyrrolidone (NMP), etc. There may be more than one species.

In the composition for forming the first adhesive layer, the solvent may be included in an amount of 10 to 80% by weight based on the total weight of the composition for forming the first adhesive layer. When the solvent satisfies the above content range, it is preferable because other components can be sufficiently dissolved and the viscosity of the composition can be appropriately adjusted.

<Composition for Forming Second Adhesive Layer>

The composition for forming the second adhesive layer according to the present invention is a silicone resin; a first hydride silicone compound represented by Formula 2; and a second hydride silicone compound represented by Formula 3, and may further include a metal catalyst, an inhibitor, and/or a solvent, but is not limited thereto.

Regarding the silicone resin, metal catalyst, inhibitor, and solvent, the contents of the silicone resin, metal catalyst, inhibitor, and solvent described in <Composition for Forming First Adhesive Layer> may be applied as they are.

First hydride silicone compound

The composition for forming the second adhesive layer includes a first hydride silicone compound represented by Formula 2 below. The first hydride silicone compound is a silicone compound having a reactive hydride at a repeating unit site, and serves to increase strength and elasticity of the adhesive layer and suppress deformation by inducing cross-linking between linear molecules.

[Formula 2]

(In Formula 2 above,

R ²¹ to R ²³ and R ²⁸ to R ³⁰ are each independently an amino group, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an acryl group having 3 to 30 carbon atoms, or It is an epoxy group.

R ²⁴ to R ²⁷ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an epoxy group or an amino group. However, at least one of R ²⁴ to R ²⁷ is a hydrogen atom.

o is an integer from 100 to 700;

p is an integer from 100 to 500.)

The weight average molecular weight (Mw) of the first hydride silicone compound may be 500 to 50,000, preferably 1,000 to 30,000. When the weight average molecular weight of the first hydride silicone compound satisfies the above range, it is preferable because sufficient reactivity can be secured and an appropriate viscosity can be induced during composition mixing.

Examples of commercially available products of the first hydride silicone compound include XL-02 (Biogen), Poly(methylhydrosiloxane) (MERCK), HF2020, HF2050, HF2060 (above, PCC), but are not limited thereto.

In the composition for forming the second adhesive layer, the first hydride silicone compound may be included in an amount of 7 to 13 parts by weight based on 100 parts by weight of the silicone resin. When the first hydride silicone compound satisfies the above content range, the strength and elasticity of the first adhesive layer can be adjusted to an appropriate range, and the strength and elasticity of the second adhesive layer can be adjusted to an appropriate range. 7 If it is less than one part by weight, the adhesive force becomes higher than necessary and the heat resistance performance is weakened. If it is 13 parts by weight or more, the adhesive strength is lower than necessary and it is difficult to maintain a level higher than that of the first adhesive layer, so it is preferable to adjust it within the corresponding range.

Second hydride silicone compound

The composition for forming the second adhesive layer includes a second hydride silicone compound represented by Formula 3 below. The second hydride silicone compound is a silicone compound having a reactive hydride at a terminal portion and serves as a chain extender that increases the length of a polymer chain.

[Formula 3]

(In Formula 3,

R ³¹ to R ³³ and R ³⁸ to R ⁴⁰ are each independently a hydrogen atom, an amino group, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylene group having 2 to 30 carbon atoms, and a carbon atom having 3 to 30 carbon atoms. It is an acrylic group or an epoxy group. However, at least one of R ³¹ to R ³³ and R ³⁸ to R ⁴⁰ is a hydrogen atom.

R ³⁴ to R ³⁷ are each independently an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an epoxy group or an amino group.

s is an integer from 100 to 700.

t is an integer from 100 to 500.)

The weight average molecular weight (Mw) of the second hydride silicone compound may be 500 to 50,000, preferably 1,000 to 30,000. When the weight average molecular weight of the second hydride silicone compound satisfies the above range, it is preferable because it has sufficient reactivity and thus has the advantage of inducing a desired reaction in an appropriate direction.

Commercially available products of the second hydride silicone compound include RF-HD (Biogen), MHX-1107 Fluid (Dow), Poly (dimethylsiloxane), hydride terminated (MERCK), HF2030 (PCC), etc. , but not limited thereto.

In the composition for forming the second adhesive layer, the second hydride silicone compound is included in an amount of 7 to 10 parts by weight based on 100 parts by weight of the silicone resin. When the above weight part range is satisfied, it is preferable because it is possible to secure a necessary level of adhesive strength to make a level difference with the first adhesive layer and not impair heat resistance and physical properties.

<Manufacture of adhesive film>

1 is a view showing an adhesive film according to the present invention. A method of manufacturing the adhesive film 100 according to the present invention will be described as an example. As shown in FIG. 1, a first substrate 110 is prepared, and the composition for forming the first adhesive layer is coated on one side of the first substrate 110 so that the thickness after drying is 85 to 150 μm, and the temperature is 150° C. dried for 4 minutes to volatilize the solvent to form the first adhesive layer 120 . Subsequently, a composition for forming a second adhesive layer is coated on the upper surface of the first adhesive layer 120 to a thickness of 20 to 90 μm after drying, and dried at 150 ° C. for 4 minutes to volatilize the solvent to form a second adhesive layer ( 130) form. Thereafter, the second substrate 140 may be laminated and bonded to the upper surface of the second adhesive layer 130 . Accordingly, the adhesive film 100 in which the first substrate 110, the first adhesive layer 120, the second adhesive layer 130, and the second substrate 140 are sequentially stacked may be manufactured.

In this case, the first substrate 110 and the second substrate 140 may be a 38 μm silicone release treatment film, but are not limited thereto. In addition, the first substrate 110 and the second substrate 140 may be applied as they are to the substrate described in <Adhesive Film>.

2 is a view showing a form in which an adhesive film according to the present invention is bonded to a wafer and a carrier. In the adhesive film 100 according to the present invention, after removing the first substrate 110 and the second substrate 140, the first adhesive layer 120 is applied to the semiconductor wafer and the second adhesive layer 130 is applied to the carrier. Adhesion or attachment may be performed, and after wafer processing, the first adhesive layer 120 may be peeled from the wafer, if necessary.

Hereinafter, examples will be described in detail to explain the present invention in detail. However, the embodiments according to the present invention can be modified in many different forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

<Example>

Synthesis Example 1: Synthesis of Acrylic Modified Silicone Resin

The acrylic modified silicone resin is prepared by the following method.

150 parts by weight of epoxy silicone oil (KF-105, Shin-Etsu), 130 parts by weight of toluene, 0.06 part by weight of tetramethylguanidine (Sigma-Aldrich), and 0.03 part by weight of hydroquinone (Sigma-Aldrich) were stirred in a four-necked flask under a nitrogen atmosphere while stirring the acrylic An acrylic modified silicone resin was synthesized by reacting for 20 hours while adding 20 parts by weight of the acid.

Preparation Examples 1-1 to 1-8: Preparation of the composition for forming the first adhesive layer

Compositions for forming the first adhesive layer of Preparation Examples 1-1 to 1-8 were prepared according to the compositions and contents of Table 1 below.

No. 1
silicone resin 2nd
silicone resin First hydride silicone compound Second hydride silicone compound inhibitor catalyst acrylic denaturation
silicone resin Initiator 1 Initiator 2 accelerant menstruum Preparation Example 1-1 90 10 15 5 0.2 One 30.00 1.50 3.00 1.00 200 Preparation Example 1-2 90 10 18 6 0.2 One 30.00 1.50 3.00 1.00 200 Preparation Example 1-3 90 10 12 4 0.2 One 30.00 1.50 3.00 1.00 200 Preparation Example 1-4 90 10 15 5 0.2 One - - - - 30 Preparation Example 1-5 90 10 15 5 0.2 One 41.00 2.05 4.10 1.37 200 Preparation Example 1-6 90 10 15 5 0.2 One 19.00 0.95 1.90 0.63 200 Production Example 1-7 90 10 7 3 0.2 One 30.00 1.50 3.00 1.00 200 Production Example 1-8 90 10 20 8 0.2 One 30.00 1.50 3.00 1.00 200

1st silicone resin: cyclic vinyl silicone resin (VPR-0600N, Biogen)

Second silicone resin: chain-type vinyl silicone resin (RF-VN0100, Biogen)

First hydride silicone compound: XL-02 (Biogen)

Second hydride silicone compound: RF-HD (Biogen)

Inhibitor: ECH (Ethynyl cyclohexanol) (Merck)

Catalyst: Platinum catalyst (CPT-037, Biogen)

Acrylic-modified silicone resin: Acrylic-modified silicone resin according to Synthesis Example 1

Initiator 1: Igacure 379 (2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one) (Ciba Specialty Chemicals)

Initiator 2: Igacure 184 (1-hydroxy-cyclohexyl-phenylketone) (Ciba Specialty Chemicals)

Accelerator: Darocure EHA

Solvent: Toluene

Preparation Examples 2-1 to 2-5: Preparation of composition for forming a second adhesive layer

Compositions for forming a second adhesive layer of Preparation Examples 2-1 to 2-5 were prepared according to the compositions and contents in Table 2 below.

No. 1 silicone resin 2nd silicone resin First hydride silicone compound Second hydride silicone compound inhibitor catalyst menstruum Preparation Example 2-1 90 10 9 9 0.2 One 30 Preparation Example 2-2 90 10 13 10 0.2 One 30 Preparation Example 2-3 90 10 7 7 0.2 One 30 Preparation Example 2-4 90 10 18 12 0.2 One 30 Preparation Example 2-5 90 10 6 6 0.2 One 30

1st silicone resin: cyclic vinyl silicone resin (VPR-0600N, Biogen)

Second silicone resin: chain-type vinyl silicone resin (RF-VN0100, Biogen)

First hydride silicone compound: XL-02 (Biogen)

Second hydride silicone compound: RF-HD (Biogen)

Inhibitor: ECH (Ethynyl cyclohexanol) (Merck)

Catalyst: Platinum catalyst (CPT-037, Biogen)

Solvent: Toluene

Examples 1 to 5 and Comparative Examples 1 to 8: Preparation of adhesive film

The composition for forming the first adhesive layer was coated on the PET surface of the base material (non-silicone release-treated film, 50 μm, Yulchon), and dried at 150° C. for 4 minutes to form the first adhesive layer. Subsequently, a second adhesive layer was formed on the first adhesive layer using the composition for forming a second adhesive layer in the same manner, and a substrate was laminated on the upper surface of the second adhesive layer to prepare an adhesive film.

The composition for forming the first adhesive layer and the composition for forming the second adhesive layer used at this time and the thicknesses of the first adhesive layer and the second adhesive layer are shown in Table 3 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 First adhesive layer (A) Preparation Example 1-1 Production Example 1-2 Production Example 1-3 Preparation Example 1-1 Preparation Example 1-1 Production Example 1-4 Production Example 1-4 Production Example 1-5 Production Example 1-6 Production Example 1-7 Production Example 1-8 Preparation Example 1-1 Preparation Example 1-1 (A) Layer thickness (μm) 100 100 100 120 90 100 100 100 100 100 100 100 100 Second adhesive layer (B) Preparation Example 2-1 Production Example 2-2 Manufacturing example 2-3 Preparation Example 2-1 Preparation Example 2-1 - Preparation Example 2-1 Preparation Example 2-1 Preparation Example 2-1 Preparation Example 2-1 Preparation Example 2-1 Manufacturing example 2-4 Production Example 2-5 (B) Layer thickness (㎛) 75 75 75 55 85 - 75 75 75 75 75 75 75

<Experimental example>

1. Evaluation of initial adhesion

The initial adhesive strength of each of the first adhesive layer and the second adhesive layer of the adhesive film according to the Examples and Comparative Examples was measured. First, a sample is prepared by cutting the adhesive film into a width of 25 mm and a length of 150 mm. After the sample was adhered and fixed to the Mirror Wafer, one side was fixed to the load cell clamp of the universal testing machine, and the initial adhesive force was measured while peeling the adhesive sheet at 90° at a speed of 300 mm/min. The initial adhesive strength was measured three times and an average value was calculated, and the results are shown in Table 4 below.

2. Evaluation of adhesion after heat treatment

After heat treatment of each of the first adhesive layer and the second adhesive layer of the adhesive film according to Examples and Comparative Examples, adhesive strength was measured. First, a sample is prepared by cutting the adhesive film into a width of 25 mm and a length of 150 mm. After attaching the sample to the Mirror Wafer, heat treatment was performed at 150° C. for 60 minutes. Then, one side was fixed to the load cell clamp of the universal testing machine, and the adhesive sheet was peeled at 90° at a speed of 300 mm/min, and the adhesive force was measured after heat treatment. After the heat treatment, the adhesive force was measured three times and the average value was calculated, and the results are shown in Table 4 below.

3. Adhesion evaluation after UV irradiation

After UV irradiation of each of the first adhesive layer and the second adhesive layer of the adhesive film according to the Examples and Comparative Examples, the adhesive strength was measured. First, a sample is prepared by cutting the adhesive film into a width of 25 mm and a length of 150 mm. After the sample was adhered to a glass without UV cut, UV of 365 nm wavelength was irradiated through the glass surface. Then, one side was fixed to the load cell clamp of the universal testing machine, and the adhesive sheet was peeled at 90° at a speed of 300 mm/min, and the adhesive force was measured after UV irradiation. After the UV irradiation, the adhesive force was measured three times and the average value was calculated, and the results are shown in Table 4 below.

4. 250 ℃ weight change rate evaluation

About 3g of the adhesive film according to Examples and Comparative Examples was sampled, put on an aluminum dish, and the initial weight was measured. Then, the aluminum dish and the sample were put into an electric furnace (MF-20, JEIOTECH) and heated at 250° C. for 5 minutes. After cooling the heated sample at room temperature, the weight reduced after heating was measured, and the weight change rate (%) at 250 ° C was calculated through Equation 1 below, and the results are shown in Table 4 below.

[Equation 1]

250 ℃ weight change rate (%) = 100 * [(initial weight of adhesive film) - (weight of adhesive film after heating for 5 minutes at 250 ℃)] / (initial weight of adhesive film)

5. Evaluation of bump cover performance

The adhesive films according to Examples and Comparative Examples were laminated on a wafer having bumps of 50 μm in height and attached while heating at 150° C. Immediately after attaching, the thickness A of the part with bumps and the thickness B of the part without bumps were measured using a static pressure thickness meter (PG-02, Techlock Co.), and the height difference between thicknesses A and B was calculated. . Bump cover performance was evaluated according to the following evaluation criteria, and the results are shown in Table 4 below. As the height difference is smaller, it means that irregularities caused by the height of the bump are buried and alleviated by the adhesive film.

<Bump Cover Performance Evaluation Criteria>

○: The height difference between the thickness A and B is less than 10 μm

×: height difference between thicknesses A and B is 10 μm or more

6. Residue Assessment

Samples were prepared by cutting the adhesive films according to Examples and Comparative Examples to 10x10 (cm), and the first adhesive layer was bonded to the wafer and the second adhesive layer was bonded to the glass, respectively. The prepared sample is heat-resistant at 150 ° C for 1 hour, left at room temperature for 30 minutes, and then injected at 85 ° C for 24 hours under 85% conditions. Then, the sample is peeled at 90 degrees. Evaluate the performance by checking whether there is any residue on the surface of each wafer or glass. The evaluation is done visually.

<Criteria for evaluation of residues>

○: Clear all wafer and glass surfaces (see '○' in FIG. 3)

×: Residues occur on one or more surfaces of wafer and glass (see 'X' in Fig. 3)

Adhesion of the first adhesive layer (N/25mm) Adhesion of the second adhesive layer (N/25mm) 250℃ weight change rate (%) bump
cover performance hangover
evaluation Early after heat treatment After UV irradiation Early after heat treatment Example 1 0.040 0.070 0.002 0.050 0.165 0.6 ○ ○ Example 2 0.038 0.060 0.002 0.040 0.160 0.5 ○ ○ Example 3 0.060 0.070 0.002 0.060 0.165 0.5 ○ ○ Example 4 0.060 0.070 0.008 0.040 0.150 0.5 ○ ○ Example 5 0.035 0.060 0.002 0.060 0.170 0.6 ○ ○ Comparative Example 1 0.050 0.070 0.050 0.050 0.050 0.6 ○ ○ Comparative Example 2 0.050 0.070 0.050 0.050 0.165 0.6 ○ ○ Comparative Example 3 0.120 0.190 0.002 0.060 0.167 0.6 ○ ○ Comparative Example 4 0.050 0.070 0.060 0.060 0.165 0.6 ○ ○ Comparative Example 5 0.130 0.210 0.020 0.060 0.165 2.4 ○ × Comparative Example 6 0.010 0.080 0.020 0.040 0.166 0.6 × ○ Comparative Example 7 0.050 0.070 0.002 0.010 0.070 0.6 ○ ○ Comparative Example 8 0.050 0.068 0.002 0.140 0.180 2.1 ○ ×

Referring to Table 4, it can be confirmed that the adhesive films according to Examples 1 to 5 of the present application exhibit excellent effects in bump cover performance and residual evaluation, and the adhesive strength after heat treatment of the first adhesive layer is 0.060 to 0.070 N/25mm , and the adhesive force after UV irradiation is adjusted to 0.010 N / 25 mm or less, while the adhesive force after heat treatment of the second adhesive layer is maintained at 0.150 to 0.200 N / 25 mm, which is higher than that of the first adhesive layer, resulting in a wafer ( 2), it can be seen that the first adhesive layer adhered to the carrier can be more easily peeled off than the second adhesive layer adhered to the carrier.

On the other hand, the adhesive film according to Comparative Example 1 including the adhesive layer formed using the composition for forming the first adhesive layer of Preparation Examples 1-4 that does not contain an acrylic-modified silicone resin is heat treated and UV irradiated on both sides of the adhesive layer. It can be seen that there is no significant difference in adhesive strength, indicating that certain surfaces cannot be peeled off more easily.

In addition, the adhesive films according to Comparative Examples 2 to 6 including the first adhesive layer formed using the composition for forming the first adhesive layer of Preparation Examples 1-5 to 1-8, the initial adhesive strength of the first adhesive layer is 0.06 It does not satisfy the desired adhesive strength range, such as exceeding N/25 mm, adhesive strength after heat treatment exceeding 0.07 N/25 mm, or adhesive strength after UV irradiation exceeding 0.01 N/25 mm, and in particular, Comparative Examples 5 and 6, respectively It can be seen that the bump capper performance and residue evaluation results also significantly deteriorated.

In addition, the adhesive films according to Comparative Examples 7 and 8 including the second adhesive layer formed using the composition for forming the second adhesive layer of Preparation Examples 2-4 and 2-5, the initial adhesive strength of the second adhesive layer was 0.06 It can be confirmed that N/25 mm is exceeded, the adhesive force after heat treatment is 0.15 N/25 mm or less, or the bump cover performance is significantly deteriorated.

Claims (12)

A first base layer;
A first adhesive layer laminated on the first substrate layer;
a second adhesive layer laminated on the first adhesive layer; and
And a second substrate layer laminated on the second adhesive layer,
The first adhesive layer is formed of a first adhesive layer comprising a silicone resin, a first hydride silicone compound represented by the following formula (2), a second hydride silicone compound represented by the following formula (3), an acrylic modified silicone resin and a photopolymerization initiator A cured product layer of a composition for
The second adhesive layer is a cured product layer of a composition for forming a second adhesive layer including a silicone resin, a first hydride silicone compound represented by Formula 2 below, and a second hydride silicone compound represented by Formula 3 below,
The composition for forming the first adhesive layer includes 12 to 18 parts by weight of the first hydride silicone compound, 4 to 6 parts by weight of the second hydride silicone compound, and 20 to 6 parts by weight of the acrylic modified silicone resin, based on 100 parts by weight of the silicone resin. 40 parts by weight,
The composition for forming the second adhesive layer includes 7 to 13 parts by weight of the first hydride silicone compound and 7 to 10 parts by weight of the second hydride silicone compound, based on 100 parts by weight of the silicone resin.
[Formula 2]

(In Formula 2 above,
R ²¹ to R ²³ and R ²⁸ to R ³⁰ are each independently an amino group, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an acryl group having 3 to 30 carbon atoms, or It is an epoxy group.
R ²⁴ to R ²⁷ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an epoxy group or an amino group. However, at least one of R ²⁴ to R ²⁷ is a hydrogen atom.
o is an integer from 100 to 700;
p is an integer from 100 to 500.)
[Formula 3]

(In Formula 3,
R ³¹ to R ³³ and R ³⁸ to R ⁴⁰ are each independently a hydrogen atom, an amino group, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylene group having 2 to 30 carbon atoms, and a carbon atom having 3 to 30 carbon atoms. It is an acrylic group or an epoxy group. However, at least one of R ³¹ to R ³³ and R ³⁸ to R ⁴⁰ is a hydrogen atom.
R ³⁴ to R ³⁷ are each independently an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an epoxy group or an amino group.
s is an integer from 100 to 700.
t is an integer from 100 to 500.) The method of claim 1,
The silicone resin comprises a first silicone resin comprising units represented by (i) to (iii) and a second silicone resin represented by the following formula (1), the adhesive film.
(i) T unit: 45 to 99 mol%

(ii) D unit: less than 60 mol%

(iii) M unit: 1 mol% or more and less than 25 mol%

(The above R ¹ to R ⁶ are each independently a hydrogen atom, an amino group, a hydroxyl group, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or a carbon number 3 to 30 It is an acrylic group.)
[Formula 1]

(In Formula 1 above,
R ¹¹ to R ²⁰ are each independently an amino group, a hydroxyl group, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a carbon number 3 to 30 acryl groups.
m is an integer from 100 to 700;
n is an integer from 100 to 500.) The method of claim 2,
The first silicone resin and the second silicone resin are included in a weight ratio of 80 to 100: 5 to 20, the adhesive film. The method of claim 1,
The acrylic-modified silicone resin comprises a compound represented by Formula 4 below, an adhesive film.
[Formula 4]

(In Formula 4 above
R ⁴¹ to R ⁴⁶ are each independently a methyl group, a group represented by the following formula (5), or a group represented by the formula (6).
R ⁴⁷ is a methyl group.
R ⁴⁸ is a methyl group or a phenyl group.
u is an integer from 100 to 1000;
v is an integer from 1 to 800.)
[Formula 5]

[Formula 6]

(In Formula 5 and Formula 6, * represents a bond with a silicon atom.) The method of claim 1,
The composition for forming the first adhesive layer further comprises at least one selected from the group consisting of a metal catalyst, an inhibitor, an accelerator, and a solvent. The method of claim 1,
The composition for forming the second adhesive layer further comprises at least one selected from the group consisting of a metal catalyst, an inhibitor, and a solvent. The method of claim 1,
The adhesive film has a weight change rate of 250 ° C. calculated through Equation 1 below of 1% or less.
[Equation 1]
(250 ℃ weight change rate) = 100 * [(initial weight of adhesive film) - (weight of adhesive film after heating at 250 ℃ for 5 minutes)] / (initial weight of adhesive film) The method of claim 1,
The first adhesive layer has an initial adhesive force of 0.03 to 0.06 N / 25 mm, and an adhesive force after heat treatment at 150 ° C. for 60 minutes is 0.03 to 0.07 N / 25 mm, an adhesive film. The method of claim 7,
The first adhesive layer has an adhesive force of 0.01 N / 25 mm or less after irradiation with ultraviolet rays having a wavelength of 365 nm. The method of claim 1,
The second adhesive layer has an initial adhesive strength of 0.03 to 0.06 N / 25 mm, and an adhesive strength of 0.15 to 0.2 N / 25 mm after heat treatment at 150 ° C. for 60 minutes. The method of claim 1,
The first base layer and the second base layer is a release film, an adhesive film. The method of claim 1,
The adhesive sheet is for semiconductor wafer processing, adhesive film.

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