TWI879063B - Use of photo-absorbing release composition and preparation method of semiconductor device - Google Patents

Abstract

A use of a photo-absorbing release composition comprises step (a), applying processing treatment to a layer to be processed of a laminate including a support carrier, a release layer, and the layer to be processed, so that the layer to be processed forms a processed layer; step (b), after step (a), using a pulsed laser to irradiate the release layer through the support carrier; step (c), simultaneously with step (b) or after step (b), separating the support carrier from the processed layer. The release layer is made from a photo-absorbing release composition including a polymer (A), a light-absorbing agent (B) and a solvent (C). The polymer (A) is formed by reacting a mixture including a tetracarboxylic dianhydride component and a diamine component. The diamine component contains at least one diamine selected from the group consisting of a diamine represented by formula (I) and a diamine represented by formula (II).

Description

Method for using light absorbing release composition and method for preparing semiconductor device

The present invention relates to a release composition, and more particularly to a method for using the light absorbing release composition.

In the past, in order to prevent a workpiece such as a semiconductor chip from being damaged such as cracking during a processing such as back grinding, the workpiece is often temporarily fixed to a support such as a glass substrate via a temporary fixture, as disclosed in U.S. Patent Publication No. 2014/0106473 and Japanese Patent Publication No. 2013171949.

Then, after the processing is performed, the temporary fixing member is irradiated with radiation such as ultraviolet rays and infrared rays to weaken the adhesion of the temporary fixing member, so that the processed object can be separated from the support body.

However, when the temporary fixing part has poor light shielding properties, the radiation will irradiate the object to be processed, which will have an adverse effect on the object to be processed. Moreover, when the temporary fixing part has poor releasability after light irradiation, it is easy to remain on the object to be processed after processing, which is not conducive to the subsequent process of the object to be processed after processing.

Therefore, the first object of the present invention is to provide a method for using a light absorbing release composition.

Therefore, the method for using the light absorbing release composition of the present invention comprises: step (a), applying a processing treatment to a to-be-processed layer of a laminate body to form a processed layer from the to-be-processed layer, wherein the laminate body defines a stacking direction and sequentially comprises a supporting carrier, a temporary fixing unit including a release layer and the The layer to be processed is selectively moved before or after the processing; step (b), after step (a), the release layer is irradiated with pulsed laser light via the support carrier; and step (c), which is performed simultaneously with step (b) or after step (b), the support carrier is separated from the processed layer to obtain the processed layer; The release layer is formed by a light absorbing release composition, and the light absorbing release composition includes a polymer (A), a light absorber (B) and a solvent (C); the polymer (A) is selected from a polyamic acid polymer, a polyimide polymer, a polyimide block copolymer or any combination thereof, and is formed by a condensation reaction of a mixture including a tetracarboxylic dianhydride component and a diamine component, wherein the diamine component includes at least one diamine compound selected from the following group: a diamine compound represented by formula (I) and a diamine compound represented by formula (II); Formula (I) ^R1 represents a single bond, -C( _CH3 ) _2- , -(CH2) _n1- , -C( _CF3 ) _2- , -O-( _CH2 ) _n2 -O-, -O-, -S-( _CH2 ) _n3 -S-, -S-, -SS-, _-SO2- , -CO-, -CONH-, or -NHCO-, n1, n2 and n3 independently represent 1 to 12, ^R2 represents a single bond, -C _{(CH3 ) 2-} , -O-, -S-, -CO-, -C( _CF3 ) _2- , or a C1 to C10 alkylene group, any hydrogen on any benzene ring may be substituted by -F, _-CH3 , _-CF3 , -OH, or a phenyl group, Formula (II) R ³ represents a single bond, -C(CH ₃ ) ₂ -, -(CH ₂ ) _m1 -, -C(CF ₃ ) ₂ -, -O-(CH ₂ ) m ₂ -O-, -O-, -S-(CH ₂ ) _m3 -S-, -S-, -SS-, -SO ₂ -, -CO-, -CONH-, or -NHCO-, m1, m2 and m3 independently represent 1 to 12, R ⁴ represents a single bond, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -O-, -S-, -CO-, or a C1 to C10 alkylene group, R ⁵ represents a single bond, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -O-, -S-, -CO-, or a C1 to C10 alkylene group, Any hydrogen on any benzene ring may be substituted with -F, -CH ₃ , -CF ₃ , -OH, or a phenyl group.

Therefore, the second object of the present invention is to provide a method for preparing a semiconductor device.

Therefore, the method for preparing a semiconductor device of the present invention comprises: processing the processed layer obtained by the method for using the light absorbing release composition to form a semiconductor device.

The effect of the present invention is that in the method for using the light absorbing release composition of the present invention, by using at least one of the diamine compound represented by formula (I) and the polymer (A) formed by the diamine compound represented by formula (II) of the diamine component, the release layer formed by the light absorbing release composition of the present invention has better light shielding property, and the release layer can have better releasability after being irradiated with pulsed laser light.

The following will describe the embodiments of the present invention, including preferred embodiments. The components such as compounds exemplified in the following description may be used alone or in combination of two or more unless otherwise specified.

The method for using the light absorbing release composition of the present invention comprises step (a), applying a processing treatment to a to-be-processed layer of a laminate body to form a processed layer from the to-be-processed layer, wherein the laminate body defines a stacking direction and sequentially comprises a supporting carrier, a temporary fixing unit including a release layer and the to-be-processed layer in the stacking direction. , before or after the processing, selectively moving the laminate; step (b), after the step (a), irradiating the release layer with pulsed laser light via the support carrier; and step (c), simultaneously with the step (b) or after the step (b), separating the support carrier from the processed layer to obtain the processed layer.

＜Step (a)＞

In the laminate, the layer to be processed is temporarily fixed on the support carrier via the temporary fixing unit. In one embodiment, the temporary fixing unit is sandwiched between the layer to be processed and the support carrier.

In step (a), a step of forming a laminate is also included. The step of forming the laminate includes, for example, forming the temporary fixing unit on the surface of the support carrier and/or the layer to be processed, and bonding the layer to be processed and the support carrier together through the temporary fixing unit, thereby temporarily fixing the layer to be processed on the support carrier. Alternatively, the layer to be processed can be temporarily fixed on the support carrier by forming the temporary fixing unit on the surface of the support carrier and forming the layer to be processed such as a resin coating or a wiring layer on the temporary fixing unit.

The temporary fixing unit may further include an adhesive layer, that is, the laminate includes the support carrier, the release layer, the adhesive layer and the layer to be processed in sequence. Due to the presence of the adhesive layer, the adverse effect on the layer to be processed caused by the heat generated by the release layer irradiated by light can be suppressed.

In order to form the release layer and the adhesive layer, for example, a release composition for forming the release layer and an adhesive composition for forming the adhesive layer can be used respectively. The coating methods of these compositions are, for example, spin coating, inkjet, slit coating and vapor deposition. After coating each composition to form a coating film, the release layer or the adhesive layer is formed by, for example, heating to evaporate the solvent. The conditions of the heat treatment can be adjusted according to the boiling point of the solvent (C), and the temperature of the heat treatment is, for example, 100° C. to 350° C. and the time is, for example, 1 minute to 60 minutes. When the temporary fixing unit does not include the adhesive layer, the method of forming the laminate includes, for example, forming a release layer on the surface of the supporting carrier and forming the layer to be processed on the release layer, or bonding them together.

In addition, when the temporary fixing unit includes the adhesive layer, the method of forming the laminate is, for example, method 1, method 2 or method 3. In method 1, the adhesive layer is formed on the surface of the layer to be processed, and the release layer is formed on the surface of the support carrier, and then they are bonded together. In method 2, the adhesive layer and the release layer are sequentially formed on the surface of the layer to be processed, and the release layer is bonded to the support carrier. In method 3, the release layer and the adhesive layer are sequentially formed on the surface of the support carrier, and the adhesive layer is bonded to the layer to be processed. Among them, from the perspective of avoiding the adhesive layer and the release layer from mixing when forming each layer, the method of forming the laminate is preferably method 1.

In the above method for forming a laminate, it is preferred to apply pressure when the layer to be processed and the support carrier are bonded together. This can be done in the stacking direction of the components of the laminate, and the conditions for pressurizing the layer to be processed and the support carrier through the temporary fixing unit are preferably 15°C to 400°C, more preferably 150°C to 400°C, 1 minute to 20 minutes, and 0.01 MPa to 100 MPa of applied pressure. After bonding, heat treatment is preferably performed at 150°C to 300°C for 10 minutes to 3 hours.

[Layer to be processed]

The layer to be processed is, for example, a semiconductor wafer, a semiconductor chip, a glass substrate, a resin substrate, a metal substrate, a metal foil, a grinding pad, a resin coating or a wiring layer. For the semiconductor wafer and the semiconductor chip, at least one structure can be formed or installed, and the structure is, for example, a copper column, wiring, a through hole, a through hole channel, an insulating film and various components. For the glass substrate, the resin substrate, and the metal substrate, various components can also be formed or installed. The resin coating includes, for example, a layer containing an organic component as a main component. Specifically, the resin coating film is, for example, a photosensitive resin layer formed of a photosensitive material, an insulating resin layer formed of an insulating material, or a photosensitive insulating resin layer formed of a photosensitive insulating resin material.

The following is an explanation of the layer to be processed having a wiring layer. In this process, the temporary fixing unit is formed on the support carrier, and then the layer to be processed having at least a wiring layer is formed on the temporary fixing unit, wherein the layer to be processed having a wiring layer is, for example, a layer independent of a semiconductor wafer or a semiconductor chip, and then, a semiconductor wafer or a semiconductor chip is arranged on the wiring layer, wherein the semiconductor wafer or the semiconductor chip includes a wafer substrate and a plurality of semiconductor elements formed on the wafer substrate. The wiring layer is electrically connected to the semiconductor wafer or the semiconductor chip and serves as a rewiring layer of the semiconductor wafer or the semiconductor chip. The present invention can also be applied to the Redistribution Layer-First (RDL-First) structure in the Fan-Out Wafer Level Package (FO-WLP) technology.

The wiring layer includes an insulating portion, a wiring portion, and a connecting conductor portion connected to the electrode of the semiconductor wafer or the semiconductor chip. The semiconductor wafer or the semiconductor chip is placed on the wiring layer, and is electrically connected to the connecting conductor portion of the wiring layer and the electrode of the semiconductor wafer or the semiconductor chip through connectors such as welding, anisotropic conductive paste, and anisotropic conductive film. When there is a gap between the semiconductor wafer or the semiconductor chip and the wiring layer, it can be filled with a filler material.

The internal structure of the wiring layer is not particularly limited. The materials of the wiring part and the connecting conductor part are, for example, metals such as copper, gold, silver, platinum, lead, tin, nickel, cobalt, indium, rhodium, chromium, tungsten, ruthenium, and alloys composed of at least two of the above metals. The material of the insulating part is, for example, a synthetic resin. The synthetic resin is, for example, polyimide resin, acrylic resin, polyether nitrile resin, polyether sulfone resin, epoxy resin, polyethylene terephthalate resin, polyethylene naphthalate resin, or polyvinyl chloride resin. The thickness of the wiring layer is generally 1 μm to 1,000 μm.

Subsequently, for example, the semiconductor wafer or chip is resin-sealed in step (a), and the temporarily fixed unit and the wiring layer are separated in step (c) described later, thereby obtaining a semiconductor device including the semiconductor wafer or chip and the wiring layer (i.e., redistribution layer).

In addition, the configuration of the layer to be processed in the temporarily fixed unit, or the configuration of the semiconductor wafer or the semiconductor chip in the wiring layer during the process of forming the wiring layer, can also be performed after alignment based on the position information of each component obtained by measuring light.

To prevent the layer to be processed from deteriorating, preferably, the measuring light is light with a wavelength of 600nm to 900nm. Preferably, the measuring light is light with a wavelength of 633nm, 670nm or 830nm. Preferably, the light source providing the measuring light is, for example, a visible light semiconductor laser or a light emitting diode.

The alignment is performed in the following manner. For the release layer, the release layer includes a film layer of a light absorber that absorbs the measurement light. Therefore, when the measurement light irradiates the release layer, the absorption of the measurement light by the release layer and the decrease in the intensity of the measurement light can be detected, thereby obtaining position information of the release layer. The installation position of the photo sensor for irradiating and detecting the measurement light is not particularly limited. Based on the obtained position information, the temporarily fixed unit and the layer to be processed are aligned, and the wiring layer and the semiconductor wafer or the semiconductor chip are aligned.

Examples of the light source of the light emitting unit include semiconductor laser light and light emitting diodes, and examples of the light receiving unit include light sensors such as photodiodes and phototransistors. Image sensors include CCD image sensors and CMOS image sensors. Examples of the device for moving each component include a robot arm.

[Support carrier]

Since the pulsed laser light irradiates the release layer through the support carrier in step (b) to deteriorate the release layer, the support carrier is preferably a support substrate that can allow pulsed laser light with a wavelength below 400nm to pass through. Preferably, the support carrier has a transmittance of more than 50% for pulsed laser light with a wavelength of 355nm, more preferably, a transmittance of 70% to 100%, and even more preferably, a transmittance of 80% to 100%. The support carrier is, for example, a glass substrate, a quartz substrate, or a transparent resin substrate. There is no particular limitation on the thickness of the support carrier, for example, 0.1mm to 2mm.

[Release layer]

The release layer is a film layer that will be degraded by absorbing pulsed laser light with a wavelength below 400nm. When the pulsed laser light is irradiated to the release layer, the release layer absorbs the pulsed laser light and degrades by decomposing the polymer (A) and other substances. Due to this degeneration, the strength and adhesion of the release layer decrease after light irradiation. When an external force is applied to the laminate, cohesion destruction occurs inside the release layer, or interface destruction occurs between the release layer and a layer in contact with the release layer. Therefore, by applying an external force to the laminated body after the pulsed laser light irradiation treatment, the supporting carrier and the processed layer can be easily separated.

In the present invention, the degradation of the release layer refers to non-thermal degradation by direct scission of chemical bonds, similar to photochemical ablation, that is, degradation caused by absorption of light energy.

Examples of the processed layer include semiconductor wafers and semiconductor chips. They are generally sensitive to light and may deteriorate when exposed to light. Preferably, the release layer is capable of shielding light so that the pulsed laser light does not reach the processed layer. At the wavelength of the pulsed laser light irradiated in step (b), for example, at a wavelength of 355 nm, the light transmittance of the release layer is preferably 30% or less, more preferably 0% to 10%, and more preferably 0% to 5%.

The light transmittance of the release layer can be measured by the following method: A layer body consisting of a transparent substrate and the release layer is formed. A base line correction is performed on the transparent substrate as needed using a spectrophotometer, and the light transmittance (%) of the layer body is measured to obtain the light transmittance (%) of the release layer.

The thickness of the release layer is, for example, less than 2 microns, preferably, 0.1 microns to 2 microns, and more preferably, 0.2 microns to 1.5 microns. When the thickness of the release layer is within the above range, it can be more effectively induced to deteriorate by the pulsed laser light and protect the processed layer from the influence of the pulsed laser light. In addition, the release layer should have sufficient adhesion to be temporarily fixed on the support carrier, and the support carrier and the release layer will not separate during step (a).

The release layer is formed by a light absorbing release composition, and the light absorbing release composition comprises a polymer (A), a light absorber (B) and a solvent (C).

＜Polymer (A)＞

The polymer (A) is selected from polyamic acid polymers, polyimide polymers, polyimide block copolymers, or any combination thereof. In some embodiments of the present invention, the polyimide block copolymer is selected from polyamic acid block copolymers, polyimide block copolymers, polyamic acid-polyimide block copolymers, or any combination thereof. In order to make the release layer formed by the light absorbing release composition have better light shielding properties, preferably, the polymer (A) is a polyamic acid polymer.

In some embodiments of the present invention, the polymer (A) is formed by reacting a mixture, and the mixture includes a tetracarboxylic dianhydride component (a) and a diamine component (b).

The tetracarboxylic dianhydride component (a) comprises at least one tetracarboxylic dianhydride compound, and the tetracarboxylic dianhydride compound is selected from aliphatic tetracarboxylic dianhydride compounds, alicyclic tetracarboxylic dianhydride compounds, or aromatic tetracarboxylic dianhydride compounds.

The aliphatic tetracarboxylic dianhydride compound includes, but is not limited to, ethanetetracarboxylic dianhydride or butanetetracarboxylic dianhydride.

The alicyclic tetracarboxylic acid dianhydride compound includes, but is not limited to, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,3-dichloro-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride , 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, cis-3,7-dibutylcycloheptyl-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, or bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, etc.

The aromatic tetracarboxylic dianhydride compound includes, but is not limited to, 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, benzene tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3'-4,4'-diphenylethane tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, Carboxylic acid dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic acid dianhydride, 1,2,3,4-furan tetracarboxylic acid dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic acid dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 2,3,3',4'-diphenyl sulfide tetracarboxylic acid dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic acid dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide phenoxy) diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic acid dianhydride, 2,2',3,3'-diphenyltetracarboxylic acid dianhydride, 2,3,3',4'-diphenyltetracarboxylic acid dianhydride, 3,3',4,4'-diphenyltetracarboxylic acid dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane Dianhydride, ethylene glycol-bis(dehydrated trimellitate), propylene glycol-bis(dehydrated trimellitate), 1,4-butanediol-bis(dehydrated trimellitate), 1,6-hexanediol-bis(dehydrated trimellitate), 1,8-octanediol-bis(dehydrated trimellitate), 2,2-bis(4-hydroxyphenyl)propane-bis(dehydrated trimellitate), 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxy-3-furanyl)-naphtho[1,2-c]- Furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-methyl-5-(tetrahydro-2,5-dioxy-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-ethyl-5-(tetrahydro-2,5-dioxy-3-furanyl)-naphtho[1,2-c]- Furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, [1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, or 5-(2,5-dioxo-tetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, etc.

The diamine component (b) includes at least one diamine compound selected from the following group: a diamine compound represented by formula (I) and a diamine compound represented by formula (II). Formula (I) Formula (II)

In formula (I), ^R1 represents a single bond, -C( _CH3 ) _2- , -(CH2) _n1- , -C( _CF3 ) _2- , -O-( _CH2 )n2-O-, -O-, -S-( _CH2 ) _{n3 -} S-, -S-, -SS-, _-SO2- , -CO-, -CONH-, or -NHCO-, and n1, n2, and n3 independently represent 1 to 12. ^R2 represents a single bond, -C( _CH3 ) _2- , -C( _CF3 ) _2- , -O-, -S-, -CO-, or a C1 to C10 alkylene group. Any hydrogen on any benzene ring may be substituted with -F, _-CH3 , _-CF3 , -OH, or _a phenyl group. The diamine compound represented by formula (I) is, for example, Formula (I-1), Formula (I-2), Formula (I-3), Formula (I-4), Formula (I-5), Formula (I-6) or Formula (I-7) etc.

In formula (II), R ³ represents a single bond, -C(CH ₃ ) ₂ -, -(CH ₂ ) _m1 , -C(CF ₃ ) ₂ -, -O-(CH ₂ ) _m2 -O-, -O-, -S-(CH ₂ ) _m3 -S-, -S-, -SS-, -SO ₂ -, -CO-, -CONH-, or -NHCO-, and m1, m2, and m3 independently represent 1 to 12. ^{R 4} represents a single bond, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -O-, -S-, -CO-, or a C1 to C10 alkylene group. R ⁵ represents a single bond, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -O-, -S-, -CO-, or a C1 to C10 alkylene group. Any hydrogen on any benzene ring may be substituted by -F, -CH ₃ , -CF ₃ , -OH, or phenyl. The diamine compound represented by the formula (II) is, for example Formula (II-1), Formula (II-2), Formula (II-3), Formula (II-4), Formula (II-5), Formula (II-6), Formula (II-7), Formula (II-8), Formula (II-9) or Formula (II-10) etc. In the formula (II-9), m1 represents 1 to 12, and m4 and m5 independently represent 1 to 2. In the formula (II-10), m1 represents 1 to 12.

In some embodiments of the present invention, based on 100 mol of the total amount of the diamine component (b), the amount of the diamine compound represented by formula (I) or formula (II) is 70 mol to 100 mol, preferably 75 mol to 100 mol, and more preferably 80 mol to 100 mol. When the diamine compound represented by formula (I) or formula (II) is not used, the release layer formed by the light absorbing release composition has poor releasability after being irradiated with pulsed laser light.

In some embodiments of the present invention, the diamine component (b) further includes at least one other diamine compound, and the other diamine compound is, for example, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 4,4'-diaminoheptane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino- 2,5-dimethylhexane, 1,7-diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylnonane, 2,11-diaminododecane, 1,12-diaminooctadecane, 1,2-bis(3-aminopropoxy)ethane, 4,4'-diamino-3,3'-dimethyldicyclohexylamine, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentane ethylenediamine, tricyclo (6.2.1.02,7) - undecylenedimethyl diamine, 4,4'-methylenebis (cyclohexylamine), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylhydroindene, 6-amino-1-(4'- 1,3,3-trimethylhydroindene, hexahydro-4,7-methylenediamine, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis(4-aminophenyl)hexafluoropropane, 1,5-bis(4-aminophenoxymethylene)adamantane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 9,10-bis(4-aminophenyl)anthracene [9,10-bis(4-aminophenyl) anthracene], 2,7-diaminofluorene, 9,9-bis(4-aminophenyl)fluorene, 4,4'-methylene-bis(2-chloroaniline), 5-[4-(4-n-pentylcyclohexyl)cyclohexyl]phenylmethylene-1,3-diaminobenzene, 1,1-bis[4-(4-aminophenoxy)phenyl]-4-(4-ethylphenyl)cyclohexane, phenyl)cyclohexane}, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, bis(4-aminophenoxy)methane, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis( 3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-bis(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)nonane, 1,9-bis(3-aminophenoxy)nonane, 1,10-bis(4-aminophenoxy)decane , 1,10-bis(3-aminophenoxy)decane, 1,11-bis(4-aminophenoxy)undecane, 1,11-bis(3-aminophenoxy)undecane, 1,12-bis(4-aminophenoxy)dodecane, 1,12-bis(3-aminophenoxy)dodecane, p-diaminobenzene, m-diaminobenzene, o-diaminobenzene, 2,5-diaminotoluene, 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4 ,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, or 1,4-bis(4'-aminophenyl)benzene, etc. Preferably, the other diamine compound is selected from p-diaminobenzene, 2,5-diaminotoluene, 4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, or 1,4-bis(4'-aminophenyl)benzene.

In some embodiments of the present invention, the mixture further comprises a solvent (c) for dissolving the components in the mixture and the polymer (A). The solvent (c) is, for example, but not limited to, a non-protonic polar solvent or a phenolic solvent. The non-protonic polar solvent is, for example, but not limited to, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethyl urea, or hexamethylphosphoric triamide. The phenolic solvent is, for example, but not limited to, meta-cresol, xylenol, phenol, or halogenated phenols. In some embodiments of the present invention, based on 100 parts by weight of the mixture, the amount of the solvent (c) is 200 to 2000 parts by weight. In some embodiments of the present invention, based on 100 parts by weight of the mixture, the amount of the solvent (c) is 300 parts by weight to 1800 parts by weight.

When the polymer (A) is a polyamic acid polymer, the preparation method of the polymer (A) of the present invention can be carried out by a conventional method, such as method 1 or method 2. The method 1 is to carry out a polycondensation reaction of the mixture at 0°C to 100°C for 1 hour to 24 hours to obtain a reaction mixture, and then the reaction mixture is introduced into an evaporator and subjected to a reduced pressure distillation treatment. The method 2 is to carry out a polycondensation reaction of the mixture at 0°C to 100°C for 1 hour to 24 hours to obtain a reaction mixture, and then the reaction mixture is contacted with a large amount of a poor solvent to obtain a precipitate, and then the precipitate is subjected to a reduced pressure drying treatment.

In some embodiments of the present invention, the mixture further comprises a poor solvent that does not cause the polyamine polymer to precipitate. The poor solvent can be used alone or in combination, and the poor solvent includes, but is not limited to, an alcohol solvent, a ketone solvent, an ester solvent, an ether solvent, a halogenated hydrocarbon solvent, or a hydrocarbon solvent. The alcohol solvent includes, but is not limited to, methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, or triethylene glycol. The ketone solvent includes, but is not limited to, acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone. The ester solvent includes, but is not limited to, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, or ethylene glycol ethyl ether acetate. The ether solvent includes, but is not limited to, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, or diethylene glycol dimethyl ether. The halogenated hydrocarbon solvent includes, but is not limited to, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, or o-dichlorobenzene. The hydrocarbon solvent includes, but is not limited to, tetrahydrofuran, hexane, heptane, octane, benzene, toluene, or xylene. In some embodiments of the present invention, the amount of the poor solvent is 0 to 60 parts by weight based on the total amount of the diamine component (b) being 100 parts by weight. Preferably, the amount of the poor solvent is 0 to 50 parts by weight based on the total amount of the diamine component being 100 parts by weight.

When the polymer (A) is a polyimide polymer, the preparation method of the polymer (A) of the present invention can adopt a conventional method, for example, subjecting the polyamic acid polymer to a dehydration ring-closing reaction (i.e., an imidization reaction) in the presence of a dehydrating agent and a catalyst, so that the amide in the polyamic acid polymer is converted into an imide.

In order to obtain the polyamide polymer with an appropriate imidization rate, the operating temperature of the dehydration ring-closing reaction is preferably 40° C. to 200° C., more preferably 40° C. to 150° C. When the operating temperature of the dehydration ring-closing reaction is lower than 40° C., the imidization reaction is incomplete, thereby reducing the imidization degree of the polyamide polymer. However, when the operating temperature of the dehydration ring-closing reaction is higher than 200° C., the weight average molecular weight of the obtained polyimide polymer is low.

The dehydrating agent is, for example, an anhydride compound. The anhydride compound is, for example, acetic anhydride, propionic anhydride or trifluoroacetic anhydride. The amount of the dehydrating agent used is 0.01 mol to 20 mol, based on the total amount of the polyamine polymer as 1 mol. The catalyst is, for example, a pyridine compound or a tertiary amine compound. The pyridine compound is, for example, pyridine, trimethylpyridine or dimethylpyridine. The tertiary amine compound is, for example, triethylamine. The amount of the catalyst used is 0.5 mol to 10 mol, based on the total amount of the dehydrating agent as 1 mol.

In some embodiments of the present invention, the dehydration ring-closing reaction is carried out in the presence of a solvent. The solvent is, for example, the solvent (c) in the above-mentioned mixture, so it is not repeated here. In some embodiments of the present invention, the amount of the solvent is 200 to 2000 parts by weight based on 100 parts by weight of the total amount of the polyamine polymer. Preferably, the amount of the solvent is 300 to 1800 parts by weight based on 100 parts by weight of the total amount of the polyamine polymer.

When the polymer (A) is a polyimide-based block copolymer, the preparation method of the polymer (A) of the present invention can adopt a conventional method, such as dissolving the reaction components in a solvent and conducting a polycondensation reaction, wherein the reaction components include at least one of a polyamic acid polymer and a polyimide polymer.

The solvent is, for example, the solvent (c) in the above-mentioned mixture, and will not be described in detail. Further, the reaction components also include a tetracarboxylic dianhydride component and a diamine component. The tetracarboxylic dianhydride component and the diamine component are, for example, the tetracarboxylic dianhydride component (a) and the diamine component (b) mentioned above, and will not be described in detail.

In some embodiments of the present invention, preferably, the amount of the solvent is 200 to 2000 parts by weight, more preferably, 300 to 1800 parts by weight, based on 100 parts by weight of the total amount of the reaction components. In some embodiments of the present invention, preferably, the operating temperature of the polycondensation reaction is 0°C to 200°C, more preferably, 0°C to 100°C.

Preferably, the reaction components include, but are not limited to (1) two polyamic acid polymers having different terminal groups and different structures; (2) two polyimide polymers having different terminal groups and different structures; (3) polyamic acid polymers and polyimide polymers having different terminal groups and different structures; (4) polyamic acid polymers, tetracarboxylic dianhydride compounds and diamine compounds, wherein the tetracarboxylic dianhydride compounds and the diamine compounds are (5) comprising a polyimide polymer, a tetracarboxylic dianhydride compound and a diamine compound, wherein at least one of the tetracarboxylic dianhydride compound and the diamine compound has a structure different from that of the tetracarboxylic dianhydride compound and the diamine compound forming the polyimide polymer; (6) comprising a polyamic acid polymer, a polyimide polymer, a tetracarboxylic dianhydride compound and a diamine compound, wherein at least one of the tetracarboxylic dianhydride compound and the diamine compound has a structure different from that of the tetracarboxylic dianhydride compound and the diamine compound forming the polyamic acid polymer or the polyimide polymer; (7) comprising two types of polyamic acid polymers, tetracarboxylic dianhydride compounds and diamine compounds having different structures; (8) comprising two types of polyimide polymers, tetracarboxylic dianhydride compounds and diamine compounds having different structures; (9) comprising two polyamic acid polymers whose terminal groups are acid anhydride groups and have different structures, and a diamine compound; (10) comprising two polyamic acid polymers whose terminal groups are amine groups and have different structures, and a tetracarboxylic dianhydride compound; (11) comprising two polyimide polymers whose terminal groups are acid anhydride groups and have different structures, and a diamine compound; (12) comprising two polyimide polymers whose terminal groups are amine groups and have different structures, and a tetracarboxylic dianhydride compound.

In the range that does not affect the efficacy of the present invention, preferably, the molecular weight of the polyamic acid polymer, the polyimide polymer and the polyimide-based block copolymer is adjusted to form a terminal-modified polymer. The terminal-modified polymer can improve the coating performance of the light-absorbing release composition.

The terminal modified polymer can be prepared by adding a monofunctional compound to the polyamine polymer during the polycondensation reaction. The monofunctional compound is, for example, but not limited to, a monoacid anhydride, a monoisocyanate compound, a monoamine compound, or the like. The monoacid anhydride is, for example, maleic anhydride, n-dodecyl succinic anhydride, phthalic anhydride, n-hexadecyl succinic anhydride, itaconic anhydride, n-tetradecyl succinic anhydride, or n-decyl succinic anhydride. The monoisocyanate compound is, for example, phenyl isocyanate or naphthyl isocyanate. The monoamine compound is, for example, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-eicosylamine, cyclohexylamine or aniline.

In some embodiments of the present invention, the polymer (A) has a weight average molecular weight of 5,000 to 50,000 according to gel permeation chromatography using polystyrene as a standard. Preferably, the polymer (A) has a weight average molecular weight of 8,000 to 45,000. More preferably, the polymer (A) has a weight average molecular weight of 10,000 to 40,000.

＜Light absorber (B)＞

The release layer preferably includes a light absorbing agent (B) that absorbs pulsed laser light having a wavelength of 400 nm or less. The light absorbing agent (B) is, for example, a light absorbing agent that absorbs light to cause a change such as decomposition of a component of the release layer.

In addition, the light absorber (B) may be a polymer having a structure that absorbs pulsed laser light of a wavelength of 400 nm or less in a repeating unit. The polymer may be, for example, a polymer having a structure containing a conjugated π-electron system, specifically, a polymer having a quinone structure, a polymer having a structure that forms a quinone structure by heat treatment, a benzene ring, a condensed ring, or a heterocyclic ring.

For example, the light absorber (B) preferably has the following functions (a) and (b) at the same time. The function (a) is to absorb and separate the light used in the pulsed laser light irradiation treatment in step (3) and cause the release layer to deteriorate. The function (b) is to absorb the measurement light (usually having a wavelength of 600 nm to 900 nm) used to detect the alignment of the release layer and each component when the components are arranged and stacked in the laminate.

The light absorber (B) can be used alone or in combination, and the light absorber (B) includes, but is not limited to, an organic light absorber, a novolac resin, or a black pigment. In some embodiments of the present invention, the light absorber (B) includes a black pigment. The organic light absorber includes, but is not limited to, a benzotriazole-based light absorber, a hydroxyphenyltriazine-based light absorber, a benzophenone-based light absorber, a salicylic acid-based light absorber, a radiation-sensitive radical polymerization initiator, or a photo-sensitive acid generator. The novolac resin is, for example, but not limited to, phenol novolak or naphthol novolak. The black pigment is not particularly limited. Preferably, the black pigment is a black pigment with heat resistance, light resistance, and solvent resistance. The black pigment can be used alone or in combination. The black pigment is, for example, a light-shielding material, a black organic pigment, or a mixed organic pigment that is a mixture of several pigments and is close to black. The light-shielding material is, for example, carbon black, chromium oxide, iron oxide, titanium black, or graphite. The carbon black may be C.I. Pigment Black 7 or a commercial product manufactured by Mitsubishi Chemical Co., Ltd. (trade name MA100, MA230, MA8, #970, #1000, #2350 or #2650). The black organic pigment may be perylene black, cyanine black or aniline black. The pigment may be red pigment, blue pigment, green pigment, purple pigment, yellow pigment, cyanine pigment or magenta pigment. The black pigment may be C.I. Pigment Black 7, C.I. Pigment Black 31, C.I. Pigment Black 32 or C.I. Pigment Black 35. Preferably, the black pigment is carbon black, and the carbon black is, for example, commercially available MA100 or MA230 manufactured by Mitsubishi Chemical.

In some embodiments of the present invention, the amount of the light absorber (B) is 5 to 200 parts by weight based on 100 parts by weight of the total amount of the polymer (A). Preferably, the amount of the light absorber (B) is 10 to 180 parts by weight based on 100 parts by weight of the total amount of the polymer (A). More preferably, the amount of the light absorber (B) is 20 to 150 parts by weight based on 100 parts by weight of the total amount of the polymer (A). When the light absorbing release composition does not contain the light absorber (B), the optical density of the release layer formed by the light absorbing release composition is poor, and the release property of the release layer after irradiation with pulsed laser light is poor.

＜Solvent (C)＞

The solvent (C) is, for example, a solvent having affinity for polyamine and its derivatives or a solvent for improving coating properties.

The solvent having affinity for polyamine and its derivatives is, for example, an aprotic polar organic solvent. The aprotic polar organic solvent may be, for example, 3-methoxy-N,N-dimethylpropanamide, N-methyl-2-pyrrolidone, dimethyl imidazolidinone, N-methyl caprolactam, N-methyl propionamide, N,N-dimethylacetamide, dimethyl sulfoxide, N,N-dimethylformamide, N,N-diethylformamide, diethyl acetamide or lactone. The lactone may be, for example, γ-butyrolactone.

The solvent used to improve coating properties includes, but is not limited to, iacetone alcohol, alkyl lactate, 3-methyl-3-methoxybutanol, tetraline, isophorone, ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, phenyl acetate, triethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, dialkyl malonate, dipropylene glycol monoalkyl ether, or ester compound. The ethylene glycol monoalkyl ether is, for example, ethylene glycol monobutyl ether. The diethylene glycol monoalkyl ether is, for example, diethylene glycol monoethyl ether. The propylene glycol monoalkyl ether is, for example, propylene glycol monomethyl ether or propylene glycol monobutyl ether. The dialkyl malonate is, for example, diethyl malonate. The dipropylene glycol monoalkyl ether is, for example, dipropylene glycol monomethyl ether. The ester compound is, for example, acetate.

Preferably, the solvent (C) is selected from 3-methoxy-N,N-dimethylpropionamide, diacetone alcohol, N-methyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether or dipropylene glycol monomethyl ether.

In some embodiments of the present invention, based on 100 parts by weight of the total amount of the polymer (A), the amount of the solvent (C) is 500 parts by weight to 4000 parts by weight. Preferably, based on 100 parts by weight of the total amount of the polymer (A), the amount of the solvent (C) is 600 parts by weight to 3500 parts by weight. More preferably, based on 100 parts by weight of the total amount of the polymer (A), the amount of the solvent (C) is 800 parts by weight to 3000 parts by weight.

The light absorbing release composition may further include at least one additive according to application requirements, and the additive may be, for example, an adhesive, an antioxidant, a polymerization inhibitor, an adhesion promoter, a surfactant, polystyrene crosslinked particles, a crosslinking agent or metal oxide particles.

[Preparation method of light-absorbing release composition]

In some embodiments of the present invention, the method for preparing the light absorbing release composition of the present invention comprises mixing the polymer (A) and the light absorber (B) with a solvent (C) at 0°C to 200°C, and continuously stirring until dissolved. Preferably, the polymer (A) and the light absorber (B) are mixed with the solvent (C) at 20°C to 60°C.

[Adhesive layer]

Such a temporary fixing unit having two or more layers can have some well-balanced functions, such as protecting the surface circuit of the processed layer or the layer to be processed, the adhesion and separation between the support carrier and the processed layer or the layer to be processed, shielding the light used during light treatment, or having heat resistance during processing or light treatment, etc. In addition, due to the presence of the adhesive layer, it can be used to suppress the adverse effects of the processed layer or the layer to be processed caused by the heat generated by the release layer through light irradiation.

The adhesive layer can be formed using a known adhesive for forming an adhesive layer. The adhesive layer is used to temporarily fix the layer to be processed on the supporting carrier and to cover and protect the surface of the layer to be processed.

The adhesive can be used alone or in combination, and the adhesive can be, for example, a thermoplastic resin adhesive, an elastic system adhesive, or a thermosetting resin adhesive, etc. The adhesive can be in a solvent form, an emulsion form, or a hot melt form.

The thermoplastic resin in the thermoplastic resin adhesive is, for example, an olefin resin, a cycloolefin resin, a terpene resin, a rosin resin, a petroleum resin, polycaprolactone, a (meth) acrylic resin, polyvinyl chloride, an ethylene-vinyl acetate copolymer, a phenolic resin, a thermoplastic polyimide resin, or a thermoplastic polyphenylimide resin. From the perspective of heat resistance, preferably, a cycloolefin resin is used. From the perspective of chemical resistance, preferably, at least one of a cycloolefin resin, a terpene resin, a rosin resin, and a petroleum resin is used.

The elastomer in the elastic system adhesive may be, for example, (meth) acrylic rubber, nitrile rubber, polyurethane rubber or styrene butadiene rubber, etc. The thermosetting resin in the thermosetting resin adhesive may be, for example, epoxy resin, phenolic resin, urea-formaldehyde resin, melamine resin, unsaturated polyester resin, phthalate resin, polyurethane resin, silicone rubber, resin containing (meth) acrylate group, thermosetting polyimide resin or thermosetting polyphenylimide resin, etc.

The adhesive may further include at least one of an antioxidant, a polymerization inhibitor, an adhesion promoter, a surfactant, polystyrene crosslinked particles, a crosslinking agent and metal oxide particles according to application requirements.

Preferably, the thickness of the adhesive layer is 10 μm to 200 μm, more preferably, 15 μm to 100 μm, and even more preferably, 20 μm to 80 μm. When the thickness of the adhesive layer is within the above range, the adhesive layer can provide sufficient adhesion to temporarily fix the layer to be processed, and the adhesive layer will not separate from the layer to be processed during step (a).

In some embodiments of the present invention, in addition to the release layer and the adhesive layer, the temporary fixing unit may also include any other layers. For example, an intermediate layer may be provided between the release layer and the adhesive layer, and other layers may be provided between the release layer and the supporting carrier or between the adhesive layer and the layer to be processed. The temporary fixing unit composed of the release layer and the adhesive layer is particularly preferred.

In step (a), the laminate is also moved before or after the processing. Moving means moving the layer to be processed, such as a semiconductor wafer, or the processed layer together with the support carrier from one device to another. The processing of the layer to be processed temporarily fixed on the support carrier includes, for example, thinning of the layer to be processed (such as cutting and back grinding), optical processing, stacking of semiconductor wafers, installation of various components, and resin sealing. The optical processing is, for example, selected from at least one processing step of forming a photolithography pattern, etching processing, sputtering film formation, electroplating processing, and electroplating reflow soldering. The etching process and the sputtering film formation are usually performed in a temperature range of 25° C. to 300° C., and the electroplating process and the electroplating reflow are usually performed in a temperature range of 225° C. to 300° C. There is no particular limitation on the processing of the layer to be processed, as long as it is performed in a temperature range that does not reduce the adhesion of the temporarily fixed unit.

For example, in the above-mentioned RDL-First, a to-be-processed layer having at least a wiring layer is formed on the temporarily fixed unit, and then at least one selected from a semiconductor wafer and a semiconductor chip is placed on the wiring layer, and then the wiring layer is electrically connected to the semiconductor wafer or chip. Subsequently, the semiconductor wafer or chip is resin-sealed as required.

＜Step (b)＞

After step (a), the release layer is irradiated from one side of the support carrier with a pulsed laser light having a wavelength of less than 400 nm and a pulse width of less than 1 nanosecond. When the release layer is exposed to the pulsed laser light, the components in the release layer absorb the pulsed laser light and deteriorate, resulting in degradation of the release layer and reduction of the strength and adhesion of the release layer. Therefore, after the release layer is irradiated with the pulsed laser light, the support carrier can be easily separated from the processed layer without heat treatment of the temporary fixing unit.

Pulsed laser light is laser light emitted from a pulsed laser generator. For the pulsed laser light, conditions are adopted that can cause the release layer to deteriorate. Laser decomposition (peeling) can be performed by two mechanisms, photothermal peeling and photochemical peeling. The photochemical peeling mechanism can be performed by using a pulsed laser light with a shorter wavelength and a smaller pulse width. Therefore, by using a pulsed laser light with a shorter wavelength and a smaller pulse width, the heat generated by the release layer due to light irradiation can be effectively suppressed, and damage to the processed layer can be prevented, and the separation process can be smoothly performed. In particular, by setting the pulse width to less than 1 nanosecond, the stripping effect can be induced in a shorter time, thereby minimizing thermal damage to the surrounding area.

The wavelength of the pulsed laser light should be below 400nm. However, when the wavelength of the pulsed laser light is too short, the pulsed laser light will not be able to pass through the support carrier, causing the support carrier to heat up, and this heat will have a negative impact on the processed layer, thereby failing to effectively process the processed layer. Therefore, the wavelength of the pulsed laser light is preferably between 300nm and 400nm. The wavelength of the pulsed laser light should be a wavelength that the release layer can absorb, so the wavelength used can be appropriately determined according to the material of the release layer.

The pulse width of the pulse laser light received by the release layer should be less than 1 nanosecond, preferably less than 100 picoseconds, and even more preferably less than 50 picoseconds. The lower limit of the pulse width is adjusted according to factors such as the laser intensity required to modify the release layer, and is generally 1 to 5 picoseconds.

The average output power of the pulsed laser light is, for example, above 1W. The irradiation interval of the pulsed laser light is adjusted based on the condition that adjacent light spots do not overlap and the release layer can be degraded. The appropriate interval is 20 microns to 300 microns, and the more ideal interval is 50 microns to 250 microns. The frequency of the pulsed laser light is preferably above 20kHz, and the more ideal frequency is 30kHz to 200kHz.

The best situation is to be able to irradiate the entire release layer uniformly so that the release layer is deformed, so that the support carrier can be easily separated from the processed layer. The release layer can also be locally irradiated with a pulsed laser beam.

In particular, it is more ideal to scan and irradiate the entire surface of the release layer from the support carrier side by pulsed laser light, and it is more ideal to focus the pulsed laser light on the release layer. There is no particular limitation on the scanning method. For example, the pulsed laser light can be linearly irradiated in the X-axis direction on the X-Y plane of the release layer, and then the irradiation area can be moved in the Y-axis direction to irradiate the entire surface, or the pulsed laser light can be irradiated in an angle shape, and the irradiation part can be moved sequentially from the center to the periphery to the outside or from the periphery to the center to the inside to irradiate the entire surface.

The irradiation device can use various types of solid lasers, such as YAG lasers, ruby lasers, glass lasers, YVO ₄ lasers, LD lasers, fiber lasers, and photo-excited semiconductor lasers, etc.; liquid lasers such as dye lasers can also be used; gas lasers such as CO ₂ lasers, excimer lasers, Ar lasers, and He-Ne lasers can also be used; and there are also semiconductor lasers. As irradiation equipment capable of irradiating with the above-mentioned short pulse width, specifically, there are HyperRapid NX series, RAPID series, Talisker series, and FLARE NX manufactured by Coherent Japan Co., Ltd.

＜Step (c)＞

In step (c), a force is applied to the processed layer or the support carrier, for example, the processed layer is peeled off from the support carrier, to separate the two. Preferably, the separation in step (c) is performed after the light irradiation in step (b) is completed, but the separation in step (c) can also be performed while the light irradiation in step (b) is being performed.

The separation method can be, for example, the following methods. Method 1 is to apply an external force to the processed layer or the supporting carrier in a direction parallel to the surface of the processed layer, so as to separate the processed layer from the supporting carrier. Method 2 is to fix one of the processed layer and the supporting carrier, and lift the other at a certain angle from a direction parallel to the surface of the processed layer, so as to separate the processed layer from the supporting carrier.

In method one, the processed layer is made to slide horizontally on the surface of the supporting carrier while the supporting carrier is fixed, or the processed layer is separated from the supporting carrier by applying a force opposite to the force applied to the processed layer to the supporting carrier.

In the second method, a slightly vertical force is applied to the surface of the processed layer to separate the processed layer from the supporting carrier. The "slightly vertical force" mentioned here refers to the vertical axis (usually the Z axis) relative to the surface of the processed layer, usually in the range of 0° to 60°, more preferably in the range of 0° to 45°, further preferably in the range of 0° to 30°, even more preferably in the range of 0° to 5°, especially 0°, that is, perpendicular to the surface of the processed layer. The direction perpendicular to the surface of the processed layer is usually the stacking direction of the various components constituting the laminate. As a separation method, for example, the following method can be performed: lift the periphery of the processed layer or the supporting carrier, and apply force in a direction approximately perpendicular to the surface of the processed layer, while peeling off sequentially from the periphery to the center (hook-pull).

In the above-mentioned separation process, it is usually carried out within a temperature range of 5°C to 100°C, preferably within a range of 10°C to 45°C, and further preferably within a range of 15°C to 30°C. The temperature here refers to the temperature of the supporting carrier. In addition, during the separation, in order to prevent damage to the processed layer, a reinforcing tape, such as a commercially available adhesive tape, may be attached to the reverse side of the temporary contact surface between the processed layer and the supporting carrier. In the present invention, as described above, the separation of the processed layer and the supporting carrier mainly occurs in the release layer. If the processed layer has bumps, the bumps must be prevented from being damaged during the separation process.

＜Step (d)＞

After the support carrier is separated from the processed layer, for example, the temporary fixing unit including the adhesive layer and the release layer can remain on the processed layer. After separation, the temporary fixing unit remaining on the processed layer can be removed by stripping treatment or by cleaning with a solvent.

In the present invention, by shortening the pulse width of the pulse laser light, the heat generated in the release layer irradiated by the light can be effectively suppressed. Therefore, when the temporary fixing unit includes the release layer and the adhesive layer, the release layer can be prevented from being irradiated by light and generating heat, which causes the adhesive layer to deteriorate by thermal curing, etc., thereby making the peeling process difficult.

In order to peel off the temporary fixing unit, preferably use adhesive tape, and the adhesive force between the adhesive tape and the temporary fixing unit can be higher than the adhesive force between the processed layer and the temporary fixing unit. The temporary fixing unit can be removed by pressing the adhesive tape layer on the temporary fixing unit and peeling off the adhesive tape together with the temporary fixing unit.

The solvent cleaning method includes, for example, immersing the processed layer in a solvent, spraying the processed layer with a solvent, immersing the processed layer in a solvent and applying ultrasonic waves, etc. The temperature of the solvent is not particularly limited, but is preferably 20°C to 80°C, more preferably 20°C to 50°C.

The solvent in the solvent cleaning method is, for example, a sulfoxide solvent, a ketone solvent, an alcohol/ether solvent, an ester/lactone solvent or a hydrocarbon solvent. The sulfoxide solvent is, for example, dimethyl sulfoxide or diethyl sulfoxide. The ketone solvent is, for example, 3-methyl-2-pyrrolidone, N,N-dimethylpropionamide, 3-butyl-2-pyrrolidone, N-methyl-2-pyrrolidone, N-(2-methylpropyl)-2-pyrrolidone, N-(tert-butyl)-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, 2-heptanone, 3-heptanone, 4-heptanone, methyl isobutyl ketone, cyclopentanone or cyclohexanone. The alcohol/ether solvent may be, for example, isopropyl alcohol, propylene glycol monomethyl ether, propylene glycol dimethyl ether, diethylene glycol monoethyl ether or diethylene glycol, etc. The ester/lactone solvent may be, for example, ethyl acetate, butyl ketone, isobutyl acetate, lactic acid ester, 3-ethoxypropionic acid ethyl ester, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, methyl propyl acetate, ethyl vinylate, propyl acrylate or γ-butyrolactone, etc. The hydrocarbon solvent may be, for example, xylene, pinene, methylcyclohexene, dipentene, pinene, tert-butyl-3,5-dimethylbenzene, tert-butylcyclohexane, hexyl-1-tert-butyl-3,5-dimethylbenzene or tert-butylcyclohexane, etc.

After the processed layer is separated from the support carrier, the processed layer can be further processed, for example, bumps are formed on the wiring layer of the RDL-First structure or it is cut into individual packages by dicing.

[Method for producing semiconductor device]

The method for preparing a semiconductor device of the present invention includes processing the processed layer obtained by the method for using the above-mentioned light-absorbing release composition to form a semiconductor device. After the semiconductor device such as a semiconductor element obtained by processing the processed layer is peeled off from the support carrier, the temporary fixing unit can be easily removed by a peeling process or a solvent cleaning process. Therefore, in the semiconductor device, the degradation caused by light irradiation during peeling is small, and the contamination such as spots and scorching caused by the temporary fixing unit is also reduced.

The present invention will be further described with respect to the following embodiments, but it should be understood that the embodiments are only for illustrative purposes and should not be interpreted as limitations on the implementation of the present invention.

Synthesis Example 1

A nitrogen inlet, a stirrer, a condenser and a thermometer are set on a 500 ml four-necked conical flask, and nitrogen is introduced. Then, 100 mol of the diamine compound represented by formula (I-1) (abbreviated as b-1-1) and 80 g of N-methyl-2-pyrrolidone (abbreviated as NMP) are introduced into the four-necked conical flask and mixed, and stirred at room temperature until the diamine compound represented by formula (I-1) is dissolved. Then, 100 mol of 2,2',3,3'-diphenyltetracarboxylic dianhydride (abbreviated as a-1) and 20 g of NMP are added, and then reacted at room temperature for 6 hours to obtain a reaction solution. The reaction solution is poured into 1500 ml of water to obtain a precipitate. Next, filtration was performed to obtain a filter cake, which was then washed with methanol, and the above filtration and washing were repeated three times. Then, the filter cake was placed in a vacuum oven and dried at a temperature of 60° C. to obtain a polymer.

Synthesis Examples 2 to 14 and Comparative Synthesis Examples 1 to 2

Synthesis Examples 2 to 14 and Comparative Synthesis Examples 1 to 2 are similar to the method of Synthesis Example 1, except that the types or amounts of the components are changed, see Tables 1 to 2.

Synthesis Example 15

A 500 ml tetrahedral flask was equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer, and nitrogen was introduced. Then, 100 mol of the diamine compound represented by formula (II-2) (abbreviated as b-2-2) and 80 g of N-methyl-2-pyrrolidone (abbreviated as NMP) were introduced into the tetrahedral flask and mixed, and stirred at room temperature until the diamine compound represented by formula (II-2) was dissolved. Then, 50 mol of 3,3',4,4'-diphenyltetracarboxylic dianhydride (abbreviated as a-2), 50 mol of 3,3',4,4'-dibenzophenonetetracarboxylic dianhydride (abbreviated as a-4) and 20 g of NMP were added. The mixture was reacted at room temperature for 6 hours, and then 97 g of NMP, 0.03 mol of acetic anhydride and 0.05 mol of pyridine were added, the temperature was raised to 110°C, and stirring was continued for 2 hours to carry out imidization reaction to obtain a reaction solution. The reaction solution was poured into 1500 ml of water to obtain a precipitate. Then, the mixture was filtered to obtain a filter cake, and the filter cake was washed with methanol, and the above filtration and washing were repeated three times. Then, the mixture was placed in a vacuum oven and dried at a temperature of 60°C to obtain a polymer with an imidization rate of 35%.

Synthesis Example 16 and Comparative Synthesis Example 3

The methods of Synthesis Example 16 and Comparative Synthesis Example 3 are similar to those of Synthesis Example 15, except that the types or amounts of the components are changed, see Table 2.

Table 1 Unit: Mol "--": Not implemented Synthesis Example 1 2 3 4 5 6 7 8 9 Tetracarboxylic dianhydride compound (a) a-1 100 0 0 100 0 0 0 0 0 a-2 0 50 0 0 50 0 50 0 0 a-3 0 0 80 0 0 50 0 50 0 a-4 0 50 0 0 50 0 0 0 100 a-5 0 0 20 0 0 0 50 0 0 a-6 0 0 0 0 0 50 0 50 0 Diamine compound (b) b-1-1 100 0 0 0 0 0 70 0 0 b-1-2 0 100 0 0 0 0 0 80 0 b-1-3 0 0 100 0 0 0 0 0 90 b-2-1 0 0 0 100 0 0 0 0 0 b-2-2 0 0 0 0 100 0 0 0 0 b-2-3 0 0 0 0 0 100 0 0 0 b-3-1 0 0 0 0 0 0 30 0 0 b-3-2 0 0 0 0 0 0 0 20 0 b-3-3 0 0 0 0 0 0 0 0 10 Acetic anhydride 0 0 0 0 0 0 0 0 0 Pyridine 0 0 0 0 0 0 0 0 0 Imidization reaction temperature (℃) -- -- -- -- -- -- -- -- -- Imidization rate (%) 0 0 0 0 0 0 0 0 0 a-1: 2,2',3,3'-diphenyltetracarboxylic dianhydride. a-2: 3,3',4,4'-diphenyltetracarboxylic dianhydride. a-3: 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride. a-4: 3,3',4,4'-benzophenone tetracarboxylic dianhydride. a-5: benzene tetracarboxylic dianhydride. a-6: 1,2,3,4-cyclobutane tetracarboxylic dianhydride. b-1-1: Formula (I-1). b-1-2: Formula (I-2). b-1-3: Formula (I-3). b-2-1: Formula (II-1). b-2-2: Formula (II-2). b-2-3: Formula (II-3). b-3-1: p-diaminobenzene. b-3-2: 2,2'-dimethyl-4,4'-diaminobiphenyl. b-3-3: 4,4'-dimethyldi(cyclohexylamine).

Table 2 Unit: Mole Synthesis Example Comparative Synthesis Example 10 11 12 13 14 15 16 1 2 3 Tetracarboxylic dianhydride compound (a) a-1 0 0 0 100 0 0 0 100 0 0 a-2 50 0 0 0 0 50 50 0 50 50 a-3 0 50 0 0 50 0 0 0 0 0 a-4 0 0 100 0 0 50 50 0 0 0 a-5 50 0 0 0 50 0 0 0 50 50 a-6 0 50 0 0 0 0 0 0 0 0 Diamine compound (b) b-1-1 0 0 0 0 40 0 0 0 0 0 b-1-2 0 0 0 50 0 0 100 0 0 0 b-1-3 0 0 0 0 0 0 0 0 0 0 b-2-1 70 0 0 0 40 0 0 0 0 0 b-2-2 0 80 0 50 0 100 0 0 0 0 b-2-3 0 0 90 0 0 0 0 0 0 0 b-3-1 30 0 0 0 0 0 0 30 0 0 b-3-2 0 20 0 0 20 0 0 70 60 60 b-3-3 0 0 10 0 0 0 0 0 40 40 Acetic anhydride 0 0 0 0 0 0.03 0.07 0 0 0.03 Pyridine 0 0 0 0 0 0.05 0.15 0 0 0.05 Imidization reaction temperature (℃) -- -- -- -- -- 110 110 -- -- 110 Imidization rate (%) 0 0 0 0 0 35 65 0 0 35 a-1: 2,2',3,3'-diphenyltetracarboxylic dianhydride. a-2: 3,3',4,4'-diphenyltetracarboxylic dianhydride. a-3: 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride. a-4: 3,3',4,4'-benzophenone tetracarboxylic dianhydride. a-5: benzene tetracarboxylic dianhydride. a-6: 1,2,3,4-cyclobutane tetracarboxylic dianhydride. b-1-1: Formula (I-1). b-1-2: Formula (I-2). b-1-3: Formula (I-3) b-2-1: Formula (II-1). b-2-2: Formula (II-2). b-2-3: Formula (II-3). b-3-1: p-diaminobenzene. b-3-2: 2,2'-dimethyl-4,4'-diaminobiphenyl. b-3-3: 4,4'-dimethyldi(cyclohexylamine).

Embodiment 1

100 parts by weight of the polymer of Synthesis Example 1, 5 parts by weight of a light absorber (manufactured by Mitsubishi Chemical; trade name MA100), 300 parts by weight of N-methyl-2-pyrrolidone and 200 parts by weight of diacetone alcohol were mixed at room temperature to obtain a light absorbing release composition.

Examples 2 to 20 and Comparative Examples 1 to 4

The methods of Examples 2 to 20 and Comparative Examples 1 to 4 are similar to those of Example 1, except that the types or amounts of the components are changed. See Tables 3 to 5.

Evaluation items

Releasability measurement: The light absorbing release compositions of Examples 1 to 20 and Comparative Examples 1 to 4 were introduced into a coating machine (brand: MIKASA; model: MS-A150), and coated on a 100 mm×100 mm glass substrate by spin coating, and then subjected to reduced pressure drying treatment at 100 mmHg for 5 seconds, then placed in an oven and pre-baked at 100°C for 2 minutes to form a pre-baked film with a film thickness of about 1 μm, and then post-baked at 350°C for 30 minutes to form a post-baked film with a film thickness of 1.0 μm.

A laser irradiation device (brand: ESI Co.; model: 5331) was used to provide laser light with a wavelength of 355nm, and the post-baked film was irradiated through the glass substrate to obtain a release film, wherein the irradiation area size was 10mm×100mm, and the light output was 4W, the repetition frequency was 40kHz, and the feed rate was 500mm/s. Then, a tape was attached to the release film, and then the tape was torn off, and the release film residue on the glass substrate was observed. Evaluation was performed according to the following standards: O: The release film completely fell off from the glass substrate; △: The release film fell off, but there was residue on the glass substrate; X: The release film could not fall off from the glass substrate.

Optical density (OD) measurement: The light absorbing release compositions of Examples 1 to 20 and Comparative Examples 1 to 4 were introduced into a coating machine (brand: MIKASA; model: MS-A150) and coated on a 100 mm×100 mm glass substrate by spin coating. Then, they were subjected to reduced pressure drying treatment at 100 mmHg for 5 seconds. Then, they were placed in an oven and pre-baked at 100°C for 2 minutes to form a pre-baked film with a film thickness of about 1 μm. Then, they were post-baked at 350°C for 30 minutes to form a post-baked film with a film thickness of 1.0 μm.

The incident light intensity (I ₀ ) and the transmitted light intensity (I) of the post-baked film were measured using a microspectrometer (manufactured by Otsuka Electronics; model MCPD 2000). Then, the incident light intensity and the transmitted light intensity were substituted into log ₁₀ (I ₀ /I) to calculate the optical density. The greater the optical density, the better the light shielding property. Evaluation was performed according to the following standards: ◎: optical density ≧1; O: 1＞optical density ≧0.8; △: 0.8＞optical density ≧0.5; ╳: optical density＜0.5.

Table 3 Unit: Weight Embodiment 1 2 3 4 5 6 7 8 Polymer (A) Synthesis Example 1 100 0 0 0 0 0 0 0 Synthesis Example 2 0 100 0 0 0 0 0 0 Synthesis Example 3 0 0 100 0 0 0 0 0 Synthesis Example 4 0 0 0 100 0 0 0 0 Synthesis Example 5 0 0 0 0 100 0 0 0 Synthesis Example 6 0 0 0 0 0 100 0 0 Synthesis Example 7 0 0 0 0 0 0 100 0 Synthesis Example 8 0 0 0 0 0 0 0 100 Light absorber (B) B-1 5 0 50 0 150 200 0 150 B-2 0 30 0 100 0 0 200 0 Solvent (C) C-1 300 0 0 0 3000 0 0 1200 C-2 0 800 0 0 0 0 1500 0 C-3 0 0 1000 1500 0 3000 0 0 C-4 200 0 500 500 0 0 500 0 C-5 0 200 0 0 0 1000 0 300 Evaluation items Separability O O O O O O O O Optical density ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ B-1: MA100 manufactured by Mitsubishi Chemical. B-2: MA230 manufactured by Mitsubishi Chemical. C-1: N-methyl-2-pyrrolidone. C-2: N-ethyl-2-pyrrolidone. C-3: 3-methoxy-N,N-dimethylpropionamide. C-4: Diacetone alcohol. C-5: Propylene glycol monobutyl ether.

Table 4 Unit: Weight Embodiment 9 10 11 12 13 14 15 16 Polymer (A) Synthesis Example 2 0 0 0 0 0 0 100 0 Synthesis Example 3 0 0 0 0 0 0 0 100 Synthesis Example 9 100 0 0 0 0 0 0 0 Synthesis Example 10 0 100 0 0 0 0 0 0 Synthesis Example 11 0 0 100 0 0 0 0 0 Synthesis Example 12 0 0 0 100 0 0 0 0 Synthesis Example 13 0 0 0 0 100 0 0 0 Synthesis Example 14 0 0 0 0 0 100 0 0 Light absorber (B) B-1 100 0 0 5 80 0 50 0 B-2 0 50 30 0 0 120 0 100 Solvent (C) C-1 0 2000 0 1000 0 0 0 2500 C-2 1200 0 1500 0 1500 1500 1800 0 C-3 0 0 0 0 0 0 0 0 C-4 300 0 500 500 300 300 200 500 C-5 0 1000 0 0 0 0 0 0 Evaluation items Separability O O O O O O O O Optical density ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ B-2: Made by Mitsubishi Chemical, trade name MA230. C-1: N-methyl-2-pyrrolidone. C-2: N-ethyl-2-pyrrolidone. C-3: 3-methoxy-N,N-dimethylpropionamide. C-4: Diacetone alcohol. C-5: Propylene glycol monobutyl ether.

Table 5 Unit: Weight Embodiment Comparison Example 17 18 19 20 1 2 3 4 Polymer (A) Synthesis Example 2 0 0 0 0 0 0 0 100 Synthesis Example 4 50 0 0 0 0 0 0 0 Synthesis Example 5 0 50 0 0 0 0 0 0 Synthesis Example 9 50 0 0 0 0 0 0 0 Synthesis Example 10 0 50 0 0 0 0 0 0 Synthesis Example 15 0 0 100 0 0 0 0 0 Synthesis Example 16 0 0 0 100 0 0 0 0 polymer Comparative Synthesis Example 1 0 0 0 0 100 0 0 0 Comparative Synthesis Example 2 0 0 0 0 0 100 0 0 Comparative Synthesis Example 3 0 0 0 0 0 0 100 0 Light absorber (B) B-1 150 0 150 0 50 0 0 0 B-2 0 100 0 30 0 50 50 0 Solvent (C) C-1 0 0 3000 0 0 0 0 0 C-2 0 0 0 800 1800 1800 1800 800 C-3 3000 2000 0 0 0 0 0 0 C-4 0 1000 0 0 200 200 200 0 C-5 300 0 0 200 0 0 0 200 Evaluation items Separability O O O O ╳ ╳ ╳ ╳ Optical density ◎ ◎ ○ ○ △ △ △ ╳ B-2: Made by Mitsubishi Chemical, trade name MA230. C-1: N-methyl-2-pyrrolidone. C-2: N-ethyl-2-pyrrolidone. C-3: 3-methoxy-N,N-dimethylpropionamide. C-4: Diacetone alcohol. C-5: Propylene glycol monobutyl ether.

As shown in Tables 3 to 5, the polymer (A) in Examples 1 to 3, Examples 7 to 9, Examples 15 to 16 and Example 20 is prepared using one of the diamine compound represented by formula (I-1), the diamine compound represented by formula (I-2) and the diamine compound represented by formula (I-3). Therefore, the release layer formed by the light-absorbing release composition containing the polymer (A) has a high optical density, and the release layer can be peeled off without residue after being irradiated with light. Based on this, the release layer formed by the light-absorbing release composition containing the polymer (A) of the present invention does have better light-shielding properties and the release layer does have better releasability after being irradiated with light.

As can be seen from Tables 3 to 5, the polymer (A) in Examples 4 to 6, Examples 10 to 12, and Examples 18 to 19 is prepared using one of the diamine compound represented by formula (II-1), the diamine compound represented by formula (II-2), and the diamine compound represented by formula (II-3). Therefore, the release layer formed by the light-absorbing release composition comprising the polymer (A) has a high optical density, and the release layer can be peeled off without residue after being irradiated with light. Based on this, the release layer formed by the light-absorbing release composition comprising the polymer (A) of the present invention does have better light-shielding properties, and the release layer does have better releasability after being irradiated with light.

As can be seen from Table 4, the polymer (A) of Example 13 is prepared using the diamine compound represented by formula (I-2) and the diamine compound represented by formula (II-2), while the polymer (A) of Example 14 is prepared using the diamine compound represented by formula (I-1) and the diamine compound represented by formula (II-1). Therefore, the release layer formed by the light-absorbing release composition containing the polymer (A) has a high optical density, and the release layer can be peeled off without residue after being irradiated with light. Based on this, the release layer formed by the light-absorbing release composition containing the polymer (A) of the present invention does have better light-shielding properties, and the release layer does have better releasability after being irradiated with light.

As can be seen from Table 5, in Example 17, a polymer (A) prepared from a diamine compound represented by formula (I-3) and a polymer (A) prepared from a diamine compound represented by formula (II-1) were used. Therefore, the release layer formed by the light-absorbing release composition comprising the polymer (A) has a high optical density, and the release layer can be peeled off without residue after being irradiated with light. Based on this, the release layer formed by the light-absorbing release composition comprising the polymer (A) of the present invention does have better light-shielding properties, and the release layer does have better releasability after being irradiated with light.

On the other hand, in Comparative Examples 1 to 4, the polymers in Comparative Examples 1 to 3 were not prepared using any of the diamine compound represented by formula (I-1), the diamine compound represented by formula (I-2), the diamine compound represented by formula (I-3), the diamine compound represented by (II-1), the diamine compound represented by formula (II-2), and the diamine compound represented by formula (II-3). Therefore, the release layer formed by the light-absorbing release composition containing the polymer has a low optical density and has a problem of poor light-shielding property, and the release layer is not easy to fall off after being irradiated with light and will remain, resulting in a problem of poor releasability.

In Comparative Example 4, although the polymer (A) prepared from the diamine compound represented by formula (I-2) was used, the absorbent (B) was not used. Therefore, the optical density of the release layer was low and the light-shielding property was poor. In addition, the release layer was not easy to fall off after being exposed to light and residues remained, resulting in poor releasability.

In summary, the release layer formed by the light absorbing release composition of the present invention by using the polymer (A) formed by at least one of the diamine compound represented by formula (I) and the diamine compound represented by formula (II) of the diamine component has better light shielding property, and the release layer has better releasability after being irradiated with pulsed laser light, so the purpose of the present invention can be achieved.

However, the above is only an embodiment of the present invention and should not be used to limit the scope of implementation of the present invention. All simple equivalent changes and modifications made according to the scope of the patent application of the present invention and the content of the patent specification are still within the scope of the present patent.

without.

Claims (8)

A method for using a light-absorbing release composition comprises: step (a), applying a processing treatment to a to-be-processed layer of a laminate body so that the to-be-processed layer forms a processed layer, wherein the laminate body defines a stacking direction and sequentially comprises a supporting carrier, a temporary fixing unit including a release layer and the to-be-processed layer in the stacking direction; step (b), after step (a), irradiating the release layer with pulsed laser light via the supporting carrier; and step (c), after step (a), simultaneously with step (b) or after step (b), irradiating the supporting carrier with the processed layer. The processed layer is obtained by layer separation; wherein the release layer is formed by a light absorbing release composition, and the light absorbing release composition includes a polymer (A), a light absorber (B) and a solvent (C), the polymer (A) is selected from polyamic acid polymers, polyimide polymers, polyimide block copolymers or any combination thereof, and is prepared by reacting a mixture including a tetracarboxylic dianhydride component and a diamine component, wherein the diamine component includes at least one diamine compound selected from the following group: a diamine compound represented by formula (I) and a diamine compound represented by formula (II),

^R1 represents a single bond, -C( _CH3 ) _2- , -( _CH2 ) _n1- , -C( _CF3 ) _2- , O-( _CH2 ) _n2 -O-, -O-, -S-( _CH2 ) _n3 -S-, -S-, -SS-, _-SO2- , -CO-, -CONH-, or -NHCO-, n1, n2 and n3 independently represent 1 to 12, ^R2 represents a single bond, -C( _CH3 ) _2- , -O-, -S-, -CO-, -C( _CF3 ) _2- , or a C1 to C10 alkylene group, any hydrogen on any benzene ring may be substituted by -F, _-CH3 , _-CF3 , -OH, or a phenyl group,

^R3 represents a single bond, -C( _CH3 ) _2- , -( _CH2 ) _m1- , -C( _CF3 ) _2- , -O-( _CH2 ) _m2 -O-, -O-, -S-( _CH2 ) _m3 -S-, -S-, -SS-, _-SO2- , -CO-, -CONH-, or -NHCO-, m1, m2 and m3 independently represent 1 to 12, ^R4 represents a single bond, -C( _CH3 ) _2- , -C( _CF3 ) _2- , -O-, -S-, -CO-, or a C1 to C10 alkylene group, ^R5 represents a single bond, -C( _CH3 ) _2- , -C( _CF3 ) ₂ -, -O-, -S-, -CO-, or C1 to C10 alkylene groups, any hydrogen on any benzene ring can be substituted by -F, -CH ₃ , -CF ₃ , -OH, or phenyl; the light transmittance of the release layer is less than 30%; the light absorber (B) absorbs pulsed laser light with a wavelength below 400nm and causes the release layer to deteriorate. A method for using a light-absorbing ion-releasing composition as described in claim 1, wherein the wavelength of the pulsed laser light is less than 400 nm. The method for using the light-absorbing release composition as described in claim 1, wherein the polymer (A) is a polyamine polymer. A method for using a light-absorbing release composition as described in claim 1, wherein the light absorber (B) contains a black pigment. The method for using the light absorbing release composition as described in claim 1, wherein, based on 100 parts by weight of the polymer (A), the amount of the light absorber (B) is 5 to 200 parts by weight, and the amount of the solvent (C) is 500 to 4000 parts by weight. A method for using a light-absorbing release composition as described in claim 1, wherein the laminate is subjected to a moving process before or after the processing. The method for using the light-absorbing release composition as described in any one of claims 1 to 6, wherein the temporary fixing unit further includes an adhesive layer, so that the laminate has the supporting carrier, the release layer, the adhesive layer and the layer to be processed in sequence. A method for preparing a semiconductor device comprises: processing a processed layer obtained by the method for using the light absorbing release composition described in any one of claims 1 to 7 to form a semiconductor device.