KR20170130279A - A sealing body manufacturing method, and a laminate - Google Patents

Abstract

Provided are a method for manufacturing a sealing body, capable of preventing a separation layer formed on a supporter from being separated when the sealing body is formed on the supporter, and a laminate. The method for forming a sealing body includes the processes of: forming a separation layer (2) deformed by emitting light to a plane part (1a) of one side of the supporter (1); removing the separation layer (2) formed around the entire peripheral part (1b) of the supporter (1); forming an adhesive layer (3) on the surface of the entire peripheral part (1b) of the supporter (1) from which the separation layer is removed; and forming the sealing body (7) on the adhesive layer (3).

Description

A SEALING BODY MANUFACTURING METHOD, AND A LAMINATE BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to a method for producing a plug, and a laminate.

In recent years, a fan-out type wafer-level package (WLP) technology has been developed to realize integration and miniaturization of semiconductor devices. In the fan-out type WLP technology, (i) a step of forming a resin wafer (a similar wafer) in which a plurality of chips are sealed with a resin on a support once and then removing the support from the resin wafer, (Patent Documents 1 to 3); and (ii) a method of forming a plug by removing the support after forming a wiring layer and a resin wafer on a support 1) is known, and in the point that high-density wiring is possible, the latter has attracted attention.

Japanese Laid-Open Patent Publication No. 2012-248598 (published on December 13, 2012) Japanese Laid-Open Patent Publication No. 2012-60100 (published on March 22, 2012) Japanese Laid-Open Patent Publication No. 2013-168594 (published on Aug. 29, 2013)

 Yoichi Kurita, "Development of ultra-compact package realizing high-reliability and high-density wiring by FO-WLP's new process RDL-first method", [online], RENESAS EDGE, [January 6, URL: http://japan.renesas.com/media/edge_ol/r_and_d/01/r70pf0030jj0101_edge.pdf>

The inventors of the present invention, based on their unique knowledge, have studied to form a separation layer on the support in advance, which is deteriorated by irradiating light, as a structure for removing the support at a desired timing in the fan-out WLP technology. As a result, in the method of forming the plugs (wiring layers and resin wafers) on the support as in the case of non-patent reference 1, a process (for example, lithography process) for forming wiring layers on the support is performed Therefore, it has been found that there may arise a problem that the separation layer formed on the support is peeled off due to the influence of the treatment (for example, the influence of the chemical solution used in the treatment).

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a method of manufacturing a plug capable of preventing peeling of a separation layer formed on a support when a plug is formed on a support, The main purpose is to provide.

In order to solve the above problems, a method of manufacturing a bag according to the present invention comprises:

A manufacturing method of a plug including a wiring layer, an element mounted on the wiring layer, and an encapsulating material encapsulating the element,

A separation layer forming step of forming a separation layer which is altered by irradiating light on one flat surface portion of a support through which light is transmitted,

A separation layer peripheral portion removing step for removing the separation layer formed around the entire periphery of the support;

An adhesive layer forming step of forming an adhesive layer on the surface of the support on the side of the entire periphery of the peripheral portion from which the separation layer is removed,

And a stick-forming step of forming the plug on the adhesive layer.

Further, in the laminate related to the present invention,

A support for transmitting light,

A separating layer which is altered by irradiating light,

An adhesive layer,

A sealing member is stacked in this order,

The sealing member includes a wiring layer, an element mounted on the wiring layer, and an encapsulating material that encapsulates the element,

The separation layer is covered with the adhesive layer other than a portion in contact with the support.

According to the present invention, it is possible to provide a method for manufacturing a plug and a laminate which can prevent peeling of the separation layer formed on the support when the plug is formed on the support.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing respective steps of a method of manufacturing a plug according to Embodiment 1 of the present invention. Fig.
2 is a view showing each step of the method for manufacturing a plug according to Embodiment 2 of the present invention.

A method of manufacturing a plug according to the present invention is a method of manufacturing a plug including a wiring layer, an element mounted on the wiring layer, and an encapsulating material encapsulating the element, A separating layer forming step of forming a separating layer which is altered by irradiating light on one of the planar portions of the supporting body; a separating layer peripheral portion removing step of removing the separating layer formed around the entire periphery of the supporting body; A step of forming an adhesive layer on the side of the entire periphery of the peripheral portion on the side from which the separation layer is removed and a step of forming the plug on the adhesive layer.

According to the above configuration, after the separation layer formed around the entire periphery of the support is removed, an adhesive layer is formed on the side of the support around which the separation layer is entirely removed, so that the separation layer is protected can do. This makes it possible to prevent the support from being peeled off by the erosion of the separation layer by the chemical liquid or the like in the plug formation step.

[Embodiment 1]

Brief Description of the Drawings Fig. 1 is a view for explaining respective steps of a method for manufacturing a plug according to an embodiment (Embodiment 1) of the present invention. Fig. The method of manufacturing the plug according to Embodiment 1 is characterized in that the separation layer forming step, the separation layer peripheral edge portion removing step, the adhesive layer forming step, the bag forming step, the adhesive layer removing step, the light irradiation step, the separation step, Conduct.

(Separation layer forming step)

1 (a), in the separation layer forming step, the one face portion 1a of one side of the support 1 that transmits light is irradiated with light (for example, light) by chemical vapor deposition (CVD) Thereby forming a separation layer 2 which is deteriorated. Note that " one plane portion " refers to one of the plane portions of the support body 1. [ Further, the " flat portion " may have fine irregularities that can be regarded as substantially flat. Details of the support 1 and the separation layer 2 and the formation sequence of the separation layer 2 will be described later.

(Separation layer edge portion removal process)

As shown in Fig. 1 (b), in the step of removing the peripheral portion of the separation layer, a separation layer (not shown) formed around the entire periphery portion 1b of the support 1, for example, 2) is removed. The peripheral edge portion 1b is a peripheral edge portion of the flat surface portion 1a. 1B, a state in which the separation layer 2 is formed on the portion surrounded by the peripheral edge portion 1b from which the separation layer 2 has been removed is shown on the flat surface portion 1a do. The details of the EBR processing will be described later.

(Adhesive layer forming step)

As shown in Fig. 1C, in the adhesive layer forming step, the adhesive layer 3 is formed on the entire periphery of the peripheral portion 1b of the support 1 on the side from which the separation layer 2 is removed . The adhesive layer 3 can be formed by applying an adhesive by a method such as spin coating, dipping, roller blade, spray coating, slit coating, or the like. As a result, the separation layer 2 is covered with the adhesive layer 3 because the peripheral edge portion 1b surrounding the separation layer 2 and the adhesive layer 3 are formed on the separation layer 2 State. Thereby, the separation layer 2 can be protected. Details of the adhesive for forming the adhesive layer 3 will be described later.

(Bag-forming step)

1 (d) to 1 (g), the plug 7 is formed on the adhesive layer 3 in the plug forming step. In the present embodiment, in the plug forming step, the wiring layer forming step, the mounting step, the sealing step and the thinning step are carried out in this order.

As shown in Fig. 1 (d), in the wiring layer forming step, the wiring layer 4 is formed on the adhesive layer 3.

In one embodiment, in order to form the wiring layer 4, first, a dielectric layer such as silicon oxide (SiOx) or photosensitive resin is formed on the adhesive layer 3. The dielectric layer made of silicon oxide can be formed by, for example, a sputtering method, a vacuum deposition method, or the like. The dielectric layer made of the photosensitive resin can be formed by applying a photosensitive resin by a method such as spin coating, dipping, roller blade, spray coating, slit coating, or the like.

Subsequently, wirings are formed on the dielectric layer by a conductor such as a metal. As a wiring formation method, a well-known semiconductor process technique such as a lithography process such as photolithography (resist lithography) or an etching process can be used.

As shown in Fig. 1 (e), the element 5 is mounted on the wiring layer 4 in the mounting step. The device 5 can be mounted on the wiring layer 4 by using, for example, a chip mounter or the like.

As shown in Fig. 1 (f), in the sealing step, the element 5 is sealed with the sealing material 6. The sealing material 6 may be injection molded using, for example, a molding die, or may be applied by a method such as spin coating, dipping, roller blade, spray coating, or slit coating.

As shown in Fig. 1 (g), in the thinning step, the sealing material 6 is thinned. The sealing material 6 may be thinned to a thickness equivalent to that of the element 5, for example.

As described above, the plugs 7 can be smoothly formed on the support 1. At this time, for example, a chemical liquid may be used in lithography processing, etching processing, and the like for forming wirings. Since the separation layer 2 often lacks chemical resistance, when the separation layer 2 comes into contact with the chemical liquid, the separation layer 2 may peel off. However, according to the present embodiment, since the separation layer 2 is protected by the adhesive layer 3, contact of the chemical solution with the separation layer 2 can be avoided. In addition, the separation layer 2 can be protected from other than the chemical solution by protecting the separation layer 2 with the adhesive layer 3. Thereby, it is possible to prevent the separation layer 2 from being peeled off during the plug forming process. Even when an oxide film, a metal layer or the like for constituting the wiring layer 4 is adhered to the vicinity of the end portion of the support 1 in the wiring layer forming step, for example, the adhesive layer 3 It is possible to easily remove the oxide film, the metal layer and the like from the support 1, and it is possible to reuse the support 1 without requiring any special cleaning.

The laminate 8 shown in Fig. 1 (g) obtained by the above process is a laminate comprising a support 1 for transmitting light, a separation layer 2 which is altered by irradiating light, an adhesive layer 3, And the plugs 7 are stacked in this order and the plugs 7 are formed by stacking a wiring layer 4 and elements 5 mounted on the wiring layer 4 and a sealing material 5 for sealing the elements 5, And the separating layer 2 is covered with the adhesive layer 3 except the portion in contact with the support 1. [ Such a layered product 8 is produced only in the course of the manufacturing method of the plug according to the present invention and can be preferably used for producing the isolated plug 7.

(Adhesive layer removing step)

As shown in FIG. 1 (h), in the adhesive layer removing step, the adhesive layer 3 formed around the entire peripheral edge portion 1b of the support 1 is removed by, for example, EBR treatment. The details of the EBR processing will be described later. Since the support member 1 and the plug 7 are bonded to each other at the portion of the adhesive layer 3 which is formed around the entire peripheral edge portion 1b of the support member 1 without interposing the separation layer 2 therebetween, The supporting body 1 and the plug 7 can be separated smoothly when the separation layer 2 is deteriorated.

Particularly, by removing the adhesive layer 3 formed on the outer side of the outer peripheral end portion 2a of the separation layer 2 formed on the support 1, the support 1 and the plug 7 are surely separated from each other, The support body 1 and the plug body 7 can be separated more smoothly when the separation layer 2 is deteriorated.

(Light irradiation step)

1 (i), in the light irradiation step, the separation layer 2 is altered by irradiating the separation layer 2 with light L through the support 1. The type and the wavelength of the light L to be irradiated may be appropriately selected depending on the permeability of the support 1 and the material of the separation layer 2. For example, a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, A solid laser such as an LD laser or a fiber laser, a liquid laser such as a dye laser, a gas laser such as a CO ₂ laser, an excimer laser, an Ar laser or a He-Ne laser, a laser beam such as a semiconductor laser, Laser light can be used. Thereby, the separation layer 2 is altered, and the support 1 and the plug 7 can be easily separated from each other.

The average output value of the laser light is preferably 1.0 W or more and 5.0 W or less, more preferably 3.0 L or less, more preferably 3.0 L or less, W or more and 4.0 W or less; The repetition frequency of the laser light is preferably 20 kHz or more and 60 kHz or less, more preferably 30 kHz or more and 50 kHz or less; The scanning speed of the laser beam is preferably 100 mm / s or more and 10000 mm / s or less.

(Separation step)

As shown in Fig. 1 (j), in the separation step, the support 1 and the plug 7 are separated. For example, the support 1 and the plug 7 are separated by applying a force in a direction in which the support 1 and the plug 7 are moved away from each other. For example, the supporting body 1 and the plug body 7 are fixed on the stage, and the other is lifted while being held by suction by a separation plate having a suction pad such as a bellows pad, And the plug body 7 can be separated from each other.

(Removal process)

As shown in Fig. 1 (k), in the removing step, the adhesive layer 3 and the separation layer 2 remaining in the bag body 7 from which the support 1 is separated are removed. For example, a cleaning process is performed to remove the adhesive layer 3 and the residue of the separation layer 2 with a cleaning liquid or the like containing an organic solvent. As the cleaning liquid, for example, a diluting solvent of an adhesive described below, a solvent showing an alkaline property (particularly, an amine compound), and the like can be used, but the present invention is not limited thereto.

Thus, the bag body 7 isolated can be obtained.

Further, the bag 7 may be further subjected to processes such as solder ball formation, dicing, and the like. Further, another element may be laminated on the plug 7.

In order to preferably remove the outer peripheral portion (the outer side of the separation layer 2) of the adhesive layer 3 in the adhesive removing step (see FIG. 1 (h)), 1). For example, the outer diameter of the plug 7 may be made smaller than the outer diameter of the support by making the outer diameter of the plug 7 smaller than that of the support, or (ii) It is preferable to apply a full cut trim to the plug body 7 in order to make the diameter smaller than the outer diameter of the support.

[EBR treatment]

An EBR treatment for removing the separation layer 2 formed around the entire circumferential portion 1b of the support 1 in the step of removing the peripheral portion of the separation layer (A), and (B) The EBR treatment for removing the adhesive layer 3 formed around the entire circumferential portion 1b of the support 1 in the removing step may be carried out by, for example, (i) A method of physically cutting off by using a cutter or a blade, and (iii) a method of removing by ashing under atmospheric pressure. Among them, a method of removing by a solvent is preferable from the viewpoints of strength and practicality.

The solvent used in the method of removing by the solvent is not particularly limited as long as it can dissolve the separation layer 2 or the adhesive layer 3 to be removed and a person skilled in the art can appropriately select . For example, a terpene type solvent such as p-menthane and d-limonene can be used as the solvent for the adhesive layer 3 formed by using a hydrocarbon-based adhesive, and an acrylic or maleimide-based adhesive As the adhesive layer 3, propylene glycol monomethyl ether acetate, cyclohexanone, 2-heptanone, ethyl acetate, methyl ethyl ketone and the like can be used as a solvent.

As the separating layer 2, for example, a solvent exhibiting alkalinity, particularly, an amine-based compound can be used. The separating layer 2 can be formed by using an aliphatic amine, an alicyclic amine, an aromatic amine , And heterocyclic amines. Of these organic amine compounds, particularly preferred are monoethanolamine, 2- (2-aminoethoxy) ethanol and 2-ethylamino Ethanol and 2-methylaminoethanol (MMA) are preferably used. The peeling liquid may be used by mixing the amine compound with another solvent, or may be mixed with a solvent described in the column of (diluting solvent) described later.

Examples of the method for supplying the solvent include a method of supplying the solvent to the object to be removed by spraying the solvent and a method of immersing the object to be removed in the solvent.

As a method of supplying the solvent to the object to be removed by spraying the solvent, a method of supplying the solvent to the object to be removed while rotating the substrate 1 is preferable in order to uniformly supply the solvent. As a method of supplying the solvent while rotating the support body 1, for example, a nozzle for spraying the solvent may be disposed directly on the outer side of the peripheral portion 1b of the support body 1, And the supporting body 1 is rotated by using a spinner while being dropped directly on the outer side of the peripheral portion 1b of the supporting member 1. [ This makes it possible to supply the solvent just outside the entire periphery of the peripheral portion 1b of the support 1. [ The number of nozzles to be arranged is not limited, and may be one or more.

In the above method involving the rotation of the support 1 and the spraying of the solvent, the rotation speed of the support 1, the flow rate of the solvent at the time of supplying the solvent from the nozzle, and the supply time of the solvent, The thickness of the object, the kind of the solvent to be used, and the degree of elimination. However, those skilled in the art can examine and determine the optimum conditions without difficulty.

After dissolving the object to be removed by the solvent, it is preferable to dry the support 1 or the like. By passing through the drying step, unnecessary solvent, solvent that has entered the separation layer 2 or the adhesive layer 3, which is not a removal target portion, can be removed.

Examples of the drying method include drying of the hair by spinning the support 1 using a spinner or the like, drying by air blowing by spraying with N ₂ gas, drying by baking, and drying by decompression have. These drying methods can be either a method using either method alone, or a method using any combination of two or more methods.

[Plug (7)]

As described above, the plug 7 has the wiring layer 4, the element 5 mounted on the wiring layer 4, and the sealing material 6 sealing the element 5 . In one embodiment, the plug 7 has a plurality of elements 5, and by dicing the plug 7, a plurality of electronic parts can be obtained.

The element 5 is a semiconductor element or other element, and may have a single layer or a multilayer structure. When the element 5 is a semiconductor element, the electronic part obtained by dicing the plug 7 becomes a semiconductor device.

The wiring layer 4 is also referred to as RDL (Redistribution Layer), and is a thin-film wiring body constituting wirings connected to the element 5, and may have a single layer structure or a plurality of layers structure. In one embodiment, the wiring layer 4 may be formed of a conductive material (for example, aluminum, copper, titanium, nickel, gold, or the like) to a dielectric (for example, silicon oxide (SiOx), photosensitive epoxy or the like, Or the like), but the present invention is not limited thereto.

As the sealing material 6, for example, an epoxy-based resin, a silicon-based resin, or the like can be used. In one embodiment, the encapsulation material 6 is not formed for each element 5 but integrally encapsulates all of the plurality of elements 5 mounted on the wiring layer 4.

[Support (1)]

In one embodiment, the support 1 may have a strength required to prevent breakage or deformation of each component of the plug 7 when the plug 7 is formed. It is also possible to transmit light for altering the separation layer 2.

As the material of the support 1, for example, glass, silicone, acrylic resin or the like can be used, but the present invention is not limited thereto. As the shape of the support 1, for example, a circular plate-like shape can be used, but it is not limited thereto.

[Adhesive Layer (3)]

In one embodiment, the adhesive layer 3 is used for securing the plugs 7 on the support 1 and is used for protecting the separation layer 2.

The thickness of the adhesive layer 3 may be suitably set according to the kind of the support 1 and the bag 7 and the treatment to be carried out in the bag-forming step, and is preferably in the range of 10 to 150 mu m, And more preferably within a range of 100 占 퐉.

As the adhesive for forming the adhesive layer 3, various adhesives known in the art such as acrylic, novolac, naphthoquinone, hydrocarbon, polyimide, elastomer and polysulfone can be used .

The resin contained in the adhesive, that is, the resin contained in the adhesive layer 3 may be any one having adhesiveness, and examples thereof include a resin such as a hydrocarbon resin, an acryl-styrene resin, a maleimide resin, an elastomer resin, A phthalic resin, and the like, or a combination thereof may be more preferably used. Hereinafter, the composition of the resin contained in the adhesive layer 3 will be described.

(Hydrocarbon resin)

The hydrocarbon resin is a resin having a hydrocarbon skeleton and polymerizing the monomer composition. As the hydrocarbon resin, at least one resin selected from the group consisting of a cycloolefin-based polymer (hereinafter also referred to as "resin (A)"), a terpene resin, a rosin-based resin and a petroleum resin Resin (B) "), but the present invention is not limited thereto.

The resin (A) may be a resin obtained by polymerizing a monomer component containing a cycloolefin-based monomer. Specific examples thereof include a ring-opening (co) polymer of a monomer component containing a cycloolefin-based monomer, and a resin obtained by addition (co) polymerization of a monomer component containing a cycloolefin-based monomer.

Examples of the cycloolefin-based monomer contained in the monomer component constituting the resin (A) include bicyclic compounds such as norbornene and norbornadiene, dicyclopentadiene, hydroxydicyclopentadiene and the like (Methyl, ethyl, propyl, butyl (meth) acrylate of a cyclic compound such as a cyclic compound such as a cyclic compound such as cyclopentadiene or cyclopentadiene or a cyclic compound such as a cyclic compound such as a cyclic compound Etc.), alkenyl (vinyl, etc.) substituents, alkylidene (ethylidene etc.) substituents, aryl (phenyl, tolyl, naphthyl, etc.) substituents and the like. Of these, norbornene monomers selected from the group consisting of norbornene, tetracyclododecene, and alkyl substituents thereof are particularly preferable.

The monomer component constituting the resin (A) may contain other monomer copolymerizable with the cycloolefin-based monomer described above, and preferably contains, for example, an alkene monomer. Examples of the alkene monomer include ethylene, propylene, 1-butene, isobutene, 1-hexene, and -olefin. The alkene monomer may be linear or branched.

Further, it is preferable that a monomer component constituting the resin (A) contains a cycloolefin monomer in view of high heat resistance (low thermal decomposition and thermogravimetric reduction). The proportion of the cycloolefin monomer to the whole monomer component constituting the resin (A) is preferably 5 mol% or more, more preferably 10 mol% or more, and still more preferably 20 mol% or more. The ratio of the cycloolefin monomer to the whole monomer component constituting the resin (A) is not particularly limited, but from the viewpoints of solubility and stability over time in the solution, it is preferably 80 mol% or less, more preferably 70 mol% Is more preferable.

As the monomer component constituting the resin (A), an alkene monomer of a linear or branched type may be contained. The proportion of the alkene monomer to the whole monomer component constituting the resin (A) is preferably from 10 to 90 mol%, more preferably from 20 to 85 mol%, still more preferably from 30 to 80 mol%, from the viewpoints of solubility and flexibility, Is more preferable.

The resin (A) is, for example, a resin having no polar group, such as a resin obtained by polymerizing a monomer component comprising a cycloolefin-based monomer and an alkene monomer, in order to suppress the generation of gas under high temperature .

The polymerization method, polymerization conditions, and the like at the time of polymerizing the monomer component are not particularly limited and may be suitably set according to a conventional method.

For example, a cycloolefin copolymer which is a copolymer of a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2) may be used as the resin (A) as an adhesive component.

[Chemical Formula 1]

(In the formula (2), n is 0 or an integer of 1 to 3.)

As such cycloolefin copolymers, APL 8008T, APL 8009T, and APL 6013T (both manufactured by Mitsui Chemicals, Inc.) can be used.

Examples of commercially available products that can be used as the resin (A) include "TOPAS" manufactured by Polyplastics Co., Ltd., "APEL" manufactured by Mitsui Chemicals, Inc., "ZEONOR" and "ZEONEX" manufactured by Nippon Zeon Co., &Quot; ARTON " manufactured by Kokusan Co., Ltd., and the like.

The glass transition temperature (Tg) of the resin (A) is preferably 60 占 폚 or higher, and particularly preferably 70 占 폚 or higher. When the glass transition temperature of the resin (A) is 60 DEG C or more, softening of the adhesive layer (3) can be further suppressed when exposed to a high temperature environment.

The resin (B) is at least one resin selected from the group consisting of a terpene resin, a rosin resin and a petroleum resin. Specifically, examples of the terpene resin include a terpene resin, a terpene phenol resin, a modified terpene resin, a hydrogenated terpene resin, and a hydrogenated terpene phenol resin. Examples of the rosin-based resin include rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, and modified rosin. Examples of the petroleum resin include an aliphatic or aromatic petroleum resin, a hydrogenated petroleum resin, a modified petroleum resin, an alicyclic petroleum resin, a coumarone-indene petroleum resin, and the like. Of these, hydrogenated terpene resins and hydrogenated petroleum resins are more preferable.

The softening point of the resin (B) is not particularly limited, but is preferably 80 to 160 ° C. When the softening point of the resin (B) is 80 to 160 占 폚, softening of the resin (B) upon exposure to a high temperature environment can be suppressed, and adhesion failure is not caused.

The weight average molecular weight of the resin (B) is not particularly limited, but is preferably 300 to 3,000. When the weight average molecular weight of the resin (B) is 300 or more, the heat resistance becomes sufficient, and the amount of degassing is reduced in a high temperature environment. On the other hand, if the weight average molecular weight of the resin (B) is 3,000 or less, the dissolution rate of the adhesive layer (3) to the hydrocarbon solvent becomes good. Therefore, it is possible to rapidly dissolve and remove the residue of the adhesive layer 3 on the plug 7 after the support 1 is separated. The weight average molecular weight of the resin (B) in the present embodiment means the molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

As the resin, a mixture of the resin (A) and the resin (B) may be used. By mixing, the heat resistance becomes good. For example, the mixing ratio of the resin (A) and the resin (B) is preferably from 80:20 to 55:45 (mass ratio) of (A) :( B) It is preferable because it is excellent.

(Acrylic-styrenic resin)

Examples of the acryl-styrene type resin include resins obtained by polymerizing a derivative of styrene or styrene with (meth) acrylic acid ester as a monomer.

(Meth) acrylic esters include, for example, (meth) acrylic acid alkyl esters having a chain structure, (meth) acrylic esters having aliphatic rings, and (meth) acrylic esters having aromatic rings. Examples of the (meth) acrylic acid alkyl ester having a chain structure include an acrylic long-chain alkyl ester having an alkyl group having a carbon number of 15 to 20 and an acrylic alkyl ester having an alkyl group having a carbon number of 1 to 14. Examples of the acrylic long chain alkyl ester include acrylic acid or methacrylic acid in which the alkyl group is n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, Of alkyl esters. The alkyl group may be branched chain.

Examples of the acrylic alkyl ester having an alkyl group having 1 to 14 carbon atoms include known acrylic alkyl esters used in conventional acrylic adhesives. For example, when the alkyl group is an acrylic acid or methacrylic acid group such as methyl, ethyl, propyl, butyl, 2-ethylhexyl, isooctyl, isononyl, isodecyl, dodecyl, lauryl, And alkyl esters of acrylic acid.

Examples of the (meth) acrylic acid ester having an aliphatic ring include cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, 1-adamantyl (meth) acrylate, norbornyl (meth) (Meth) acrylate, tricyclodecanyl (meth) acrylate, tetracyclododecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate and the like can be given, but isobornyl methacrylate, Cyclopentanyl (meth) acrylate is more preferable.

The (meth) acrylic ester having an aromatic ring is not particularly limited, and examples of the aromatic ring include a phenyl group, a benzyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthracenyl group, , A phenoxyethyl group, and the like. The aromatic ring may have a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, phenoxyethyl acrylate is preferable.

(Maleimide resin)

Examples of the maleimide-based resin include monomers such as N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N- N-heptylmaleimide, Nn-octylmaleimide, N-laurylmaleimide, N-heptylmaleimide, N-heptylmaleimide, N-heptylmaleimide, N-tert-butylmaleimide, Maleimide having an alkyl group such as stearyl maleimide, N-cyclopropyl maleimide, N-cyclobutyl maleimide, N-cyclopentyl maleimide, N-cyclohexyl maleimide, N-cycloheptyl maleimide, N- Maleimide having an aliphatic hydrocarbon group such as cyclooctylmaleimide, aromatic maleimide having an aryl group such as N-phenylmaleimide, Nm-methylphenylmaleimide, No-methylphenylmaleimide and Np-methylphenylmaleimide, etc. Can be .

(Elastomer)

The elastomer preferably contains a styrene unit as a constitutional unit of the main chain, and the " styrene unit " may have a substituent. Examples of the substituent include an alkyl group of 1 to 5 carbon atoms, an alkoxy group of 1 to 5 carbon atoms, an alkoxyalkyl group of 1 to 5 carbon atoms, an acetoxy group, and a carboxyl group. It is more preferable that the content of the styrene unit is in the range of 14 wt% or more and 50 wt% or less. The elastomer preferably has a weight average molecular weight of 10,000 or more and 200,000 or less.

When the content of the styrene unit is in the range of 14% by weight or more and 50% by weight or less and the weight average molecular weight of the elastomer is in the range of 10,000 or more and 200,000 or less, it is easily dissolved in the hydrocarbon solvent described later, And the adhesive layer 3 can be quickly removed. The styrene unit content and the weight average molecular weight are within the above ranges, and therefore, excellent resistance to a resist (eg, PGMEA, PGME, etc.), acid (hydrofluoric acid, etc.), and alkali (TMAH, etc.) used in resist lithography .

The above-mentioned (meth) acrylic acid ester may be further mixed in the elastomer.

The content of the styrene unit is more preferably 17% by weight or more, and still more preferably 40% by weight or less.

A more preferable range of the weight average molecular weight is 20,000 or more, and a more preferable range is 150,000 or less.

As the elastomer, various elastomers can be used so long as the content of the styrene unit is in the range of 14% by weight or more and 50% by weight or less, and the weight average molecular weight of the elastomer is 10,000 or more and 200,000 or less. Styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), styrene-butadiene-butylene-styrene block copolymers Styrene block copolymer (SBBS), and hydrogenated products thereof, styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (styrene-isoprene- styrene block copolymer) (SEPS), a styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), a styrene-ethylene-ethylene-propylene-styrene block copolymer having a styrene block as a reactive crosslinking type (Septon V9461 A styrene-ethylene-butylene-styrene block copolymer (having a reactive polystyrene-based hard block, Septon V9827 (Kuraray Co., Ltd.)) in which the styrene block is a reactive crosslinked type, (Ethylene-ethylene / propylene) block-polystyrene block copolymer (SEEPS-OH: terminal hydroxyl group-modified), and the elastomer having a styrene unit content and a weight average molecular weight within the above- .

Among the elastomers, a hydrogenated product is more preferable. Hydrogenation improves the stability to heat and does not cause degradation such as decomposition or polymerization. It is more preferable from the viewpoints of solubility in a hydrocarbon solvent and resistance to a resist solvent.

Further, among the elastomers, it is more preferable that both ends are styrene block polymers. This is because styrene having high heat stability is blocked at both ends to exhibit higher heat resistance.

More specifically, it is more preferable that the elastomer is a hydrogenation product of a block copolymer of styrene and a conjugated diene. Stability against heat is improved, and deterioration such as decomposition or polymerization does not occur well. Further, styrene having high thermal stability is blocked at both ends to exhibit higher heat resistance. It is more preferable from the viewpoints of solubility in a hydrocarbon solvent and resistance to a resist solvent.

Examples of commercially available products that can be used as the elastomer included in the adhesive constituting the adhesive layer 3 include "Septon (trade name)" manufactured by Kuraray Co., Ltd., "Hiabra (trade name)" manufactured by Kuraray Co., (Trade name) manufactured by JSR Corporation, and "DYNARON (trade name)" manufactured by JSR Corporation.

The content of the elastomer contained in the adhesive constituting the adhesive layer 3 is preferably from 50 parts by weight to 99 parts by weight, more preferably from 60 parts by weight or more, for example, 100 parts by weight as the total amount of the adhesive composition , 99 parts by weight or less, and most preferably 70 parts by weight or more and 95 parts by weight or less. By keeping these ranges, the plugs 7 can be preferably fixed to the support 1 while maintaining the heat resistance.

The elastomer may be mixed with a plurality of kinds. In other words, the adhesive constituting the adhesive layer 3 may contain a plurality of kinds of elastomers. At least one of the plural kinds of elastomers may contain a styrene unit as a constitutional unit of the main chain. When at least one of the plural kinds of elastomers has a styrene unit content of 14 wt% or more and 50 wt% or less, or a weight average molecular weight of 10,000 or more and 200,000 or less, to be. When a plurality of kinds of elastomers are contained in the adhesive constituting the adhesive layer 3, the content of the styrene units may be adjusted so as to be in the above range as a result of mixing. For example, when Septon 4033 (trade name) manufactured by Kuraray Co., Ltd. having a styrene unit content of 30% by weight and Septon 2063 (trade name) having a styrene unit content of 13% by weight are mixed at a weight ratio of 1: 1, The styrene content of the whole elastomer contained in the adhesive is 21 to 22 wt%, and therefore, it is 14 wt% or more. For example, when the weight ratio of styrene units is 10 wt% to 60 wt% is 1: 1, the weight ratio is 35 wt%, which is within the above range. The present invention may be of such a form. It is most preferable that all of the plural kinds of elastomers contained in the adhesive constituting the adhesive layer 3 contain styrene units within the above-mentioned range, and the weight average molecular weight within the above range is the most preferable.

Further, it is preferable to form the adhesive layer 3 using a resin other than the photocurable resin (for example, UV curable resin). By using a resin other than the photocurable resin, residues can be prevented from being generated around the minute unevenness of the plugs 7 after the adhesive layer 3 is peeled or removed. Particularly, it is preferable that the adhesive constituting the adhesive layer 3 is not dissolved in all the solvents but dissolved in a specific solvent. This is because the adhesive layer 3 can be removed by dissolving the adhesive layer 3 in a solvent without applying a physical force to the plug 7. The adhesive layer 3 can be easily removed from the plug 7 having a low strength without removing the plug 7 or damaging the plug 7 in removing the adhesive layer 3. [

(Polysulfone resin)

The adhesive for forming the adhesive layer 3 may contain a polysulfone resin. The adhesive layer 3 is formed by the polysulfone resin so that the adhesive layer 3 is dissolved in the subsequent step even if the high temperature treatment is performed in the bag member forming step, Can be peeled off. If the adhesive layer 3 contains a polysulfone resin, a high-temperature process for treating at a high temperature of, for example, 300 DEG C or higher can be used in the bag-forming process.

The polysulfone resin has a structure comprising at least one structural unit selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4).

(2)

(Wherein R ¹ , R ² and R ³ in the general formula (3) and R ¹ and R ² in the general formula (4) are each independently selected from the group consisting of a phenylene group, a naphthylene group and an anthrylene group And X 'is an alkylene group having a carbon number of 1 or more and 3 or less).

The polysulfone resin has at least one of the polysulfone constitutional unit represented by the formula (3) and the polyethersulfone constitutional unit represented by the formula (4) It is possible to prevent the adhesive layer 3 from being insolubilized by decomposition, polymerization, or the like even if a treatment under a high temperature condition is performed in the plug forming step after the adhesive layer 3 is formed on the adhesive layer 3. Further, the polysulfone resin is stable even when heated to a higher temperature, as long as it is a polysulfone resin comprising the polysulfone constitutional unit represented by the formula (3). Therefore, it is possible to prevent the residue resulting from the adhesive layer (3) from being generated in the bag (7) after cleaning.

The polysulfone resin preferably has a weight average molecular weight (Mw) of 30,000 or more and 70,000 or less, more preferably 30,000 or more and 50,000 or less. When the weight average molecular weight (Mw) of the polysulfone resin is within the range of 30,000 or more, an adhesive composition which can be used at a high temperature of, for example, 300 DEG C or more can be obtained. When the weight average molecular weight (Mw) of the polysulfone resin is within the range of 70,000 or less, it can be preferably dissolved by a solvent. In short, an adhesive composition which can be preferably removed by a solvent can be obtained.

(Diluting solvent)

Examples of the diluent for use in forming the adhesive layer 3 include linear hydrocarbons such as hexane, heptane, octane, nonane, isononane, methyloctane, decane, undecane, dodecane and tridecane , Branched chain hydrocarbons having 4 to 15 carbon atoms such as cyclic hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, naphthalene, decahydronaphthalene and tetrahydronaphthalene, p-menthane, o-menthane, m- Menthane, diphenylmethane, 1,4-terpine, 1,8-terpine, borane, norbornane, pyrazine, tolan, carane, longpolyene, geraniol, nerol, linalool, Terpineol-1-ol, terpinene-4-ol, dihydroterpineacetate, 1-tert-butylphenol, 1-methylphenol, Terpene solvents such as 4-cineol, 1,8-cineol, borneol, carboen, yonon, turmeric, camphor, d-limonene, l-limonene and dipentene; lactones such as? -butyrolactone; Ketones such as acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl isopentyl ketone and 2-heptanone; Polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol; A compound having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; a monomethyl ether, monoethyl ether, Monoalkyl ethers such as monopropyl ether and monobutyl ether, and compounds having an ether bond such as monophenyl ether (among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) is preferred); Cyclic ethers such as dioxane and esters such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methoxybutyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate and ethyl ethoxypropionate Ryu; Aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether and the like.

(Other components)

The adhesive constituting the adhesive layer (3) may further contain other miscible substances in the range that does not impair the intrinsic properties. For example, various additives commonly used such as an additive resin for improving the performance of the adhesive, a plasticizer, an adhesion promoter, a stabilizer, a colorant, a thermal polymerization inhibitor and a surfactant may be further used.

[Separation layer (2)]

As described above, the separation layer 2 is adapted to be altered by irradiating light. In one embodiment, the support 1 can be separated from the plug 7 by irradiating the separation layer 2 with light via the support 1 to deteriorate the separation layer 2.

The thickness of the separation layer 2 is more preferably in the range of 0.05 탆 or more and 50 탆 or less, and more preferably in the range of 0.3 탆 or more and 1 탆 or less. If the thickness of the separation layer 2 is in the range of 0.05 占 퐉 or more and 50 占 퐉 or less, desired deterioration can be caused in the separation layer 2 by irradiation with light for a short time and irradiation with low energy light. It is particularly preferable that the thickness of the separation layer 2 falls within a range of 1 占 퐉 or less from the viewpoint of productivity.

Further, another layer may be additionally formed between the separation layer 2 and the support 1. In this case, the other layer may be made of a material that transmits light. Thereby, it is possible to appropriately add a layer having desirable properties without interfering with the light incident on the separation layer 2. Depending on the kind of the material constituting the separation layer 2, the wavelength of the usable light is different. Therefore, the material constituting the other layer is not required to transmit all the light, but can be appropriately selected from a material capable of transmitting light having a wavelength capable of deteriorating the material constituting the separation layer 2.

It is preferable that the separation layer 2 is formed only from a material having a structure for absorbing light, but it is preferable that the separation layer 2 does not have a structure for absorbing light The separation layer 2 may be formed by adding a material. It is preferable that the surface of the separation layer 2 facing the adhesive layer 3 is planar (unevenness is not formed), whereby the separation layer 2 can be easily formed In addition, it is possible to evenly attach the adhesive sheet to the adhesive sheet.

(Fluorocarbon)

The separating layer 2 may be made of fluorocarbon. The separating layer 2 is constituted by fluorocarbon, so that it is deformed by absorption of light, and as a result, it loses its strength or adhesion before it is irradiated with light. Therefore, the separating layer 2 is broken by applying a slight external force (for example, by lifting the support 1), so that the support 1 and the plug 7 can be easily separated from each other . The fluorocarbon constituting the separation layer 2 can be preferably formed by a plasma CVD (chemical vapor deposition) method.

Fluorocarbon absorbs light having a wavelength in a specific range depending on its kind. By irradiating the separation layer 2 with light having a wavelength in the range that the fluorocarbon used in the separation layer 2 absorbs, the fluorocarbon can be preferably altered. The absorption rate of light in the separation layer 2 is preferably 80% or more.

As the light to be irradiated to the separation layer 2, for example, a solid laser such as a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, an LD laser, a fiber laser or the like may be used depending on the wavelength at which the fluorocarbon can be absorbed. A gas laser such as a liquid laser such as a laser, a CO ₂ laser, an excimer laser, an Ar laser, or a He-Ne laser, a laser beam such as a semiconductor laser or a free electron laser, or a non-laser beam may be suitably used. The wavelength at which the fluorocarbon can be altered is not limited to this. For example, a wavelength in the range of 600 nm or less can be used.

(A polymer containing a structure having light absorption properties in the repeating unit)

The separation layer 2 may contain a polymer containing a light absorbing structure in the repeating unit. The polymer is altered by irradiation with light. The deterioration of the polymer occurs when the structure absorbs the irradiated light. The separation layer 2 lost strength or adhesiveness before being irradiated with light as a result of alteration of the polymer. Therefore, the separating layer 2 is broken by applying a slight external force (for example, lifting the support plate 2), so that the supporting body 1 and the plug body 7 can be separated easily have.

The above structure having light absorption property is a chemical structure that absorbs light and changes the polymer containing the structure as a repeating unit. The structure thereof is, for example, an atomic group containing a conjugated pi-electron system consisting of a substituted or unsubstituted benzene ring, a condensed ring or a heterocyclic ring. More specifically, the structure may be a carbodiimide structure, a benzophenone structure, a diphenyl sulfoxide structure, a diphenyl sulfone structure (biphenyl sulfone structure), a diphenyl structure or a diphenylamine structure in a side chain of the polymer Structure.

When the structure is present in the side chain of the polymer, its structure can be represented by the following formula.

(3)

(Wherein, R is each independently an alkyl group, an aryl group, a halogen, a hydroxyl group, a ketone group, a sulfoxide group, a sulfone group or an ^{N (R 4) (R 5} ) , and (wherein, R ⁴ and R ⁵ are each independently Z is an unsubstituted or -CO-, -SO ₂ -, -SO- or -NH- group, and n is 0 or an integer of 1 to 5 .)

The polymer may contain repeating units represented by, for example, any of the following formulas (a) to (d), or may be represented by (e) It is included in the main chain.

[Chemical Formula 4]

X is an integer represented by the formula (3) in (a) to (e), (f) is an integer of 1 or more, , Y ₁ and Y ₂ are each independently -CO- or SO ₂ - in any of the formulas shown in the above-mentioned "formula (3)" or not, and 1 is preferably an integer of 10 or less .)

Examples of the benzene ring, condensed ring and heterocyclic ring shown in the above-mentioned "Formula 3" include phenyl, substituted phenyl, benzyl, substituted benzyl, naphthalene, substituted naphthalene, anthracene, substituted anthracene, anthraquinone, substituted anthraquinone, , Substituted acridine, azobenzene, substituted azobenzene, fluoride, substituted fluoride, fluorimone, substituted fluorimone, carbazole, substituted carbazole, N-alkylcarbazole, dibenzofuran, substituted dibenzofuran, phenan Threne, substituted phenanthrene, pyrene and substituted pyrene. When the exemplified substituent further has a substituent, the substituent can be, for example, an alkyl, aryl, halogen atom, alkoxy, nitro, aldehyde, cyano, amide, dialkylamino, sulfonamide, imide, Acid, carboxylic acid ester, sulfonic acid, sulfonic acid ester, alkylamino and arylamino.

Among the substituents represented by the above-mentioned "Formula 3 ", examples of the case where Z is -SO ₂ - as the fifth substituent having two phenyl groups include bis (2,4-dihydroxyphenyl) sulfone, bis (3,4-dihydroxyphenyl) sulfone, bis (3,5-dihydroxyphenyl) sulfone, bis (3,5-dihydroxyphenyl) sulfone, bis (Hydroxyphenyl) sulfone, bis (2-hydroxyphenyl) sulfone, and bis (3,5-dimethyl-4-hydroxyphenyl) sulfone.

Among the substituents represented by the above-mentioned "Formula 3 ", examples of the case where Z is -SO- as the fifth substituent having two phenyl groups include bis (2,3-dihydroxyphenyl) sulfoxide, bis Dihydroxyphenyl) sulfoxide, bis (2,4-dihydroxyphenyl) sulfoxide, bis (2,4-dihydroxy-6-methylphenyl) sulfoxide, bis (2,5-dihydroxyphenyl) sulfoxide, bis (3,4-dihydroxyphenyl) sulfoxide, bis (3,5-di (2,3,4-trihydroxyphenyl) sulfoxide, bis (2,3,4-trihydroxyphenyl) sulfoxide, bis (2,3,4-trihydroxy- (2,4,6-trihydroxyphenyl) sulfoxide, bis (2,4,6-trihydroxyphenyl) sulfoxide, bis (5-chloro-2,4,6- .

Among the substituents represented by the above-mentioned "Formula 3 ", examples of the case where Z is -C (= O) - as a fifth substituent having two phenyl groups include 2,4- Tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2', 5,6'-tetrahydroxybenzophenone, 2-hydroxy-4- 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,6-di Hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-amino-2'-hydroxybenzophenone, 4-dimethylamino- Hydroxybenzophenone, 4-dimethylamino-4'-methoxy-2'-hydroxybenzophenone, 4-dimethylamino-2 ', 4'-dihydro Hydroxybenzophenone, and 4-dimethylamino-3 ', 4'-dihydroxybenzophenone.

When the structure is present in the side chain of the polymer, the proportion of the repeating unit having the structure in the polymer is preferably in the range of 0.001% or more and 10% or less in the light transmittance of the separation layer (2) . When the polymer is prepared so that the ratio falls within such a range, the separation layer 2 absorbs light sufficiently and can be surely and quickly deteriorated. That is, it is easy to remove the support 1 from the plugs 7, and the irradiation time required for the removal thereof can be shortened.

The structure can absorb light having a wavelength in a desired range by selection of the kind. For example, the wavelength of the absorbable light of the above structure is more preferably in the range of 100 nm or more and 2,000 nm or less. Within this range, the wavelength of the light absorbable by the above structure is on the shorter wavelength side, for example, in the range of 100 nm or more and 500 nm or less. For example, the above structure may deform the polymer containing the structure, preferably by absorbing ultraviolet light having a wavelength within a range of about 300 nm or more and 370 nm or less.

(Wavelength: 254 nm or more, 436 nm or less), KrF excimer laser (wavelength: 248 nm), ArF excimer laser (wavelength: 193 nm), F2 excimer laser (Wavelength: 157 nm), XeCl laser (wavelength: 308 nm), XeF laser (wavelength: 351 nm) or solid UV laser (wavelength: 355 nm) Line (wavelength: 405 nm) or an i-line (wavelength: 365 nm).

Although the above-described separation layer 2 contains a polymer containing the above structure as a repeating unit, the separation layer 2 may further include components other than the polymer. Examples of the components include fillers, plasticizers, and components capable of improving the releasability of the support plate 2 and the like. These components are appropriately selected from conventionally known materials or materials that do not interfere with or accelerate the absorption of light by the above structure and the deterioration of the polymer.

(Mineral)

The separation layer 2 may be made of an inorganic material. The separating layer 2 is constituted by an inorganic substance, so that it is deformed by absorbing light, and as a result, the strength or adhesiveness before light irradiation is lost. Therefore, the separating layer 2 is broken by applying a slight external force (for example, by lifting the support 1), so that the support 1 and the plug 7 can be easily separated from each other .

The inorganic material may be modified so as to absorb light. For example, one or more inorganic materials selected from the group consisting of metals, metal compounds and carbon may be preferably used. The metal compound refers to a compound containing a metal atom, and may be, for example, a metal oxide or a metal nitride. In this example of such minerals include, but are not limited to this, but gold, silver, copper, iron, nickel, aluminum, titanium, chromium, SiO _2, SiN, Si ₃ N _4, TiN, and selected from the group consisting of carbon And at least one kind of inorganic substance. Also, carbon is a concept that can include carbon isotopes, and can be, for example, diamond, fullerene, diamond like carbon, carbon nanotubes, and the like.

The inorganic material absorbs light having a wavelength in a specific range depending on the kind thereof. By irradiating the separation layer 2 with light having a wavelength within a range that the inorganic material used in the separation layer 2 absorbs, the inorganic material can be preferably altered.

As the light to be irradiated to the separation layer 2 made of an inorganic material, a solid laser such as a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, an LD laser, a fiber laser, , A liquid laser such as a dye laser, a gas laser such as a CO ₂ laser, an excimer laser, an Ar laser, or a He-Ne laser, a laser beam such as a semiconductor laser or a free electron laser, or a non-laser beam.

The separation layer 2 made of an inorganic material can be formed on the support plate 2 by a known technique such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, spin coating or the like. The thickness of the separating layer 2 made of an inorganic material is not particularly limited and may be any thickness that can sufficiently absorb light to be used. For example, it is preferable that the thickness of the separating layer 2 is in the range of 0.05 탆 to 10 탆 desirable. It is also possible to previously apply an adhesive to both sides or one side of an inorganic film (for example, a metal film) made of an inorganic material constituting the separation layer 2 and to affix it to the support 1.

When a metal film is used as the separation layer 2, reflection of the laser or electrification of the film may occur depending on conditions such as the film quality of the separation layer 2, the type of the laser light source, the laser output, and the like . Therefore, it is preferable to form an antireflection film or an antistatic film on the upper or lower part of the separation layer 2, or to take measures against them.

(A compound having an infrared absorbing structure)

The separation layer 2 may be formed of a compound having an infrared absorbing structure. The compound is altered by absorbing infrared rays. The separation layer 2 lost strength or adhesiveness before irradiation with infrared rays as a result of deterioration of the compound. Therefore, the separating layer 2 is broken by applying a slight external force (for example, by lifting the support 1), so that the support 1 and the plug 7 can be easily separated from each other .

Examples of the compound including a structure having an infrared absorbing property or a structure having an infrared absorbing property include an alkane, an alkene (vinyl, a trans, a cis, a vinylidene, a trisubstituted, a tetrasubstituted, a conjugated, Alcohol, and phenols (free OH, intramolecular hydrogen bonds, intermolecular hydrogen bonds, saturated secondary alcohols, saturated aliphatic alcohols), monocyclic aromatic (benzene, monosubstituted, Unsaturated secondary or tertiary unsaturated tertiary), acetal, ketal, aliphatic ether, aromatic ether, vinyl ether, oxirane ring ether, peroxide ether, ketone, dialkylcarbonyl, aromatic carbonyl, 1,3- (Dimers, carboxylic anions), formic acid esters, acetic acid esters, conjugated esters, non-conjugated esters, aromatic esters, lactones, lactones, (? -,? -,? (aliphatic, aromatic), aliphatic acid chloride, aromatic acid chloride, acid anhydride (conjugated, non-conjugated, cyclic, acyclic), primary amide, secondary amide, lactam, primary amine (Aliphatic, aromatic), primary amine salt, secondary amine salt, tertiary amine salt, ammonium ion, aliphatic nitrile, aromatic nitrile, carbodiimide, An aromatic isothiocyanate ester, an aliphatic nitro compound, an aromatic nitro compound, a nitroamine, a nitrosamine, a nitrate ester, a nitrile ester, an isocyanate ester, Sulfur compounds such as nitrite, nitrite, nitrite, nitrite, nitroso ester (aliphatic, aromatic, monomer, dimer), mercaptane and thiophenol and thiol acid, thiocarbonyl group, sulfoxide, sulfone, Class 2-sulfonamide, sulfuric acid ester, a carbon-halogen bond, a bond Si-A ¹ (A ¹ is, H, C, O, or halogen), PA ² bond (A ² is, H, C, or O), or Ti -O bond.

The structure containing the carbon-halogen bond includes, for example, -CH ₂ Cl, -CH ₂ Br, -CH ₂ I, -CF ₂ -, -CF ₃ , -CH═CF ₂ , -CF═CF _{2 2} , fluoroaryl, and aryl chloride.

A structure including the combination Si-A ¹ _{is, SiH, SiH 2, SiH 3} , Si-CH 3, Si-CH 2 -, Si-C 6 H 5, SiO- aliphatic, Si-OCH _3, Si- OCH ₂ CH ₃ , Si-OC ₆ H ₅ , Si-O-Si, Si-OH, SiF, SiF ₂ and SiF ₃ . The structure containing a Si-A ¹ bond preferably forms a siloxane skeleton and a silsesquioxane skeleton.

Examples of the structure including the PA ² bond include PH, PH ₂ , P-CH ₃ , P-CH ₂ -, PC ₆ H ₅ , A ³ ₃ -PO (A ³ is an aliphatic or aromatic), (A ⁴ O ) ₃ -PO (A ⁴ is alkyl), P-OCH ₃ , P-OCH ₂ CH ₃ , P-OC ₆ H ₅ , POP, P-OH and O═P-OH.

The above structure can absorb infrared rays having a desired wavelength range according to the selection of the type. Specifically, the wavelength of infrared rays capable of absorbing the above structure is, for example, in the range of 1 占 퐉 or more and 20 占 퐉 or less and more preferably in a range of 2 占 퐉 to 15 占 퐉. When the structure is a Si-O bond, a Si-C bond and a Ti-O bond, it may be in the range of 9 탆 or more and 11 탆 or less. In addition, the wavelength of infrared rays capable of absorbing each structure can be easily understood by those skilled in the art. For example, as an absorption band in each structure, a method of determining the absorption spectrum of an organic compound (fifth edition) -SM combined with IR, NMR, and UV- (1992), SILVERSTEIN BASSLER MORRILL Published on pages 146 to 151 can be referred to.

As the compound having an infrared absorbing structure used in the formation of the separation layer 2, a compound having the above-described structure can be dissolved in a solvent for application and can be solidified to form a high layer It is not particularly limited. However, in order to effectively deteriorate the compound in the separation layer 2 and facilitate the separation of the support 1 and the plug 7, it is necessary that the absorption of infrared rays in the separation layer 2 is large, that is, , It is preferable that the infrared ray transmittance is low when the separating layer 2 is irradiated with infrared rays. Specifically, the transmittance of infrared rays in the separating layer 2 is preferably lower than 90%, and it is more preferable that the transmittance of infrared rays is lower than 80%.

For example, the compound having a siloxane skeleton may be a resin that is a copolymer of a repeating unit represented by the following formula (5) and a repeating unit represented by the following formula (6), or a resin represented by the following formula (5) A resin which is a copolymer of a repeating unit and an acrylic compound-derived repeating unit can be used.

[Chemical Formula 5]

(In the formula (6), R ⁶ is hydrogen, an alkyl group having 10 or less carbon atoms, or an alkoxy group having 10 or less carbon atoms.)

Among them, the compound having a siloxane skeleton is more preferably a t-butylstyrene (TBST) -dimethylsiloxane copolymer which is a copolymer of a repeating unit represented by the above formula (5) and a repeating unit represented by the following formula (7) A TBST-dimethylsiloxane copolymer containing a repeating unit represented by the formula (5) and a repeating unit represented by the following formula (7) in a ratio of 1: 1 is more preferable.

[Chemical Formula 6]

As the compound having a silsesquioxane skeleton, for example, a resin which is a copolymer of a repeating unit represented by the following formula (8) and a repeating unit represented by the following formula (9) can be used.

(7)

(8), R ⁷ is hydrogen or an alkyl group having a carbon number of 1 or more and 10 or less, and in the formula (9), R ⁸ is an alkyl group having a carbon number of 1 or more and 10 or less or a phenyl group.

Examples of compounds having a silsesquioxane skeleton include compounds disclosed in JP-A-2007-258663 (published on October 4, 2007), JP-A-2010-120901 (published on June 3, 2010) Each silsesquioxane resin disclosed in Japanese Patent Laid-Open Publication No. 2009-263316 (published on November 12, 2009) and Japanese Patent Laid-Open Publication No. 2009-263596 (published on November 12, 2009) Can be used.

Among them, as the compound having a silsesquioxane skeleton, a copolymer of a repeating unit represented by the following formula (10) and a repeating unit represented by the following formula (11) is more preferable, and a repeating unit represented by the following formula And a repeating unit represented by the following chemical formula (11) in a ratio of 7: 3.

[Chemical Formula 8]

The polymer having a silsesquioxane skeleton may have a random structure, a ladder structure, and a basket structure, but any structure may be used.

Examples of the compound containing a Ti-O bond include (i) tetra-i-propoxy titanium, tetra-n-butoxy titanium, tetrakis (2-ethylhexyloxy) titanium, alkoxytitaniums such as -i-propoxy octylene glycolate; (ii) titanium chelates such as di-i-propoxy bis (acetylacetonato) titanium and propanedioxy titanium bis (ethylacetoacetate); _{(iii) iC 3 H 7 O} - [- Ti (OiC 3 H 7) 2 -O-] n -iC 3 H 7, and _{nC 4 H 9 O - [-} Ti (OnC 4 H 9) 2 -O- ] _n- nC ₄ H ₉ ; (iv) an acyl group such as tri-n-butoxytitanium monostearate, titanium stearate, di-i-propoxytitanium diisostearate, and (2-n-butoxycarbonylbenzoyloxy) Lattice titanium; (v) water-soluble titanium compounds such as di-n-butoxy-bis (triethanolaminato) titanium and the like.

Among these, a compound containing a Ti-O bond, di -n- butoxy-bis (triethanolamine Oh Minato) titanium _{(Ti (OC 4 H 9)} 2 [OC 2 H 4 N (C 2 H 4 OH) ₂ ] ₂ ) is preferable.

Although the above-described separation layer 2 contains a compound having an infrared absorbing structure, the separation layer 2 may further include components other than the above-mentioned compounds. Examples of the components include fillers, plasticizers, and components capable of improving the releasability of the support plate 2 and the like. These components are appropriately selected from conventionally known materials or materials that do not interfere with or accelerate the absorption of infrared rays by the structure and the deterioration of the compound.

(Infrared absorbing material)

The separation layer 2 may contain an infrared absorbing material. The separating layer 2 is constituted by containing an infrared absorbing material, so that the separating layer 2 is deformed by absorbing the light, and as a result, the separating layer 2 loses strength or adhesiveness before being irradiated with light. Therefore, the separating layer 2 is broken by applying a slight external force (for example, by lifting the support 1), so that the support 1 and the plug 7 can be easily separated from each other .

The infrared absorbing material can be any structure that is altered by absorbing infrared rays. For example, carbon black, iron particles, or aluminum particles can be preferably used. The infrared absorbing material absorbs light having a wavelength in a specific range depending on its type. The infrared absorbing material can be preferably altered by irradiating the separation layer 2 with light having a wavelength in a range that the infrared absorbing material used in the separation layer 2 absorbs.

(Reactive polysilsesquioxane)

The separating layer 2 can be formed by polymerizing reactive polysilsesquioxane, whereby the separating layer 2 has high chemical resistance and high heat resistance.

In the present specification, the reactive polysilsesquioxane is a polysilazquioxane having a silanol group at the end of the polysilsesquioxane skeleton or a functional group capable of forming a silanol group by hydrolysis, and the silanol group Or by condensing a functional group capable of forming a silanol group. When the reactive polysilsesquioxane is provided with a silanol group or a functional group capable of forming a silanol group, those having a silsesquioxane skeleton such as a random structure, a basket structure and a ladder structure are employed .

It is more preferable that the reactive polysilsesquioxane has a structure represented by the following formula (12).

[Chemical Formula 9]

In formula (12), R "is independently selected from the group consisting of hydrogen and alkyl groups having 1 to 10 carbon atoms, more preferably selected from the group consisting of hydrogen and alkyl groups having 1 to 5 carbon atoms When R "is hydrogen or an alkyl group having a carbon number of 1 or more and 10 or less, the reactive polysilsesquioxane represented by the formula (12) is preferably condensed by heating in the step of forming the separation layer (2) .

In the formula (12), p is preferably an integer of 1 or more and 100 or less, and more preferably an integer of 1 or more and 50 or less. The reactive polysilsesquioxane has a repeating unit represented by the formula (12), so that the content of Si-O bonds is larger than that formed by using other materials, and the infrared rays (0.78 탆 or more and 1000 탆 or less) (Preferably at least 3 탆 and not more than 1000 탆), and more preferably at least 9 탆 and not more than 11 탆.

In the formula (12), R '' are each independently the same or different organic group. Here, R is, for example, an aryl group, an alkyl group, and an alkenyl group, and these organic groups may have a substituent.

When R 'is an aryl group, examples thereof include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group, and more preferably a phenyl group. The aryl group may be bonded to the polysilsesquioxane skeleton via an alkylene group having 1 to 5 carbon atoms.

When R 'is an alkyl group, examples of the alkyl group include a linear, branched, or cyclic alkyl group. When R is an alkyl group, the number of carbon atoms is preferably 1 to 15, more preferably 1 to 6. When R is a cyclic alkyl group, it may be monocyclic or an alkyl group having 2 to 4 ring structures.

When R 'is an alkenyl group, as in the case of an alkyl group, there may be mentioned a linear, branched, or cyclic alkenyl group. The alkenyl group preferably has 2 to 15 carbon atoms, Is more preferable. When R is a cyclic alkenyl group, it may be monocyclic or an alkenyl group having 2 to 4 ring structures. Examples of the alkenyl group include a vinyl group, an allyl group and the like.

Examples of the substituent that R 'may have include a hydroxyl group and an alkoxy group. When the substituent is an alkoxy group, there may be mentioned a linear, branched, or cyclic alkylalkoxy group, and the number of carbon atoms in the alkoxy group is preferably 1 to 15, more preferably 1 to 10.

In one aspect, the siloxane content of the reactive polysilsesquioxane is preferably 70 mol% or more and 99 mol% or less, and more preferably 80 mol% or more and 99 mol% or less. When the siloxane content of the reactive polysilsesquioxane is 70 mol% or more and 99 mol% or less, it is preferably modified by irradiating with infrared rays (preferably far-infrared rays, more preferably light having a wavelength of 9 탆 or more and 11 탆 or less) The separating layer 2 can be formed.

In one aspect, the weight average molecular weight (Mw) of the reactive polysilsesquioxane is preferably 500 or more and 50,000 or less, more preferably 1,000 or more and 10,000 or less. When the weight average molecular weight (Mw) of the reactive polysilsesquioxane is 500 or more and 50,000 or less, the reactive polysilsesquioxane can be preferably dissolved in a solvent and can be preferably applied onto a support plate.

Examples of commercially available products usable as the reactive polysilsesquioxane include SR-13, SR-21, SR-23 and SR-33 manufactured by Konishi Chemical Industry Co., Ltd.

[Embodiment 2]

Another embodiment (Embodiment 2) of the present invention will be described below. For convenience of explanation, the members having the same functions as those described in the above embodiments are denoted by the same reference numerals, and a description thereof will be omitted. The method for manufacturing a plug according to Embodiment 2 is characterized in that the separation layer forming step, the separation layer peripheral edge portion removing step, the adhesive layer forming step, the plug forming step, the adhesive layer removing step, the light irradiation step, Conduct.

(Separation layer forming step to adhesive layer forming step)

As shown in Figs. 2A to 2C, the separation layer forming step, the separation layer peripheral edge portion removing step, and the adhesive layer forming step are the same as those in Embodiment 1, and a description thereof will be omitted.

(Bag-forming step)

2 (d) to 2 (g), the plug 7 is formed on the adhesive layer 3 in the plug forming step. In the plug forming step in the present embodiment, the element placing step, the sealing step, the thinning step and the wiring layer forming step are performed in this order.

As shown in Fig. 2 (d), in the element disposing step, the element 5 is disposed on the adhesive layer 3. Fig. The arrangement of the element 5 on the adhesive layer 3 can be carried out using, for example, a chip mounter or the like.

As shown in FIG. 2 (e), in the sealing step, the element 5 is sealed with the sealing material 6. The sealing material 6 may be injection molded using, for example, a molding die, or may be applied by a method such as spin coating, dipping, roller blade, spray coating, or slit coating.

As shown in Fig. 2 (f), in the thinning step, the sealing material 6 is thinned. The sealing material 6 may be thinned, for example, until the terminal portion of the element 5 is exposed from the sealing material 6.

As shown in Fig. 2 (g), in the wiring layer forming step, the wiring layer 4 is formed on the element 5 sealed by the sealing material 6.

In one embodiment, in order to form the wiring layer 4, first, a dielectric layer such as silicon oxide (SiOx) or photosensitive resin is formed on the element 5 sealed by the sealing material 6. The dielectric layer made of silicon oxide can be formed by, for example, a sputtering method, a vacuum deposition method, or the like. The dielectric layer made of the photosensitive resin can be formed by applying a photosensitive resin by a method such as spin coating, dipping, roller blade, spray coating, slit coating, or the like.

Subsequently, wirings are formed on the dielectric layer by a conductor such as a metal. As a wiring formation method, a well-known semiconductor process technique such as a lithography process such as photolithography (resist lithography) or an etching process can be used.

As described above, the plugs 7 can be smoothly formed on the support 1. Also in the present embodiment, since the separation layer 2 is protected by the adhesive layer 3 as in the first embodiment, it is possible to avoid contact of the chemical solution with the separation layer 2. In addition, the separation layer 2 can be protected from other than the chemical solution by protecting the separation layer 2 with the adhesive layer 3. Thereby, it is possible to prevent the separation layer 2 from being peeled off during the plug forming process.

The laminate 9 shown in Fig. 2 (g) obtained by the above process is a laminate composed of the support 1 for transmitting light, the separation layer 2 which is altered by irradiating light, the adhesive layer 3, And the plugs 7 are stacked in this order and the plugs 7 are formed by stacking a wiring layer 4 and elements 5 mounted on the wiring layer 4 and a sealing material 5 for sealing the elements 5, And the separating layer 2 is covered with the adhesive layer 3 except the portion in contact with the support 1. [ Such a layered product 9 is produced only in the course of the manufacturing method of the plug according to the present invention and can be preferably used for producing the isolated plug 7.

(Adhesive layer removing step to removing step)

2 (h) to 2 (k), the adhesive layer removing step, the light irradiation step, the separating step and the removing step are different from each other in the vertical direction of the plug 7, Since it is the same as the form 1, its explanation is omitted.

Thus, in the same manner as in Embodiment 1, the isolated plug 7 can be obtained. Further, the bag 7 may be further subjected to processes such as solder ball formation, dicing, and the like. Further, another element may be laminated on the plug 7.

As in the first embodiment, (i) the outer diameter of the molding die of the plug body 7 is made smaller than that of the support body 1, the plug body 7 is formed smaller than the outer diameter of the support body 1, (ii) After molding of the plugs 7, the plugs 7 may be subjected to a full cut trim so that the plugs 7 become smaller than the outer diameter of the support 1.

The present invention is not limited to the above-described embodiments, but various modifications may be made within the scope of the claims, and embodiments obtained by appropriately combining the technical means disclosed in the different embodiments may be included in the technical scope of the present invention. do.

The support separating method according to the present invention can be suitably used in the manufacturing process of the miniaturized semiconductor device.

1 support
1a plane portion
1b
2 separation layer
2a outer peripheral end
3 adhesive layer
4 wiring layer
5 element
6 bags
7 bags
8, 9 laminate

Claims (8)

A manufacturing method of a plug including a wiring layer, an element mounted on the wiring layer, and an encapsulating material encapsulating the element,
A separation layer forming step of forming a separation layer which is altered by irradiating light on one flat surface portion of a support through which light is transmitted,
A separation layer peripheral portion removing step for removing the separation layer formed around the entire periphery of the support;
An adhesive layer forming step of forming an adhesive layer on the surface of the support on the side of the entire periphery of the peripheral portion from which the separation layer is removed,
And a step of forming a plug body on the adhesive layer to form the plug body. The method according to claim 1,
Further comprising an adhesive layer removing step of removing the adhesive layer formed around the entire periphery of the support after the bag-forming process. 3. The method of claim 2,
Wherein the adhesive layer removing step removes the adhesive layer formed on the outer side of the outer peripheral end of the separation layer formed on the support. The method according to claim 2 or 3,
A light irradiation step of irradiating light to the separation layer via the support after the adhesive layer removal step to deteriorate the separation layer,
And a separating step of separating the support from the bag after the light irradiation step. 5. The method of claim 4,
Further comprising a removing step of removing the adhesive layer and the separating layer remaining on the plug after the separating step. The method according to claim 1,
Wherein the sealing material forming step includes forming the wiring layer on the adhesive layer, mounting the element on the wiring layer, and sealing the element with the sealing material. The method according to claim 1,
The sealing material forming step includes disposing the element on the adhesive layer, sealing the element with the sealing material, and forming the wiring layer on the element encapsulated by the sealing material Of the bag. A support for transmitting light,
A separating layer which is altered by irradiating light,
An adhesive layer,
A sealing member is stacked in this order,
The sealing member includes a wiring layer, an element mounted on the wiring layer, and an encapsulating material that encapsulates the element,
Wherein the separation layer is covered with the adhesive layer other than the portion in contact with the support.

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