TW201402739A - Temporary adhesive agent for producing semiconductor device and adhesive support body using the same and method for producing semiconductor device - Google Patents

Abstract

The invention provides a temporary adhesive agent for producing a semiconductor device and an adhesive support body using the same and a method for producing the semiconductor device. When a component to be treated (such as a semiconductor wafer) is under a mechanical treatment or a chemical treatment, the temporary adhesive agent for producing the semiconductor device could certainly and easily support a component to be treated temporarily, and would not damage a treated component, and then easily relieve a temporary support from the treated component. The temporary adhesive agent for producing the semiconductor device and the adhesive support body using the same and the method for producing the semiconductor device are provided. The temporary adhesive agent for producing the semiconductor device includes: (A) a resin; (B) a cross-linking compound; (C) a solvent; (D) a reaction initiator; and (E) a sensitizing dye.

Description

Temporary adhesive for semiconductor device, adhesive support using the same, and method for manufacturing semiconductor device

The present invention relates to a temporary adhesive for manufacturing a semiconductor device, an adhesive support using the same, and a method of manufacturing the semiconductor device.

Conventionally, in a manufacturing process of a semiconductor device such as an integrated circuit (IC) or a large scale integrated circuit (LSI), a plurality of IC chips are usually formed on a semiconductor germanium wafer, and are cut by Uniform.

With the demand for further miniaturization and high performance of electronic equipment, IC chips mounted on electronic devices are required to be further miniaturized and integrated, but the product of the integrated circuit in the surface direction of the substrate is high. The body is approaching the limit.

In the prior art, a wire bonding method has been widely known as an electrical connection method from an integrated circuit in an IC chip to an external terminal of an IC chip. However, in order to reduce the size of an IC chip, it has been known in recent years. A method is provided in which a through hole is provided in a substrate, and a metal plug as an external terminal is connected to the integrated circuit so as to penetrate through the hole (so-called through-electrode is formed) (Through-Silicon Via, TSV) method). However, only by the method of forming the ruthenium-through electrode, the above-mentioned demand for further high integration of the IC wafer in recent years cannot be sufficiently satisfied.

In view of the above, there has been known a technique of increasing the total body area per unit area of a tantalum substrate by multilayering an integrated circuit in an IC wafer. However, the multilayering of the integrated circuit increases the thickness of the IC wafer, and therefore the thickness of the member constituting the IC wafer is required. In order to reduce the thickness of the ruthenium substrate, for example, the thickness reduction of the ruthenium substrate is not only related to the miniaturization of the IC wafer, but also the step of manufacturing the through-hole of the ruthenium substrate in the manufacture of the ruthenium-through electrode is labor-saving. have a future.

As a semiconductor germanium wafer used in a manufacturing process of a semiconductor device, a semiconductor germanium wafer having a thickness of about 700 μm to 900 μm is widely known. In recent years, attempts have been made to make a semiconductor germanium wafer for miniaturization of an IC wafer. The thickness is reduced to 200 μm or less.

However, the semiconductor germanium wafer having a thickness of 200 μm or less is extremely thin, and the member for manufacturing a semiconductor device using the substrate as a base material is also very thin. Therefore, further processing of such members or movement of such members is performed. In the case or the like, it is difficult to support the member stably and without causing damage.

In order to solve the above problems, there has been known a technique in which a semiconductor wafer before thinning and a processing support substrate on which a device is provided on the surface are temporarily covered with an anthrone adhesive, and the back surface of the semiconductor wafer is ground. After thinning, the semiconductor wafer is perforated to provide a 矽-through electrode, and thereafter, for processing The support substrate is detached from the semiconductor wafer (see Patent Document 1). According to this technique, heat resistance during the back grinding of the semiconductor wafer, heat resistance during the anisotropic dry etching step, chemical resistance during plating or etching, and final processing support substrate can be simultaneously achieved. Smooth peeling and low contamination of the adherend.

Further, as a method of supporting a wafer, there is also known a technique of supporting a wafer by a support layer system, and the technique is constructed by plasma deposition (Plasma Deposition) The obtained plasma polymer layer acts as a separation layer between the wafer and the support layer system, and the subsequent bonding between the support layer system and the separation layer is greater than the subsequent bonding between the wafer and the separation layer, when When the wafer is detached from the support layer system, the wafer is easily detached from the separation layer (see Patent Document 2).

Prior technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 2011-119427

Patent Document 2: Japanese Patent Laid-Open Publication No. 2009-528688

However, the surface of the semiconductor wafer on which the device is provided (that is, the device surface of the device wafer) and the support substrate (carrier substrate) are temporarily passed through the layer containing the adhesive known in Patent Document 1 or the like. In order to stably support the semiconductor wafer, a certain strength of adhesion is required for the adhesive layer.

Therefore, when the entire surface of the device surface of the semiconductor wafer and the support substrate are temporarily stopped via the adhesive layer, the temporary bonding of the semiconductor wafer and the support substrate becomes sufficient, and the semiconductor crystal is stably and without damage. Round, but semiconductor The temporary adhesion of the wafer and the support substrate is too strong, and it is more likely that the semiconductor wafer is detached from the support substrate when the semiconductor wafer is detached from the support substrate, or the device is detached from the semiconductor wafer.

Further, as in Patent Document 2, in order to suppress the subsequent adhesion of the wafer and the support layer system, a plasma polymer layer as a separation layer is formed between the wafer and the support layer system by plasma deposition. The method has the following problems: (1) Generally, the equipment for performing the plasma deposition method is expensive; (2) When the layer is formed by the plasma deposition method, the vacuuming or the deposition of the monomer in the plasma device It takes time; and (3) even if a separation layer including a plasma polymer layer is provided, it is difficult to support the wafer for processing, and the subsequent bonding of the wafer and the separation layer is sufficient. In the case of releasing the support of the wafer, it is controlled such that the wafer is easily detached from the separation layer.

The present invention has been made in view of the above circumstances, and an object of the invention is to provide a temporary adhesive for manufacturing a semiconductor device, and an adhesive support using the same, and a method for manufacturing a semiconductor device, wherein the temporary adhesive for semiconductor device manufacturing is processed in a pair When the member (semiconductor wafer or the like) is subjected to mechanical treatment or chemical treatment, the member to be processed can be temporarily and reliably supported, and the temporary support for the processed member can be easily released without causing damage to the processed member.

In order to solve the above problems, the inventors of the present invention have found that (A) a resin, (B) a crosslinkable compound, (C) a solvent, (D) a reaction initiator, and (E) sensitization are contained. a composition of a pigment used as a semiconductor wafer and a support substrate As a result of the temporary adhesive in the subsequent step, the member to be processed can be surely temporarily supported, and after the treatment of the member to be processed, the actinic ray or radiation or heat induced by the sensitizing dye is applied to the adhesive layer. The irradiation is performed, and temporary support for the processed member can be easily released, thereby completing the present invention.

That is, the present invention is as follows.

[1] A temporary adhesive for producing a semiconductor device, comprising: (A) a resin, (B) a crosslinkable compound, (C) a solvent, (D) a reaction initiator, and (E) a sensitizing dye.

[2] The temporary adhesive for semiconductor device manufacturing according to the above [1], wherein the sensitizing dye has a sensitization of an absorption maximum value in at least one of a wavelength region of 500 nm or less and a wavelength region of 700 nm or more. pigment.

[3] The temporary adhesive for semiconductor device manufacturing according to the above [1], wherein the sensitizing dye is a sensitizing dye having an absorption maximum in a wavelength region of 1100 nm or more.

[4] An adhesive support comprising: a substrate, and an adhesive layer formed on the substrate by a temporary adhesive for manufacturing a semiconductor device according to any one of the above [1] to [3] .

[5] A method of manufacturing a semiconductor device, comprising: a step of: connecting a first surface of the member to be processed and an adhesive layer of the adhesive support according to [4] above; a step of obtaining a treated member by performing mechanical treatment or chemical treatment on the second surface different from the first surface; a step of irradiating actinic rays or radiation or heat induced by the sensitizing dye on the adhesive layer of the adhesive support; and performing an adhesive layer on the first surface of the processed member from the adhesive support The step of detaching, and the semiconductor device has the above-described processed member.

[6] A method of producing a semiconductor device, comprising: pattern-exposed the adhesion layer of the adhesive support according to [4] above, thereby providing a high adhesion region and a low layer in the adhesive layer; a step of bringing the first surface of the member to be processed into contact with the adhesive layer of the adhesive support; and performing mechanical treatment or chemical treatment on the second surface of the member to be processed different from the first surface a step of obtaining a processed member; performing a step of irradiating the actinic ray or the radiation or heat induced by the sensitizing dye on the adhesive layer of the adhesive support; and causing the first surface of the processed member to be self-treated The step of detaching the adhesive layer on the adhesive layer, and the semiconductor device has the processed member.

[7] A method of producing a semiconductor device, comprising: irradiating an actinic ray or radiation or heat to the adhesive layer of the adhesive support according to [4] above, such that adhesion is from the adhesive layer a step of lowering an inner surface of the substrate side toward an outer surface; a step of adhering the first surface of the member to be processed to the adhesive layer of the adhesive support; and performing mechanical treatment or chemical treatment on the second surface of the member to be processed different from the first surface to obtain a processed member a step of irradiating actinic rays or radiation or heat induced by the sensitizing dye on the adhesive layer of the adhesive support; and allowing the first surface of the processed member to be from the adhesive support The step of detaching from the next layer, and the semiconductor device has the above-described processed member.

The method for producing a semiconductor device according to any one of the above-mentioned [5], wherein at least one of the substrate and the processed member in the adhesive support comprises the sensitizing dye. The actinic ray or the material that is radiated or thermally transmitted.

[9] The method of manufacturing a semiconductor device according to any one of the above [5], wherein the actinic ray or radiation or heat induced by the sensitizing dye is near-infrared light.

According to the present invention, there is provided a temporary adhesive for manufacturing a semiconductor device, and an adhesive support using the same, and a method for manufacturing a semiconductor device, wherein the semiconductor device manufacturing temporary adhesive is used to mechanically process a member (semiconductor wafer or the like) When the treatment or chemical treatment, the member to be processed can be temporarily and reliably supported, and the damaged member can be damaged, and the member to be processed can be easily released. Temporary support.

11, 11', 21, 31‧‧‧

12‧‧‧ Carrier substrate

21A, 31A‧‧‧Low-adjacent areas

21B, 31B‧‧‧High adhesion area

31a‧‧‧Outer surface

31b‧‧‧ inner surface

40‧‧‧ mask

41‧‧‧Lighting area

42‧‧‧ shading area

50‧‧‧Acradiation rays or radiation

50'‧‧‧Acradiation rays or radiation or heat

60‧‧‧ device wafer

60'‧‧‧ Thin device wafer

61‧‧‧矽 substrate

61a‧‧‧ surface

61b‧‧‧Back

61b'‧‧‧Back

62‧‧‧ device wafer

63‧‧‧Bumps

70‧‧‧ Tape

100, 100', 110, 120‧‧‧ Continuing support

101, 102, 201, 202‧‧‧矽 wafer

103‧‧‧ glass substrate

104‧‧‧PET film

A‧‧‧Vertical direction

1A and 1B are schematic cross-sectional views showing a temporary splicing of an adhesive support and a device wafer, and a schematic cross-sectional view showing a state in which a device wafer temporarily surrounded by an adhesive support is thinned.

FIG. 2 is a schematic cross-sectional view for explaining the release of the temporary adhesion state of the previous adhesive support and the device wafer.

3A is a schematic cross-sectional view showing exposure to an adhesive support, and FIG. 3B is a schematic plan view showing a mask.

4A is a schematic cross-sectional view showing the pattern-exposed adhesive support, and FIG. 4B is a schematic plan view showing the pattern-exposed adhesive support.

Fig. 5 is a schematic cross-sectional view showing irradiation of actinic rays or radiation or heat to an adhesive support.

Fig. 6 is a schematic perspective view of a test piece for an adhesive support for evaluation of peelability.

Fig. 7 is a schematic cross-sectional view of a test piece for an adhesive support for adhesion evaluation.

Hereinafter, embodiments of the present invention will be described in detail.

In the description of the group (atomic group) in the present specification, the unsubstituted and unsubstituted expressions are not described as including a group having no substituent (atomic group), and also includes The substituent group (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The "actinic ray" or "radiation" in the present specification means, for example, infrared rays (near infrared rays, etc.), visible light rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like. In the present invention, "light" means actinic rays or radiation.

In addition, the "exposure" in this specification refers not only to the use of infrared rays, mercury lamps, far ultraviolet rays typified by excimer lasers, X-rays, Extreme Ultraviolet (EUV), etc., unless otherwise specified. It also refers to the use of particle beams such as electron beams and ion beams.

In the present specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylic" means acrylic acid and methacrylic acid, and "(meth)acryloyl group" means propylene. Mercapto and methacrylonitrile. In addition, in this specification, "single quantity" and "monomer" have the same meaning. The monomer in the present invention is different from the oligomer and the polymer, and means a compound having a weight average molecular weight of 2,000 or less. In the present specification, the crosslinkable compound means a compound containing a crosslinkable group, and may be a single amount or a polymer. The crosslinkable group refers to a group that participates in a crosslinking reaction.

In the embodiments described below, the description of the components and the like that have been described with reference to the drawings will be simplified or omitted.

A temporary adhesive for manufacturing a semiconductor device of the present invention (hereinafter, also referred to as only The "temporary adhesive" includes: (A) a resin, (B) a crosslinkable compound, (C) a solvent, (D) a reaction initiator, and (E) a sensitizing dye.

According to the temporary adhesive for manufacturing a semiconductor device of the present invention, it is possible to reliably and easily temporarily support the member to be processed when performing mechanical treatment or chemical treatment on the member to be processed, and it is possible to easily damage the member to be processed, and easily A temporary adhesive for semiconductor device manufacturing that releases temporary support for the processed member.

In one embodiment of the temporary adhesive for producing a semiconductor device of the present invention, a temporary adhesive for producing a semiconductor device for forming a ruthenium through electrode is preferable. The formation of the ruthenium through electrode will be described later.

Hereinafter, each component which can be contained in the temporary adhesive for semiconductor device manufacturing of this invention is demonstrated in detail.

(A) Resin

The temporary adhesive of the present invention contains the resin (A).

As the resin, a (meth)acrylic polymer, a polyurethane resin, a polyvinyl alcohol resin, a polyvinyl butyral resin, a polyvinyl formal resin, a polyamide resin, a polyester resin, or a ring can be used. Oxygen resin, novolak resin, and the like. In particular, a (meth)acrylic polymer, a polyurethane resin, a novolak resin, a polyvinyl butyral resin, a polyester resin, more preferably a (meth)acrylic polymer, may be preferably used. Polyurethane resin, novolak resin.

In the present invention, the term "(meth)acrylic polymer" means (meth)acrylic acid, (meth)acrylate (alkyl ester, aryl ester, allyl ester, etc.), (A) (meth)acrylic acid derivatives such as acrylamide and (meth) acrylamide derivatives It is a copolymer of a polymeric component.

The "polyurethane resin" refers to a polymer produced by a condensation reaction of a compound having two or more isocyanate groups and a compound having two or more hydroxyl groups.

As a suitable example of the above-mentioned polyurethane resin, paragraph number [0099] to paragraph number [0210] of Japanese Patent Laid-Open No. 2007-187836, and paragraph number of Japanese Patent Laid-Open No. 2008-276155 [ 0019]~Paragraph No. [0100], paragraph number [0018] to paragraph number [0107] of Japanese Patent Laid-Open No. 2005-250438, paragraph number [0021] to paragraph number [0083] of Japanese Patent Laid-Open No. 2005-250158 The polyurethane resin described in the above.

The "novolac resin" refers to a polymer produced by a condensation reaction of a phenol (phenol or cresol) with an aldehyde (formaldehyde or the like). Further, a polymer having a substituent introduced by a method of reacting another compound with a residual hydroxyl group or the like is also included.

A suitable example of the novolak resin is phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, meta/p-mixed cresol formaldehyde resin, phenol/cresol (may be m-cresol, pair) Any one of cresol or m/p mixed cresol is mixed with a novolak resin such as a formaldehyde resin. A novolak resin having a weight average molecular weight of 500 to 20,000 and a number average molecular weight of 200 to 10,000 is preferred. Further, in the present invention, the hydroxyl group (i.e., the phenolic hydroxyl group) of the novolac resin can be regarded as an acid group to be described later.

In addition, it is also preferred to use other compounds to form hydroxyl groups in the novolak resin. A compound in which a substituent is introduced by a reaction is introduced.

The resin (A) may contain an acid group.

Here, the acid group generally means a substituent having a pKa of 14 or less, preferably a substituent having a pKa of 12 or less, and most preferably a substituent having a pKa of 11 or less. Specifically, it means a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group, a sulfonylamino group, a phenolic hydroxyl group, or the like.

The acid group may, for example, be a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group or a sulfonylamino group, and particularly preferably a carboxylic acid group.

A part of the acid group may also be neutralized by a basic compound. Examples of the basic compound include a basic nitrogen-containing compound, an alkali metal hydroxide, and an alkali metal quaternary ammonium salt.

The acid group-containing resin (A) is preferably a carboxylic acid group-containing polyurethane resin, a (meth)acrylic polymer, or a novolak resin.

The acid group-containing resin (A) is preferably a resin having a repeating unit containing an acid group, and as the repeating unit containing an acid group, a repeating unit derived from (meth)acrylic acid or a general formula of the following formula may preferably be used. (I) The repeating unit represented.

In the above formula (I), R ²¹¹ represents a hydrogen atom or a methyl group, and R ²¹² represents a single bond or a n ₂₁₁ +1 valent linking group. A ²¹¹ represents an oxygen atom or -NR ²¹³ -, and R ²¹³ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. n ₂₁₁ represents an integer of 1 to 5.

The linking group represented by R ²¹² in the above formula (I) is a group containing a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom, and the number of atoms is preferably from 1 to 80. Specific examples thereof include an alkylene group, a substituted alkylene group, an extended aryl group, a substituted aryl group, and the like, and may also have a guanamine bond, an ether bond, a urethane bond, a urea bond, or Any one of the ester bonds is a structure in which a plurality of the above-mentioned divalent groups are linked. As R ²¹² , it is preferred to use a guanamine bond, an ether bond, a urethane bond, a urea bond, or an ester bond to bond a plurality of single bonds, an alkyl group, a substituted alkyl group, and a stretch. a structure in which an alkyl group and/or a substituted alkylene group are bonded, and more preferably a plurality of single bonds are used by any one of a guanamine bond, an ether bond, a urethane bond, a urea bond, and an ester bond. An alkylene group having 1 to 5 carbon atoms, a substituted alkylene group having 1 to 5 carbon atoms, an alkylene group having 1 to 5 carbon atoms, and/or a substituted alkyl group having 1 to 5 carbon atoms A structure in which an alkyl group is bonded, and particularly preferably a plurality of single bonds and a hydrocarbon having a carbon number of 1 to 3 by using any of a guanamine bond, an ether bond, a urethane bond, a urea bond, or an ester bond a structure in which a substituted alkyl group having 1 to 3 carbon atoms and an alkylene group having 1 to 3 carbon atoms and/or a substituted alkyl group having 1 to 3 carbon atoms are bonded.

Examples of the substituent which the linking group represented by the above-mentioned R ²¹² has may be a monovalent non-metal atomic group other than a hydrogen atom, and examples thereof include a halogen atom (-F, -Br, -Cl, -I) and a hydroxyl group. , cyano, alkoxy, aryloxy, decyl, alkylthio, arylthio, alkylcarbonyl, arylcarbonyl, carboxyl and conjugated bases thereof, alkoxycarbonyl, aryloxycarbonyl, amine Mercapto, aryl, alkenyl, alkynyl and the like.

R ^{213 is} preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, particularly preferably a hydrogen atom or a methyl group.

n _{211 is} preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1.

The resin may have a repeating unit containing an acid group or may have no repeating unit containing an acid group. When having a repeating unit containing an acid group, the repeating unit containing an acid group is in the resin (A) from the viewpoint of peeling property. The proportion (% by mole) of all repeating units is preferably from 1% to 70%. When considering the coexistence of peeling property and adhesion property, it is more preferably 5% to 60%, and particularly preferably 10% to 50%.

Further, the resin (A) preferably contains a crosslinkable group. Here, the crosslinkable group is typically a group which can crosslink the resin (A) by irradiation with actinic rays or radiation or by the action of a radical or an acid. The crosslinkable group is not particularly limited as long as it is a group having such a function. For example, a functional group capable of undergoing addition polymerization reaction is preferred, and as the functional group capable of undergoing addition polymerization, an ethylenically unsaturated bond is exemplified. Base, amine group, epoxy group, and the like. In addition, the crosslinkable group may be a functional group capable of generating a radical by irradiation with actinic rays or radiation, and examples of such a crosslinkable group include a thiol group and a halogen group. Among them, the crosslinkable group is preferably an ethylenically unsaturated bond group. The ethylenically unsaturated bond group is preferably a styryl group, a (meth)acryl fluorenyl group or an allyl group.

The resin (A) having a crosslinkable group is added to a crosslinkable group, for example, a radical (a polymerization starting radical or a growth radical in a polymerization process of a polymerizable compound), and an addition polymerization is directly carried out between the polymers. Or polymerization via a polymeric compound Addition polymerization is carried out by chains to form crosslinks and harden between polymer molecules. Alternatively, an atom in the polymer (for example, a hydrogen atom on a carbon atom adjacent to the functional crosslinking group) is extracted by a radical to form a polymer radical which is bonded to each other to thereby polymerize the polymer molecule It forms crosslinks and hardens.

When the resin (A) contains a crosslinkable group, the resin (A) preferably has a repeating unit containing a crosslinkable group.

The content of the crosslinkable group in the resin (A) (the content of the unsaturated double bond which can be radically polymerized by iodine titration) is preferably 0.01 mmol to 10.0 mmol, more preferably 1 g of the resin (A). It is 0.05 mmol to 9.0 mmol, and particularly preferably 0.1 mmol to 8.0 mmol.

The resin (A) (particularly a (meth)acrylic polymer) may also have a repeating unit derived from an alkyl (meth)acrylate or an aralkyl (meth)acrylate derived from (meth)acrylic acid. a repeating unit of a guanamine or a derivative thereof, a repeating unit derived from α-hydroxymethyl acrylate, or a repeating unit derived from a styrene derivative as a repeating unit containing the acid group and a repeating group containing a crosslinking group A repeating unit other than the unit. The alkyl group of the alkyl (meth)acrylate is preferably an alkyl group having 1 to 5 carbon atoms, an alkyl group having 2 to 8 carbon atoms and the above substituent, and more preferably a methyl group.

Examples of the aralkyl (meth)acrylate include benzyl (meth)acrylate. Examples of the (meth)acrylamide derivative include N-isopropylacrylamide, N-phenylmethacrylamide, and N-(4-methoxycarbonylphenyl)methacrylamide. , N,N-dimethyl methacrylamide, morpholinyl acrylamide, and the like. Examples of the α-hydroxymethyl acrylate include α-hydroxyethyl methacrylate and α-hydroxymethyl methacrylate. Styrene derived Examples of the substance include styrene and 4-tert-butylstyrene.

Further, the resin (A) preferably contains a hydrophilic group. The hydrophilic group contributes to imparting releasability to the temporary adhesive. In particular, by allowing the crosslinkable group and the hydrophilicity to coexist in the resin (A), the releasability and the adhesion can be further achieved.

The hydrophilic group which may be contained in the resin (A) may, for example, be a hydroxyl group, an alkylene oxide structure, an amine group, an ammonium group, an amidino group or a sulfo group. Among them, it is preferably one to nine. An alkylene oxide structure of an alkylene oxide unit having 2 or 3 carbon atoms. When a hydrophilic group is to be added to the resin (A), for example, a monomer containing a hydrophilic group can be copolymerized at the time of synthesis of the resin (A).

The weight average molecular weight (Mw) of the resin (A) is preferably 2,000 or more, more preferably 2,000 to 50,000, in terms of polystyrene equivalent value by Gel Permeation Chromatography (GPC). The average molecular weight (Mn) is preferably 1,000 or more, and more preferably 1,000 to 30,000, as a polystyrene equivalent value by the GPC method. The polydispersity (weight average molecular weight / number average molecular weight) is preferably from 1.1 to 10.

The GPC method is based on the following method: using HLC-8020GPC (manufactured by Tosoh Co., Ltd.), using TSKgel SuperHZM-N, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mml D × 15 cm) as the column A method of using Tetrahydrofuran (THF) as an eluent.

The resin (A) may be used singly or in combination of two or more.

From the viewpoint of good adhesion strength and peelability, relative to the above temporary connection The content of the total solid content of the agent, the resin (A) is preferably 5% by mass to 75% by mass, more preferably 10% by mass to 70% by mass, still more preferably 10% by mass to 60% by mass.

(B) crosslinkable compound

The temporary adhesive of the present invention contains the crosslinkable compound (B).

Adhesion and adhesion can be imparted by containing a crosslinkable compound in a temporary adhesive. The crosslinkable compound is preferably a compound having good compatibility with respect to the resin (A).

The crosslinkable compound (B) is a compound containing a crosslinkable group, and the crosslinkable group is typically a group which can be crosslinked by irradiation with actinic rays or radiation or by the action of a radical or an acid. In particular, the crosslinkable compound (B) is preferably a group which can be crosslinked (presenting a crosslinking reaction) by the action of a radical or an acid.

Further, the crosslinkable compound is preferably a compound different from the above resin (A), and is typically a low molecular compound, preferably a low molecular weight compound having a molecular weight of 9000 or less, more preferably a low molecular weight compound having a molecular weight of 1,500 or less. . Further, the molecular weight is usually 100 or more.

The crosslinkable compound (B) and the reaction initiator (D) described later are contained together by the temporary adhesive of the present invention, for example, by performing the adhesive layer in the adhesive support as will be described later in detail. The pattern is exposed, and a crosslinking reaction of the crosslinkable compound is carried out in the exposed portion, whereby a high adhesion region and a low adhesion region can be provided in the adhesive layer.

Further, for example, the adhesive layer caused by the crosslinkable compound is irradiated with an actinic ray or radiation or heat to the adhesive layer of the adhesive support before the adhesive support and the member to be processed. Can form the adhesion from the inside of the substrate side An adhesive layer with the surface falling toward the outer surface. In other words, the adhesion between the substrate and the adhesive layer in the adhesive support can be increased, and the adhesion of the adhesive layer to the member to be processed can be lowered.

The crosslinkable group is preferably a functional group capable of undergoing addition polymerization, and examples of the functional group capable of undergoing addition polymerization include an ethylenically unsaturated bond group, an amine group, and an epoxy group. In addition, the crosslinkable group may be a functional group capable of generating a radical by light irradiation, and examples of such a crosslinkable group include a thiol group and a halogen group. Among them, the crosslinkable group is preferably an ethylenically unsaturated bond group. The ethylenically unsaturated bond group is preferably a styryl group, a (meth)acryl fluorenyl group or an allyl group.

Specific examples of the crosslinkable compound include a radical polymerizable compound (B1) and an ionic polymerizable compound (B2).

Examples of the radically polymerizable compound include a (meth)acrylamide compound (B11) having a carbon number of 3 to 35, a (meth)acrylate compound (B12) having a carbon number of 4 to 35, and a carbon number of An aromatic vinyl compound (B13) of 6 to 35, a vinyl ether compound (B14) having 3 to 20 carbon atoms, and other radical polymerizable compound (B15). The radically polymerizable compound (B1) may be used alone or in combination of two or more. Further, a polymerization inhibitor such as hydroquinone or methyl ether hydroquinone may be used in combination as needed.

Examples of the (meth) acrylamide compound (B11) having a carbon number of 3 to 35 include (meth) acrylamide, N-methyl (meth) acrylamide, and N-ethyl (A). Acrylamide, N-propyl (meth) acrylamide, N-n-butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-butoxy Methyl (meth) acrylamide, N- Isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (methyl) Acrylamide and (meth)acryloylmorpholine.

Examples of the (meth) acrylate compound (B12) having 4 to 35 carbon atoms include the following monofunctional to hexafunctional (meth) acrylates.

Examples of the monofunctional (meth) acrylate include ethyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and trioctyl (meth)acrylate. , isoamyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, (A) Base) cyclohexyl acrylate, 4-n-butylcyclohexyl (meth)acrylate, borneol (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, 2-ethyl Hexyl diglycol (meth) acrylate, butoxyethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 4-bromobutyl (meth) acrylate, cyanide (meth) acrylate Ethyl ethyl ester, benzyl (meth) acrylate, butoxymethyl (meth) acrylate, methoxy propylene monoacrylate, 3-methoxybutyl (meth) acrylate, alkyl (meth) acrylate Oxymethyl ester, 2-ethylhexyl carbitol (meth) acrylate, alkoxyethyl (meth) acrylate, 2-(2-methoxyethoxy)ethyl (meth) acrylate , 2-(2-butoxyethoxy)ethyl (meth)acrylate, ( 2,2,2-tetrafluoroethyl acrylate, 1H, 1H, 2H, 2H-perfluorodecyl methacrylate, 4-butylphenyl (meth) acrylate, benzene (meth) acrylate Ester, 2,4,5-tetramethylphenyl (meth)acrylate, 4-chlorophenyl (meth)acrylate, phenoxymethyl (meth)acrylate, phenoxyethyl (meth)acrylate Ester, glycidyl (meth)acrylate, glycidyl (meth)acrylate, glycidoxyethyl (meth)acrylate, glycidoxypropyl (meth)acrylate, diethylene Alcohol monovinyl ether monoacrylate, Tetrahydrofurfuryl (meth) acrylate, hydroxyalkyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy (meth) acrylate Propyl ester, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, ( Methyl) dimethylaminopropyl acrylate, diethylaminopropyl (meth) acrylate, trimethoxy decyl propyl (meth) acrylate, trimethyl decyl propyl (meth) acrylate, poly Ethylene oxide monomethyl ether (meth) acrylate, oligoethylene oxide monomethyl ether (meth) acrylate, polyethylene oxide (meth) acrylate, oligomeric ethylene oxide (A Acrylate, oligoethylene oxide monoalkyl ether (meth) acrylate, polyethylene oxide monoalkyl ether (meth) acrylate, dipropylene glycol (meth) acrylate, polyepoxy Propane monoalkyl ether (meth) acrylate, oligomeric propylene oxide monoalkyl ether (meth) acrylate, 2-methyl propylene methoxyethyl succinic acid, 2-methyl propylene decyloxy Hexahydrophthalic acid, phthalic acid 2-Methyl propylene oxime ethyl 2-hydroxypropyl ester, butoxy diethylene glycol (meth) acrylate, trifluoroethyl (meth) acrylate, perfluorooctyl (meth) acrylate Ethyl ester, 2-hydroxy-3-phenoxypropyl (meth)acrylate, EO modified phenol (meth) acrylate, EO modified cresol (meth) acrylate, EO modified phenol (A) Acrylate, PO modified indophenol (meth) acrylate, and EO modified - 2-ethylhexyl (meth) acrylate. In the above and below, EO represents ethylene oxide, and PO represents propylene oxide.

Examples of the difunctional (meth) acrylate include 1,4-butane di(meth)acrylate, 1,6-hexane diacrylate, polypropylene diacrylate, and 1,6-hexanediol. Di(meth)acrylate, 1,10-nonanediol di(meth)acrylate, neopentyl diacrylate, neopentyl glycol di(meth)acrylate, 2,4-dimethyl-1 , 5-pentanediol di(methyl) Acrylate, butyl ethyl propylene glycol (meth) acrylate, ethoxylated cyclohexane methanol di(meth) acrylate, polyethylene glycol di (meth) acrylate, oligoethylene glycol bis ( Methyl) acrylate, ethylene glycol di(meth) acrylate, 2-ethyl-2-butyl-butanediol di(meth) acrylate, hydroxytrimethyl acetic acid neopentyl glycol di(a) Acrylate, EO modified bisphenol A di(meth)acrylate, bisphenol F polyethoxy di(meth)acrylate, polypropylene glycol di(meth)acrylate, oligomeric polypropylene glycol (A) Acrylate, 1,4-butanediol di(meth)acrylate, 2-ethyl-2-butyl-propylene glycol di(meth)acrylate, 1,9-decane di(methyl) Acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate, tricyclodecane di(meth)acrylate, and the like.

Examples of the trifunctional (meth) acrylate include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, and trimethylolpropane alkylene oxide. Modified tris(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, trimethylolpropane tris((meth)acryloxypropyl)ether, different Cyanuric acid alkylene oxide modified tris(meth)acrylate, dipentaerythritol tris(meth)acrylate, tris((meth)acryloxyethyl)isocyanate, hydroxyl Trimethylacetaldehyde modified dimethylolpropane tri(meth)acrylate, sorbitol tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate and ethoxylate Glycerol triacrylate and the like.

Examples of the tetrafunctional (meth) acrylate include pentaerythritol tetra(meth)acrylate, sorbitol tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, and propionic acid. Dipentaerythritol tetra(meth)acrylate and ethoxylated pentaerythritol tetra(meth)acrylate.

Examples of the pentafunctional (meth) acrylate include sorbitol penta (meth) acrylate and dipentaerythritol penta (meth) acrylate.

Examples of the hexafunctional (meth) acrylate include dipentaerythritol hexa(meth) acrylate, sorbitol hexa(meth) acrylate, and phosphazene alkylene oxide modified hexa(meth) acrylate. And caprolactone modified dipentaerythritol hexa (meth) acrylate and the like.

Examples of the aromatic vinyl compound (B13) having a carbon number of 6 to 35 include vinylthiophene, vinylfuran, vinylpyridine, styrene, methylstyrene, trimethylstyrene, and ethylstyrene. , isopropyl styrene, chloromethyl styrene, methoxy styrene, ethoxylated styrene, chlorostyrene, dichlorostyrene, bromostyrene, methyl benzoate, 3-methyl Styrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene, 4-propylstyrene, 3-butylstyrene, 4-butylbenzene Ethylene, 3-hexylstyrene, 4-hexylstyrene, 3-octylstyrene, 4-octylstyrene, 3-(2-ethylhexyl)styrene, 4-(2-ethylhexyl)benzene Ethylene, allyl styrene, isopropenyl styrene, butenyl styrene, octenyl styrene, 4-tert-butoxycarbonyl styrene, 4-methoxy styrene and 4-third butyl Oxystyrene and the like.

Examples of the vinyl ether compound (B14) having 3 to 35 carbon atoms include the following monofunctional vinyl ethers or polyfunctional vinyl ethers.

Examples of the monofunctional vinyl ether include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, tert-butyl vinyl ether, and 2-ethylhexylethylene. Ether, n-decyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4-methylcyclohexyl methyl vinyl ether, Benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenyloxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxy Ethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxy polyethylene glycol vinyl ether, tetrahydrofurfuryl vinyl ether, 2 - hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene Glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, chloroethoxyethyl vinyl ether, phenyl ethyl vinyl ether and phenoxy polyethylene glycol vinyl ether.

Examples of the polyfunctional vinyl ether include ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, and butanediol divinyl ether. Divinyl ethers such as hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether; trimethylolethane trivinyl ether, trihydroxyl Methylpropane trivinyl ether, di-trimethylolpropane tetravinyl ether, glycerol trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol penta vinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide Addition of trimethylolpropane trivinyl ether, propylene oxide addition trimethylolpropane trivinyl ether, ethylene oxide addition di-trimethylolpropane tetravinyl ether, propylene oxide addition Di-trimethylolpropane tetravinyl ether, ethylene oxide addition pentaerythritol tetravinyl ether, propylene oxide addition pentaerythritol tetravinyl ether, ethylene oxide addition dipentaerythritol hexavinyl ether, and ring Oxypropane is added to dipentaerythritol hexavinyl ether.

Examples of the other radical polymerizable compound (B15) include vinyl ester compounds (vinyl acetate, vinyl propionate, and versatic acid B). Allyl esters, etc., allyl ester compounds (allyl acetate, etc.), halogen-containing monoliths (such as vinylidene chloride and vinyl chloride), and olefin compounds (such as ethylene and propylene).

Among these, from the viewpoint of the curing rate, a (meth) acrylamide compound (B11) and a (meth) acrylate compound (B12) are preferred, and a (meth) acrylate compound (particularly preferred) B12).

The ionic polymerizable compound (B2) may, for example, be an epoxy compound (B21) having 3 to 20 carbon atoms or an oxetane compound (B22) having 4 to 20 carbon atoms.

Examples of the epoxy compound (B21) having 3 to 20 carbon atoms include the following monofunctional epoxy compounds or polyfunctional epoxy compounds.

Examples of the monofunctional epoxy compound include phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, and allyl glycidyl ether. 1,2-butylene oxide, 1,3-butadiene monooxide, 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, ring Cyclohexene oxide, 3-methacryloxymethyl epoxy cyclohexane, 3-propenyloxymethyl epoxy cyclohexane, and 3-vinyl epoxy cyclohexane.

Examples of the polyfunctional epoxy compound include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, and brominated bisphenol F. Diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3 , 4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy Cyclohexane-m-dioxane, bis(3,4-epoxycyclohexylmethyl) adipate, vinyl epoxycyclohexane, 4-vinyl epoxycyclohexane, bis ( 3,4-Epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'- Methylcyclohexanecarboxylate, methylene bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol bis(3,4-epoxycyclohexyl Ether, ethyl bis(3,4-epoxycyclohexanecarboxylate), dioctyl hexahydrophthalate, di-2-oxophthalic acid di-2-phthalate Ethylhexyl ester, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol II Glycidyl ether, polypropylene glycol diglycidyl ether, 1,1,3-tetradecadiene dioxide, limonene dioxide, 1,2,7,8-dicyclooxyoctane and 1,2 , 5,6-dicyclooxycyclooctane.

Among these epoxy compounds, from the viewpoint of excellent curing speed, an aromatic epoxide and an alicyclic epoxide are preferable, and an alicyclic epoxide is particularly preferable.

The oxetane compound (B22) having 4 to 20 carbon atoms may, for example, be a compound having one to six oxetane rings.

Examples of the compound having one oxetane ring include 3-ethyl-3-hydroxymethyloxetane and 3-(methyl)allyloxymethyl-3-ethyl Oxetane, (3-ethyl-3-oxetanylmethoxy)methylbenzene, 4-fluoro-[1-(3-ethyl-3-oxetanylmethoxy)methyl] Benzene, 4-methoxy-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene, [1-(3-ethyl-3-oxetanylmethoxy)B Phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl 3-oxetanylmethyl)ether, isobornyl (3-ethyl-3-oxetanylmethyl)ether, 2-ethylhexyl(3-ethyl-3-oxetanylmethyl)ether Ethyl diethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxy Ethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydroindenyl (3-ethyl-3) -oxetanylmethyl)ether, tetrabromophenyl(3-ethyl-3-oxetanylmethyl)ether, 2-tetrabromophenoxyethyl(3-ethyl-3-oxetanylethyl) Ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2 -hydroxyethyl(3-ethyl-3-oxetanylmethyl)ether, 2-hydroxypropyl(3-ethyl-3-oxetanylmethyl)ether, butoxyethyl (3-ethyl 3--3-oxetanylmethyl)ether, pentachlorophenyl(3-ethyl-3-oxetanylmethyl)ether, pentabromophenyl(3-ethyl-3-oxetanylmethyl) Ether and borneol (3-ethyl-3-oxetanylmethyl) ether.

Examples of the compound having 2 to 6 oxetane rings include 3,7-bis(3-oxetanyl)-5-oxa-decane and 3,3'-(1). ,3-(2-methylene)propanediylbis(oxymethylene))bis-(3-ethyloxetane), 1,4-bis[(3-ethyl-3- Oxetanylmethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl) 3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl bis(3-ethyl-3-oxo Heterocyclic butyl methyl)ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, three Cyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl)ether, trimethylolpropane tris(3-ethyl-3-oxetanylmethyl)ether, 1,4 - bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3- Oxetanylmethoxy)hexane, pentaerythritol tris(3-ethyl-3-oxetanylmethyl)ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl)ether, polyethylene glycol Bis(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol penta(3-ethyl-3-oxocyclohexane Butylmethyl)ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl)ether, caprolactone modified dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl)ether, Ester-modified dipentaerythritol penta(3-ethyl-3-oxetanylmethyl)ether, di-trimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl)ether, EO modified double Phenol A bis(3-ethyl-3-oxetanylmethyl)ether, PO modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, EO modified hydrogenated bisphenol A double (3-Ethyl-3-oxetanylmethyl)ether, PO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, and EO modified bisphenol F (3- Ethyl-3-oxetanylmethyl)ether.

Among these crosslinkable compounds, a radical polymerizable compound can be preferably used from the viewpoint of adhesion and releasability, and further, radical polymerizable property having a urethane bond can be optimally used. Compound.

The content of the crosslinkable compound (B) is preferably from 5% by mass to 75% by mass, more preferably 10% by mass, based on the total solid content of the temporary adhesive, from the viewpoint of good adhesion strength and peelability. ~70% by mass, and more preferably 20% by mass to 65% by mass.

Further, the ratio (mass ratio) of the content of the crosslinkable compound (B) and the resin (A) is preferably from 90/10 to 10/90, more preferably from 20/80 to 80/20.

(C) solvent

The temporary adhesive of the present invention contains a solvent (usually an organic solvent). Solvent as long as The solubility of each component or the coatability of a temporary adhesive is not particularly limited.

As the organic solvent, examples of the ester include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, butyl propionate, isopropyl butyrate, and butyl. Ethyl acetate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (eg methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg methyl methoxyacetate, methoxy) Ethyl acetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-oxopropionate (for example: methyl 3-oxopropionate, 3 -ethyl oxypropionate or the like (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.) , 2-oxopropionic acid alkyl esters (for example: methyl 2-oxopropionate, ethyl 2-oxopropionate, propyl 2-oxopropionate, etc. (for example, methyl 2-methoxypropionate, Ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-oxy-2-methyl Methyl propyl propionate and ethyl 2-oxy-2-methylpropanoate (eg methyl 2-methoxy-2-methylpropanoate, 2-ethoxy-2-methyl propyl) Ethyl ester, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutyrate, Γ-butyrolactone or the like; and, as the ether, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate can be suitably used. Ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether An acid ester, propylene glycol monopropyl ether acetate, etc.; and, as a ketone, a methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc. are mentioned suitably, for example. Further, examples of the aromatic hydrocarbons include toluene and xylene.

From the viewpoint of improvement of the coated surface, etc., a form in which two or more kinds of the above solvents are mixed is also preferable. In this case, it is particularly preferred to comprise a methyl ester selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, and diethylene glycol. Methyl ether, butyl acetate, methyl 3-methoxypropionate, γ-butyrolactone, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, A mixed solution of two or more kinds of propylene glycol methyl ether and propylene glycol methyl ether acetate.

From the viewpoint of the coating property, the content of the solvent in the temporary adhesive is preferably such that the total solid content of the temporary adhesive becomes 5% by mass to 80% by mass, and more preferably the temporary adhesive. The total solid content concentration is 5% by mass to 70% by mass, and particularly preferably the total solid content concentration of the temporary adhesive is 10% by mass to 60% by mass.

(D) Reaction initiator

The temporary adhesive of the present invention contains a reaction initiator (D). Thereby, the crosslinking reaction in the crosslinkable group-containing resin and the crosslinkable compound (C) which are the resin (A) can be started.

The reaction initiator (D) may, for example, be a compound (D-1) which generates a radical or an acid by irradiation with actinic rays or radiation, and a compound which generates a radical or an acid by heat ( D-2). Hereinafter, these compounds will be described in detail.

(D-1) a compound which generates a radical or an acid by irradiation with actinic rays or radiation

As a combination of radicals or acids generated by irradiation of actinic rays or radiation As the material (D-1), for example, a compound known as a polymerization initiator described below can be used.

The polymerization initiator is not particularly limited, and can be appropriately selected from known polymerization initiators. For example, a polymerization initiator which is photosensitive from an ultraviolet region to visible light is preferred. Further, it may be an initiator which generates an acid corresponding to the kind of the monomer and starts the polymerization of the cation.

As the polymerization initiator, a known compound can be used without limitation, and examples thereof include a halogenated hydrocarbon derivative (for example, a halogenated hydrocarbon compound having a triazine skeleton, a halogenated hydrocarbon compound having a oxadiazole skeleton, and a trihalomethyl group). a halogenated hydrocarbon compound, etc.), a mercaptophosphine compound such as a mercaptophosphine oxide, an antimony compound such as a hexaarylbiimidazole or an anthracene derivative, an organic peroxide, a sulfur compound, a ketone compound, an aromatic onium salt, a ketoxime, Aminoacetophenone compound, hydroxyacetophenone, azo compound, azide compound, metallocene compound, organoboron compound, iron aromatic hydrocarbon complex, and the like.

Examples of the halogenated hydrocarbon compound having a triazine skeleton include a compound described in J. Lin et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), British Patent No. 1,388,492. The compound described in the specification, the compound described in JP-A-53-133428, the compound described in the specification of German Patent No. 3337024, and the Journal of Organic Chemistry (J. Org. Chem.) by FC Schaefer et al. The compound described in Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Compound, as described in the specification of US Pat. No. 4,212,976 Compounds, etc.

Examples of the compound described in the above specification of U.S. Patent No. 4,212,976 include compounds having an oxadiazole skeleton (e.g., 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5-(4-chlorophenyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(1-naphthyl)-1,3,4-oxadiazole , 2-trichloromethyl-5-(2-naphthyl)-1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2 -tribromomethyl-5-(2-naphthyl)-1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2- Trichloromethyl-5-(4-chlorostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-methoxystyryl)-1,3, 4-oxadiazole, 2-trichloromethyl-5-(1-naphthyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-n-butoxystyrene Base)-1,3,4-oxadiazole, 2-tribromomethyl-5-styryl-1,3,4-oxadiazole, etc.).

Further, examples of the polymerization initiator other than the above include an acridine derivative (for example, 9-phenyl acridine, 1,7-bis(9,9'-acridinyl)heptane, etc.), N-benzene. a glycosidic acid or the like, a polyhalogen compound (for example, carbon tetrabromide, phenyltribromomethylhydrazine, phenyltrichloromethyl ketone, etc.), a coumarin (for example, 3-(2-benzofuran) -7-diethylamine coumarin, 3-(2-benzofurancarbenyl)-7-(1-pyrrolidinyl)coumarin, 3-benzylidene-7-diethylamine Coumarin, 3-(2-methoxybenzimidyl)-7-diethylamine coumarin, 3-(4-dimethylaminobenzimidyl)-7-diethylamino Coumarin, 3,3'-carbonylbis(5,7-di-n-propoxycoumarin), 3,3'-carbonylbis(7-diethylaminocoumarin), 3-phenyl Mercapto-7-methoxycoumarin, 3-(2-furylmercapto)-7-diethylamine coumarin, 3-(4-diethylamino cinnamyl)-7-di Ethyl coumarin, 7-methoxy-3-(3-pyridylcarbonyl)coumarin, 3-benzylidene-5,7-dipropoxycoumarin, 7-benzotriene Zin-2-yl coumarin, In addition, Japanese Patent Laid-Open No. Hei 5-19475, Japanese Patent Laid-Open No. Hei 7-271028, Japanese Patent Laid-Open Publication No. 2002-363206, Japanese Patent Laid-Open Publication No. 2002-363207, No. 2002-363208 The coumarin compound or the like described in Japanese Patent Laid-Open Publication No. 2002-363209, etc., and fluorenylphosphine oxides (for example, bis(2,4,6-trimethylbenzylidene)-phenyl oxide Phosphine, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphenylphosphine oxide, LucirinTPO, etc.), metallocenes (eg bis(η5-2, 4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, η5-cyclopentadienyl-η6-cumene Base-iron (1+)-hexafluorophosphate (1-), etc., Japanese Patent Laid-Open No. Sho 53-133428, Japanese Patent Publication No. Sho 57-1819, Japanese Patent Publication No. Sho 57-6096, And the compounds described in the specification of U.S. Patent No. 3,615,455.

Examples of the ketone compound include diphenyl ketone, 2-methyl diphenyl ketone, 3-methyl diphenyl ketone, 4-methyl diphenyl ketone, and 4-methoxy diphenyl ketone. , 2-chlorodiphenyl ketone, 4-chlorodiphenyl ketone, 4-bromodiphenyl ketone, 2-carboxydiphenyl ketone, 2-ethoxycarbonyldiphenyl ketone, diphenyl ketone tetracarboxylate Acid or its tetramethyl ester, 4,4'-bis(dialkylamino)diphenyl ketone (eg 4,4'-bis(dimethylamino)diphenyl ketone, 4,4'-double (dicyclohexylamino)diphenyl ketone, 4,4'-bis(diethylamino)diphenyl ketone, 4,4'-bis(dihydroxyethylamino)diphenyl ketone, 4-methyl Oxy-4'-dimethylaminodiphenyl ketone, 4,4'-dimethoxydiphenyl ketone, 4-dimethylaminodiphenyl ketone, 4-dimethylamino acetophenone, Benzil, hydrazine, 2-tert-butyl fluorene, 2-methyl hydrazine, phenanthrenequinone, xanthone, thioxanthone, 2-chloro-sulfur Xanthone, 2,4-diethylthioxanthone, anthrone, 2-benzyl-dimethylamino-1-(4-morpholinylphenyl)-1-butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-1-propanone, 2-hydroxy-2-methyl-[4-(1-methylvinyl)benzene Propyl alcohol oligomer, benzoin, benzoin ether (eg benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloranil Pyridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone, and the like.

As the polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a mercaptophosphine compound can also be suitably used. More specifically, for example, an amino acetophenone-based initiator as described in JP-A-10-291969, and a sulfhydryl phosphine oxide-based initiator described in Japanese Patent No. 42258899 can be used. .

As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF Corporation) which are commercially available products can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179, which is a wavelength of a long-wavelength source such as 365 nm or 405 nm, can be used. Further, as the mercaptophosphine-based initiator, IRGACURE-819 or DAROCUR-TPO (trade name: all manufactured by BASF Corporation) which is a commercially available product can be used.

As a polymerization initiator, a quinone compound is more preferable. As a specific example of the oxime-based initiator, the one described in JP-A-2001-233842 can be used. The compound described in Japanese Laid-Open Patent Publication No. 2000-80068, and the compound described in JP-A-2006-342166.

As the ruthenium compound such as an anthracene derivative which can be suitably used as a polymerization initiator in the present invention, for example, 3-benzylideneoxyimidobutan-2-one and 3-ethyloxyimide can be cited. Butyral-2-one, 3-propoxy methoxyiminobutan-2-one, 2-ethoxymethoxyiminopentan-3-one, 2-ethyloxyimino group- 1-phenylpropan-1-one, 2-benzylideneoxyimido-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2- A ketone, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like.

As the oxime ester compound, for example, "The British Chemical Society, JC Perkin II" (1979) pp. 1653-1660, JCS Perkin II (1979) pp. 156-162, "Light" Compounds described in Journal of Photopolymer Science and Technology, 1995, pp. 202-232, and JP-A-2000-66385, Japanese Patent Laid-Open Publication No. 2000-80068, Japan A compound or the like described in each of the publications of Japanese Laid-Open Patent Publication No. Hei. No. 2006-342166.

Commercially available products such as IRGACURE-OXE01 (manufactured by BASF Corporation) and IRGACURE-OXE02 (manufactured by BASF Corporation) can be suitably used.

In addition, as the oxime ester compound other than the above, a compound described in Japanese Patent Laid-Open Publication No. 2009-519904, in which N is attached to the N-position of the carbazole, and a hetero substituent introduced into the diphenyl ketone moiety may be used. The compound described in the U.S. Patent No. 7,626,957, the disclosure of the Japanese Patent Publication No. 2010-15025, and the Japanese Patent Publication No. 2009-292039 The ketone-based compound described in Japanese Laid-Open Patent Publication No. 2009-131189, and the compound described in U.S. Patent No. 7,556,910, which contains a triazine skeleton and an anthracene skeleton in the same molecule, has an absorption maximum at 405 nm. A compound or the like described in JP-A-2009-221114, which has a good sensitivity to a g-ray source.

The cyclic anthraquinone compound described in JP-A-2007-2320, and JP-A-2007-322744 is preferably used. Among the cyclic ruthenium compounds, the cyclic ruthenium compound which is condensed in the carbazole dye described in Japanese Patent Laid-Open Publication No. 2010-185072, and the like, has high light absorbing property. It is preferable from the viewpoint of high sensitivity.

In addition, the compound described in JP-A-2009-242469, which has an unsaturated bond at a specific site of a ruthenium compound, can be highly reproducible by regenerating a living radical from a polymerization inert radical. Use as appropriate.

The ruthenium compound having a specific substituent as shown in JP-A-2007-269779 or the ruthenium compound having a thioaryl group as shown in JP-A-2009-191061 is exemplified.

Specifically, as the oxime polymerization initiator, a compound represented by the following formula (OX-1) is preferred. Further, the N-O bond of ruthenium may be a ruthenium compound of the (E) form, a ruthenium compound of the (Z) form, or a mixture of the (E) form and the (Z) form.

[Chemical 2]

(In the formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group)

In the above formula (OX-1), a monovalent substituent represented by R is preferably a monovalent non-metal atomic group.

The monovalent non-metal atomic group may, for example, be an alkyl group, an aryl group, a decyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group or an arylthiocarbonyl group. Further, these groups may have one or more substituents. Further, the above substituent may be further substituted with another substituent.

The substituent may, for example, be a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, a decyloxy group, a decyl group, an alkyl group or an aryl group.

The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, and a decyl group. Diyl, octadecyl, isopropyl, isobutyl, t-butyl, tert-butyl, 1-ethylpentyl, cyclopentyl, cyclohexyl, trifluoromethyl, 2-ethylhexyl, Benzomethazine methyl, 1-naphthylmethylmethyl, 2-naphthylmethylmethyl, 4-methylmercaptobenzylidenemethyl, 4-phenylmercaptobenzylidenemethyl, 4-dimethyl Amido benzamidine methyl, 4-cyanobenzhydrylmethyl, 4-methylbenzimidylmethyl, 2-methylbenzimidylmethyl, 3-fluorobenzhydrylmethyl, 3-tri Fluoromethyl benzamidine methyl, and 3-nitrobenzhydrylmethyl.

The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, and specific examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 9-fluorenyl group. , 9-phenanthryl, 1-fluorenyl, 5-thick tetraphenyl, 1-indenyl, azulenyl, 9-fluorenyl, terphenyl, quaterphenyl ), o-tolyl, m-tolyl, p-tolyl, xylyl, o- cumenyl, m-cumenyl and p-cumenyl, 2,4,6-trimethylphenyl (mesityl), and cyclopentane Pentalenyl, binaphthalenyl, naphthyl, tetratetraphthyl, heptalenyl, biphenylenyl, dicyclopentadienyl ( Indacenyl), fluoranthenyl, acenaphthylenyl, aceanthrylenyl, phenalenyl, fluorenyl, fluorenyl, hydrazino, hydrazine Alkyl, hydrazinyl, anthraquinolyl, phenanthryl, triphenylenyl, fluorenyl, Chrysenyl, condensed tetraphenyl, pleiadenyl, picenyl, perylenyl, pentaphenyl, pentacenyl, tetraphenylenyl , hexaphenyl, hexaphenyl, rubicenyl, coronenyl, trinaphthylenyl, heptaphenyl, hexaphenyl, pyranthrenyl, and fluorenyl (ovalenyl).

The fluorenyl group which may have a substituent is preferably a fluorenyl group having 2 to 20 carbon atoms, and specific examples thereof include an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, a trifluoroethyl fluorenyl group, a pentamidine group, and a benzene group. Mercapto, 1-naphthylmethyl, 2-naphthylmethyl, 4-methylmercaptobenzyl, 4-phenylmercaptobenzyl, 4-dimethylaminobenzylidene, 4 -diethylaminobenzhydryl, 2-chlorobenzhydryl, 2-methylbenzhydryl, 2-methoxybenzimidyl, 2-butyl Oxylbenzylidene, 3-chlorobenzylidene, 3-trifluoromethylbenzylidene, 3-cyanobenzylidene, 3-nitrobenzhydryl, 4-fluorobenzhydrazide Base, 4-cyanobenzylidene, and 4-methoxybenzimidyl.

The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, and specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and a butoxy group. Alkylcarbonyl, hexyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, octadecyloxycarbonyl, and trifluoromethoxycarbonyl.

Specific examples of the aryloxycarbonyl group which may have a substituent include a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group, a 4-methylnonylphenoxycarbonyl group, and a 4-benzene group. Phenyl phenoxycarbonyl, 4-dimethylaminophenoxycarbonyl, 4-diethylaminophenoxycarbonyl, 2-chlorophenoxycarbonyl, 2-methylphenoxycarbonyl, 2-methoxy Phenoxycarbonyl, 2-butoxyphenoxycarbonyl, 3-chlorophenoxycarbonyl, 3-trifluoromethylphenoxycarbonyl, 3-cyanophenoxycarbonyl, 3-nitrophenoxy Alkylcarbonyl, 4-fluorophenoxycarbonyl, 4-cyanophenoxycarbonyl, and 4-methoxyphenoxycarbonyl.

The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.

Specifically, a thienyl group, a benzo[b]thienyl group, a naphtho[2,3-b]thienyl group (naphtho[2,3-b] can be exemplified. Thienyl group), thianthrenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, Xanthenyl group, phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group (pyridyl group), pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-吲哚3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group, 4H-quinolizinyl group, isoquinoline Isoquinolyl group, quinolyl group, phthalazinyl group, Naphthyridinyl group, quinoxalinyl group, quinazolinyl group, Cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenidinyl group (phenanthridinyl group), acridinyl group, Perimidinyl group, phenanthrolinyl group, phenazinyl group, phenarsazinyl group, isothiazolyl group, phenothiazinyl group, different Isozolyl group, furazanyl group, phenoxazinyl group, different Isochromanyl group, Chromyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazoline Pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, Quinuclidinyl group, morpholinyl group, and thioxantholyl group.

As the alkylthiocarbonyl group which may have a substituent, specifically, a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, a octylthiocarbonyl group, a sulfonylthiocarbonyl group, and an eighteenth An alkylthiocarbonyl group, and a trifluoromethylthiocarbonyl group.

Specific examples of the arylthiocarbonyl group which may have a substituent include 1-naphthylthiocarbonyl, 2-naphthylthiocarbonyl, 4-methylnonylphenylthiocarbonyl, and 4-phenylmercaptophenylthio. Carbonyl, 4-dimethylaminophenylthiocarbonyl, 4-diethylaminophenylthiocarbonyl, 2-chlorophenylthiocarbonyl, 2-methylphenylthiocarbonyl, 2-methoxyphenylthiocarbonyl , 2-butoxyphenylthiocarbonyl, 3-chlorophenylthiocarbonyl, 3-trifluoromethylphenylthiocarbonyl, 3-cyanophenylthiocarbonyl, 3-nitrophenylthiocarbonyl, 4- Fluorophenylthiocarbonyl, 4-cyanophenylthiocarbonyl, and 4-methoxyphenylthiocarbonyl.

In the above formula (OX-1), the monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group. Further, these groups may have one or more substituents. The substituent may be exemplified as the substituent. Further, the above substituent may be further substituted with another substituent.

Among them, the structure shown below is particularly preferable.

In the following structures, the meanings of Y, X, and n are the same as Y, X, and n in the formula (OX-2) to be described later, and preferred examples are also the same.

[Chemical 3]

In the above formula (OX-1), examples of the divalent organic group represented by A include an alkylene group having a carbon number of 1 to 12, a cycloalkylene group, and an alkynylene group. Further, these groups may have one or more substituents. The substituent may be exemplified as the substituent. Further, the above substituent may be further substituted with another substituent.

Among them, as A in the formula (OX-1), an unsubstituted alkylene group or an alkyl group (for example, a methyl group) is preferred from the viewpoint of improving sensitivity and suppressing coloration caused by heating over time. , ethyl, tert-butyl, dodecyl) substituted alkyl, alkenyl (eg vinyl, allyl) substituted alkyl, aryl (eg phenyl, p-tolyl, A tolyl, cumenyl, naphthyl, anthracenyl, phenanthryl, styryl) substituted alkylene group.

In the above formula (OX-1), the aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, and may have a substituent. The substituent is the same as the substituent in the substituted aryl group exemplified as a specific example of the aryl group which may have a substituent.

Among them, a substituted or unsubstituted phenyl group is preferred from the viewpoint of improving sensitivity and suppressing coloring caused by heating.

In the formula (OX-1), from the viewpoint of sensitivity, the structure of "SAr" formed by Ar in the above formula (OX-1) and S adjacent to Ar is preferably The structure shown below. Further, Me represents a methyl group, and Et represents an ethyl group.

The hydrazine compound is preferably a compound represented by the following formula (OX-2).

(In the formula (OX-2), R and X each independently represent a monovalent substituent, A and Y each independently represent a divalent organic group, Ar represents an aryl group, and n is an integer of 0 to 5)

The meanings of R, A, and Ar in the formula (OX-2) are the same as those of R, A, and Ar in the above formula (OX-1), and preferred examples are also the same.

In the above formula (OX-2), examples of the monovalent substituent represented by X include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a decyloxy group, a decyl group, and an alkoxycarbonyl group. Amine group, heterocyclic group, halogen atom. Further, these groups may have one or more substituents. The substituent may be exemplified as the substituent. Further, the above substituent may be further substituted with another substituent.

Among these, X in the formula (OX-2) is preferably an alkyl group from the viewpoint of improving solvent solubility and absorption efficiency in a long wavelength region.

Further, n in the formula (2) represents an integer of 0 to 5, preferably an integer of 0 to 2.

In the above formula (OX-2), examples of the divalent organic group represented by Y include the structures shown below. In addition, in the base shown below, "*" represents the bonding position of Y and the adjacent carbon atom in the above formula (OX-2).

[Chemical 6]

Among them, from the viewpoint of high sensitivity, the structure shown below is preferable.

Further, the ruthenium compound is preferably a compound represented by the following formula (OX-3).

[化8]

(In the formula (OX-3), R and X each independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n is an integer of 0 to 5)

The meanings of R, X, A, Ar, and n in the formula (OX-3) are the same as those of R, X, A, Ar, and n in the above formula (OX-2), and preferred examples are also the same.

Specific examples (B-1) to (B-10) of the ruthenium compound which can be suitably used are shown below, but the present invention is not limited to these specific examples.

[Chemistry 9]

The ruthenium compound has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably a ruthenium compound having a high absorbance at 365 nm and 455 nm.

From the viewpoint of sensitivity, the molar absorption coefficient of the cerium compound at 365 nm or 405 nm is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, particularly preferably from 5,000 to 200,000.

The molar absorption coefficient of the compound can be determined by a known method. Specifically, for example, it is preferably an ultraviolet-visible spectrophotometer (Carry-5 spctrophotometer manufactured by Varian), and uses acetic acid B. The ester solvent was measured at a concentration of 0.01 g/L.

The polymerization initiator to be used in the invention may be used in combination of two or more kinds as needed.

The compound (D-1) which generates a radical or an acid by irradiation with actinic rays or radiation is preferably selected from the group consisting of a trihalomethyltriazine compound and a benzyl dimethyl group from the viewpoint of exposure sensitivity. Ketal ketone compound, α-hydroxyketone compound, α-amino ketone compound, mercaptophosphine compound, phosphine oxide compound, metallocene compound, hydrazine compound, triallyl imidazole dimer, hydrazine compound, benzothiazole compound , diphenyl ketone compound, acetophenone compound and its derivatives, cyclopentadiene-benzene-iron complex and its salt, halomethyl oxadiazole compound, 3-aryl substituted coumarin compound Compounds in the group.

More preferably, it is a trihalomethyltriazine compound, an α-amino ketone compound, a mercaptophosphine compound, a phosphine oxide compound, an anthraquinone compound, a triallyl imidazole dimer, an anthraquinone compound, a diphenylketone compound, or a phenylethyl group. The ketone compound is preferably at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-amino ketone compound, an anthraquinone compound, a triallyl imidazole dimer, and a diphenyl ketone compound. It is best to use a ruthenium compound.

Further, among the compound (D-1) which generates a radical or an acid by irradiation with actinic rays or radiation, a compound which generates an acid having a pKa of 4 or less is preferable. More preferably, it is a compound which produces an acid having a pKa of 3 or less.

Examples of the acid generating compound include trichloromethyl-s-triazine, sulfonium or phosphonium salt, quaternary ammonium salt, diazomethane compound, sulfhydryl sulfonate compound, and sulfonic acid. Ester compound and the like. Among these, from the viewpoint of high sensitivity, an oxime sulfonate compound is preferably used. These acid generators may be used alone or in combination of two or more.

Specific examples of the acid generator include the acid generators described in paragraphs [0073] to [0095] of JP-A-2012-8223.

The content of the compound (D-1) which generates a radical or an acid by irradiation with actinic rays or radiation of the present invention (the total content in the case of two or more kinds) is preferably the total solid content of the temporary adhesive. 0.1% by mass or more and 50% by mass or less, more preferably 0.1% by mass or more and 30% by mass or less, still more preferably 0.1% by mass or more and 20% by mass or less.

(D-2) a compound which generates a radical or an acid by heat

The temporary adhesive of the present invention may contain a compound (D-2) which generates a radical or an acid by heat.

[Compounds that generate free radicals by heat]

A known thermal radical generator can be used as a compound which generates a radical by heat (hereinafter, simply referred to as a thermal radical generator).

The thermal radical generating agent is a compound which generates a radical by thermal energy, and starts or promotes a crosslinking reaction in a resin containing a crosslinkable group and a crosslinkable compound. Things.

The preferred thermal radical generating agent may, for example, be the compound (D-1) which generates an acid or a radical by irradiation with actinic rays or radiation, but it is preferable to use a thermal decomposition point of 130 ° C to 250. °C, preferably a compound in the range of 150 ° C to 220 ° C.

Examples of the thermal radical generating agent include aromatic ketones, phosphonium salt compounds, organic peroxides, sulfur compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azine oxime compounds, and metallocene compounds. An active ester compound, a compound having a carbon halogen bond, an azo compound, or the like. Among them, an organic peroxide or an azo compound is more preferred, and an organic peroxide is particularly preferred.

Specifically, a compound described in paragraphs 0074 to 0118 of JP-A-2008-63554 can be cited.

Examples of the borate compound include butyltrinaphthylborate and tetrakis(3,5-bis(trifluoromethyl)phenyl)borate. Examples of the counter cation of the borate include an alkali metal cation (preferably a sodium cation), an alkaline earth metal cation, an ammonium cation (preferably a tetrabutylammonium cation), a phosphonium cation, a phosphonium cation, a phosphonium cation, and a heavy A known cation such as a nitrogen cation or a sulfonium cation.

[A compound that generates an acid by heat]

A known thermal acid generator can be used as a compound which generates an acid by heat (hereinafter, simply referred to as a thermal acid generator).

The thermal acid generator may be a compound having a thermal decomposition point of preferably from 130 ° C to 250 ° C, more preferably from 150 ° C to 220 ° C.

As a thermal acid generator, for example, a sulfonic acid, a carboxylic acid, a disulfonate is produced by heating. A compound of a low nucleophilic acid such as decyl imine.

The acid produced as the autothermal acid generator is preferably a sulfonic acid having a pKa of 2 or less or an alkyl or aryl carboxylic acid substituted with an electron withdrawing group, and a disulfonyl group substituted with an electron withdrawing group.醯imine and so on. Examples of the electron withdrawing group include a halogen atom such as a fluorine atom, a halogenated alkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.

As the thermal acid generator, the above (D-1) photoacid generator which generates an acid by irradiation with actinic rays or radiation can be applied. For example, an onium salt such as a phosphonium salt or a phosphonium salt, an N-hydroxy sulfenium sulfonate compound, an oxime sulfonate or an o-nitrobenzyl sulfonate can be mentioned.

Further, in the present invention, it is also preferred to use a sulfonate which does not substantially generate an acid by irradiation with actinic rays or radiation, and generates an acid by heat.

The acid which is not substantially caused by the irradiation of actinic rays or radiation can be determined by the infrared absorption (IR) spectrum and the nuclear magnetic resonance (NMR) spectrum before and after the exposure of the compound, and the spectrum is not changed. .

The molecular weight of the sulfonate is preferably from 230 to 1,000, more preferably from 230 to 800.

As the sulfonic acid ester which can be used in the present invention, a commercially available sulfonic acid ester can be used, and a sulfonic acid ester synthesized by a known method can also be used. The sulfonate can be synthesized, for example, by reacting sulfonium chloride or a sulfonic acid anhydride with a corresponding polyol under basic conditions. The thermal acid generator may be used alone or in combination of two or more.

The content of the compound (D-2) which generates a radical or an acid by heat in the temporary adhesive of the present invention is preferably 0.01 with respect to the total solid content of the temporary adhesive. The mass % to 50% by mass, more preferably 0.1% by mass to 20% by mass, most preferably 0.5% by mass to 10% by mass.

(E) sensitizing pigment

The temporary adhesive of the present invention contains a sensitizing dye (E).

The sensitizing dye is typically an absorbing illuminating ray or radiation or heat to become an excited state, and energy is supplied to the reaction initiator by electron movement, energy transfer or heat generation, thereby enhancing the reaction initiation function of the reaction initiator. .

Thereby, the actinic layer induced by the sensitizing dye from the adhesive layer formed of the temporary adhesive of the present invention is irradiated with actinic rays or radiation or heat, whereby the reaction initiator starts the reaction starting species due to the above action, and as a result, the result is obtained. The crosslinking reaction of the crosslinkable compound starts. As a result, it is considered that the crosslinkable group exhibiting adhesiveness and viscosity in the adhesive layer is reduced, whereby the adhesion can be lowered.

The sensitizing dye is preferably a sensitizing dye having an absorption maximum value in at least one of a wavelength region of 500 nm or less and a wavelength region of 700 nm or more.

The sensitizing dye having an absorption maximum in a wavelength region of 500 nm or less is preferably a sensitizing dye having an absorption maximum in a wavelength region of 200 nm to 500 nm, and has an absorption maximum in a wavelength region of 200 nm to 500 nm. Examples of the sensitizing dye include polynuclear aromatics (for example, ruthenium, osmium, and triphenylene) and xanthene (for example, fluorescein, eosin, and erythrosine). , rose red B (rhodamine B), rose bengal (rose bengal), cyanine (such as thiacarbocyanine, oxacarbocyanine), merocyanine (merocyanine) ( For example, flower Cyanotic carbomerocyanine, thiazides (such as thionine, methylene blue, toluidine blue), acridine (such as acridine orange) ), chloroflavin, acriferlavin, phthalocyanine (eg, phthalocyanine, metal phthalocyanine), porphyrin (eg tetraphenylporphyrin, central metal) Substituted porphyrins, chlorophylls (eg, chlorophyll, chlorophyllin, central metal-substituted chlorophyll), metal complexes, terpenoids (eg, ruthenium), squarylium (eg, Squaric acid compound), diphenyl ketones (such as diphenyl ketone), benzotriazoles (such as 1,2,3-benzotriazole), benzimidazoles, benzoquinones, thioxanthene Ketones, naphthoquinones, salicylates, benzoates, stilbenes, biaryl polyenes, ferrocenes, anthraquinones, azobenzenes, coumarins, chlorophylls , phthalocyanines, benzopyrans, carotenes (eg, alpha-carotene, beta-carotene), indigo, diarylamines (eg, diphenylamine), and the like.

For example, a styrene-based dye described in Japanese Patent Publication No. Sho. No. Sho. No. Sho-63-143044, Japanese Patent Publication No. Sho 62-143044 The quinoxaline sulfonium salt described in Japanese Patent Laid-Open Publication No. Sho 59-53104, Japanese Laid-Open Patent Publication No. SHO-64-56767 The benzoxanthene dye described in Japanese Laid-Open Patent Publication No. 2-1714, the acridines described in the Japanese Patent Publication No. Hei 2-226148, and the Japanese Patent Publication No. Hei 2-226149, Japanese Patent Publication No. Sho 40-28499 The pyranthene salt described in the publication, the cyanine type described in Japanese Patent Publication No. Sho 46-42363, Japanese Patent Laid-Open The conjugated ketone dye described in each of the above-mentioned publications of Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. The azobenzene allyl derivative described in Japanese Patent Publication No. Hei 2-30321, and the cyanine dye described in Japanese Patent Laid-Open No. Hei 1-287105, Japanese Patent Laid-Open No. 62-31844, Japan The oxonium-based dye described in each of the Japanese Patent Publication No. Sho 62-143043, and the aminostyryl ketone described in Japanese Patent Publication No. Sho 59-28325, Japanese Patent Publication No. Sho. Japanese Unexamined Patent Application Publication No. Hei No. Hei. No. Hei. No. Hei. The merocyanine dye described in Japanese Patent Laid-Open No. Hei 59-89803, the phthalocyanine dye described in Japanese Patent Laid-Open No. Hei 8-129257, and the benzene described in Japanese Patent Laid-Open No. Hei 8-334897 Pyranose pigment . For example, benzimidazoles, benzoquinones, thioxanthones, naphthoquinones, salicylates, benzoates, stilbenes, biaryl polyenes, ferrocenes can be used. , anthraquinones, azobenzenes, coumarins, chlorophylls, phthalocyanines, benzopyrans, terpenoids, carotenes, indigo, acridines, acridones, thiopurines Pyridones, diarylamines, porphins, merocyanines, and the like. In addition to this, you can also use the "Pigment Handbook (Kodansha Scientific)" and "Dye Notes (Editor of the Organic Synthetic Chemistry Association)".

As a form of the sensitizing dye having an absorption maximum in a wavelength region of 200 nm to 500 nm, it is preferably in a wavelength region of 200 nm to 350 nm. In the sensitizing dye having a maximum absorption, the sensitizing dye having an absorption maximum in a wavelength region of 200 nm to 350 nm is preferably a dye represented by the following formula (I).

(In the formula (I), Ra and Rb each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, and a substituted group. Or an unsubstituted aromatic heterocyclic residue, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, a substituted or unsubstituted amino group, or a halogen atom)

Further, as the sensitizing dye having an absorption maximum in a wavelength region of from 200 nm to 350 nm, a sensitizing dye represented by the following formula (II) or formula (III) can be suitably used.

(In the formula (II), the meanings of Ra and Rb are the same as those of Ra and Rb in the formula (I))

(In the formula (III), Rc, Rd, and Re each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, Or substituted or unsubstituted aromatic heterocyclic residue)

Further, as one form of the sensitizing dye having an absorption maximum value in a wavelength region of 200 nm to 500 nm, a sensitizing dye having an absorption maximum in a wavelength region of 350 nm to 450 nm is preferable, and from the viewpoint of high sensitivity. In other words, the sensitizing dye having an absorption maximum in a wavelength region of 350 nm to 450 nm is preferably a dye represented by the following formula (IX).

In (Formula (IX), A represents an aromatic ring group or heterocyclic substituent, X represents an oxygen atom, a sulfur atom or ^{N- (R 3) .R 1,} R 2 and R ³ are each independently A monovalent non-metal atomic group, A and R ¹ , and R ² and R ³ may be bonded to each other to form an aliphatic or aromatic ring)

The general formula (IX) will be described in more detail. R ¹ , R ² and R ³ are each independently a monovalent non-metal atomic group, preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group. A substituted, unsubstituted or unsubstituted aromatic heterocyclic residue, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, a halogen atom.

Next, A in the general formula (IX) will be described. A represents an aromatic ring group or a heterocyclic group which may have a substituent, and specific examples of the aromatic ring or the hetero ring which may have a substituent include R ¹ , R ² and R ³ in the formula (IX). The specific examples described in the above are the same.

As a specific example of such a sensitizing dye, the compound described in JP-A-2007-58170 [0047] to [0053] can be preferably used.

Further, a sensitizing dye represented by the following general formula (V) to formula (VI) can also be used.

In the formula (V), R ¹ to R ¹⁴ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a cyano group or a halogen atom. Here, at least one of R ¹ to R ¹⁰ represents an alkoxy group having 2 or more carbon atoms.

In the formula (VI), R ¹⁵ to R ³² each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a cyano group or a halogen atom. Here, at least one of R ¹⁵ to R ²⁴ represents an alkoxy group having 2 or more carbon atoms.

As a specific example of such a sensitizing dye, a compound described in European Patent Application Laid-Open No. 13940001 or WO2005/029187 can be preferably used.

Further, as one form of the sensitizing dye having an absorption maximum value in a wavelength region of 200 nm to 500 nm, a sensitizing dye having an absorption maximum in a wavelength region of 450 nm to 500 nm is preferable, and from the viewpoint of high sensitivity. In other words, the sensitizing dye having an absorption maximum in a wavelength region of 450 nm to 500 nm is preferably a dye represented by the following formula (IV).

[Chemistry 16]

(In the general formula (IV), the meanings of Ra and Rb are the same as those of Ra and Rb in the general formula (I))

In addition, Japanese Patent Laid-Open Publication No. 2005-509192, Japanese Patent Laid-Open No. Hei. No. 2007-171406, Japanese Patent Laid-Open No. Hei. No. 2007-206216, Japanese Patent Laid-Open No. 2007-206217, and Japanese Patent No. The sensitizing dye described in JP-A-2007-225702, JP-A-2007-225702, JP-A-2007-316582, and JP-A-2007-328243.

The sensitizing dye having an absorption maximum in a wavelength region of 700 nm or more is typically an infrared absorbing agent, preferably a sensitizing dye having an absorption maximum in a wavelength region of 760 nm to 1500 nm.

The sensitizing dye having an absorption maximum in a wavelength region of 700 nm or more is preferably a dye or a pigment, and from the viewpoint of the effect, a dye is preferred.

As the dye, a commercially available dye and a known dye described in the literature such as "Dye Handbook" (edited by the Society of Organic Synthetic Chemistry, 1970) can be used. Specific examples thereof include an azo dye, a metal mis-salt azo dye, a pyrazolone azo dye, a naphthoquinone dye, an anthraquinone dye, an anthocyanine dye, a carbon anthraquinone dye, a quinone imine dye, and a secondary armor. Dyes such as a base dye, a cyanine dye, a squaraine compound dye, a pyrylium salt, a metal thiolate complex, and the like.

As a preferable dye, for example, a cyanine dye described in Japanese Patent Laid-Open Publication No. SHO-58-125246, Japanese Patent Laid-Open No. Sho 59-84356, and Japanese Patent Laid-Open No. Sho 60-78787, and the like, Japanese Patent No. The methine dye described in Japanese Patent Laid-Open No. Sho 58-181690, Japanese Patent Laid-Open No. Sho 58-194595, and the like, Japanese Patent Laid-Open No. SHO 58-112793, Japanese Patent No. Japanese Laid-Open Patent Publication No. SHO-59-48-187, Japanese Patent Laid-Open No. Sho 59-48187, Japanese Patent Laid-Open No. Sho 59-73996, Japanese Patent Laid-Open No. Sho 60-52940, No. 60-63744, and the like. The naphthoquinone dye is a squaraine dye as described in JP-A-58-112792, and the cyanine dye described in British Patent No. 434,875.

Further, a near-infrared absorption sensitizer described in U.S. Patent No. 5,156,938 may be suitably used, and a substituted arylbenzo(thio)pyranium described in U.S. Patent No. 3,881,924 may also be preferably used. The salt of the present invention is described in Japanese Patent Laid-Open No. Sho 57-142645 (U.S. Patent No. 4,327,169), the entire disclosure of which is incorporated herein by reference. Japanese Patent Laid-Open No. 59-41363, Japanese Patent Laid-Open No. Sho 59-84248, Japanese Patent Laid-Open No. Sho 59-84249, Japanese Patent Laid-Open No. 59-146063, and Japanese Patent Laid-Open No. 59-146061 The pyridinium compound described in Japanese Patent Laid-Open No. 59-216146, the pentamethylthiopyranium salt described in U.S. Patent No. 4,283,475, or the Japanese Patent Special The pyrylium sulfonium compound disclosed in Japanese Patent Laid-Open No. Hei 5-19712. Further, as another preferred example of the dye, the specification of U.S. Patent No. 4,756,993 is incorporated. The near-infrared absorbing dyes described in the formulae (I) and (II).

In addition, as another preferable example of the sensitizing dye having an absorption maximum in the wavelength region of 700 nm or more, Japanese Patent Laid-Open Publication No. 2001-247137 and Japanese Patent Laid-Open No. 2002-278057, which are exemplified below, are exemplified. The specific indolenine cyanine pigment described in the bulletin.

Among these dyes, examples of the dyes which are particularly preferred include cyanine dyes, squaraine compound dyes, pyrylium salts, nickel thiolate complexes, and false phthalocyanine dyes, which are caused by movement of electrons. From the viewpoint of color change and stability, it is preferred to divide It has a 5-membered ring, especially a 5-membered heterocyclic ring containing a nitrogen atom. Furthermore, a cyanine dye or a ruthenium cyanine dye is preferable, and a cyanine dye represented by the following general formula (i) is mentioned as a particularly preferable example.

In the formula (i), X ¹ represents a hydrogen atom, a halogen atom, -NPh ₂ , X ² -L ¹ or a group shown below. Here, X ² represents an oxygen atom, a nitrogen atom or a sulfur atom, and L ¹ represents a hydrocarbon group having 1 to 12 carbon atoms, an aromatic ring containing a hetero atom, and a hydrocarbon group having 1 to 12 carbon atoms containing a hetero atom. . Here, the term "hetero atom" means N, S, O, a halogen atom, and Se.

In the formula shown below, X _a ^- is defined in the same manner as Z _a ^- described later, and R ^a represents a substituent selected from a hydrogen atom, an alkyl group, an aryl group, a substituted or unsubstituted amine group, and a halogen atom. base.

R ¹ and R ² each independently represent a hydrocarbon group having 1 to 12 carbon atoms. In the storage stability of the recording layer coating liquid, R ¹ and R ^{2 are} preferably a hydrocarbon group having two or more carbon atoms, and more preferably, R ¹ and R ² are bonded to each other to form a 5-membered ring or 6-member ring.

Ar ¹ and Ar ² may be the same or different, and each represents an aromatic hydrocarbon group which may have a substituent. As a preferable aromatic hydrocarbon group, a benzene ring and a naphthalene ring are mentioned. In addition, as a preferable substituent, a hydrocarbon group having 12 or less carbon atoms, a halogen atom, an alkoxy group having 12 or less carbon atoms, and preferably a hydrocarbon group having 12 or less carbon atoms and carbon are mentioned. The number of atoms is 12 or less alkoxy groups. Y ¹ and Y ² may be the same or different, and each represents a sulfur atom or a dialkylmethylene group having 12 or less carbon atoms. R ³ and R ⁴ may be the same or different, and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. The preferable substituent is an alkoxy group having 12 or less carbon atoms, a carboxyl group or a sulfo group, and an alkoxy group having 12 or less carbon atoms is preferable. R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different, and each represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. In terms of availability of the raw material, a hydrogen atom is preferred. In addition, Z _a ^- represents a counter anion. However, the cyanine dye represented by the general formula (i) has an anionic substituent in its structure, and when neutralization of charge is not required, Z _a ^{- is} not required. In terms of storage stability of the recording layer coating liquid, preferred Z _a ^- is a halogen ion, a perchloric acid ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonic acid ion, particularly preferably _a perchlorinated ion. Acid ions, tetrafluoroborate ions, hexafluorophosphate ions, and arylsulfonate ions.

Further, from the viewpoint of improving visibility, Z _a ^{- is} preferably a counter anion of an inorganic anion or a strong acid, and from this point of view, PF ₆ ^- , BF ₄ ^- , CF ₃ SO ₃ ^- , C ₄ F ₉ SO ₃ ^-, wherein most preferably PF ₆ ^-.

In the present invention, specific examples of the cyanine dye represented by the general formula (i) which can be suitably used include Paragraph No. [0017] to Paragraph No. [0019] of JP-A-2001-133969. The examples described.

In addition, as a further preferable example, the specific false phthalocyanine dye described in the above-mentioned Japanese Patent Laid-Open Publication No. 2001-247137, and the Japanese Patent Laid-Open Publication No. 2002-278057.

Further, the sensitizing dye having an absorption maximum in a wavelength region of 700 nm or more is preferably a sensitizing dye having an absorption maximum in a wavelength region of 1100 nm or more, and in this case, particularly when ruthenium is used for adhesion. When at least one of the substrate and the member to be processed is supported, the sensitizer can be efficiently irradiated with near-infrared light.

In addition, the sensitizing dye having an absorption maximum in a wavelength region of 700 nm or more is preferably an ammonium salt compound represented by the following formula (2).

[Chemistry 20]

In the formula (2), R each independently represents a hydrogen atom or a lower alkyl group, and X represents an anion.

In addition, the sensitizing dye having an absorption maximum in a wavelength region of 700 nm or more is preferably a diimonium compound represented by the following formula (3).

In the formula (3), R each independently represents a hydrogen atom or a lower alkyl group, X represents an anion, and n represents 1 or 2.

In the general formula (2) and the general formula (3), as the lower alkyl group represented by R, a linear or branched alkyl group having 1 to 10 carbon atoms can be preferably used. As a better low As the alkyl group, a linear lower alkyl group having a carbon number of 1 to 5 such as a methyl group, an ethyl group, a propyl group, a butyl group or a pentyl group, and an isopropyl group, a second butyl group and a third group are preferably used. A branched lower alkyl group such as butyl.

In the general formula (2) and the general formula (3), examples of the anion represented by X include a perchloric acid anion, a benzoic acid anion, a hexafluorophosphate anion, a tetrafluoroborate anion, and a p-toluenesulfonic acid anion. Methanesulfonic acid anion, ethanesulfonic acid anion, benzenesulfonic acid anion, trifluoroacetic acid anion, hexafluoroantimonate anion, trifluoromethanesulfonate anion, molybdate anion, and the like.

The compound of the formula (2) may, for example, be a monoperchlorate of N,N,N',N'-tetrakis(p-dibutylaminophenyl)p-phenylenediamine.

Examples of the compound of the formula (3) include a diperchlorate of N,N,N',N'-tetrakis(p-dibutylaminophenyl)p-benzoquinium diimide.

In the above, the sensitizing dye having a maximum absorption value in a wavelength region of 500 nm or less and the sensitizing dye are sensitizing dyes having an absorption maximum in a wavelength region of 700 nm or more, but the present invention has been described. The sensitizing dye used in the wavelength region of 500 nm or less and the wavelength region of 700 nm or more may have a maximum sensitizing dye. For example, the sensitizing dye may be suitably used. The ammonium salt compound represented by the formula (2) and the diimonium salt compound represented by the above formula (3).

The content of the sensitizing dye in the temporary adhesive of the present invention is preferably from 0.01% by weight to 10% by weight, more preferably from 0.05% by weight to 5% by weight, based on the total solid content of the temporary adhesive. 0.1wt%~1wt%.

(F) surfactant

In the temporary adhesive of the present invention, various surfactants may be added from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an anthrone-based surfactant can be used.

In particular, the temporary adhesive of the present invention further improves liquid characteristics (particularly fluidity) when it is prepared as a coating liquid by containing a fluorine-based surfactant, so that uniformity of coating thickness or liquid-saving property can be further improved. .

In other words, when a film is formed using a coating liquid to which a temporary adhesive containing a fluorine-based surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is lowered, whereby the wettability to the coated surface is obtained. It is improved and the coatability to the coated surface is improved. Therefore, even when a film having a thickness of about several μm is formed with a small amount of liquid, it is effective to obtain a film having a uniform thickness with a small thickness unevenness.

The fluorine content in the fluorine-based surfactant is suitably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, particularly preferably 7% by mass to 25% by mass. The fluorine-containing surfactant is effective in the uniformity of the thickness of the coating film or the liquid-saving property in the range of the fluorine-based surfactant, and the solubility in the temporary adhesive is also good.

Examples of the fluorine-based surfactant include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, and Megafac F479. Megafac F482, Megafac F554, Megafac F780, Megafac F781 (above, Di Ai Manufactured by DIC (share), Fluorad FC430, Fluorad FC431, Fluorad FC171 (above, Sumitomo 3M), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC -104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (Ouno) Law (made by OMNOVA), etc.

Specific examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, Glycerol ethoxylate, etc., polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol Dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, manufactured by BASF Corporation, 904, 150R1), Solsperse20000 (made by Lubrizol (share), etc.).

Specific examples of the cation-based surfactant include phthalocyanine derivative (trade name: EFKA-745, manufactured by Morishita Industry Co., Ltd.), and organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (meth)acrylic (co)polymers Polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like.

Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusho Co., Ltd.).

Examples of the anthrone-based surfactant include Toray. "Toray Silicone DC3PA", "Toray Silicone SH7PA", "Toray Silicone SH11PA", "Toray Silicone SH28PA", "Toray Silicone SH29PA", "Toray Silicone SH30PA", "Toray" manufactured by Dow Corning (share) Silicone SH8400", "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460", "TSF-4452" manufactured by Momentive Performance Materials, Shin-Etsu "KP341", "KF6001", "KF6002" manufactured by Shinetsu Silicon Co., Ltd., "BYK307", "BYK323", "BYK330" manufactured by BYK-Chemie.

The surfactant may be used alone or in combination of two or more.

The amount of the surfactant added is preferably 0.001% by mass to 2.0% by mass, and more preferably 0.005% by mass to 1.0% by mass based on the total solid content of the temporary adhesive.

(G) polymerization inhibitor

In the temporary adhesive of the present invention, in order to prevent unnecessary thermal polymerization of the crosslinkable compound during or during the production of the adhesive support, it is preferred to add a small amount of the thermal polymerization inhibitor.

Examples of the thermal polymerization preventive agent include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, gallic phenol, tert-butylcatechol, benzoquinone, and 4. 4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitro- N-phenylhydroxylamine aluminum salt.

The amount of thermal polymerization inhibitor added is higher than the total solid content of the temporary adhesive Preferably, it is from about 0.01% by mass to about 5% by mass.

Further, the temporary adhesive of the present invention may be formulated with various additives such as a hardener, a hardening catalyst, a decane coupling agent, a filler, a adhesion promoter, an antioxidant, and an ultraviolet absorption, as long as the effects of the present invention are not impaired. Agent, anti-coagulant, etc.

Next, an adhesive support using the temporary adhesive for semiconductor device manufacturing of the present invention described above and a method of manufacturing the semiconductor device will be described.

1A and 1B are schematic cross-sectional views showing a temporary splicing of an adhesive support and a device wafer, and a schematic cross-sectional view showing a state in which a device wafer temporarily surrounded by an adhesive support is thinned.

In the embodiment of the present invention, as shown in FIG. 1A, first, the adhesive support 100 in which the adhesive layer 11 is provided on the carrier substrate 12 is prepared.

The material of the carrier substrate 12 is not particularly limited, and examples thereof include a ruthenium substrate, a glass substrate, a metal substrate, a resin film, and the like, and may be used in view of the fact that the ruthenium substrate used as a representative substrate of a semiconductor device is not easily contaminated. The viewpoint of the electrostatic chuck which is common in the manufacturing steps of the semiconductor device is preferably a germanium substrate.

The thickness of the carrier substrate 12 is, for example, in the range of 50 μm to 5 mm, but is not particularly limited.

The subsequent layer 11 can be formed by using a conventionally known spin coating method, a spray method, a roll coating method, a flow coating method, a knife coating method, a dipping method, or the like, and a temporary adhesive for manufacturing a semiconductor device of the present invention. It is coated on the carrier substrate 12 and then dried.

The thickness of the subsequent layer 11 is, for example, in the range of 1 μm to 500 μm, but is not particularly limited.

Next, the temporary support of the above-described support and the wafer of the device, the thinning of the device wafer, and the detachment of the device wafer from the adhesive support will be described in detail.

As shown in FIG. 1A, the device wafer 60 (processed member) is formed by providing a plurality of device wafers 62 on the surface 61a of the ruthenium substrate 61.

Here, the thickness of the ruthenium substrate 61 is, for example, in the range of 200 μm to 1200 μm.

Further, the surface 61a of the ruthenium substrate 61 is pressed against the adhesive layer 11 of the adhesive support 100. Thereby, the surface 61a of the ruthenium substrate 61 and the adhesive layer 11 are followed, and the adhesive support 100 and the device wafer 60 are temporarily stopped.

Further, it is necessary to heat the adhesive body of the adhesive support 100 and the device wafer 60 as needed in the subsequent view, thereby improving the adhesion. The heating temperature is preferably from 50 ° C to 300 ° C.

Then, the back surface 61b of the ruthenium substrate 61 is subjected to mechanical treatment or chemical treatment, specifically, a thinning treatment such as gliding or chemical mechanical polishing (CMP) is performed, thereby making it as shown in FIG. 1B. The thickness of the ruthenium substrate 61 is reduced (for example, the thickness is changed to 1 μm to 200 μm), and the thin device wafer 60' is obtained.

Further, as the mechanical treatment or the chemical treatment, if necessary, after the thinning treatment, a through hole (not shown) penetrating the substrate from the back surface 61b' of the thin device wafer 60' may be formed, and A tantalum penetration electrode (not shown) is formed in the through hole.

Then, the subsequent layer 11 of the adhesive support 100 is irradiated with actinic rays or radiation or heat induced by the sensitizing dye contained in the adhesive layer 11.

In particular, when the sensitizing dye is a sensitizing dye having an absorption maximum in a wavelength region of 500 nm or less, it is preferred that the actinic ray or radiation or heat applied to the adhesive layer 11 is used as the sensitizing dye. Light having a wavelength of 500 nm or less.

In particular, when the sensitizing dye is a sensitized color having an absorption maximum value in a wavelength region of 700 nm or more, it is preferred that the actinic ray or radiation or heat applied to the adhesive layer 11 is used as the sensitizing dye. Light having a wavelength of 700 nm or more (typically infrared light, preferably near-infrared light). Further, the term "near-infrared light" generally means light having a wavelength of from 700 nm to 2,500 nm.

In particular, when the sensitizing dye is a sensitizing dye (so-called heat sensitizing dye) that induces heat, it is preferred that the actinic ray or radiation or heat applied to the adhesive layer 11 is the sensitizing dye. .

Here, it is preferable that at least one of the carrier substrate 12 in the adhesive support 100 and the thin device wafer 60' as the processed member includes actinic rays or radiation or heat transmitted by the sensitizing dye. s material. In other words, the actinic ray or radiation or heat induced by the sensitizing dye is preferably at least one selected from the carrier substrate 12 in the adhesive support 100 and the thin device wafer 60' as the processed member. Medium passer.

For example, when the treated member contains ruthenium, it is easy to transmit near-infrared light, so it is preferable to use the sensitizing dye as a sensitizing dye that induces near-infrared light, and adopts a near Infrared light is used as the actinic ray or radiation or heat induced by the sensitizing dye.

Further, for example, when the treated member contains glass or polyethylene terephthalate (PET), the materials are easily transmitted through light having a wavelength of 500 nm or less (typically ultraviolet light), and thus it is preferred. The sensitizing dye is a sensitizing dye that induces light having a wavelength of 500 nm or less, and light having a wavelength of 500 nm or less is used as an actinic ray or radiation or heat induced by the sensitizing dye.

According to the above, only the surface of the member including at least one of the carrier substrate 12 and the thin device wafer 60' and containing the actinic ray or the radiation or heat transmitted by the sensitizing dye is irradiated with sensitization. The actinic ray or radiation or heat induced by the dye, whereby the sensitizing dye absorbs actinic rays or radiation or heat to become an excited state, and the self-sensitizing dye provides energy to the reaction initiator, and the reaction initiator is provided. A reaction starting species is produced. As a result, the crosslinking reaction of the crosslinkable compound starts, and the crosslinkable group of the crosslinkable compound decreases, and the adhesion of the adhesive layer 11 can be easily and sufficiently reduced.

Then, the surface 61a of the thin device wafer 60' is detached from the adhesive layer 11 of the adhesive support 100.

The method of detachment is not particularly limited, and it is preferably carried out by attaching a tape such as a dicing tape to the thin device wafer 60' as needed, and making the thin device wafer 60' relative to the adhesive support. 100 slides or strips the thin device wafer 60' from the adhesive support 100. Further, after the adhesive layer 11 is brought into contact with a known alkaline aqueous solution or a release solvent, a tape such as a dicing tape may be attached to the thin film as needed. The device wafer 60' is then detached from the thin device wafer 60'.

As described above, the adhesion of the adhesive layer 11 is sufficiently lowered by the actinic ray or the irradiation of radiation or heat induced by the sensitizing dye, so that the detachment is extremely easy. That is, by using the temporary adhesive of the present invention, the temporary adhesion of the surface 61a of the adhesive layer 11 and the thin device wafer 60' can be easily released.

After the thin device wafer 60' is detached from the adhesive support 100, various known processes are performed on the thin device wafer 60' as needed to manufacture a semiconductor device having the thin device wafer 60'.

The semiconductor device obtained in the above manner can be suitably mounted on a liquid crystal display (LCD) or a solid-state imaging device (for example, a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS). ) etc.). Further, it can be suitably mounted on an image display device such as an electronic paper or an organic electroluminescence (EL).

Next, the previous embodiment will be described.

FIG. 2 is a schematic cross-sectional view for explaining the release of the temporary adhesion state of the previous adhesive support and the device wafer.

In the prior embodiment, as shown in Fig. 2, as the adhesive support, an adhesive support 100' in which the adhesive layer 11' formed by the previous temporary adhesive is provided on the carrier substrate 12 is used. In addition, in the same manner as the procedure described with reference to FIGS. 1A and 1B, the adhesive support 100' and the device wafer are temporarily followed, and then the thinning process of the germanium substrate in the device wafer is performed, and then, Reference Similarly to the procedure described with reference to FIGS. 2A and 2C, the thin device wafer 60' is peeled off from the adhesive support 100'.

However, according to the prior temporary adhesive, it is difficult to temporarily and easily support the member to be processed, and damage to the processed member is not caused, and temporary support for the processed member is easily released. For example, in order to make the temporary adhesion of the device wafer and the carrier substrate sufficiently sufficient, a temporary adhesive having a high adhesiveness in the previous temporary adhesive is used, and the temporary tendency of the device wafer and the carrier substrate is too strong. . Therefore, in order to release the excessively strong temporary end, for example, as shown in FIG. 2, an adhesive tape (for example, a dicing tape) 70 is attached to the back surface 61b' of the thin device wafer 60', and is attached to the adhesive support 100'. When the thin device wafer 60' is peeled off, the bumps 63 are detached from the device wafer 62 on which the bumps 63 are provided, and the device wafer 62 is easily broken.

On the other hand, when the temporary adhesive having low adhesion in the conventional temporary adhesive is used, the temporary adhesion of the device wafer and the carrier substrate is too weak, and the defect that the carrier wafer cannot be reliably supported by the carrier substrate is likely to occur. Happening.

However, the adhesive layer formed by the temporary adhesive of the present invention exhibits sufficient adhesion, and the temporary bonding of the device wafer 60 and the adhesive support 100 can be sensitized to the adhesive layer 11 by the above-described manner. The actinic rays or radiation or the heat induced by the dye is easily released. That is, according to the temporary adhesive of the present invention, the device wafer 60 can be temporarily and reliably supported, and the temporary support for the thin device wafer 60' can be easily released without causing damage to the thin device wafer 60'.

Further, the adhesive layer 11 formed by the temporary adhesive of the present invention It is an adhesive layer which is reduced by irradiation with actinic rays or radiation or heat. In other words, it is a layer having an adhesive layer before the adhesive layer is irradiated with actinic rays or radiation or heat, but is exposed to light. A layer of radiation or a region of radiation or heat that is subsequently lowered or disappears.

Therefore, in the present invention, after the adhesive layer is converted into an adhesive layer in which a low adhesion region and a high adhesion region are formed, the use of the adhesive support of the member to be processed may be temporarily performed. Hereinafter, this embodiment will be described.

3A is a schematic cross-sectional view showing exposure to an adhesive support, and FIG. 3B is a schematic plan view showing a mask.

First, the adhesive layer 11 or the radiation 50 (ie, exposure) is irradiated to the adhesive layer 11 of the adhesive support 100 via the mask 40.

As shown in FIG. 3A and FIG. 3B, the mask 40 includes a light-transmitting region 41 provided in the central region and a light-shielding region 42 provided in the peripheral region.

Therefore, the above exposure exposes the central region of the adhesive layer 11, but does not expose the pattern that exposes the peripheral region surrounding the central region.

4A is a schematic cross-sectional view showing the pattern-exposed adhesive support, and FIG. 4B is a schematic plan view showing the pattern-exposed adhesive support.

As described above, the adhesive layer 11 is an adhesive layer whose adhesion is reduced by irradiation of actinic rays or radiation. Therefore, by performing the above-described pattern exposure, the adhesive support 100 is converted into as shown in FIGS. 4A and 4B. The adhesive support 110 having the adhesive layer 21 has a low adhesion region 21A and a high adhesion region 21B formed in the central region and the peripheral region, respectively.

Here, the "low adhesion region" in the present specification means a region having low adhesion compared to the "high adhesion region", and includes a region having no adhesion (that is, a "non-adhesion region"). Similarly, the "high adhesion region" refers to a region having high adhesion compared to the "low adhesion region".

The adhesive support 110 is exposed by a pattern using the mask 40, and is provided with a low adhesion region 21A and a high adhesion region 21B. The area and shape of each of the light transmission region and the light shielding region in the mask 40 can be Controlled in micron or nanoscale. Therefore, the area and shape of each of the high adhesion region 21B and the low adhesion region 21A formed in the adhesive layer 21 of the adhesive support 110 by pattern exposure can be precisely controlled, so that it is possible to accurately and easily The adhesion as the entire adhesive layer is controlled to the extent that the germanium substrate 61 of the device wafer 60 can be temporarily and reliably supported, and the thin device wafer 60' can be damaged without being damaged. The temporary support for the 矽 substrate of the thin device wafer 60' is released.

In addition, the surface physical properties of the high adhesion region 21B and the low adhesion region 21A in the adhesive support body 110 are different due to pattern exposure, but are integrated as a structure. Therefore, in the high adhesion region 21B and the low adhesion region 21A, there is no large difference in mechanical properties, even if the adhesive layer 21 of the adhesive support 110 and the surface 61a of the germanium substrate 61 of the device wafer 60 are followed, and then The back surface 61b of the ruthenium substrate 61 is subjected to a thinning treatment or a process of forming a ruthenium-through electrode, and corresponds to a region corresponding to the back surface 61b of the high-adhesion region 21B of the adhesive layer 21 and a back surface 61b corresponding to the low-adhesion region 21A. Between the regions, the pressure of the above treatment (for example, grinding pressure or grinding pressure, etc.) is also difficult to produce a difference, and the high adhesion region 21B, The low adhesion region 21A has little influence on the processing accuracy in the above processing. This is particularly effective in the case of obtaining a thin device wafer 60' having a thickness of 1 μm to 200 μm, which is easy to cause the above problems.

Therefore, it is preferable to use the form of the adhesive support 110 as follows: When the above-described processing is performed on the ruthenium substrate 61 of the device wafer 60, the influence on the processing accuracy is suppressed, and the support can be temporarily and reliably supported. The substrate 61, and without damaging the thin device wafer 60', can more easily release temporary support for the thin device wafer 60'.

Further, as described above, the adhesive layer 11 is an adhesive layer whose adhesion is reduced by irradiation with actinic rays or radiation or heat, and thus such an adhesive property can also be irradiated by irradiating actinic rays or radiation or heat. After the layer is converted into an adhesive layer in which the inner surface of the substrate on the substrate side is lowered toward the outer surface, the subsequent support of the member to be processed is temporarily followed. Hereinafter, this embodiment will be described.

Fig. 5 is a schematic cross-sectional view for explaining irradiation of actinic rays or radiation or heat to an adhesive support.

First, the outer surface of the adhesive layer 11 is irradiated with actinic rays or radiation or heat 50', whereby the adhesive support 100 is converted into an inner surface 31b having an adhesion from the substrate side toward the outer surface 31a as shown in FIG. The adhesive support 120 of the descending adhesive layer 31.

That is, the adhesive layer 31 has a low adhesion region 31A on the outer surface 31a side and a high adhesion region 31B on the inner surface 31b side.

Such an adhesive layer 31 can be easily formed by irradiating an amount of actinic ray or radiation or heat 50' as follows: the outer surface 31a is sufficiently irradiated with actinic rays or radiation or heat 50', but The actinic ray or radiation or heat 50' does not reach the inner surface 31b.

Here, the change of the irradiation amount can be easily performed by changing the setting of the exposure machine or the heating device, so that the equipment cost can be suppressed, and the formation of the adhesive layer 21 and the adhesive layer 31 does not require a large amount of time.

Further, in the above-described embodiment of the present invention, the above-described adhesive layer 11 and the above-described irradiation method are combined as a structure, but the adhesion on the outer surface 31a is positively lower than the inner surface 31b. Since the upper adhesive layer 31 is provided, it is not necessary to provide another layer such as a separation layer.

As described above, the above-described adhesive layer 31 is easily formed.

Further, the adhesion on the outer surface 31a and the adhesion on the inner surface 31b can be accurately controlled by the selection of the material constituting the adhesive layer 11, the adjustment of the actinic ray or the irradiation amount of radiation or heat, and the like. control.

As a result, the adhesion between the adhesive layer 31 and the substrate 12 and the ruthenium substrate 61 can be controlled with high precision and easily to the extent that the ruthenium substrate 61 of the device wafer 60 can be reliably and easily supported. Moreover, temporary damage to the 矽 substrate of the thin device wafer 60' can be easily eliminated without causing damage to the thin device wafer 60'.

Therefore, it is preferable to use the form of the adhesive support 120 as follows: when the above-described processing is performed on the ruthenium substrate 61 of the device wafer 60, it is more sure The ruthenium substrate 61 is easily supported temporarily, and the temporary support for the thin device wafer 60' can be more easily removed without causing damage to the thin device wafer 60'.

The method for manufacturing the semiconductor device of the present invention is not limited to the above embodiment, and suitable modifications, improvements, and the like can be made.

For example, the mask used in pattern exposure may be a binary mask or a halftone mask.

Further, the exposure is performed by exposure of a mask through a mask, but it may be selective exposure by drawing using an electron beam or the like.

Further, in the above embodiment, the adhesive layer has a single layer structure, but the adhesive layer may have a multilayer structure. The method of forming the adhesive layer of the multilayer structure includes a method of applying the adhesive composition stepwise by the above-described conventional method before irradiating the actinic ray or radiation; or after irradiating the actinic ray or radiation A method of coating an adhesive composition by the above-described conventionally known method. In the form in which the adhesive layer has a multilayer structure, the adhesion between the layers is reduced by irradiation with actinic rays or radiation or heat, whereby the adhesion as the entire adhesive layer can be reduced.

Further, in the above-described embodiment, the tantalum substrate is exemplified as the member to be processed supported by the adhesive support. However, the present invention is not limited thereto, and may be used for mechanical processing or in a method of manufacturing a semiconductor device. Any treated component that is chemically treated.

For example, a compound semiconductor substrate may be mentioned as the member to be processed, and specific examples of the compound semiconductor substrate include a SiC substrate, a SiGe substrate, and ZnS. A substrate, a ZnSe substrate, a GaAs substrate, an InP substrate, a GaN substrate, or the like.

Further, in the above-described embodiment, the mechanical treatment or the chemical treatment of the tantalum substrate supported by the adhesive support is a thinning treatment of the tantalum substrate and a formation process of the tantalum through electrode, but the invention is not limited thereto. For the processing, for example, any processing required in the method of manufacturing the semiconductor device, such as processing in a three-dimensional laminated package of an integrated circuit or processing in formation of a minute electric mechanical element, may be mentioned.

Further, as long as the cost-effective invention is achieved, the light-transmitting region and the light-shielding region in the mask exemplified in the above embodiment, the high-adhesive region and the low-adhesive region in the adhesive layer, and the device wafer in the device wafer The shape, size, number, arrangement position, and the like are arbitrary and are not limited.

Example

Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited to the following examples as long as the scope of the invention is not exceeded. In addition, "parts" and "%" are quality standards unless otherwise specified.

<Formation of an adhesive support>

Each of the temporary adhesives of Examples 1 to 9 and Comparative Example 1 having the compositions shown in Table 1 below was prepared by a spin coater (Opticoat MS-A100 manufactured by Mikasa, 1200 rpm, 30 seconds). After being coated on a 4 吋Si (矽) wafer having a thickness of 525 μm, it was baked at 100 ° C for 60 seconds to form a tantalum wafer 101 provided with an adhesive layer having a thickness of 10 μm (ie, an adhesive support). ).

The abbreviations described in Table 1 are as follows. Further, the dye I and the dye J are sensitizing dyes having an absorption maximum value in a wavelength region of 500 nm or less and a wavelength region of 700 nm or more.

[Chem. 24]

Polymerization initiator F: tetrabutylammonium = butyl trinaphthyl borate Polymerization initiator G: tetrakis(3,5-bis(trifluoromethyl)phenyl)borate=sodium salt

Pigment I: N, N, N', N'-tetrakis (p-dibutylaminophenyl) p-phenylenediamine ammonium monoperchlorate (absorption maximum wavelength: 400 nm, 1000 nm)

Pigment J: N, N, N', N'-tetrakis (p-dibutylaminophenyl) p-benzoquinone diammonium diperchlorate (absorption maximum wavelength: 330 nm, 1130 nm)

CH: cyclohexanone

EL: ethyl lactate

PGMEA: propylene glycol monomethyl ether acetate

The peelability evaluation of the adhesive support produced as described above was performed by the following method.

(Removability evaluation 1)

The tantalum wafer 101 provided with the adhesive layer prepared in the above manner was cut into a rectangle of 0.5 cm × 2 cm.

The tantalum wafer 102 having no surface coated with any substance was cut into a square of 1 cm × 1 cm. The region from the end portion in the longitudinal direction of the bonding layer of the germanium wafer 101 to 0.5 cm is superimposed on the germanium wafer 102 in such a manner that the center line and the germanium wafer in the longitudinal direction of the bonding layer of the germanium wafer 101 are formed. One side of 102 is formed at a right angle, and the center point of the one side passes, and then the tantalum wafer 101 and the tantalum wafer 102 are pressed at 20 N/cm ² (see a schematic perspective view of the test piece shown in FIG. 6).

Then, using an IR light source (MHAB-100W-IR-100V) manufactured by Molex Co., Ltd., the side of the tantalum wafer 102 of the test piece from which the tantalum wafer 101 and the tantalum wafer 102 are formed is irradiated for 5 minutes. Infrared light (here, the germanium wafer is a material that transmits near-infrared light). Thereafter, the adhesive tape was attached to the rectangular enamel wafer 101, and the adhesive tape was stretched in the vertical direction A while the ruthenium wafer 102 was fixed, and the presence or absence of peeling was confirmed. The results are shown in Table 2 below. The case where peeling is possible is expressed as A, and the case where peeling is impossible is expressed as B.

(Removability evaluation 2)

The tantalum wafer 101 provided with the adhesive layer prepared in the above manner was cut into a rectangle of 0.5 cm × 2 cm.

The glass substrate 103 whose surface was not coated with any substance was cut into a square of 1 cm × 1 cm. A region from the end portion in the longitudinal direction of the adhesive layer of the tantalum wafer 101 to 0.5 cm is superposed on the glass substrate 103 in such a manner that the center line in the longitudinal direction of the adhesive layer of the tantalum wafer 101 and the glass substrate 103 are While forming a right angle and passing the center point of the one side, the wafer 101 and the glass substrate 103 were pressed at 20 N/cm ² (see a schematic perspective view of the test piece shown in FIG. 6).

Then, an ultraviolet (Ultraviolet, UV) exposure apparatus (LC8 manufactured by Hamamatsu Photonics) was used, and the tantalum wafer 101 was bonded from the glass substrate 103 side at an exposure amount of 1000 mJ/cm ² (wavelength: 254 nm). The glass substrate 103 is subsequently irradiated with a test piece (here, the glass substrate 103 is a material that transmits ultraviolet light). Thereafter, the adhesive tape was attached to the rectangular ruthenium wafer 101, and the adhesive tape was stretched in the vertical direction A while the glass substrate 103 was fixed, and the presence or absence of peeling was confirmed. The results are shown in Table 2 below. The case where peeling is possible is expressed as A, and the case where peeling is impossible is expressed as B.

(Removability evaluation 3)

The tantalum wafer 101 provided with the adhesive layer prepared in the above manner was cut into a rectangle of 0.5 cm × 2 cm.

The PET film 104 whose surface was not coated with any substance was cut into a square of 1 cm × 1 cm. A region from the end portion in the longitudinal direction of the adhesive layer of the tantalum wafer 101 to 0.5 cm is superposed on the PET film 104 in such a manner that the center line in the longitudinal direction of the adhesive layer of the tantalum wafer 101 and the PET film 104 are The right angle was formed and passed through the center point of the one side, and then the tantalum wafer 101 and the PET film 104 were pressed at 20 N/cm ² (see a schematic perspective view of the test piece shown in Fig. 6).

Then, using a UV exposure apparatus (LC8 manufactured by Hamamatsu Photonics), a test piece in which the tantalum wafer 101 and the PET film 104 were bonded from the PET film 104 side at an exposure amount of 1000 mJ/cm ² (in terms of wavelength 254 nm) was used. Irradiation is performed (here, the PET film 104 is a material that transmits ultraviolet light). Thereafter, the adhesive tape was attached to the rectangular enamel wafer 101, and the adhesive tape was stretched in the vertical direction A while the PET film 104 was fixed, and the presence or absence of peeling was confirmed. The results are shown in Table 2 below. The case where peeling is possible is expressed as A, and the case where peeling is impossible is expressed as B.

As described above, in Comparative Example 1 in which a temporary adhesive which does not contain a reaction initiator and a sensitizing dye is used, the adhesiveness can be obtained, but the peeling property is not sufficient. In contrast, in the examples, the present embodiment is used. In the temporary adhesive of the present invention, the adhesiveness and the peeling property can be coexisted (the adhesive agent of the embodiment shows sufficient adhesion, and the shearing force when the exposure amount in Table 3 below is 0 mJ/cm ² ).

Therefore, the temporary adhesive of the present invention can surely temporarily support the member to be processed when performing mechanical treatment or chemical treatment on the member to be processed (semiconductor wafer or the like), and can be easily released without causing damage to the processed member. Temporary support for processed components.

<exposure>

An adhesive layer side-to-adhesion layer of the tantalum wafer 101 as an adhesive support formed in the above manner using a UV exposure apparatus (LC8 manufactured by Hamamatsu Photonics) The entire face is exposed. The exposure was carried out by changing the exposure amount as shown in Table 3 below in each of the adhesive supports formed using the temporary adhesives of the examples and the comparative examples.

<Production of test piece>

The exposed enamel wafer 201 of the adhesive layer was cut into a rectangle of 0.5 cm x 2 cm.

The tantalum wafer 202 on which the surface was not coated with any substance was cut into a rectangle of 0.5 cm × 2 cm. The wafer is stacked on the 20N/cm ² by superimposing the region from the end portion in the longitudinal direction of the tantalum wafer 201 to 0.5 cm from the end portion of the tantalum wafer 202 from the end portion in the longitudinal direction to 0.5 cm. 201 and the crucible wafer 202 are pressed (see a schematic cross-sectional view of the test piece shown in FIG. 7).

<Continue force measurement>

The tensile strength of the test piece prepared as described above was subjected to tensile measurement under the conditions of 250 mm/min using a tensile tester (manufactured by IMADA).

The shearing force with respect to "no exposure" can be made good by the exposure amount of 100 mJ/cm ² or 1000 mJ/cm ² by 50% or more (determined as A). Even if the decrease in the shear adhesion force is less than 50% by the exposure amount of 1000 mJ/cm ² , the change is small (determined as B).

The results are shown in Table 3 below.

As can be seen from Table 3, even if any of the temporary adhesives of Examples 1 to 9 was used to form the adhesive layer, the adhesion of the adhesive layer was also reduced. On the other hand, when the temporary adhesive of the comparative example was used, even if it was exposed by exposure, the fall of the adhesiveness of the adhesive layer was inadequate.

Therefore, the adhesive layer of the adhesive support is formed using the temporary adhesive of the present invention, and the adhesive layer is subjected to pattern exposure (that is, the exposed portion and the unexposed portion are provided), whereby the adhesive layer can be disposed in the adhesive layer. Sexual area and low-adhesive area, so as described above, when mechanical treatment or chemical treatment is applied to the member to be treated, the inhibition is performed. The effect of precision is ensured, and the member to be processed can be temporarily and reliably supported, and damage to the processed member can be prevented, and temporary support for the processed member can be more easily released.

Further, as is clear from Table 3, it is possible to obtain a correlation in which the shearing force becomes smaller as the exposure amount is larger. As a result, according to the temporary adhesives of Examples 1 to 9, the adhesion of the outer surface of the adhesive layer and the adhesion of the inner surface can be controlled with high precision by the adjustment of the exposure amount.

Therefore, by forming the adhesive layer of the adhesive support using the temporary adhesive of the present invention and exposing the adhesive layer, it is possible to control the adhesion to a degree that can be accurately and easily controlled as follows: The member is processed and damage to the treated member may be avoided, and temporary support for the processed member is easily released. As a result, as described above, when the member to be processed is subjected to mechanical treatment or chemical treatment, the member to be processed can be temporarily and reliably supported, and damage to the member to be processed can be prevented, and the member to be treated can be more easily released. Temporary support.

[Industrial availability]

According to the present invention, there is provided a temporary adhesive for manufacturing a semiconductor device, and an adhesive support using the same, and a method for manufacturing a semiconductor device, wherein the semiconductor device manufacturing temporary adhesive is used to mechanically process a member (semiconductor wafer or the like) When the treatment or chemical treatment is performed, the member to be processed can be temporarily and reliably supported, and the temporary treatment of the treated member can be easily released without causing damage to the treated member.

Although the invention has been described in detail and with reference to specific embodiments It is apparent to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.

The present application is based on Japanese Patent Application No. 2012-134191, filed on Jun.

11‧‧‧Adhesive layer

12‧‧‧ Carrier substrate

60‧‧‧ device wafer

61‧‧‧矽 substrate

61a‧‧‧ surface

61b‧‧‧Back

62‧‧‧ device wafer

100‧‧‧Adhesive support

Claims (9)

A temporary adhesive for producing a semiconductor device, comprising: (A) a resin, (B) a crosslinkable compound, (C) a solvent, (D) a reaction initiator, and (E) a sensitizing dye. The sensitizing dye for semiconductor device manufacturing according to the first aspect of the invention, wherein the sensitizing dye is a sensitizing dye having an absorption maximum value in at least one of a wavelength region of 500 nm or less and a wavelength region of 700 nm or more. . The temporary adhesive for semiconductor device manufacturing according to the first aspect of the invention, wherein the sensitizing dye is a sensitizing dye having an absorption maximum in a wavelength region of 1100 nm or more. An adhesive support comprising: a substrate, and an adhesive layer formed on the substrate by a temporary adhesive for manufacturing a semiconductor device according to any one of claims 1 to 3. A method of manufacturing a semiconductor device, comprising: a step of: bringing a first surface of a member to be processed and the above-described adhesive layer of the adhesive support according to item 4 of claim 4; a step of obtaining a processed member by performing mechanical treatment or chemical treatment on the second surface different from the first surface; and performing the actinic ray or radiation or heat induced by the sensitizing dye on the adhesive layer of the adhesive support a step of irradiating; and a step of separating the first surface of the processed member from the adhesive layer of the adhesive support, and The above semiconductor device has the above-described processed member. A method of manufacturing a semiconductor device, comprising: pattern-exposed the adhesion layer of the adhesive support according to item 4 of claim 4, thereby providing a high adhesion region and a low adhesion in the adhesive layer a step of bringing the first surface of the member to be processed and the above-mentioned adhesive layer of the adhesive support; and performing mechanical treatment or chemical treatment on the second surface of the member to be treated different from the first surface a step of obtaining a processed member; performing the step of irradiating actinic rays or radiation or heat induced by the sensitizing dye on the adhesive layer of the adhesive support; and forming a first surface of the processed member a step of detaching from the adhesive layer of the adhesive support, and the semiconductor device has the processed member. A method of manufacturing a semiconductor device, comprising: irradiating an actinic ray or radiation or heat to the adhesive layer of the adhesive support according to item 4 of claim 4, wherein the adhesion is from the above-mentioned adhesive layer a step of lowering the inner surface of the substrate side toward the outer surface; a step of advancing the first surface of the member to be processed and the adhesive layer of the adhesive support; and a second difference from the first surface of the member to be processed Performing a mechanical treatment or a chemical treatment to obtain a processed member; a step of irradiating actinic rays or radiation or heat induced by the sensitizing dye on the adhesive layer of the adhesive support; and performing the first surface of the processed member from the adhesive support The step of detaching from the layer, and the above semiconductor device has the above-described processed member. The method for producing a semiconductor device according to any one of the fifth aspect, wherein the at least one of the substrate and the processed member in the adhesive support comprises the sensitizing dye. The actinic ray or the material that is radiated or thermally transmitted. The method for producing a semiconductor device according to any one of the items 5 to 8, wherein the actinic ray or radiation or heat induced by the sensitizing dye is near-infrared light.