TWI640437B - Laminate and application thereof - Google Patents

Abstract

The present invention provides that when a mechanical or chemical treatment is applied to a member to be treated, the member to be treated can be temporarily supported by a high adhesion force without causing damage to the treated member, and the temporary support for the treated member can be easily released. The laminate, the protective layer forming composition, the adhesive layer precursor or the adhesive layer forming composition, and a kit thereof.

The build-up system has (B) an adhesive layer precursor, (C) a protective layer, and (D) device wafer on the (A) support, and the (B) adhesive layer precursor contains (b-1) The polymerizable monomer and/or the polymerizable oligomer, and the polymerization ratio of the polymerizable monomer and/or the polymerizable oligomer is 10 to 70%.

Description

Laminated body and its application

The present invention relates to a laminate, a protective layer forming composition, an adhesive layer precursor or an adhesive layer forming composition, and a kit thereof. More specifically, a laminate for temporarily bonding to an adhesive support using a temporary adhesive for semiconductor device manufacturing, a composition for forming a protective layer, an adhesive layer precursor or a composition for forming an adhesive layer, and The kit comprising the protective layer forming composition and the adhesive layer precursor or the adhesive layer forming composition.

Conventionally, in a semiconductor device such as an IC (integrated circuit) or an LSI (large integrated circuit), a large number of IC chips are usually formed on a semiconductor germanium wafer, and are singulated by dicing.

With the demand for further miniaturization and high performance of electronic devices, IC chips mounted on electronic devices are also required to be smaller and more integrated, but the integrated circuits in the surface direction of the substrate are highly integrated. The chemical system is close to the limit.

A wire bonding method has been widely known as an electrical connection method for an external terminal of an IC chip from an integrated circuit in an IC chip. However, in order to reduce the size of the IC wafer, it has been known in recent years to provide a through hole in the germanium substrate. To insert a metal plug as an external terminal through the through hole A method of connecting to an integrated circuit (a method of forming a through-electrode (TSV)). However, in the method of forming only the tantalum penetration electrode, the above-mentioned IC wafer of recent years cannot sufficiently cope with the demand for further high integration.

In view of the above, it is known to increase the total body area per unit area of the tantalum substrate by multilayering the integrated circuits in the IC wafer. However, since the multilayering of the integrated circuit increases the thickness of the IC wafer, it is necessary to reduce the thickness of the members constituting the IC wafer. In order to reduce the thickness of the ruthenium substrate, for example, it is not only related to the miniaturization of the IC wafer, but also the labor-saving process of the ruthenium substrate in the manufacture of the ruthenium-through electrode is saved. I think there is hope.

A semiconductor wafer used in the process of a semiconductor device is widely known to have a thickness of about 700 to 900 μm. However, in recent years, attempts have been made to reduce the thickness of a semiconductor wafer to 200 μm for the purpose of miniaturization of an IC wafer. So far.

However, a semiconductor germanium wafer having a thickness of 200 μm or less is very thin, and the member for manufacturing a semiconductor device using the substrate as a base material is also very thin, so that further processing is performed on such a member, or only such a member is moved. 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, it is known that the semiconductor wafer and the processing support substrate which are thinned before the device is provided on the surface by the oxygen-adhesive adhesive, and the back surface of the semiconductor wafer is ground and thinned. A technique in which a semiconductor wafer is perforated and a through electrode is provided, and the processing support substrate is detached from the semiconductor wafer (see Patent Document 1) . According to this technique, it is possible to simultaneously achieve heat resistance during the back grinding of the semiconductor wafer, heat resistance in the anisotropic dry etching step, chemical resistance during plating or etching, and final processing support substrate. Smooth peeling and low contamination of the attached body.

Moreover, as a method of supporting a wafer, a method of supporting a wafer by a support layer system is also known, wherein a plasma polymer layer obtained by a plasma deposition method is used as a separation layer between a wafer and a support layer system. The bonding between the support layer system and the separation layer is greater than the bonding between the wafer and the separation layer, and when the self-supporting layer system is detached from the wafer, the wafer is easily separated from the separation layer. Technology (refer to Patent Document 2).

Further, it is known to use a technique in which a polyether oxime and a binder are temporarily used to release the temporary adhesion by heating (see Patent Document 3).

Further, a technique in which a mixture of a carboxylic acid and an amine is temporarily followed by a heating and a temporary release is also known (see Patent Document 4).

Further, it is known that a bonding layer formed of a cellulose polymer or the like is heated, and the wafer of the device and the supporting substrate are pressed together, and then self-supporting by sliding laterally under heating A technique in which a substrate is detached from a device wafer (see Patent Document 5).

Further, an adhesive film comprising a pair of 1,2-polybutadiene and a photopolymerization initiator and having a subsequent change in force by irradiation of radiation is known (see Patent Document 6).

Furthermore, it is known that the substrate and the semiconductor wafer are temporarily supported by an adhesive made of a polycarbonate, and the semiconductor wafer is processed. A technique of irradiating an irradiation line and secondarily removing the processed semiconductor wafer from the support substrate by heating (refer to Patent Document 7).

In addition, it is known that the substrate and the semiconductor wafer are temporarily supported by two layers having different softening points, and after the semiconductor wafer is processed, the substrate and the semiconductor wafer are separated from each other by heating under temperature (see Patent Document 8).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-119427

[Patent Document 2] Japanese Patent Publication No. 2009-528688

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2011-225814

[Patent Document 4] Japanese Patent Publication No. 2011-052142

[Patent Document 5] Japanese Patent Publication No. 2010-506406

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2007-045939

[Patent Document 7] US Patent Publication No. 2011/0318938

[Patent Document 8] US Patent Publication No. 2012/0034437

However, when 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 surrounded by a layer made of an adhesive known from Patent Document 1 or the like, In order to stably support the semiconductor wafer, a certain degree of adhesion is required in the adhesive layer.

Therefore, the device for temporarily stopping the semiconductor wafer via the adhesive layer When the surface is fully integrated with the support, the semiconductor wafer and the support are temporarily more fully supported, and the semiconductor wafer can be supported more stably and without damage, but on the other hand, the semiconductor wafer and the support are temporarily attached. Too strong, when the self-supporting body is detached from the semiconductor wafer, the device is easily damaged or the device is detached from the semiconductor wafer.

Further, as disclosed in Patent Document 2, in order to suppress the subsequent deformation of the wafer and the support layer system, a method of forming a plasma polymer layer as a separation layer by a plasma deposition method between the wafer and the support layer system is performed. There are the following problems: (1) the equipment used for the plasma deposition method is generally expensive; (2) the layer formation by the plasma deposition method is required for vacuuming or stacking of monomers in the plasma apparatus. And (3) providing a separation layer composed of a plasma polymer layer to support the wafer to be processed, although the wafer and the separation layer are subsequently bonded sufficiently, but on the other hand, when the wafer is unsupported It is not easy to control the subsequent bonding in which the wafer is easily detached from the separation layer.

Further, as described in Patent Documents 3, 4, 5, and 8, in the method of releasing the temporary contact by heating, when the semiconductor wafer is detached, the device is likely to be damaged.

Further, as in Patent Documents 6 and 7, in the method of irradiating the irradiation line and releasing the temporary connection, it is necessary to use a support which can penetrate the irradiation line.

Further, in Patent Document 8, when the softening point of the bonding layer on the semiconductor wafer side is larger than the softening point of the bonding layer on the substrate side by 20 ° C or more, the bonding layer on the substrate side after the peeling is transferred to the semiconductor wafer side The bonding layer causes a problem that the detergency of the semiconductor wafer is lowered.

The present invention has been completed in view of the above background, and its purpose is When it is provided for mechanical or chemical treatment of a member to be processed (semiconductor wafer, etc.), the member to be processed can be temporarily supported by a high adhesion force, and even after a vacuum or high temperature process, it is not treated. When the member is damaged, the laminate for the temporary support of the treated member, the protective layer forming composition, the adhesive layer precursor or the adhesive layer forming composition, and the set thereof can be easily released (with high peeling property) .

The present inventors have intensively reviewed in order to solve the above problems, and as a result, found that a laminate having (B) an adhesive layer precursor and (C) a protective layer in order (A) is sequentially used. D) device wafer, the above (B) comprising (b-1) a polymerizable monomer and/or a polymerizable oligomer, and a polymerization ratio of the polymerizable monomer and/or the polymerizable oligomer is 10 to 70% The present invention can be finally completed by temporarily supporting the device wafer and the support by a high adhesion force while easily releasing the temporary support of the device wafer.

Without being bound by any theory, in the laminate of the present invention, a protective layer and an adhesive precursor (polymerizable monomer and/or) are used as a polymer of a polymerizable monomer and/or a polymerizable oligomer. The interface between the polymer of the polymerizable oligomer and the polymerizable monomer and/or the polymerizable oligomer) exhibits an appropriate anchoring effect, and further polymerization is carried out after that, and the elastic modulus of the adhesive layer can be set high. Therefore, the adhesion at the time of thinning the wafer and the peeling property after thinning can coexist.

Based on the above findings, it was found that an adhesive layer having high adhesion and easy peeling can be formed, and the present invention has finally been completed.

Specifically, the above problem is solved by the following means <1> and more by <2> to <23>.

<1> A laminate comprising (B) an adhesive layer precursor, (C) a protective layer, (D) device wafer, and (B) an adhesive layer precursor, in order, on the (A) support. (b-1) A polymerizable monomer and/or a polymerizable oligomer, and a polymerization ratio of a polymerizable monomer and/or a polymerizable oligomer is 10 to 70%.

<2> The layered product according to <1>, wherein the (b-1) polymerizable monomer and/or the polymerizable oligomer contains at least one of three or more functional groups of a radical polymerizable monomer.

<3> The laminate according to <1> or <2>, wherein (b-1) the polymerizable monomer and/or the polymerizable oligomer contains at least one kind of radical having a fluorine atom and/or a ruthenium atom. Polymeric compound.

The layered product according to any one of the above aspects, wherein the (b-1) polymerizable monomer and/or the polymerizable oligomer contains a bifunctional or less radical polymerizable monomer and A trifunctional or higher radical polymerizable monomer.

The laminate according to any one of <1> to <4> wherein the adhesive layer precursor further contains (b-2) a photo radical initiator.

The laminate according to any one of <1> to <4> wherein the adhesive layer precursor further contains (b-3) a thermal radical initiator.

The laminate according to any one of <1> to <6> wherein the adhesive layer precursor further contains (b-4) a polymer compound.

<8> A laminate comprising (B2) an adhesive layer, (C) a protective layer, (D) device wafer, and (B2) an adhesive layer-based adhesive layer precursor on the (A) support. The cured product of the material, the adhesive layer precursor contains (b-1) a polymerizable monomer and/or a polymerizable oligomer, and the polymerization ratio of the polymerizable monomer and/or the polymerizable oligomer is 10 to 70%. .

<9> The laminated body according to any one of <1> to <8>, wherein (C) The softening point of the protective layer is 170 ° C or more and 250 ° C or less.

The laminated body according to any one of <1> to <9> wherein the (C) protective layer is a thermoplastic resin.

The laminate according to any one of <1> to <10> wherein the (C) protective layer comprises a polyether oxime resin, a polyimide resin, a polyester resin, a polybenzimidazole resin, and a poly At least one thermoplastic resin selected from the group consisting of an amidoxime resin, a polycarbonate resin, a polystyrene resin, and a polyetheretherketone resin.

The laminated body according to any one of <1> to <11> wherein the (D) device wafer has a structure having a height of 1 μm or more and 150 μm or less on the surface.

The composition for forming a protective layer for a protective layer of a laminate according to any one of the above aspects, which comprises a resin and a solvent.

<14> The composition for forming a protective layer according to <13>, wherein the softening point of the resin is 170 ° C or more and 250 ° C or less.

<15> A composition layer precursor of the laminate according to any one of <1> to <7> and <9> to <12> or an adhesive layer as described in <8>. The composition used includes a solvent and (b-1) a polymerizable monomer and/or a polymerizable oligomer.

<16> The composition according to <15>, wherein the (b-1) polymerizable monomer and/or the polymerizable oligomer contains at least one of three or more functionalized radical polymerizable monomers.

<17> The composition according to <15> or <16>, wherein (b-1) the polymerizable monomer and/or the polymerizable oligomer contains at least one of having a fluorine atom A radically polymerizable compound of a sub and/or a ruthenium atom.

The composition according to any one of <15>, wherein the (b-1) polymerizable monomer and/or polymerizable oligomer contains a bifunctional or less radical polymerizable monomer and A trifunctional or higher radical polymerizable monomer.

<19> The composition according to any one of <15> to <18> which further contains (b-2) a photo radical initiator.

<20> The composition according to any one of <15> to <18> which further comprises (b-3) a thermal radical initiator.

The composition according to any one of <15> to <20> which further comprises (b-4) a polymer compound.

<22> A kit comprising: a protective layer forming composition containing a resin and a solvent; and an adhesive layer precursor or an adhesive layer containing a solvent and a polymerizable monomer and/or a polymerizable oligomer Use the composition.

<23> The kit for a laminate according to any one of <1> to <12>, wherein the kit according to any one of <1> to <12>.

According to the present invention, it is possible to temporarily support the member to be processed by a high adhesion force while imparting mechanical or chemical treatment to the member to be treated, while not causing damage to the treated member, and the member for the treated member can be easily released. The laminate, the protective layer forming composition, the adhesive layer precursor or the adhesive layer forming composition, and the kit thereof, which are temporarily supported.

11‧‧‧Adhesive layer precursor composition

12‧‧‧Support (carrier substrate)

13‧‧‧Adhesive layer precursor

60‧‧‧ device wafer

60'‧‧‧ Thin device wafer

61'‧‧‧矽 substrate

61a‧‧‧矽 Surface of the substrate

61b‧‧‧矽 on the back of the substrate

61b’‧‧‧The back of the thin device wafer

62‧‧‧ device wafer

63‧‧‧Bumps

71‧‧‧Protective layer

100,100'‧‧‧adhesive support

Fig. 1 (A), Fig. 1 (B), Fig. 1 (C), and Fig. 1 (D) FIG. 1(E) and FIG. 1(F) are schematic cross-sectional views showing the temporary connection of the support and the device wafer, respectively, showing that the device wafer temporarily attached to the support is thinned and the support is peeled off. A schematic cross-sectional view of the state of the body and the device wafer, and the state of the surface of the support and the wafer of the device.

Fig. 2 is a schematic cross-sectional view showing the release of the temporary support state of the adhesive support and the device wafer.

[Formation of the Invention]

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

In the description of the radical (atomic group) of the present specification, the description of the substituent and the unsubstituted is also not included, and the substituent is not included. For example, the "alkyl group" is not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The "active light" or "radiation" in the present specification means, for example, visible light, ultraviolet light, far ultraviolet light, electron light, X-ray, or the like. Further, the term "light" as used in the present invention means active light or radiation.

In addition, the term "exposure" as used in the present specification means not only exposure of far ultraviolet rays, X-rays, EUV lights, etc. represented by mercury lamps, ultraviolet rays, excimer lasers, but also means electron beams. And the drawing of particle lines such as ion beams.

In the present specification, "(meth) acrylate" means acrylate and methacrylate, and "(meth) propylene group" means propylene group. And a methacryl group, "(meth) acryloyl group" means an acryl fluorenyl group and a methacryl fluorenyl group. In addition, in the present specification, "monomer" is synonymous with "monomer". The single system in the present invention is distinguished from the oligomer and the polymer by a compound having a mass average molecular weight of 2,000 or less.

In the embodiments described below, the description of the components and the like, which are described in the drawings, will be simplified or omitted.

Laminate: The laminate of the present invention is characterized by having (B) an adhesive layer precursor, (C) a protective layer, (D) device wafer, and the above (B) adhesive on the (A) support. The layer precursor contains (b-1) a polymerizable monomer and/or a polymerizable oligomer, and the polymerization ratio of the polymerizable monomer and/or the polymerizable oligomer is 10 to 70%.

Further, the laminated body of the present invention is also a laminated body in which the laminated body is more hardened. That is, the (B2) adhesive layer, the (C) protective layer, and the (D) device wafer are sequentially provided on the (A) support, and the (B2) adhesive layer (B) adhesive layer precursor is hardened. Things.

The layered body of the present invention can be used in an environment of 250 ° C or higher and has a high point value.

According to the laminated body of the present invention, when the mechanically or chemically treated member is subjected to mechanical or chemical treatment, the member to be processed can be temporarily supported by a high adhesion force without causing damage to the treated member, and the processed member can be easily released. Temporary support.

The laminate of the present invention is preferably used for the formation of a tantalum through electrode. The formation of the through electrode will be described in detail later.

Hereinafter, each component which can be contained in the laminated body of this invention is demonstrated in detail.

<(B) Adhesive layer precursor>

The laminate of the present invention has (B) an adhesive layer precursor, and the adhesive layer precursor contains (b-1) a polymerizable monomer and/or a polymerizable oligomer, and a polymerizable monomer and/or a polymerizable oligomer The polymerization rate of the polymer is 10 to 70%. Hereinafter, the components contained in the precursor layer of the adhesive layer forming the adhesive layer will be described.

<<Binder layer precursor>>

((b-1) polymerizable monomer and/or polymerizable oligomer)

The (b-1) polymerizable monomer and/or polymerizable oligomer is contained in the adhesive layer precursor.

Any polymerizable monomer can be used, and it can be arbitrarily selected from the radically polymerizable monomer and/or the polymerizable oligomer described below.

From the viewpoint of adhesion and releasability, it is preferred to contain at least one of two or more functional monomers, and more preferably at least one of three or more functional monomers. Further, from the viewpoint of coexistence of appropriate hardness and softness of the adhesive precursor, a mixture of a polymerizable monomer having two or less functional groups and a polymerizable monomer having three or more functional groups is more preferable.

Further, the polymerizable monomer and/or the polymerizable oligomer preferably contains a fluorine atom and/or a ruthenium atom, and more preferably contains at least a fluorine atom. In the present invention, the (b-1) polymerizable monomer and/or the polymerizable oligomer are preferably a polymerizable compound containing 5% by mass or more of a fluorine atom, and more preferably 10% by mass or more. The polymerizable compound which is a fluorine atom is particularly preferably a polymerizable compound containing 20% by mass or more of a fluorine atom.

The polymerization ratio of the polymerizable monomer and/or the polymerizable oligomer in the precursor of the layer is 10 to 70%, preferably 20 to 60%, more preferably 25 to 50%. In this way, by bonding the semi-hardened layer of the adhesive to the device wafer provided with the protective layer, the anchor hardening and the elastic modulus can be appropriately moderated.

The method of adjusting the polymerization rate of the polymerizable monomer and/or the polymerizable oligomer to 10 to 70% includes a composition containing a polymerizable monomer and/or a polymerizable oligomer (adhesive layer). The precursor formation composition) is heated at 50 to 300 ° C, the method of irradiating active light or radiation, and the selection of a polymerization initiator.

The heating temperature in the method of heating the composition for forming the adhesive layer precursor at 50 to 300 ° C is preferably 50 to 300 ° C, more preferably 100 to 200 ° C, and particularly preferably 140 to 170 ° C. The heating time is preferably from 30 seconds to 10 minutes, more preferably from 1 to 7 minutes, and particularly preferably from 2 to 5 minutes.

The method of irradiating the active light or the radiation, for example, by exposing the composition for forming an adhesive layer precursor precursor by using a UV exposure apparatus, polymerizes the polymerizable monomer and/or the polymerizable oligomer. The exposure amount is preferably from 100 to 5,000 mJ/cm ² , more preferably from 300 to 3,000 mJ/cm ² , and particularly preferably from 400 to 1,500 mJ/cm ² .

The polymerization rate of the polymerizable monomer and/or the polymerizable oligomer can be, for example, IR measurement before and after polymerization of the polymerizable monomer and/or polymerizable oligomer, and the reduction of the peak area from 800 to 820 cm ^-1 Rate to determine.

The polymerizable monomer and/or polymerizable oligomer means a compound having a polymerizable group, but as a polymerizable group, a radical polymerization is preferred. Synthetic base. In other words, the polymerizable monomer and/or the polymerizable oligomer are preferably a radical polymerizable monomer and/or a polymerizable oligomer. The number of functional groups of the radical polymerizable monomer and/or the polymerizable oligomer in the present invention means the number of radical polymerizable groups in one molecule. The radical polymerizable group is typically a polymerizable group by irradiation with active light or radiation or by the action of a radical.

Further, the polymerizable single system is a compound different from the polymer compound. The polymerizable monomer is typically a low molecular compound, preferably a low molecular weight compound having a molecular weight of 2,000 or less, more preferably a low molecular weight compound of 1,500 or less, and particularly preferably a low molecular weight compound having a molecular weight of 900 or less. Further, the molecular weight is usually 100 or more. Further, the polymerizable oligomer is typically a relatively low molecular weight polymer, preferably a polymer having 10 to 100 monomers bonded thereto. The polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method is preferably from 2,000 to 20,000, more preferably from 2,000 to 15,000, most preferably from 2,000 to 10,000.

The polymerizable group is preferably a functional group capable of undergoing addition polymerization, and examples of the functional group capable of addition polymerization include an ethylenically unsaturated bonding group. The ethylenically unsaturated bonding group is preferably a styryl group, a (meth)acryl fluorenyl group and an allyl group, and more preferably a (meth) acrylonitrile group. That is, the radical polymerizable monomer used in the present invention is preferably a (meth) acrylate monomer, more preferably an acrylate monomer.

The radical polymerizable monomer may be, for example, any of a chemical form of a monomer, a prepolymer, that is, a dimer, a trimer, an oligomer, or a mixture thereof, and a polymer thereof. By.

More specifically, as an example of a monomer and a prepolymer thereof, An unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or an ester thereof, a guanamine, and the like, preferably no An ester of a saturated carboxylic acid and a polyol compound, and an amide of an unsaturated carboxylic acid and a polyamine compound, and a polymer thereof. Further, an unsaturated carboxylic acid ester or decylamine having a nucleophilic substituent such as a hydroxyl group, an amine group or a fluorenyl group, an addition reaction with a monofunctional or polyfunctional isocyanate or an epoxy group, or a monofunctional or A dehydration condensation reaction product of a polyfunctional carboxylic acid or the like can also be applied. Further, an unsaturated carboxylic acid ester or guanamine having an electrophilic substituent such as an isocyanate group or an epoxy group, or an addition reaction product with a monofunctional or polyfunctional alcohol, an amine or a thiol, Further, a substituted carboxylic acid ester or a decylamine having a detachable substituent such as a halogen group or a tosyloxy group, and a substituted reactant of a monofunctional or polyfunctional alcohol granule, an amine or a thiol are also suitable. Further, as another example, in place of the above unsaturated carboxylic acid, a compound group such as a vinylbenzene derivative such as an unsaturated phosphonic acid or styrene, a vinyl ether or an allyl ether may be used.

Specific examples of the monomer of the polyol compound and the ester of the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3-butylene glycol diacrylate in the acrylate. Tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris(propylene methoxypropyl) ether, trihydroxyl Methyl ethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate Dipentaerythritol hexaacrylate, pentaerythritol IV Acrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tris(propylene oxyethyl) isomeric cyanurate, heterotrimerization Cyanic acid ethylene oxide (EO) modified triacrylate, polyester acrylate oligomer, and the like.

Examples of the methacrylate include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, and trimethylolpropane trimethacrylate. Trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, Pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, double [ P-(3-methacryloxy-2-hydroxypropoxy)phenyl]dimethylmethane, bis-[p-(methacryloxyethoxy)phenyl]dimethylmethane Wait.

As the econic acid ester, there are ethylene glycol dicone ester, propylene glycol diconconate, 1,3-butanediol diconcanate, 1,4-butanediol diconcanate, and four. Methylene glycol diconconate, pentaerythritol diconconate, sorbitol tetraconcanate, and the like.

Examples of the crotonate include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitan dicrotonate.

Examples of the isocrotonate include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

As a maleate, there are ethylene glycol dimaleate, triethyl Diol dimaleate, pentaerythritol dimaleate, sorbitol tetramaleate, and the like.

For example, the aliphatic alcohol-based esters described in Japanese Patent Publication No. Sho 57-196231, and the Japanese Patent Publication No. Sho 57-196231, or JP-A-59-196231, Also applicable to those having an aromatic skeleton described in Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei.

Further, specific examples of the monomer of the polyamine compound and the decylamine of the unsaturated carboxylic acid include methylene bis acrylamide, methylene bis methacrylamide, and 1,6-hexamethylene bis propylene. Indoleamine, 1,6-hexamethylene bismethyl acrylamide, diethylene glycol amine propylene amide, phthaldimethyl bis decyl amide, benzyl dimethyl methacrylamide, and the like.

Examples of other preferred amide-based monomers include those of the cyclohexene structure described in JP-A-54-21726.

In addition, a urethane-based addition polymerizable single system produced by an addition reaction of an isocyanate and a hydroxyl group is also suitable, and as such a specific example, for example, it is described in Japanese Patent Publication No. Sho 48-41708. In the polyisocyanate compound having two or more isocyanate groups per molecule, a hydroxyl group-containing vinyl monomer represented by the following formula (A) is added, and two or more polymerizable vinyl groups are contained in one molecule. A vinyl urethane compound or the like.

CH ₂ =C(R ⁴ )COOCH ₂ CH(R ⁵ )OH (A)

(R, R ⁴ and R ⁵ represent H or CH ₃ ).

In addition, as disclosed in Japanese Patent Laid-Open No. 51-37193, Japan’s special fair The urethane acrylates described in Japanese Patent Publication No. 2-16765, Japanese Patent Publication No. Hei. No. 2-16765, Japanese Patent Publication No. SHO 58-49860, Japanese Patent Publication No. SHO 56-17654, and Japanese Patent Publication No. 62-39417 A urethane compound having an ethylene oxide skeleton described in Japanese Patent Publication No. 62-39418 is also suitable.

Further, as the radical polymerizable monomer, the compound described in Paragraph No. 0095 to Paragraph No. 0108 of JP-A-2009-288705 can also be used in the present invention.

Moreover, as the radical polymerizable monomer, a compound having an ethylenically unsaturated group having at least one addition-polymerizable vinyl group and having a boiling point of 100 ° C or higher at normal pressure is also preferable. Examples thereof include monofunctional acrylates or methacrylic acids such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate. Ester; polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexane diol (meth) acrylate, trimethylolpropane tri (propylene oxy propylene propylene) (meth)acrylic acid, tris(propylene methoxyethyl) isomeric cyanurate, polyfunctional alcohol such as glycerin or trimethylolethane, followed by ethylene oxide or propylene oxide The urethane (meth) acrylates described in each of the publications of Japanese Patent Publication No. Sho 48-41708, Japanese Patent Publication No. Sho 50-6034, and JP-A-53-37193, and Japanese Patent Laid-Open Polyester acrylates, epoxy resins and (described in Japanese Patent Publication No. Sho 49-43191, Japanese Patent Publication No. Sho 52-30490) A polyfunctional acrylate or methacrylate such as an epoxy acrylate such as a reaction product of methyl)acrylic acid and a mixture thereof.

Further, a polyfunctional (meth)acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated group such as glycidyl (meth)acrylate may be mentioned.

In addition, as the other preferable radically polymerizable monomer, an anthracene ring having a bifunctional group as described in JP-A-2010-160418, JP-A-2010-129825, and Japanese Patent No. 4,364,216, etc. The above compound of an ethylenic polymerizable group or a cardo resin.

Further, as another example of the radically polymerizable monomer, a specific unsaturated compound described in JP-A-46-43946, JP-A No. 1-40337, and JP-A No. 1-40336 can be cited. Or a vinylphosphonic acid-based compound described in JP-A No. 2-25493. Further, in some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Further, it can also be referred to as a photocurable monomer and oligomer in Japanese Association of Associations vol. 20, No. 7, 300-308 (1984).

Further, as a compound having a boiling point of 100 ° C or more at normal pressure and having at least one addition-polymerizable ethylenically unsaturated group, it is also suitable in paragraphs 0254 to 0257 of JP-A-2008-292970. The compound described.

In addition to the above, a radical polymerizable monomer represented by the following formula (MO-1) to (MO-5) can also be used. Further, when T is an oxyalkylene group, R is bonded to the terminal of the carbon atom side.

In the above formula, n is an integer from 0 to 14, and m is an integer from 1 to 8. The R and T lines present in a single molecule may be the same or different.

In each of the radical polymerizable monomers represented by the above formulas (MO-1) to (MO-5), at least one of the plural R represents -OC(=O)CH=CH ₂ or - OC(=O)C(CH ₃ )=the group represented by CH ₂ .

Specific examples of the radical polymerizable monomer represented by the above formula (MO-1) to (MO-5) may be used in the present invention in paragraphs 0248 to 0251 of JP-A-2007-269779. The compound described.

Further, it is also possible to carry out the addition of ethylene oxide or propylene oxide to the polyfunctional alcohol described above as a specific example of the general formulae (1) and (2) in JP-A-10-62986 (methyl group). An acrylated compound is used as a radical polymerizable monomer.

Among them, as the radical polymerizable monomer, dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available as KAYARAD D-) are preferred. 320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth) acrylate (city) The product sold is KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., and the structure in which the (meth) acrylonitrile group is separated by ethylene glycol or propylene glycol residues. These oligomer types can also be used.

The radically polymerizable single-system polyfunctional monomer may have an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. Therefore, when the ethylene compound is a mixture as described above, it may be used as long as it has an unreacted carboxyl group, but may be introduced by reacting a hydroxyl group of the above-mentioned ethylenic compound with a non-aromatic carboxylic anhydride, if necessary. Acid base. In this case, specific examples of the non-aromatic carboxylic acid anhydride to be used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and alkylated hexahydrobenzene. Formic anhydride, succinic anhydride, maleic anhydride.

The precursor of the adhesive layer in the present invention may be a monomer having an acid group.

In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and preferably has an unreacted hydroxyl group of the aliphatic polyhydroxy compound reacted with a non-aromatic carboxylic anhydride. An acid group-based polyfunctional monomer, particularly preferably in this ester, the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. As a commercial item, for example, M-510, M-520, etc. are mentioned among the poly acid-modified acrylic oligomer manufactured by the East Asia Synthetic Co., Ltd.

In the present invention, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as a monomer, as needed.

The preferred acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH/g, particularly preferably 5 to 30 mg-KOH/g. When the acid value of the polyfunctional monomer is too low, the development solubility is lowered, and if it is too high, the production or handling becomes difficult, the photopolymerization performance is lowered, and the hardenability such as surface smoothness of the pixel tends to be deteriorated. Therefore, when a polyfunctional monomer of two or more different acid groups is used in combination, or when a polyfunctional monomer having no acid group is used in combination, it is necessary to adjust the acid groups of all the polyfunctional monomers to the above range.

Further, as the radical polymerizable monomer, a polyfunctional monomer having a caprolactone structure is preferable.

The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in its molecule, and for example, trimethylolethane or tris(hydroxymethyl) Polyols such as alkane, trimethylolpropane, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerin, trimethylol melamine, etc. The ε-caprolactone-modified polyfunctional (meth) acrylate obtained by esterification of methyl acrylate and ε-caprolactone. Among them, a polyfunctional monomer having a caprolactone structure represented by the following formula (B) is preferred.

(In the formula, all of the six R groups are groups represented by the following formula (C), or one to five of the six R groups are groups represented by the following formula (C), and the remainder is the following formula (D) shows the base).

(wherein R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and "*" represents a bond).

(wherein R ¹ represents a hydrogen atom or a methyl group, and "*" represents a bond).

Such a polyfunctional monomer having a caprolactone structure is commercially available, for example, from the KAYARAD DPCA series, and is a DPCA-20 (in the above formula (B) to (D), m. =1, the number of the base represented by the general formula (C) = 2, the compound of which R ¹ is a hydrogen atom), DPCA-30 (the same formula, m = 1, the number of the base represented by the general formula (C) = 3, compounds in which R ¹ is a hydrogen atom), DPCA-60 (the same formula, m = 1, the number of groups represented by the formula (C) = 6, and the compound in which R ¹ is a hydrogen atom), DPCA-120 (in the same formula, m = 2, the number of groups represented by the formula (C) = 6, a compound in which R ^{1 is a} hydrogen atom) and the like.

In the present invention, the polyfunctional single system having a caprolactone structure may be used alone or in combination of two or more.

Further, as the polyfunctional monomer, at least one selected from the group consisting of compounds represented by the following formula (i) or (ii) is also preferable.

In the above formulae (i) and (ii), E each independently represents -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)-, y each independently An integer of 0 to 10 is represented, and X each independently represents an acryloyl group, a methacryloyl group, a hydrogen atom or a carboxyl group.

In the above formula (i), the total of (meth)acrylonyl groups is three or four, and m each independently represents an integer of from 0 to 10, and the total of each of m is an integer of from 0 to 40. However, when the total of each m is 0, any one of X is a carboxyl group.

In the above formula (ii), the total of (meth)acrylonyl groups is 5 or 6, and n each independently represents an integer of 0 to 10, and the total of n is an integer of 0 to 60. However, when the total of each n is 0, any one of X is a carboxyl group.

In the above formula (i), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.

Further, the total of each of m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.

In the above formula (ii), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.

Further, the total of n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.

Further, -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)- in the formula (i) or the formula (ii) is preferably an oxygen atom side The end of the bond is in the form of X.

In particular, in the general formula (ii), it is preferred that the six X forms are all acrylonitrile groups.

The compound represented by the above formula (i) or (ii) can be synthesized by a known procedure, and can be combined with ring opening by subjecting ethylene oxide or propylene oxide to a cycloaddition reaction of pentaerythritol or dipentaerythritol. The step of the skeleton is synthesized by, for example, a step of reacting (meth)acrylofluorene chloride with a terminal hydroxyl group of the ring-opening skeleton to introduce a (meth)acrylonitrile group. Each step is a well-known step, and the compound of the formula (i) or (ii) can be easily synthesized by a person skilled in the art.

Among the compounds represented by the above formula (i) or (ii), a pentaerythritol derivative and/or a dipentaerythritol derivative are more preferred.

Specific examples thereof include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as "exemplary compounds (a) to (f)"), and among them, preferred compounds (a) and (b) are exemplified. ), (e), (f).

The commercially available product of the radical polymerizable monomer represented by the formula (i) or (ii) is, for example, SR-494 having a tetrafunctional acrylate having four ethylene oxide chains, which is manufactured by SARTOMER Co., Ltd. A DPCA-60 having 6 pentyloxylate-functional 6-functional acrylates, a TPA-330 having 3 difunctional butyloxy chains, and the like.

Further, the radical polymerizable monomer is also suitably used in, for example, Japanese Patent Publication No. Sho 48-41708, Japanese Patent Laid-Open No. Sho 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765. The urethane acrylates described in the Japanese Patent Publication No. Sho 58-49860, Japanese Patent Publication No. SHO 56-17654, Japanese Patent Publication No. Sho 62-39417, and Japanese Patent Publication No. SHO 62-39418 A urethane compound having an ethylene oxide skeleton. In addition, as the polymerizable monomer, an amine group structure in the molecule can be used as described in JP-A-63-277653, JP-A-63-260909, and JP-A-10-15238. Or an addition polymerizable compound of a thiololine structure.

The commercially available product of the radical polymerizable monomer is urethane oligomer UAS-10, UAB-140 (manufactured by Shanyang Guoce PULP Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA- 40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoei Co., Ltd.), Blemmer PME400 (made by Nippon Oil Co., Ltd.) Wait.

The polymerizable monomer in the present invention may be used alone or in combination of two or more kinds of radically polymerizable monomers and three or more functionally polymerizable monomers, and it is preferred to use two or more kinds in combination. In view of the three-dimensional crosslinked structure, it is preferred to include at least one of three or more functional groups. A mixture of a radical polymerizable monomer and a trifunctional or less radical polymerizable monomer and a trifunctional or higher radical polymerizable monomer.

As the radical polymerizable monomer, it is preferred to have at least one of 1,3-adamantyl dimethanol di(meth)acrylate and trishydroxyl from the viewpoint of easy peelability after a high temperature process at 250 °C. Methylpropane tri(meth)acrylate, isomeric cyanuric acid modified di(meth)acrylate, isomeric cyanuric acid modified tri(meth)acrylate, pentaerythritol Tris(meth)acrylate, pentaerythritol tetra(meth)acrylate, dimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, Tetramethylolmethane tetra(meth)acrylate.

In addition, it is preferable that at least one of the radically polymerizable monomer having at least two functional groups and the radically polymerizable monomer having at least one functional group is contained in one molecule, from the viewpoint of the adhesiveness and the detachability. The number of atoms between the two radical polymerizable groups is 9 atoms or more. In other words, when three or more polymerizable groups are contained in one molecule, it means that the number of atoms between any two polymerizable groups is 9 atoms or more apart.

Examples of the linking group composed of 9 or more atoms connecting any two radical polymerizable groups contained in one molecule include -CO-, -O-, -NH-, and 2 to 4 Preferably, the divalent or higher linking group (generally, the valence corresponding to the number of the functional groups) selected from the group consisting of a valence aliphatic group, a 2 to 6 valent aromatic group, and a combination thereof is preferable. It is a divalent linking group selected from the group consisting of -CO-, -O-, and a divalent aliphatic group and a combination thereof. Here, the aliphatic group and the aromatic group may have a substituent.

The number of atoms between any two radical polymerizable groups contained in one molecule of the radically polymerizable monomer having two or less functional groups and/or one or more functional groups of the radically polymerizable monomer When the number of atoms is too large, the releasability is lowered. Therefore, the divalent linking group is preferably 9 to 100 atoms, more preferably 10 to 80 atoms, and particularly preferably 12 to 50 atoms. The number of atoms between any two radical polymerizable groups contained in one molecule is the number of atoms between the radically polymerizable ethylenically unsaturated groups, and is specifically calculated by the following examples.

At least one of the radically polymerizable monomer having two or less functional groups and the radically polymerizable monomer having three or more functional groups preferably has a polyoxyalkylene partial structure represented by the following formula (1).

(In the formula (1), R ²¹ represents a hydrogen atom or an alkyl group; a represents an integer of 1 to 5; and represents an integer of 2 to 150).

The alkyl group represented by R ²¹ may, for example, be a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group and a t-butyl group. , isoamyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl and the like.

As R ²¹ , a hydrogen atom is particularly preferred.

a is preferably 1 or 2, and particularly preferably 1.

1 is preferably an integer of 2 to 50, more preferably an integer of 2 to 25, and particularly preferably an integer of 2 to 10.

A monomer which is bonded to a linking group having two or more valences of 9 or more atoms in the number of atoms of any two radical polymerizable groups contained in one molecule, preferably a free radical having 2 or less functional groups The polymerizable monomer is more preferably a bifunctional radical polymerizable monomer. Further, it is preferred that the radically polymerizable single system having two or less functional groups has a polyoxyalkylene moiety structure represented by the formula (1), and more preferably a bifunctional radical polymerizable single system having a formula (1) The polyoxyalkylene moiety is shown.

In addition, as the radically polymerizable monomer having two or less functional groups, a bifunctional monomer represented by the following formula (2) is particularly preferable.

(In the formula (2), R ²¹ , R ²² and R ²³ each represent a hydrogen atom or an alkyl group; a represents an integer of 1 to 5; l represents an integer of 2 to 150; X ¹ , X ² , Y ¹ and Y ² each represents a single bond or a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aromatic group, and a combination thereof. .

Examples of the alkyl group represented by R ²¹ , R ²² and R ²³ include a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and each of them may be a methyl group, an ethyl group, a propyl group or an octyl group. Isopropyl, tert-butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl and the like.

R ^{21 is} preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

Each of R ²² and R ^{23 is} particularly preferably a hydrogen atom or a methyl group.

Each of a and l is synonymous with a and l in the formula (1), and the preferred range is also the same.

And X ¹ and X ² each represent a single bond or a group consisting of -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aromatic group, and a combination thereof The two-valent linkage.

Specific examples of X ¹ and X ² include the following L1 to L18. In the following examples, the left side is bonded to Y ¹ or Y ² , and the right side is bonded to an ethylenically unsaturated bond.

L1: -CO-NH-2 valence aliphatic-O-CO-NH-2 valency aliphatic-O-CO-

L2:-CO-NH-2 valency aliphatic group-O-CO-

L3:-CO-2 valency aliphatic group-O-CO-

L4:-CO-O-2 valency aliphatic group-O-CO-

L5: -2 valence aliphatic group - O-CO-

L6:-CO-NH-2 valence aromatic group-O-CO-

L7:-CO-2 valence aromatic group-O-CO-

L8:-2 valence aromatic group-O-CO-

L9:-CO-O-2 valency aliphatic-CO-O-2 valency aliphatic-O-CO-

L10: -CO-O-2 valence of aliphatic group-O-CO-2 valency aliphatic group-O-CO-

L11:-CO-O-2 valence aromatic group-CO-O-2 valency aliphatic group-O-CO-

L12:-CO-O-2 valence aromatic group-O-CO-2 valency aliphatic group-O-CO-

L13:-CO-O-2 valence of aliphatic group-CO-O-2 valence aromatic group-O-CO-

L14:-CO-O-2 valence of aliphatic group-O-CO-2 valence aromatic group-O-CO-

L15:-CO-O-2 valence aromatic group-CO-O-2 valence aromatic group-O-CO-

L16:-CO-O-2 valence aromatic group-O-CO-2 valence aromatic group-O-CO-

L17:-CO-O-2 valence aromatic group-O-CO-NH-2 valency aliphatic group-O-CO-

L18:-CO-O-2 valence of aliphatic group-O-CO-NH-2 valency aliphatic group-O-CO-

Here, the divalent aliphatic group means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group or a polyalkylene group. Among them, an alkyl group, a substituted alkyl group, an alkenyl group and a substituted alkenyl group are preferred, and an alkyl group and a substituted alkyl group are more preferred. These groups preferably have no substituents.

The divalent aliphatic group chain structure is better than the ring structure, and the linear structure is better than the branched chain structure. The number of carbon atoms of the divalent aliphatic group is preferably from 1 to 20, more preferably from 1 to 15, particularly preferably from 1 to 12, particularly preferably from 1 to 10, particularly preferably from 1 to 8, particularly preferably 1~4.

Examples of the substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxyl group, a carboxyl group, an amine group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, and an anthracene group. Alkyl, alkoxycarbonyl, aryloxycarbonyl, decyloxy, monoalkylamino, dialkylamino, arylamino and diarylamine.

Examples of the divalent aromatic group include a phenylene group, a substituted phenyl group, an anthranyl group and a substituted anthranyl group, and a phenyl group is preferred. Examples of the substituent of the divalent aromatic group include an alkyl group in addition to the substituent of the above divalent aliphatic group.

Y ¹ and Y ² each represent a single bond or 2 selected from the group consisting of -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aromatic group, and a combination thereof. Price linkage. Any of Y ¹ and Y ² preferably has a divalent aromatic group or a polyoxyalkylene structure, and particularly preferably has a divalent aromatic group and a polyoxyalkylene structure. The divalent aromatic group is preferably composed of one or two or more benzene rings, more preferably a phenyl group.

In the present invention, the radically polymerizable monomer having at least two functional groups and/or the radically polymerizable monomer having three or more functional groups are preferably selected from only carbon atoms, oxygen atoms, hydrogen atoms and nitrogen atoms. It is composed of atoms, and more preferably consists of only carbon atoms, oxygen atoms, and hydrogen atoms.

The radical polymerizable monomer to which the radical polymerizable group having the most recent radical polymerizable group is bonded by a divalent linking group of at least 9 atoms is specifically a radical polymerizable monomer represented by the following structure, but Limited by these.

(Me stands for methyl).

The ratio (mass ratio) of the radically polymerizable monomer having two or less functional groups to the radically polymerizable monomer having three or more functional groups is preferably 95/5 to 20/80, more preferably 85/15 to 20/80, particularly Good for 80/20~20/80, especially better for 80/20~40/60, especially good for 80/20~50/50.

The commercially available product of a bifunctional or less radical polymerizable monomer and a trifunctional or more radical polymerizable monomer includes Blemmer PME400 (manufactured by Nippon Oil Co., Ltd.) and NK Ester A-BPE-4. NK Ester A-BPE-10, NK Ester A-TMP-3EO, NK Ester AD-TMP, NK Ester A-DPH (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Divinylbenzene (Wako Pure Chemical Industries Co., Ltd.) , Light Acrylate TMP-A (manufactured by Kyoeisha Chemical Co., Ltd.), triallyl cyanurate (manufactured by Tokyo Chemical Industry Co., Ltd.), and the like.

The content of the polymerizable monomer is preferably from 20 to 100% by mass, more preferably from 30 to 95% by mass, based on the total adhesive strength of the adhesive layer precursor from the viewpoint of good adhesion strength and peelability. , Especially good is 50~90% by mass. The polymerizable single system may be only one type or two or more types. When the number of the polymerizable monomers is two or more, the total amount is preferably in the above range.

[Polymerizable monomer and/or polymerizable oligomer having a fluorine atom or a halogen atom]

The polymerizable monomer and/or polymerizable oligomer in the present invention is particularly preferably a polymerizable compound having a fluorine atom and/or a ruthenium atom. The polymerizable compound having a fluorine atom and/or a ruthenium atom is preferably a radical polymerizable monomer and/or a polymerizable oligomer containing one or more fluorine atoms or ruthenium atoms in one molecule, and particularly preferably one molecule. A polymerizable monomer and/or a polymerizable oligomer having two or more fluorine atoms and having a group generally referred to as a perfluoro group.

The radically polymerizable compound having a fluorine atom and/or a ruthenium atom is a radical polymerizable functional group, and the radical polymerizable functional group is not particularly limited, but is preferably an unsaturated group (ethylenically unsaturated bond). Knot base, etc.).

The radically polymerizable compound having a fluorine atom and/or a ruthenium atom preferably has two or more radical polymerizable functional groups, whereby the temporary treatment of the processed member after the high temperature process of the laminate can be further improved. The peeling of the support.

[[Polymerizable monomer and/or polymerizable oligomer having a fluorine atom]]

The polymerizable monomer having a fluorine atom and/or the polymerizable oligomer may be selected from well-known monomers, and a crosslinking agent having a polymerizable group as a crosslinkable group is preferred. Examples of the crosslinkable group include a decyl group having a hydroxyl group or a hydrolyzable group (for example, an alkoxyalkyl group, a decyloxyalkyl group, etc.), and a group having a reactive unsaturated double bond ((meth)) Acrylhydrazine, allyl, vinyloxy, etc.), ring-opening polymerization reactive group (epoxy group, oxetane group, An azole group or the like, a group having an active hydrogen atom (for example, a hydroxyl group, a carboxyl group, an amine group, an amine methyl sulfonyl group, a decyl group, a β-ketoester group, a hydrodecyl group, a decyl alcohol group, etc.), an acid anhydride, a nucleophilic agent a substituted group (active halogen atom, sulfonate, etc.) or the like.

The radically polymerizable monomer having a fluorine atom and/or the polymerizable oligomer is preferably a compound represented by the following formula (1).

General formula (I): Rf{-LY}n (wherein Rf contains at least a carbon atom and a fluorine atom, and may contain either an oxygen atom or a hydrogen atom, and represents a chain or cyclic n-valent group, n An integer of 2 or more; L represents a single bond or a divalent linking group; and Y represents a polymerizable group).

In the above formula (I), the Y-based polymerizable group is, for example, a decyl group having a hydroxyl group or a hydrolyzable group (e.g., an alkoxyalkyl group, a decyloxyalkyl group, etc.), and a group having a reactive unsaturated double bond. ((meth)acryloyl group, allyl group, vinyloxy group, etc.), ring-opening polymerization reactive group (epoxy group, oxetane group, An azole group or the like, a group having an active hydrogen atom (for example, a hydroxyl group, a carboxyl group, an amine group, an amine methyl sulfonyl group, a decyl group, a β-ketoester group, a hydrodecyl group, a decyl alcohol group, etc.), an acid anhydride, a nucleophilic agent a substituted group (active halogen atom, sulfonate, etc.) or the like.

Y preferably represents a radical polymerizable group, and more preferably a group having a reactive unsaturated double bond. Specifically, T preferably represents a radical polymerizable functional group represented by the following formula (9).

(In the formula (9), R ⁹⁰¹ to R ⁹⁰³ each independently represent a hydrogen atom, an alkyl group or an aryl group; and a broken line indicates a bond to a group to which L is bonded).

The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a tert-butyl group, an isopentyl group, and a 2-ethylhexyl group. , 2-methylhexyl, cyclopentyl and the like. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. As R ⁹⁰¹ to R ⁹⁰³ , a hydrogen atom or a methyl group is particularly preferable.

L represents a single bond or a divalent linking group. The divalent linking group represents a divalent aliphatic group, a divalent aromatic group, -O-, -S-, -CO-, -N(R)-, and two or more of these are combined. Price linkage. However, the above R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

When L has an alkylene group or an extended aryl group, the alkyl group and the aryl group are preferably substituted by a halogen atom, more preferably by a fluorine atom.

Rf contains at least a carbon atom and a fluorine atom, and may contain either an oxygen atom or a hydrogen atom, and represents a chain or a cyclic n-valent group. Rf may also be a linear or branched polymer structure having a repeating unit having a fluorine atom.

As the monomer having a fluorine atom as described above, the compound described in Paragraph No. 0019 to 0033 of JP-A-2011-48358 is preferably used, and the contents are incorporated in the specification.

Further, the radical polymerizable monomer having a fluorine atom is preferably a compound represented by the following structural formulas (1), (2), (3), (4) and (5). Choose at least one of them.

CH ₂ =CR ¹ COOR ² R ^f . . . Structural formula (1)

In (formula ^(1), R 1 represents a hydrogen atom or a methyl group; R ² represents _{-C p H 2p -, - C} (C p H 2p + 1) H -, - CH 2 C (C p H 2p + ₁ ) H- or -CH ₂ CH ₂ O-; R ^f represents -C _n F _2n+1 , -(CF ₂ ) _n H, -C _n F _2n+1 -CF ₃ , -(CF ₂ ) _p OC _n H _2n C _i F _2i+1 , -(CF ₂ ) _p OC _m H _2m C _i F _2i H, -N(C _p H _2p+1 )COC _n F _2n+1 or -N(C _p H _{2p +1} )SO ₂ C _n F _2n+1 ; However, p represents an integer from 1 to 10, n represents an integer from 1 to 16, m represents an integer from 0 to 10, and i represents an integer from 0 to 16.

CF ₂ =CFOR ^g . . . Structural formula (2)

(In the structural formula (2), R ^g represents a fluoroalkyl group having 1 to 20 carbon atoms).

CH ₂ =CHR ^g . . . Structural formula (3)

(In the structural formula (3), R ^g represents a fluoroalkyl group having 1 to 20 carbon atoms).

CH ₂ =CR ³ COOR ⁵ R ^j R ⁶ OCOCR ⁴ =CH ₂ . . . Structural formula (4)

(In Structural Formula (4), R ³ and R ⁴ represent a hydrogen atom or a methyl group; and R ⁵ and R ⁶ represent -C _q H _2q -, -C(C _q H _2q+1 )H-, -CH ₂ C (C _q H _2q+1 )H- or -CH ₂ CH ₂ O-, R ^j represents -C _t F _2t ; q is an integer from 1 to 10, and t is an integer from 1 to 16).

CH ₂ =CHR ⁷ COOCH ₂ (CH ₂ R ^k )CHOCOCR ⁸ =CH ₂ . . . Structural formula (5)

(In Structural Formula (5), R ⁷ and R ⁸ represent a hydrogen atom or a methyl group; R ^k is -CyF _2y+1 ; y is an integer of 1 to 16).

Examples of the monomer represented by the above structural formula (1) include CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ OCOCH=CH ₂ , CF ₃ CH ₂ OCOCH=CH ₂ , and CF ₃ (CF ₂ ) _{4 .} CH ₂ CH ₂ OCOC(CH ₃ )=CH ₂ , C ₇ F ₁₅ CON(C ₂ H ₅ )CH ₂ OCOC(CH ₃ )=CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N(CH ₂ )CH ₂ CH ₂ OCOCH=CH ₂ , CF ₂ (CF ₂ ) ₇ SO ₂ N(C ₃ H ₇ )CH ₂ CH ₂ OCOCH=CH ₂ , C ₂ F ₅ SO ₂ N(C ₃ H ₇ )CH ₂ CH ₂ OCOC(CH ₃ )=CH ₂ , (CF ₃ ) ₂ CF(CF ₂ ) ₆ (CH ₂ ) ₃ OCOCH=CH ₂ , (CF ₃ ) ₂ CF(CF ₂ ) ₁₀ (CH ₂ ) ₃ OCOC (CH ₃ )=CH ₂ , CF ₃ (CF ₂ ) ₄ CH(CH ₃ )OCOC(CH ₃ )=CH ₂ , CF ₃ CH ₂ OCH ₂ CH ₂ OCOCH=CH ₂ , C ₂ F ₅ (CH ₂ CH ₂ O) ₂ CH ₂ OCOCH=CH ₂ , (CF ₃ ) ₂ CFO(CH ₂ ) ₅ OCOCH=CH ₂ , CF ₃ (CF ₂ ) ₄ OCH ₂ CH ₂ OCOC(CH ₃ )=CH ₂ , C ₂ F ₅ CON( C ₂ H ₅ )CH ₂ OCOCH=CH ₂ , CF ₃ (CF ₂ ) ₂ CON(CH ₃ )CH(CH ₃ )CH ₂ OCOCH=CH ₂ , H(CF ₂ ) ₆ C(C ₂ H ₅ )OCOC (CH ₃ )=CH ₂ ,H(CF ₂ ) ₈ CH ₂ OCOCH=CH ₂ , H(CF ₂ ) ₄ CH ₂ OCOCH=CH ₂ , H(CF ₂ )CH ₂ OCOC(CH ₃ )=CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N(CH ₃ )CH ₂ CH ₂ OCOC(CH ₃ )=CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N(CH ₃ )(CH _{2 10} OCOCH=CH ₂ , C ₂ F ₅ SO ₂ N(C ₂ H ₅ )CH ₂ CH ₂ OCOC(CH ₃ )=CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N(CH ₃ )(CH _{2 4} OCOCH=CH ₂ , C ₂ F ₅ SO ₂ N(C ₂ H ₅ )C(C ₂ H ₅ )HCH ₂ OCOCH=CH ₂ and the like. These may be used alone or in combination of two or more.

Examples of the fluoroalkylated olefin represented by the above structural formula (2) or (3) include C ₃ F ₇ CH=CH ₂ , C ₄ F ₉ CH=CH ₂ , and C ₁₀ F ₂₁ CH=CH _{2 .} C ₃ F ₇ OCF=CF ₂ , C ₇ F ₁₅ OCF=CF ₂ , C ₈ F ₁₇ OCF=CF ₂ and the like.

As the monomer of formula (4) or (5) of, for example, include _{CH 2 = CHCOOCH 2 (CF 2} ) 3 CH 2 OCOCH = CH 2, CH 2 = CHCOOCH 2 (CF 2) 6 CH 2 OCOCH=CH ₂ , CH ₂ =CHCOOCH ₂ CH(CH ₂ C ₈ F ₁₇ )OCOCH=CH ₂ and the like.

Further, as the radical polymerizable monomer having a fluorine atom and/or the polymerizable oligomer, an oligomer having a repeating unit having a fluorine atom and a repeating unit having a radical polymerizable functional group is preferably used.

The repeating unit having a fluorine atom is preferably selected from at least one of the repeating units represented by the following formulas (6), (7) and (10).

In the formula (6), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group or a monovalent organic group, and at least one of R ¹ , R ² , R ³ and R ⁴ . It is a fluorine atom or a monovalent organic group having a fluorine atom.

In the formula (7), R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group or a monovalent organic group, and Y ¹ represents a single bond or by -CO-, -O-, -NH- A divalent linking group selected from the group consisting of a divalent aliphatic group, a divalent aromatic group, and a combination thereof. Rf represents a fluorine atom or a monovalent organic group having a fluorine atom.

In the formula (10), R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group or a monovalent organic group, and Y ² and Y ³ represent a single bond or a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aromatic group, and a combination thereof. Rf represents a divalent organic group having a fluorine atom.

The monovalent organic group having a fluorine atom in the formulae (6) and (7) is not particularly limited, but is preferably a fluorine-containing alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. Particularly preferred is a fluorine-containing alkyl group having 1 to 15 carbon atoms. The fluorine-containing alkyl group may be linear (for example, -CF ₂ CF ₃ , -CH ₂ (CF ₂ ) ₄ H, -CH ₂ (CF ₂ ) ₈ CF ₃ , -CH ₂ CH ₂ (CF ₂ ) ₄ H And so on, may also have a branched structure (for example, -CH(CF ₃ ) ₂ , -CH ₂ CF(CF ₃ ) ₂ , -CH(CH ₃ )CF ₂ CF ₃ , -CH(CH ₃ )(CF ₂ ) ₅ CF ₂ H, etc.), and may also have an alicyclic structure (preferably a 5-membered ring or a 6-membered ring, such as a perfluorocyclohexyl group, a perfluorocyclopentyl group or an alkyl group substituted therewith), or Has an ether linkage (eg, -CH ₂ OCH ₂ CF ₂ CF ₃ , -CH ₂ CH ₂ OCH ₂ C ₄ F ₈ H, -CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F ₁₇ , -CH ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ H, etc.). Further, it may be a perfluoroalkyl group.

The divalent organic group having a fluorine atom in the formula (10) is not particularly limited, but is preferably a fluorine-containing alkylene group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably A fluorine-containing alkyl group having 1 to 15 carbon atoms. The fluorine-containing alkyl group may be linear (for example, -CF ₂ CF ₂ -, -CH ₂ (CF ₂ ) ₄ -, -CH ₂ (CF ₂ ) ₈ CF ₂ -, -CH ₂ CH ₂ (CF _{2 4} -etc), may also have a branched structure (eg -CH(CF ₃ )CF ₂ -, -CH ₂ CF(CF ₃ )CF ₂ -, -CH(CH ₃ )CF ₂ CF ₂ -, -CH( CH ₃ )(CF ₂ ) ₅ CF ₂ -etc.), and may also have an alicyclic structure (preferably a 5-membered ring or a 6-membered ring, such as perfluorocyclohexyl, perfluorocyclopentyl or such The linking group of the substituted alkyl group or the like may also have an ether bond (for example, -CH ₂ OCH ₂ CF ₂ CF ₂ -, -CH ₂ CH ₂ OCH ₂ C ₄ F ₈ -, -CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F ₁₆ -, -CH ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ -, -CH ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ -, polyperfluoroalkylene ether chain, etc.). Further, it may be a perfluoroalkylene group.

The monovalent organic group in the formulae (6), (7), and (10) is preferably an organic group composed of a non-metal atom having 3 to 10 valences, and examples thereof include 1 to 60 carbon atoms. 0 to 10 nitrogen atoms, 0 to 50 oxygen An organic group composed of at least one element selected from the group consisting of an atom, one to 100 hydrogen atoms, and 0 to 20 sulfur atoms.

More specifically, an organic group which is constituted by a combination of the following structures, alone or in combination, may be mentioned.

The monovalent organic group may further have a substituent. Examples of the substituent which may be introduced include a halogen atom, a hydroxyl group, a carboxyl group, a sulfonate group, a nitro group, a cyano group, a decylamino group, an amine group, an alkyl group, and an alkene group. Alkyl, alkynyl, aryl, substituted oxy, substituted sulfonyl, substituted carbonyl, substituted sulfinyl, sulfo, phosphonium, phosphonate, decyl, heterocyclic, and the like. Further, the organic group may further contain an ether bond, an ether bond, or a urea bond.

The monovalent organic group is preferably an alkyl group, an alkenyl group, an alkynyl group or an aryl group. The alkyl group is more preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a tert-butyl group, an isopentyl group, a 2-ethylhexyl group, and 2 - Methylhexyl, cyclopentyl and the like. The alkenyl group and the alkenyl group having 2 to 20 carbon atoms are preferable, and examples thereof include a vinyl group, an allyl group, a prenyl group, a geranyl group, and an oil group. The alkynyl group is preferably an alkynyl group having 3 to 10 carbon atoms, an ethynyl group, a propargyl group, a trimethyldecyl ethynyl group or the like. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. Further, the heterocyclic group is preferably a heterocyclic group having 2 to 10 carbon atoms, and examples thereof include a furyl group, a phenylthio group, and a pyridyl group.

R ¹ , R ² , R ³ and R ⁴ in the formula (6), R ⁵ , R ⁶ and R ⁷ in the formula (7), R ⁸ , R ⁹ , R ¹⁰ and R in the formula (10) ^{11. The} monovalent organic group represented by R ¹² and R ^{13 is} preferably an alkyl group or an aryl group.

The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a tert-butyl group, an isopentyl group, and a 2-ethylhexyl group. , 2-methylhexyl, cyclopentyl and the like. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. As R ⁹⁰¹ to R ⁹⁰³ , a hydrogen atom or a methyl group is particularly preferable.

Hereinafter, -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aromatic group represented by Y ¹ in the formula (7) and Y ² and Y ³ in the formula (10), Specific examples of the divalent linking group selected from the group consisting of a group and a combination thereof. Further, in the following examples, the left side is bonded to the main chain, and the right side is bonded to Rf.

L1: -CO-NH-2 valence aliphatic-O-CO-NH-2 valency aliphatic-O-CO-

L2:-CO-NH-2 valency aliphatic group-O-CO-

L3:-CO-2 valency aliphatic group-O-CO-

L4:-CO-O-2 valency aliphatic group-O-CO-

L5: -2 valence aliphatic group - O-CO-

L6:-CO-NH-2 valence aromatic group-O-CO-

L7:-CO-2 valence aromatic group-O-CO-

L8:-2 valence aromatic group-O-CO-

L9:-CO-O-2 valency aliphatic-CO-O-2 valency aliphatic-O-CO-

L10: -CO-O-2 valence of aliphatic group-O-CO-2 valency aliphatic group-O-CO-

L11:-CO-O-2 valence aromatic group-CO-O-2 valency aliphatic group-O-CO-

L12:-CO-O-2 valence aromatic group-O-CO-2 valency aliphatic group-O-CO-

L13:-CO-O-2 valence of aliphatic group-CO-O-2 valence aromatic group-O-CO-

L14:-CO-O-2 valence of aliphatic group-O-CO-2 valence aromatic group-O-CO-

L15:-CO-O-2 valence aromatic group-CO-O-2 valence aromatic group-O-CO-

L16:-CO-O-2 valence aromatic group-O-CO-2 valence aromatic group-O-CO-

L17:-CO-O-2 valence aromatic group-O-CO-NH-2 valency aliphatic group-O-CO-

L18:-CO-O-2 valence of aliphatic group-O-CO-NH-2 valency aliphatic group-O-CO-

L19: a 2-valent aromatic 2-valent aliphatic group

L20: a 2-valent aromatic 2-valent aliphatic group-O-2 valent aliphatic group -

L21: a 2-valent aromatic 2-valent aliphatic group-O-2 valent aliphatic group-O-

L22: -CO-O-2 valency aliphatic group -

L23:-CO-O-2 valency aliphatic group-O-

Here, the divalent aliphatic group means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group or a polyalkylene group. Among them, an alkyl group, a substituted alkyl group, an alkenyl group and a substituted alkenyl group are preferred, and an alkyl group and a substituted alkyl group are more preferred.

The divalent aliphatic group chain structure is better than the ring structure, and the linear structure is better than the branched chain structure. Divalent aliphatic group The number of carbon atoms is preferably from 1 to 20, more preferably from 1 to 15, particularly preferably from 1 to 12, particularly preferably from 1 to 10, more preferably from 1 to 8, and particularly preferably from 1 to 4.

Examples of the substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxyl group, a carboxyl group, an amine group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, and an anthracene group. Alkyl, alkoxycarbonyl, aryloxycarbonyl, decyloxy, monoalkylamino, dialkylamino, arylamino and diarylamine.

Examples of the divalent aromatic group include a phenylene group, a substituted phenyl group, an anthranyl group and a substituted anthranyl group, and a phenyl group is preferred. Examples of the substituent of the divalent aromatic group include an alkyl group in addition to the substituent of the above divalent aliphatic group.

The content of the repeating unit having a fluorine atom is preferably from 2 mol% to 98 mol%, more preferably from 10 mol% to 90 mol%, based on all the repeating units of the radical polymerizable oligomer having a fluorine atom. ear%.

The repeating unit having a radical polymerizable functional group is preferably a repeating unit represented by the following formula (8).

(In the formula (8), R ⁸⁰¹ to R ⁸⁰³ each independently represent a hydrogen atom, an alkyl group or a halogen atom; Y ⁸ represents a single bond or a -CO-, -O-, -NH-, divalent aliphatic group a divalent linking group selected from the group consisting of a divalent aromatic group and a combination thereof; T represents a structure having a radical polymerizable functional group).

The alkyl group of R ⁸⁰¹ to R ⁸⁰³ is preferably an alkyl group having 1 to 6 carbon atoms.

T preferably represents a radical polymerizable functional group represented by the formula (9).

(In the formula (9), R ⁹⁰¹ to R ⁹⁰³ each independently represent a hydrogen atom, an alkyl group or an aryl group; and a broken line indicates a bond to a group bonded to Y ⁸ ).

The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a tert-butyl group, an isopentyl group, and a 2-ethylhexyl group. , 2-methylhexyl, cyclopentyl and the like. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. As R ⁹⁰¹ to R ⁹⁰³ , a hydrogen atom or a methyl group is particularly preferable.

Y ⁸ represents a single bond or a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aromatic group, and a combination thereof. Specific examples of the Y ⁸ formed by the combination will be described below. Further, in the following examples, the left side is bonded to the main chain, and the right side is bonded to the formula (9).

L1: -CO-NH-2 valence aliphatic-O-CO-NH-2 valency aliphatic-O-CO-

L2:-CO-NH-2 valency aliphatic group-O-CO-

L3:-CO-2 valency aliphatic group-O-CO-

L4:-CO-O-2 valency aliphatic group-O-CO-

L5: -2 valence aliphatic group - O-CO-

L6:-CO-NH-2 valence aromatic group-O-CO-

L7:-CO-2 valence aromatic group-O-CO-

L8:-2 valence aromatic group-O-CO-

L9:-CO-O-2 valency aliphatic-CO-O-2 valency aliphatic-O-CO-

L10: -CO-O-2 valence of aliphatic group-O-CO-2 valency aliphatic group-O-CO-

L11:-CO-O-2 valence aromatic group-CO-O-2 valency aliphatic group-O-CO-

L12:-CO-O-2 valence aromatic group-O-CO-2 valency aliphatic group-O-CO-

L13:-CO-O-2 valence of aliphatic group-CO-O-2 valence aromatic group-O-CO-

L14:-CO-O-2 valence of aliphatic group-O-CO-2 valence aromatic group-O-CO-

L15:-CO-O-2 valence aromatic group-CO-O-2 valence aromatic group-O-CO-

L16:-CO-O-2 valence aromatic group-O-CO-2 valence aromatic group-O-CO-

L17:-CO-O-2 valence aromatic group-O-CO-NH-2 valency aliphatic group-O-CO-

L18:-CO-O-2 valence of aliphatic group-O-CO-NH-2 valency aliphatic group-O-CO-

Here, the divalent aliphatic group means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group or a polyalkylene group. Among them, an alkyl group, a substituted alkyl group, an alkenyl group and a substituted alkenyl group are preferred, and an alkyl group and a substituted alkyl group are more preferred.

The divalent aliphatic group chain structure is better than the ring structure, and the linear structure is better than the branched chain structure. The number of carbon atoms of the divalent aliphatic group is preferably from 1 to 20, more preferably from 1 to 15, particularly preferably from 1 to 12, particularly preferably from 1 to 10, particularly preferably from 1 to 8, particularly preferably 1~4.

Examples of the substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxyl group, a carboxyl group, an amine group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, and an anthracene group. Alkyl, alkoxycarbonyl, aryloxycarbonyl, decyloxy, monoalkylamino, dialkylamino, arylamino and diarylamine.

Examples of the divalent aromatic group include a phenylene group, a substituted phenyl group, an anthranyl group and a substituted anthranyl group, and a phenyl group is preferred. Examples of the substituent of the divalent aromatic group include an alkyl group in addition to the substituent of the above divalent aliphatic group.

The content of the repeating unit having a radical polymerizable functional group is preferably from 2 mol% to 98 mol%, more preferably 10 mol%, based on the total repeating unit of the radical polymerizable oligomer having a fluorine atom. %~90% by mole.

The polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method of a radically polymerizable oligomer having a fluorine atom is preferably from 2,000 to 20,000, more preferably from 2,000 to 15,000, most preferably It is 2000~10000.

When the precursor layer precursor contains a radical polymerizable monomer having a fluorine atom and/or a polymerizable oligomer, the content of the radical polymerizable monomer having a fluorine atom and/or the polymerizable oligomer is not particularly limited. Although it is limited, it is preferably 0.01% by mass or more and 20% by mass or less based on the total solid content of the adhesive layer precursor. If it is less than 0.01% by mass, there is peeling The tendency for sexual variability to be inadequate. On the other hand, when it exceeds 20 mass%, the adhesiveness tends to fall.

The radically polymerizable monomer and/or the polymerizable oligomer having a fluorine atom may be used alone or in combination of two or more types. When the number of the polymerizable monomers is two or more, the total amount is preferably in the above range.

[Free radical polymerizable monomer and/or polymerizable oligomer having a ruthenium atom]

The radically polymerizable monomer and/or polymerizable oligomer having a ruthenium in the present invention is preferably a oxime monomer or a ruthenium oxy oligomer, and examples thereof include polydimethyl siloxane coupling. The at least one terminal is a compound having an ethylenically unsaturated group such as a (meth)acryl fluorenyl group or a styryl group, and preferably a compound having a (meth) acrylonitrile group.

The number average molecular weight in terms of polystyrene measured by gel permeation chromatography of the radically polymerizable oligomer having a ruthenium atom is preferably from 1,000 to 10,000. When the number average molecular weight in terms of polystyrene measured by gel permeation chromatography measured by gel permeation chromatography is less than 1,000 or 10,000, the radically polymerizable oligomer having a ruthenium atom is difficult to exhibit properties such as peeling property by a ruthenium atom.

As the radical polymerizable monomer having a ruthenium atom in the present invention, a compound represented by the formula (11) or (12) is preferably used.

(In the general formulae (11) and (12), R ¹¹ to R ¹⁹ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group or an aryl group; and Z ¹¹ , Z ¹² and Z ¹³ each independently represent The radical polymerizable group; L ¹¹ , L ¹² and L ¹³ each independently represent a single bond or a divalent linking group; and n and m each independently represent an integer of 0 or more).

In the general formulae (11) and (12), R ¹¹ to R ¹⁹ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group or an aryl group.

The alkyl group may be linear or branched, and is preferably an alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a n-propyl group, and an isopropyl group. The alkoxy group means -OR ²⁰ , and R ²⁰ represents an alkyl group (preferably an alkyl group having 1 to 5 carbon atoms), and specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group. , butoxy and the like. The alkoxycarbonyl group means -C(=O)R ²¹ , and R ²¹ represents an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms), and specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, and a C. Oxycarbonyl or the like. Examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group, and the like may have a substituent, and examples thereof include a phenylmethyl group (benzyl group), a phenylethyl group, a phenylpropyl group, and a phenylbutyl group. Naphthylmethyl and the like.

L ¹¹ , L ¹² and L ¹³ each independently represent a single bond or a divalent linking group. The divalent linking group represents a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aromatic group, and a combination thereof.

n and m each independently represent an integer of 0 or more, preferably an integer of 0 to 100, more preferably an integer of 0 to 50.

Z ¹¹ , Z ¹² and Z ¹³ each independently represent a radical polymerizable group, and particularly preferably a functional group represented by any one of the following general formulae (i) to (iii).

(In the formula (i), R ¹⁰¹ to R ¹⁰³ each independently represent a hydrogen atom or a monovalent organic group; X ¹⁰¹ represents an oxygen atom, a sulfur atom or -N(R ¹⁰⁴ )-, and R ¹⁰⁴ represents a hydrogen atom or a monovalent group. Organic base).

In the formula (i), R ¹⁰¹ to R ¹⁰³ each independently represent a hydrogen atom or a monovalent organic group. R ^{101 is} preferably a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom and a methyl group are preferable, and the radical reactivity is high. Further, R ¹⁰² and R ¹⁰³ are each independently preferably a hydrogen atom, a halogen atom, an amine group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, and a substituent group. An aryl group, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamine group which may have a substituent, an arylamine group which may have a substituent, an alkylsulfonium group which may have a substituent The arylsulfonyl group which may have a substituent, and preferably a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, is highly reactive with a radical.

X ¹⁰¹ represents an oxygen atom, a sulfur atom or -N(R ¹⁰⁴ )-, and R ¹⁰⁴ represents a hydrogen atom or a monovalent organic group. The monovalent organic group may, for example, be an alkyl group which may have a substituent. R ^{104 is} preferably a hydrogen atom, a methyl group, an ethyl group or an isopropyl group, and has high radical reactivity.

The substituent which may be introduced may, for example, be an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an amine group, an alkylamino group, an arylamine group, a carboxyl group or an alkoxy group. A carbonyl group, a sulfo group, a nitro group, a cyano group, a decylamino group, an alkylsulfonyl group, an arylsulfonyl group or the like.

(In the formula (ii), R ²⁰¹ to R ²⁰⁵ each independently represent a hydrogen atom or a monovalent organic group; Y ²⁰¹ represents an oxygen atom, a sulfur atom or -N(R ²⁰⁶ )-; and R ²⁰⁶ represents a hydrogen atom or a monovalent group. Organic base).

In the formula (ii), R ²⁰¹ to R ²⁰⁵ each independently represent a hydrogen atom or a monovalent organic group; and R ²⁰¹ to R ²⁰⁵ are each independently preferably a hydrogen atom, a halogen atom, an amine group, a carboxyl group, an alkoxycarbonyl group, Sulfo group, nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkyl group which may have a substituent An amine group, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, or an arylsulfonyl group which may have a substituent, more preferably a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, or An alkyl group of a substituent or an aryl group which may have a substituent.

The substituent which can be introduced is the same as the substituent of the formula (i).

Y ²⁰¹ represents an oxygen atom, a sulfur atom or -N(R ²⁰⁶ )-. R ²⁰⁶ is synonymous with R ^{104 of the} formula (i), and preferred examples are also the same.

(In the formula (iii), R ³⁰¹ to R ³⁰³ each independently represent a hydrogen atom or a monovalent organic group; and Z ³⁰¹ represents an oxygen atom, a sulfur atom, -N(R ³⁰⁴ )- or a phenyl group which may have a substituent ; R ³⁰⁴ is synonymous with R ^{104 of the} formula (i)).

In the formula (iii), R ³⁰¹ to R ³⁰³ each independently represent a hydrogen atom or a monovalent organic group. R ³⁰¹ is preferably a hydrogen atom or an optionally substituted alkyl group, wherein more preferably a hydrogen atom or a methyl group because of high radical reactivity. R ³⁰² and R ³⁰³ are each independently preferably a hydrogen atom, a halogen atom, an amine group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, and an aryl group which may have a substituent. An alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamine group which may have a substituent, an arylamine group which may have a substituent, an alkylsulfonyl group which may have a substituent, The arylsulfonyl group which may have a substituent, more preferably a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, or an aryl group which may have a substituent, has high radical reactivity.

The substituent which can be introduced is the same as the substituent of the formula (i). Z ³⁰¹ represents an oxygen atom, a sulfur atom, -N(R ³⁰⁴ )- or a stretched phenyl group which may have a substituent. ^R304 is synonymous with R ^{104 of the} formula (i), and examples of the monovalent organic group include an alkyl group which may have a substituent, and the like, and among them, a methyl group, an ethyl group and an isopropyl group are preferred, and a radical reaction is possible. High sex.

When the precursor layer precursor contains a radical polymerizable monomer having a germanium atom and/or a polymerizable oligomer, the content of the radical polymerizable monomer and/or the polymerizable oligomer having a germanium atom is relative to the content of the polymerizable oligomer. The total solid content of the agent precursor is preferably 0.01% by mass or more and 20% by mass or less. When it is less than 0.01% by mass, the peeling property tends to be lowered. On the other hand, when it exceeds 20 mass%, the adhesiveness tends to fall.

The radically polymerizable monomer or oligomer having a ruthenium atom may be only One type may be two or more types. When the number of the radical polymerizable monomers or oligomers having a ruthenium atom is 2 or more, the total amount is preferably in the above range.

Examples of the radical polymerizable monomer and/or polymerizable oligomer having a fluorine atom or a ruthenium atom include RS-75, RS-72-K, RS-76-E, and DAIKIN manufactured by DIC Corporation. Industrial Co., Ltd. Optool DAC-HP, Shin-Etsu Chemical Co., Ltd. X-22-164, X-22-164AS, X-22-164A, X-22-164B, X-22-164, X -22-164C, X-22-164E, EBECRYL 350 manufactured by DAICEL CYTEC Co., Ltd., EBECRYL 1360, TEGORad 2700 manufactured by DEGUSSA, etc.

<<(b-2) photoradical initiator, (b-3) thermal radical initiator>>

The adhesive layer precursor of the present invention preferably contains a radical polymerization initiator, that is, (b-2) a compound which generates a radical due to irradiation of active light or radiation (light irradiation) (photo-free radical initiator (light free) The base polymerization initiator)) or (b-3) a compound which generates a radical due to heat (a thermal radical initiator (thermal radical polymerization initiator)). In the presence of a radical polymerization initiator, by irradiating light or heating the radical polymerizable monomer or oligomer, a hardening reaction due to a radical occurs, and the polymerization rate of the precursor of the adhesive layer can be adjusted, and Adjustable adhesion.

[Photoradical initiator]

As the photo radical initiator, for example, those known as polymerization initiators described below can be used.

As the photo-radical initiator, as long as it has an initiation The ability of the polymerization reaction (crosslinking reaction) in the reactive compound having a polymerizable group of the polymerizable monomer is not particularly limited, and may be appropriately selected from known polymerization initiators. For example, it is preferred that the ultraviolet region is photosensitive to visible light. Further, it may be any active agent acting on the photoexcited sensitizer to form an active radical active agent.

Further, the polymerization initiator preferably contains at least one compound having a molecular absorption coefficient of at least about 50 in the range of about 300 nm to 800 nm, preferably 330 nm to 500 nm.

As the photo-radical initiator, a well-known compound can be used without limitation, and for example, a halogenated hydrocarbon derivative (for example, having three Skeleton a sulfonium compound such as a bisazole skeleton, a trihalomethyl group or the like, a mercaptophosphine oxide, a fluorenyl compound such as a hexaarylbisimidazole or an anthracene derivative, an organic peroxide, a sulfur compound, or a ketone compound An aromatic sulfonium salt, a ketoxime ether, an aminoacetophenone compound, a hydroxyacetophenone, an azo compound, an azide compound, a metallocene compound, an organoboron compound, an iron arene complex, and the like.

As the aforementioned has three Examples of the halogenated hydrocarbon compound of the skeleton include a compound described in Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in the specification of British Patent No. 1,388,492, and Japanese Patent Laid-Open No. 53-133428. The compound described in the publication, the compound described in the specification of the German Patent No. 3337024, the compound described in J. Org. Chem.; 29, 1527 (1964) of FC Schaefer et al., the compound described in JP-A-62-58241, and the Japanese Patent Laid-Open The compound described in the publication No. 5-281728, the compound described in Japanese Patent Publication No. Hei 5-34920, and the compound described in the specification of U.S. Patent No. 4,212,976.

The compound described in the specification of the aforementioned U.S. Patent No. 4,212,976 includes, for example, a compound of the diazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4- Diazole, 2-trichloromethyl-5-(4-chlorophenyl)-1,3,4- Diazole, 2-trichloromethyl-5-(1-naphthyl)-1,3,4- Diazole, 2-trichloromethyl-5-(2-naphthyl)-1,3,4- Diazole, 2-tribromomethyl-5-phenyl-1,3,4- Diazole, 2-tribromomethyl-5-(2-naphthyl)-1,3,4- Diazole; 2-trichloromethyl-5-styryl-1,3,4- Diazole, 2-trichloromethyl-5-(4-chlorostyryl)-1,3,4- Diazole, 2-trichloromethyl-5-(4-methoxystyryl)-1,3,4- Diazole, 2-trichloromethyl-5-(1-naphthyl)-1,3,4- Diazole, 2-trichloromethyl-5-(4-n-butoxystyryl)-1,3,4- Diazole, 2-tribromomethyl-5-styryl-1,3,4- Diazole, etc.).

Further, examples of the photoradical initiator other than the above include an acridine derivative (for example, 9-phenyl acridine, 1,7-bis(9,9'-acridinyl)heptane, etc.), and N- Phenylglycine, etc., polyhalogen compounds (for example, carbon tetrabromide, phenyltribromomethylhydrazine, phenyltrichloromethyl ketone, etc.), coumarins (for example, 3-(2-benzofuranium) -7-diethylamino coumarin, 3-(2-benzofuranyl)-7-(1-pyrrolidinyl)coumarin, 3-benzylidene-7-di Ethylamino coumarin, 3-(2-methoxybenzimidyl)-7-diethylamino coumarin, 3-(4-dimethylaminobenzimidyl)-7 -diethylamino coumarin, 3,3'-carbonyl bis(5,7-di-n-propoxycoumarin), 3,3'-carbonyl bis(7-diethylamino coumarin , 3-benzylidene-7-methoxycoumarin, 3-(2-furanyl)-7-diethylaminocoumarin, 3-(4-diethylamino) Gui Benzyl)-7-diethylamino coumarin, 7-methoxy-3-(3-pyridylcarbonyl)coumarin, 3-benzylidene-5,7-dipropoxy Coumarin, 7-benzotriazol-2-ylcoumarin, and Japanese Laid-Open Patent Publication No. Hei 5-19475, Japanese Patent Laid-Open No. Hei 7-271028, Japanese Patent Laid-Open Publication No. 2002-363206, and JP-A-2002 a coumarin compound or the like described in JP-A-2002-363208, JP-A-2002-363209, and the like, and a mercaptophosphine oxide (for example, bis(2,4,6-three) Methyl benzhydryl)-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO Equivalent), such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl Titanium, η5-cyclopentadienyl-η6-isopropylphenyl-iron (1+)-hexafluorophosphate (1-), etc., JP-A-53-133428, and JP-A-57- A compound or the like described in the specification of No. 1819, Japanese Patent No. 57-6096, and Japanese Patent No. 3615455.

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'- Bis-dicyclohexylamino)diphenyl ketone, 4,4'-bis(diethylamino)diphenyl ketone, 4,4'-bis(dihydroxyethylamino)diphenyl ketone, 4 -Methoxy-4'-dimethylaminodiphenyl ketone, 4,4'-dimethoxydiphenyl ketone, 4-dimethylaminodiphenyl ketone, 4-dimethylamine Acetophenone, benzoin, anthracene, 2-tert-butylhydrazine, 2-methylindole, phenanthrenequinone, xanthone, thioxanthone, 2-chloro-thioxanthone, 2,4 -Diethylthioxanthone, anthrone, 2-benzyl-dimethylamino-1-(4- Phenylphenyl)-1-butanone, 2-methyl-1-[4-(methylthio)phenyl]-2- Lolinyl-1-propanone, 2-hydroxy-2-methyl-[4-(1-methylvinyl)phenyl]propanol oligomer, benzoin, benzoin ether (eg benzoin) Methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloroacridone N-methylacridone, N-butylacridone, N-butyl-chloroacridone, and the like.

Among the commercial products, Kayacure DETX (made by Nippon Kayaku Co., Ltd.) is also applicable.

As the photo radical initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a mercaptophosphine compound can also be used. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and a mercaptophosphine oxide-based initiator described in Japanese Patent No. 4,258,899 can be used.

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

As the photoradical initiator, a quinone compound is more preferable. As a specific example of the lanthanide initiator, Japanese special opening can be used. A compound described in JP-A-2000-80068, and a compound described in JP-A-2006-342166.

Examples of the hydrazine compound which is used as a photo-radical initiator in the present invention, such as an anthracene derivative, include 3-benzylideneoxyimidobutan-2-one and 3-ethyloxyiminoimide. Butan-2-one, 3-propenyloxyimidobutan-2-one, 2-ethyloxyiminopentan-3-one, 2-ethyloxyimino-1-phenyl Propan-1-one, 2-benzylideneoxyimido-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2- Ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.

Examples of the oxime ester compound include JCS Perkin II (1979) pp. 1653-1660), JCS Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232. The compound described in each of the publications of JP-A-2000-66385, JP-A-2000-80068, JP-A-2004-534797, and JP-A-2006-342166.

Among the commercial products, IRGACURE-OXE01 (manufactured by BASF Corporation) and IRGACURE-OXE02 (manufactured by BASF Corporation) are also applicable.

In addition, as the oxime ester compound other than the above-mentioned description, a compound described in JP-A-2009-519904, in which a carbazole is bonded to the N-position of the carbazole, and a US-incorporated compound having a hetero substituent introduced at a diphenyl ketone site may be used. The compound described in Japanese Patent Laid-Open Publication No. 2010-125039, and the ketone described in Japanese Laid-Open Patent Publication No. 2009-292039, and the ketone described in Japanese Laid-Open Patent Publication No. 2009-131189 Lanthanide compound, containing three in the same molecule The compound described in Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

The cyclic ruthenium compound described in JP-A-2007-2320 and JP-A-2007-322744 is also applicable. Among the cyclic ruthenium compounds, the cyclic ruthenium compound which is condensed in the carbazole dye described in Japanese Laid-Open Patent Publication No. 2010-185072, and the like, has high light absorbing properties. The viewpoint of high sensitivity is better.

In addition, the compound described in JP-A-2009-242469, which has an unsaturated bond at a specific site, can regenerate the active radical by polymerizing an inactive radical to achieve high sensitivity, and can be suitably used.

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

The Mohr absorbance coefficient of the compound can be a well-known method, and specifically, for example, it is preferably carried out by using an ultraviolet-visible spectrophotometer (Carry-5 spctrophotometer manufactured by Varian Co., Ltd.) using an ethyl acetate solvent at a concentration of 0.01 g/L. Determination.

As a photo radical initiator, from the viewpoint of exposure sensitivity, it is preferably trihalomethyltri a compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, a mercaptophosphine compound, a phosphine oxide compound, a metallocene compound, an anthraquinone compound, a triallyl imidazole dimer, Antimony compound, benzothiazole compound, diphenyl ketone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halomethyl A compound selected from the group consisting of an oxazolyl compound and a 3-aryl-substituted coumarin compound.

More preferred is trihalomethyl three a compound, an α-amino ketone compound, a mercaptophosphine compound, a phosphine oxide compound, an anthraquinone compound, a triaryl imidazole dimer, an anthracene compound, a diphenyl ketone compound, an acetophenone compound, preferably a trihalomethyl group three As the at least one compound selected from the group consisting of a compound, an α-amino ketone compound, an anthracene compound, a triaryl imidazole dimer, and a diphenyl ketone compound, an oxime compound is preferably used.

When the adhesive layer precursor of the present invention has a photo-radical initiator, the content of the photo-radical initiator is preferably 0.1% by mass or more and 50% by mass or less based on the total solid content of the adhesive layer precursor. It is 0.1% by mass or more and 30% by mass or less, and particularly preferably 0.1% by mass or more and 20% by mass or less.

The photoradical initiator may be one type or two or more types. When the amount of the photo radical initiator is two or more, the total amount is preferably in the above range.

[thermal free radical initiator]

As the thermal radical initiator, a well-known thermal radical generator can be used.

A thermal radical initiator is a compound which generates a radical due to the energy of heat and starts or promotes a polymerization reaction of a polymerizable monomer. The member to be treated and the adhesive support are irradiated after the heat is applied to the adhesive layer precursor formed using the temporary adhesive by adding a thermal radical generator. In the case of the temporary continuation, the crosslinking reaction in the reactive compound having a crosslinkable group by heat, as described later in detail, can improve the adhesion (ie, adhesion) of the adhesive layer precursor. Adhesiveness) is lowered in advance.

On the other hand, in the case where the heat of the adhesive layer precursor in the adhesive support is irradiated to the adhesive member after the temporary contact between the member to be treated and the adhesive support, the reactivity of the crosslinkable group due to heat is obtained. The crosslinking reaction in the compound proceeds. As a result, a stronger adhesive layer can suppress the cohesive failure of the adhesive layer precursor which is likely to occur during mechanical or chemical treatment of the member to be treated. The adhesion in the precursor of the adhesive layer can be improved.

Preferred examples of the thermal radical initiator include the above-mentioned compounds which generate radicals by irradiation with active rays or radiation, and it is preferred to use a thermal decomposition point of 130 ° C to 250 ° C, preferably 150 ° C to 220 ° C. Range of compounds.

Examples of the thermal radical initiator include aromatic ketones, phosphonium salt compounds, organic peroxides, sulfur compounds, hexaarylbisimidazole compounds, ketoxime compounds, borate ester compounds, and oxime compounds. An azinium compound, a metallocene compound, 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 preferred, and an organic peroxide is particularly preferred.

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

Among the commercially available products, Perbutyl Z (manufactured by Nippon Oil Co., Ltd.) can be suitably used.

When the adhesive layer precursor in the present invention contains (b-3) a thermal radical polymerization initiator as a radical polymerization initiator (more preferably contains (b-2) When the photoradical polymerization initiator and the (b-3) thermal radical polymerization initiator are used, in particular, the adhesion at a high temperature (for example, 100 ° C) can be further improved.

The adhesive layer precursor of the present invention preferably contains (b-2) a photoradical polymerization initiator.

Further, the adhesive layer precursor in the present invention may contain one or more kinds of radical polymerization initiators.

When the agent layer precursor has a thermal radical initiator, the content of the thermal radical initiator is preferably 0.1% by mass or more and 50% by mass or less, more preferably 0.1% by mass based on the total solid content of the adhesive layer precursor. % or more is 30% by mass or less, and particularly preferably 0.1% by mass or more and 20% by mass or less.

The thermal radical initiator may be one type or two or more types. When the number of the thermal radical initiators is 2 or more, the total amount is preferably in the above range.

<<(b-4) Polymer Compound>>

The adhesive layer precursor of the present invention may have a polymer compound as needed in order to adjust coatability. In addition, the coating property as used herein means the film thickness uniformity after coating or the film formation property after coating.

In the present invention, any of the polymer compounds can be used.

For example, a hydrocarbon resin or a polystyrene resin (for example, an acrylonitrile/butadiene/styrene copolymer (ABS resin), an acrylonitrile/styrene copolymer (AS resin), methyl methacrylate/benzene may be mentioned. Ethylene copolymer (MS resin)), novolak resin, phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyurethane resin, polyimide resin, Polyethylene resin, polypropylene, polyvinyl chloride Resin, polyvinyl acetate resin, Teflon (registered trademark), (meth)acrylic resin, polyamide resin, polyacetal resin, polycarbonate resin, polyphenylene ether resin, polybutylene terephthalate resin , synthetic resin such as polyethylene terephthalate resin, polyphenylene sulfide resin, polyfluorene resin, polyether oxime resin, polyarylate resin, polyetheretherketone resin, polyamidoximine resin, or natural A natural resin such as rubber. Among them, a hydrocarbon resin, an ABS resin, an AS resin, an MS resin, a polyurethane resin, a novolak resin, a polyimine resin, preferably a hydrocarbon resin, an MS resin, or preferably an acrylic resin, is preferred. ABS resin, AS resin, MS resin.

In the present invention, the binder may be used in combination of two or more kinds as needed.

In the present invention, any of the hydrocarbon resins can be used.

The hydrocarbon resin in the present invention means a resin consisting essentially of only carbon atoms and hydrogen atoms, but the side chain may contain other atoms as long as the basic skeleton is a hydrocarbon resin. That is, in a hydrocarbon resin composed only of carbon atoms and hydrogen atoms, such as an acrylic resin, a polyvinyl alcohol resin, a polyvinyl acetal resin, or a polyvinylpyrrolidone resin, a functional group other than a hydrocarbon group directly bonded to a main chain The case is also included in the hydrocarbon resin of the present invention. In this case, the content of the repeating unit in which the hydrocarbon group is directly bonded to the main chain is preferably 30 mol% or more based on all the repeating units of the resin.

Examples of the hydrocarbon resin satisfying the above conditions include a polystyrene resin, a terpene resin, a terpene phenol resin, a modified terpene resin, a hydrogenated terpene resin, a hydrogenated terpene phenol resin, a rosin, a rosin ester, and a hydrogenated rosin. , hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, modified rosin, rosin modified phenol resin, alkyl phenol resin, aliphatic petroleum resin, aromatic Aromatic petroleum resin, hydrogenated petroleum resin, modified petroleum resin, alicyclic petroleum resin, coumarone petroleum resin, ruthenium petroleum resin, polystyrene-polyolefin copolymer, olefin polymer (for example, methylpentene copolymer) And a cyclic olefin polymer (for example, a norbornene copolymer, a dicyclopentadiene copolymer, a tetracyclododecene copolymer) or the like.

The hydrocarbon resin is preferably a polystyrene resin, a terpene resin, a rosin, a petroleum resin, a hydrogenated rosin, a polymerized rosin, an olefin polymer or a cycloolefin polymer, more preferably a polystyrene resin, a terpene resin, or a rosin. An olefin polymer or a cycloolefin polymer, particularly preferably a polystyrene resin, a terpene resin, a rosin, an olefin polymer, a polystyrene resin or a cycloolefin polymer, more preferably a polystyrene resin or a terpene resin. A rosin, a cycloolefin polymer or an olefin polymer, particularly preferably a polystyrene resin or a cycloolefin monomer polymer.

Specific examples of the polystyrene resin include polystyrene, styrene-acrylonitrile resin, acrylonitrile-butadiene-styrene resin, and methyl methacrylate-styrene resin. Preferred is methyl methacrylate-styrene resin. From the viewpoint of heat resistance for the high-temperature treatment step of the semiconductor substrate, the amount of exhaust gas generated when heated at 250 ° C is preferably 3% by mass or less. More preferably, it is 2 mass % or less of resin. As a commercial product of methyl methacrylate-styrene resin, it is possible to use Estyrene MS-200NT, Estyrene MS-300, Estyrene MS-500, Estyrene MS-600 (Nippon Steel & Metal Chemical Co., Ltd.) or Cevian MAS10, MAS30 (DAICEL POLYMER).

Examples of the cycloolefin polymer include a norbornene-based polymer, a monocyclic cyclic olefin polymer, and a cyclic conjugated diene polymer. , vinyl alicyclic hydrocarbon polymers, and hydrides of such polymers, and the like. Preferred examples of the cycloolefin polymer include an addition (co)polymer containing at least one or more repeating units represented by the following formula (II), and further containing the formula (I). Addition (co)polymer of at least one of the repeating units. Further, as another preferred example of the cycloolefin polymer, a ring-opening (co)polymer containing at least one cyclic repeating unit represented by the formula (III) may be mentioned.

Where m represents an integer from 0 to 4. R ¹ to R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and each of X ¹ to X ³ and Y ¹ to Y ³ represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, and a halogen atom. Substituted hydrocarbon group having 1 to 10 carbon atoms, -(CH ₂ )nCOOR ¹¹ , -(CH ₂ )nOCOR ¹² , -(CH ₂ )nNCO, -(CH ₂ )nNO ₂ , -(CH ₂ )nCN, -( CH ₂ )nCONR ¹³ R ¹⁴ , —(CH ₂ )nNR ¹⁵ R ¹⁶ , —(CH ₂ )nOZ, —(CH ₂ )nW, or by X ¹ and Y ¹ , X ² and Y ² , or X ³ (-CO) ₂ O, (-CO) ₂ NR ¹⁷ composed of Y ³ . R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ each represent a hydrogen atom or a hydrocarbon group (preferably a hydrocarbon group having 1 to 20 carbon atoms), and Z represents a hydrocarbon group or a halogen-substituted hydrocarbon group, SiR ¹⁸ _p D _3-p (R ¹⁸ represents a hydrocarbon group having 1 to 10 carbon atoms, D represents a halogen atom, -OCOR ¹⁸ or -OR ¹⁸ , and p represents an integer of 0 to 3). n represents an integer from 0 to 10.

The norbornene-based polymer is disclosed in Japanese Laid-Open Patent Publication No. Hei 10-7732, Japanese Patent Publication No. 2002-504184, No. 2004/229157 A1, or WO2004/070463A1. The norbornene-based polymer can be obtained by subjecting a norbornene-based polycyclic unsaturated compound to addition polymerization. Further, if desired, the norbornene-based polycyclic unsaturated compound may be copolymerized with ethylene, propylene, butylene, such as butadiene or isoprene, such as ethylidene norbornene. The conjugated diene is subjected to addition polymerization. The norbornene-based polymer is commercially available from Mitsui Chemicals Co., Ltd. under the trade name of Apel, and has a glass transition temperature (Tg) such as APL8008T (Tg70°C), APL6013T (Tg125°C), or APL6015T (Tg145°C). grade. The TOPAS 8007, the same 5013, the same 6013, the same 6015 and the like are sold by POLYPLASTICS.

Furthermore, Appear 3000 is available from Ferrania.

The norbornene-based polymer hydride system is disclosed in Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. JP-A-2003-159979 or JP-A-2004-309979 discloses that a polycyclic unsaturated compound is subjected to addition polymerization or metathesis ring-opening polymerization, followed by hydrogenation.

In the above formula (III), R ⁵ and R ^{6 are} preferably a hydrogen atom or a methyl group, and X ³ and Y ^{3 are} preferably a hydrogen atom, and other groups may be appropriately selected. This norbornene-based resin is sold by JSR (shares) under the trade names of Arton G or Atong F, and by Zeon (Zeonor) ZF14, ZF16, and Rayonak. (Zeonex) 250, the same as 280, the same as the 480R trade name, can be used.

The polystyrene-equivalent weight average molecular weight of the polymer compound as measured by gel permeation chromatography (GPC) is preferably 10,000 to 1,000,000, more preferably 50,000 to 500,000, and particularly preferably 100,000 to 300,000.

When the polymer layer precursor has a polymer compound, the content of the polymer compound is preferably 5% by mass or more, and more preferably 10% by mass or more, more preferably 10% by mass or more based on the total solid content of the adhesive layer precursor of the present invention. It is 20% by mass or more.

In addition, the content of the polymer compound is preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, based on the total solids of the adhesive layer precursor of the present invention, and particularly preferably 40% by mass or less.

The polymer compound may be used alone or in combination of two or more types. When the polymer compound is two or more types, the total amount thereof is preferably in the above range.

Further, the content ratio (mass ratio) of the polymerizable monomer and the polymer compound (radical polymerizable monomer/polymer compound) is preferably 100/0 to 10/90, more preferably 100/0 to 20/80. , especially good for 100/0~30/70.

<Non-polymerizable polymer compound having a fluorine atom>

The adhesive precursor layer of the present invention preferably contains a non-polymerizable polymer compound having a fluorine atom. As the polymer compound having a non-polymerizable fluorocarbon, a polymer composed of one or two or more kinds of fluorine-containing monofunctional monomers is preferably used. More specifically, it may be exemplified by tetrafluoroethylene, hexafluoropropylene, tetrafluoroethylene oxide, hexafluoropropylene oxide, perfluoroalkyl vinyl ether, chlorotrifluoroethylene, vinylidene fluoride, and perfluoro-containing Alkyl (methyl) a homopolymer of one or more fluorine-containing monofunctional monomers selected from the group consisting of acrylates, a copolymer of such monomers, a copolymer of one or more of the fluorine-containing monofunctional monomers and ethylene And at least one fluorine-containing resin selected from the group consisting of one or two or more kinds of fluorine-containing monofunctional monomers and a copolymer of chlorotrifluoroethylene.

The non-polymerizable polymer compound having a fluorine atom is preferably a perfluoroalkyl group-containing (meth)acrylic resin which can be synthesized from a perfluoroalkyl group-containing (meth) acrylate.

The (meth) acrylate containing a perfluoroalkyl group is specifically preferably a compound represented by the following formula (101).

In the formula (101), R ¹⁰¹ , R ¹⁰² and R ¹⁰³ each independently represent a hydrogen atom, an alkyl group or a halogen atom. Y ¹⁰¹ represents a single bond or a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aromatic group, and a combination thereof. Rf has at least one fluorine atom or one fluorine group organic atom.

In the formula (101), examples of the alkyl group represented by R ¹⁰¹ , R ¹⁰² and R ^{103 are} preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group and an octyl group. , isopropyl, tert-butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl and the like. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. R ¹⁰¹ to R ^{103 are} particularly preferably a hydrogen atom or a methyl group.

Y ¹⁰¹ represents a single bond or a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aromatic group, and a combination thereof. The divalent aliphatic group chain structure is better than the ring structure, and the linear structure is better than the branched chain structure. The number of carbon atoms of the divalent aliphatic group is preferably from 1 to 20, more preferably from 1 to 15, particularly preferably from 1 to 12, particularly preferably from 1 to 10, particularly preferably from 1 to 8, particularly preferably 1~4. Examples of the divalent aromatic group include a stretched phenyl group, a substituted phenylene group, an extended naphthyl group, and a substituted —naphthyl group, and more preferably a stretched phenyl group.

Y ^{101 is} preferably a divalent linear aliphatic group.

The monovalent organic group having a fluorine atom represented by Rf is not particularly limited, but is preferably a fluorine-containing alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 20 carbon atoms. A fluorine-containing alkyl group of 15. The fluorine-containing alkyl group may be linear {e.g., -CF ₂ CF ₃ , -CH ₂ (CF ₂ ) ₄ H, -CH ₂ (CF ₂ ) ₈ CF ₃ , -CH ₂ CH ₂ (CF ₂ ) ₄ H Etc., may also have a branched configuration {eg, -CH(CF ₃ ) ₂ , -CH ₂ CF(CF ₃ ) ₂ , -CH(CH ₃ )CF ₂ CF ₃ , -CH(CH ₃ )(CF ₂ ) ₅ CF ₂ H or the like, and may also have an alicyclic structure (preferably a 5-membered ring or a 6-membered ring, such as a perfluorocyclohexyl group, a perfluorocyclopentyl group or an alkyl group substituted therewith), or Has an ether linkage (eg, -CH ₂ OCH ₂ CF ₂ CF ₃ , -CH ₂ CH ₂ OCH ₂ C ₄ F ₈ H, -CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F ₁₇ , -CH ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ H, etc.). Further, it may be a perfluoroalkyl group.

In other words, the perfluoroalkyl group-containing (meth)acrylic resin specifically has a repeating unit represented by the following formula (102).

In the formula (102), R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , Y ¹⁰¹ and Rf are each synonymous with the formula (101), and preferred embodiments are also synonymous.

The perfluoroalkyl group-containing (meth)acrylic resin may be selected from the viewpoint of releasability in addition to any perfluoroalkyl group-containing (meth) acrylate. Examples of the radically polymerizable compound capable of forming a copolymerization component include acrylates, methacrylates, N,N-2 substituted acrylamides, and N,N-2 substituted methacrylamides. A radically polymerizable compound selected from the group consisting of styrenes, acrylonitriles, methacrylonitriles and the like.

More specifically, for example, acrylates such as alkyl acrylate (the alkyl group preferably has 1 to 20 carbon atoms) (for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, etc.) may be mentioned. Amyl acrylate, ethylhexyl acrylate, octyl acrylate, third octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane Acrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, decyl acrylate, tetrahydrofurfuryl acrylate, etc., aryl acrylate (eg, phenyl acrylate, etc.), A a methacrylate such as an alkyl acrylate (the carbon atom of the alkyl group is preferably from 1 to 20) (for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid) Propyl ester, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, benzyl chloride methacrylate, octyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, methyl propyl acrylate Acid 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, methacrylic Ethylene methacrylate, methacrylate, tetrahydrofurfuryl methacrylate, etc., aryl methacrylate (for example, phenyl methacrylate, toluene methacrylate, naphthyl methacrylate, etc.) Styrene such as styrene or alkylstyrene (for example, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl Styrene, hexyl styrene, cyclohexyl styrene, mercapto styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, ethoxymethyl methyl Styrene, etc.), alkoxystyrene (eg, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogen styrene (eg, chlorostyrene) , Dichlorostyrene, Trichlorostyrene, Tetrachlorostyrene, Pentachlorostyrene, Bromostyrene, Dibromostyrene, Iodostyrene, Fluorostyrene, Trifluorostyrene, 2-Bromo-4-III Fluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc., acrylonitrile, methacrylonitrile acrylic acid, free radical polymerization containing carboxylic acid a compound (acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, p-carboxystyrene, a metal salt of such an acid group, an ammonium salt compound, etc.), from the viewpoint of peelability In particular, a (meth) acrylate having a hydrocarbon group of 1 to 24 carbon atoms is exemplified, and examples thereof include methyl (meth)acrylate, butyl ester, 2-ethylhexyl ester, lauryl ester, and octadecyl ester. A glycidyl ester or the like is particularly preferably a (meth) acrylate of a higher alcohol such as 2-ethylhexyl ester, lauryl ester or octadecyl ester, especially an acrylate.

Examples of the non-polymerizable polymer compound having a fluorine atom include Teflon (registered trademark) (Du Pont), Tefzel (Du Pont), Fluon (Asahi Glass), and Halar (Solvay). Solexis), Heiler (Solvay Solexis), Lumiflon (Asahi Glass Co., Ltd.), Aflas (Asahi Glass Co., Ltd.), Cefral Soft (CENTRAL Glass Co., Ltd.), Cefral Coat (CENTRAL Glass Co., Ltd.), fluororesin, Viton (Du Pont), Kalrez (Du Pont), SIFEL (Shin-Etsu Chemical) Industrial company), such as fluororubber, Krytox (Du Pont), Fomblin (Daitoku Tech), Demnum (DAIKIN Industries), etc., various types of fluoro oil, or Daifree FB series (DAIKIN Industrial Co., Ltd.), a fluorine-containing release agent such as the Megafac series (DIC Corporation), etc., but not limited thereto, as long as it is a non-polymerizable polymer compound having a fluorine atom, applicable.

The polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method of a non-polymerizable polymer compound having a fluorine atom is preferably from 2,000 to 100,000, more preferably from 2,000 to 50,000, most preferably It is 2000~10000.

When a polymer compound having a fluorine atom having a non-polymerizable group contains a radical polymerizable compound having a fluorine atom in the precursor of the adhesive layer, the effect of improving the releasability is large, and a radical polymerizable compound having a fluorine atom is used. The combination with a non-polymerizable polymer compound having a fluorine atom is preferred by the user.

In the present invention, the ratio (mass ratio) of the radically polymerizable compound having a fluorine atom to the nonpolymerizable polymer compound having a fluorine atom in the precursor of the adhesive layer is preferably 5:95 to 50:50. More preferably 10:90~40:60, especially 15:85~30:70.

The content of the non-polymerizable polymer compound having a fluorine atom is relative to the above-mentioned adhesive layer from the viewpoint of good peelability The total solid content of the precursor is preferably from 1 to 99% by mass, more preferably from 3 to 95% by mass, even more preferably from 5 to 90% by mass.

<<chain transfer agent>>

The adhesive layer precursor of the present invention preferably contains a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by the Society of Polymerics, 2005) at pages 683-684. As the chain transfer agent, for example, a compound group having SH, PH, SiH, or GeH in the molecule is used. These hydrogens are supplied to low-active radical species to form free radicals, or after being oxidized, free radicals can be generated by deprotonation. In the temporary adhesive, it is particularly preferable to use a thiol compound (for example, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoene) Azole, 3-mercaptotriazole, 5-mercaptotetrazole, etc.).

When the agent layer precursor has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass based on 100 parts by mass of the total solid content of the adhesive layer precursor. It is preferably 1 to 5 parts by mass.

The chain transfer agent may be used alone or in combination of two or more types. When the chain transfer agent is two or more types, the total amount thereof is preferably in the above range.

<<Polymerization inhibitor>>

In the adhesive layer precursor of the present invention, in order to prevent unnecessary thermal polymerization of the polymer compound and the radical polymerizable monomer during the production or storage of the adhesive layer precursor, it is preferred to add a small amount of polymerization. Inhibitor.

As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, and tert-butylcatechol can be suitably used. , benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) , N-nitroso-N-phenylhydroxylamine aluminum salt.

When the agent layer precursor has a polymerization inhibitor, the amount of the polymerization inhibitor added is preferably from about 0.01 to about 5 mass% based on the total solid content of the adhesive layer precursor.

The polymerization inhibitor may be used in only one type or two or more types. When the polymerization inhibitor is two or more types, the total amount thereof is preferably in the above range.

<<Advanced fatty acid derivatives, etc.>>

In the adhesive layer precursor of the present invention, in order to prevent polymerization inhibition by oxygen, behenic acid or a higher fatty acid derivative such as decyl behenate may be added to cause a bias in the drying process after coating. The surface of the precursor of the layer is then applied.

When the agent layer precursor has a higher fatty acid derivative, the amount of the higher fatty acid derivative added is preferably from about 0.1 to about 10% by mass based on the total solid content of the adhesive layer precursor.

The higher fatty acid derivative or the like may be one type or two or more types. When two or more types of higher fatty acid derivatives are used, the total amount is preferably in the above range.

<<Solvent>>

When the precursor of the adhesive layer of the present invention is applied to form a layer, it is preferred to blend a solvent.

As long as the solvent can form an adhesive layer, a well-known person can be used without limitation.

As an organic solvent, in an ester, for example, it can be suitably mentioned Ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, Methyl lactate, ethyl lactate, alkyl oxyacetate (eg methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg methyl methoxyacetate, ethyl methoxyacetate, A) Butyl oxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-oxopropionate (eg methyl 3-oxypropionate, 3-oxypropionic acid) Ethyl ester or the like (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2- Alkyl oxypropionates (for example: methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (for example, methyl 2-methoxypropionate, 2 -ethyl methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-oxy-2-methyl Methyl propionate and ethyl 2-oxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc. ), acetone , ethyl pyruvate, propyl pyruvate, methyl acetate methyl acetate, ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and in ethers, For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate can be suitably used. , 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 acetate Examples of the ester, propylene glycol monopropyl ether acetate, and the ketones include, for example, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and N-methyl-2. The pyrrolidone or the like, and the aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene or the like can be suitably used.

The solvent is preferably a mixture of two or more kinds from the viewpoint of improvement in coating surface shape and the like. In this case, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether , butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether and propylene glycol methyl A mixed solution of two or more selected from the group consisting of ether acetates.

When the solvent layer precursor has a solvent, the content of the solvent in the composition for forming the precursor layer precursor is preferably the total solid concentration of the composition for forming the precursor layer of the adhesive layer from the viewpoint of coatability. It is 5 to 80% by mass, more preferably 5 to 70% by mass, and particularly preferably 10 to 60% by mass.

The solvent system may be only one type or two or more types. When the solvent is two or more types, the total amount thereof is preferably in the above range.

<<Interfacial active agent>>

In the adhesive layer precursor 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 a ruthenium-based surfactant can be used.

In particular, by containing a fluorine-based surfactant, the liquid properties (especially fluidity) at the time of preparation as a coating liquid are further improved, so that uniformity of coating thickness or liquid-saving property can be further improved.

In other words, when the film formation is carried out using a coating liquid containing a fluorine-based surfactant, the interfacial tension between the surface to be coated and the coating liquid is lowered to improve. The wettability to the surface to be coated is improved to coat the surface to be coated. Therefore, even when a film having a thickness of about several μm is formed in a small amount of liquid, it is effective to form a film having a uniform thickness having a small thickness unevenness.

The fluorine content in the fluorine-based surfactant is preferably from 3% by mass to 40% by mass, more preferably from 5% by mass to 30% by mass, even more preferably from 7% by mass to 25% by mass. The fluorine-based surfactant having a fluorine content within this range is effective in the uniformity of the thickness of the coating film or the liquid-saving property, and the solubility is also good.

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

Specific examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol B). Oxylate, 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, Solsperse 20000 (made by LUBRIZOL Co., Ltd., Japan).

Specific examples of the cation-based surfactant include a phthalocyanine derivative (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), and an 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 Yusei Co., Ltd.), and the like.

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

Examples of the oxime-based surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, and Toray Dow Corning. Toray Silicone SH29PA, "Toray Silicone SH30PA", "Toray Silicone SH8400", "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460", "TSF-4452" by Momentive Performance Materials "KP341", "KF6001", "KF6002" manufactured by Shin-Etsu SILICONE Co., Ltd., "BYK307", "BYK323", "BYK330" manufactured by BYK Chemical Co., Ltd., etc.

When the agent layer precursor has a surfactant, the amount of the surfactant added is preferably 0.001% by mass to 2.0% by mass, more preferably 0.005% by mass to 1.0% by mass based on the total solid content of the adhesive layer precursor. %.

The surfactant may be used in only one type or two or more types. When the amount of the surfactant is two or more, the total amount is preferably in the above range.

<<Other additives>>

The adhesive layer precursor of the present invention may be blended with various additives such as a hardener, a hardening catalyst, a decane coupling agent, a filler, a adhesion promoter, and the like, as long as the effects of the present invention are not impaired. An oxidizing agent, an ultraviolet absorber, an anti-agglomerating agent, and the like. When these additives are blended, the total blending amount thereof is preferably 3% by mass or less based on the solid content of the binder layer precursor.

In order to form an adhesive layer precursor or an adhesive layer, a composition for forming an adhesive layer precursor precursor (for example, an adhesive layer precursor coating liquid) can be used by a conventional spin coating method, a spray method, or a roll coating method. Coating by a method such as a flow coating method, a knife coating method, or a dipping method is carried out by drying (baking). Drying can be carried out, for example, at 60 to 150 ° C for 10 seconds to 2 minutes.

The thickness of the layer precursor and the adhesive layer is preferably from 1 to 500 μm, more preferably from 1 to 100 μm, still more preferably from 1 to 10 μm.

The storage elastic modulus of the precursor of the layer at 25 ° C is preferably 1 M to 10 GPa, more preferably 10 M to 10 GPa, and particularly preferably 100 M to 10 GPa. The elastic modulus can be measured, for example, by a viscoelasticity measuring device Rheosol-G1000 (manufactured by UBM). By using such a modulus of elasticity, and by making the protective layer have an elastic modulus as will be described later, it is possible to more effectively suppress irregularities generated in the polishing apparatus, and it is possible to reduce the thickness of the device wafer to be described later. The strong adhesion is more effective in coexistence with the easy peeling of the device wafer.

<(A) Support>

The laminate of the present invention has (A) a support (also referred to as a carrier substrate).

The material of the support is not particularly limited, and for example, a sulfhydryl group may be mentioned. In the case of a board, a glass substrate, a metal substrate, or the like, it is preferable that the point of the substrate to be used as a substrate of the semiconductor device is not easily contaminated, or the point of the electrostatic chuck commonly used in the process of the semiconductor device can be used. Substrate.

The thickness of the support is, for example, in the range of 300 μm to 5 mm, but is not particularly limited.

<(C) protective layer>

The laminate of the present invention has a (C) protective layer. By providing a protective layer, irregularities during polishing can be suppressed.

The protective layer can be used without any limitation, but it is preferable to reliably protect the device wafer described later.

As the material constituting the protective layer, a well-known compound can be used without limitation for the purpose of protecting the substrate to be treated. Specifically, a phenol resin, an epoxy resin, a melamine resin, a urea resin, an unsaturated polyester resin, an alkyd resin, a polyurethane, a polyimide, a polyethylene, a polypropylene, a poly Vinyl chloride, polystyrene, polyvinyl acetate, Teflon (registered trademark), ABS resin, AS resin, acrylic resin, polyamide, polyacetal, polycarbonate, polyphenylene ether, polybutylene terephthalate a synthetic resin such as ester, polyethylene terephthalate, cyclic polyolefin, polyphenylene sulfide, polyfluorene, polyether oxime, polyarylate, polyetheretherketone, polyamidoximine, or rosin, Natural resin such as natural rubber, hydrocarbon resin. As a commercial item, ZEONEX 480R (made by Japan ZEON Co., Ltd.) etc. can be used preferably. The material constituting the protective layer may be only one type or two or more types.

The softening point of the protective layer is preferably 170 ° C or more and 250 ° C or less. More preferably, it is 200 ° C or more and 250 ° C or less. A polyether oxime resin, a polycarbonate resin, a polystyrene resin, a hydrocarbon resin, and a polyetheretherketone resin having a softening point of 170 ° C or more and 250 ° C or less is more preferable, and a polyether oxime having a softening point of 170 ° C or more and 250 ° C or less is preferable. Resins, polycarbonate resins, polystyrene resins, and polyetheretherketone resins are preferred.

The softening point of the protective layer is preferably lower than the softening point of the adhesive layer precursor and the adhesive layer. When the softening point of the protective layer is lower than the softening point of the adhesive of the adhesive layer, the detergency of the protective layer tends to increase. The difference between the softening point of the protective layer and the softening point of the precursor of the adhesive layer is preferably from 10 ° C to 200 ° C, more preferably from 30 ° C to 200 ° C.

Further, the protective layer may contain a compound which may be contained in the above-mentioned adhesive layer precursor, as long as the effects of the present invention are not impaired.

In order to form a protective layer, the composition for forming a protective layer (protective layer coating liquid) can be applied by a conventional spin coating method, a spray method, a roll coating method, a flow coating method, a knife coating method, a dipping method, or the like. Next, it is formed by drying (baking). Drying can be carried out, for example, at 60 to 150 ° C for 10 seconds to 2 minutes. The protective layer coating liquid preferably contains the above resin and solvent.

The thickness of the protective layer is preferably from 1 to 300 μm, more preferably from 10 to 200 μm, still more preferably from 20 to 150 μm. When there is a structure on the surface of the device wafer, it preferably exceeds the thickness of the structure.

The storage elastic modulus of the protective layer at 25 ° C is preferably 10 M to 1 GPa, more preferably 100 M to 5 GPa, and particularly preferably 1000 M to 3 GPa.

The storage elastic modulus of the protective layer is preferably lower than the storage elastic modulus of the adhesive layer precursor, [storage elastic modulus of the protective layer] / [adhesive layer precursor The value of the storage elastic modulus of the material is preferably from 0.9 to 0.01, more preferably from 0.8 to 0.05, most preferably from 0.5 to 0.1.

The protective layer of the present invention is preferably a polymer compound containing a non-polymerizable fluorine atom. In addition, a preferred embodiment of the non-polymerizable polymer compound having a fluorine atom is preferably the same as those described for the non-polymerizable polymer compound having a fluorine atom contained in the precursor of the adhesive layer. The scope is the same.

The content of the polymer compound having a fluorine atom which is not polymerizable is preferably 0.01 to 99% by mass, more preferably 0.03 to 50% by mass from the viewpoint of good releasability, with respect to the protective layer and all solid components. %, especially preferably 0.05 to 10% by mass.

When a polymerizable compound having a fluorine atom and a polymerizable compound having a fluorine atom is contained in the precursor of the adhesive layer, the effect of improving the releasability is large, and a radically polymerizable compound having a fluorine atom and It is preferred that the user has a combination of a non-polymerizable polymer compound having a fluorine atom.

The non-polymerizable polymer compound having a fluorine atom is preferably contained in at least one of the protective layer or the adhesive layer precursor, or may be contained in both layers. From the viewpoint of the releasability, it is preferably contained in any one of the protective layer or the adhesive layer precursor, and in order to form the adhesive layer having a softening point of 250 ° C or more in the present invention, it is preferably contained in the protective layer. .

In the present invention, the ratio (mass ratio) of the radical polymerizable compound having a fluorine atom in the precursor of the adhesive layer to the polymer compound having a fluorine atom in the protective layer is preferably 5:95. ~95:5 More preferably, it is 10:90~90:10, and the best is 15:85~30:70.

<(D) device wafer>

The laminate of the present invention has (D) device wafers.

The device wafer can be used without any limitation, and examples thereof include a MEMS, a sensor device, and the like.

The device wafer preferably has a structure on the surface, and the structure is preferably a structure having a height of 1 μm or more and 150 μm or less, and preferably a metal structure (also referred to as a metal bump) having a height of 1 μm or more and 150 μm or less. The height of the structure is preferably 5 to 100 μm.

The device wafer preferably has a film thickness of 500 μm or more, more preferably 600 μm or more, and particularly preferably 700 μm or more.

As will be described later, the device wafer is mechanically or chemically treated on the opposite side of the surface in contact with the protective layer, and is preferably thinned to a film thickness of less than 500 μm. A more preferable film thickness is 400 μm or less, and a film thickness is particularly preferably 300 μm or less.

The kit of the present invention relates to a kit comprising: a composition for forming a protective layer containing a resin and a solvent; and a composition for forming an adhesive layer or a layer for forming an adhesive layer containing a solvent and a polymerizable monomer.

The laminate for forming an adhesive layer precursor is applied onto a support to form an adhesive layer precursor, and then a composition for forming a protective layer is applied, whereby the laminate of the present invention can be produced. Further, the protective layer forming composition may be applied to the device to be cured.

The composition of each of the composition layer precursor or the adhesive layer forming composition and the protective layer forming composition, a preferred range, and the like are as described above. The same is true for the following description of the agent layer precursor and the protective layer.

A method for producing a laminate; and a method for producing a semiconductor device: a method for producing a semiconductor device, comprising: a step of transmitting a protective layer and an adhesive layer precursor of the present invention, and then a first surface of the member to be processed; and a substrate; a step of mechanically or chemically treating the second surface opposite to the first surface of the member to be treated to obtain a treated member; and separating the precursor of the adhesive layer precursor or the adhesive layer precursor The step of treating the member (the adhesive layer) with the above-mentioned treated member.

Moreover, it is preferable that the method of manufacturing the semiconductor device is such that after the step of transmitting the protective layer and the adhesive layer precursor, the first surface of the member to be processed and the substrate, and the first surface opposite to the member to be processed The second surface of the side is subjected to a mechanical or chemical treatment to obtain a treated member, and further has a step of heating the precursor layer precursor at a temperature of from 150 ° C to 300 ° C. In particular, the laminate system of the present invention is suitable for use in a use environment of 250 ° C or higher.

Further, the laminate of the present invention is characterized in that (B2) an adhesive layer, (C) a protective layer, and (D) device wafer are sequentially provided on the (A) support. Such a layered system can be produced by a method in which the (A) support having the (B) adhesive layer precursor and the (D) device wafer having the (C) protective layer are followed.

The polymer layer precursor is a polymerizable monomer and/or polymerizable property in the composition for forming an adhesive layer precursor by irradiating active light rays or radiation or heat to the composition for forming a precursor layer of the adhesive layer. The polymerization rate of the oligomer is adjusted to 10 to 70%, and is converted into an adhesive layer precursor. At this time, the heating temperature is preferably from 50 ° C to 220 ° C, more preferably from 100 to 210 ° C, and particularly preferably from 160 to 200 ° C.

Further, after forming the laminate of the present invention, the polymerization rate of the polymerizable monomer and/or the polymerizable oligomer in the adhesive layer precursor is adjusted to a step of irradiating active light or radiation or heat to 50 to 100%, which becomes an adhesive layer, and improves adhesion and easy peelability. At this time, the heating temperature is preferably from 150 ° C to 300 ° C, more preferably from 170 to 250 ° C, and particularly preferably from 180 to 220 ° C.

Hereinafter, the details of the above-described layers, the method for producing the laminated body of the present invention, and the method for producing the semiconductor device are not limited to the following.

Fig. 1 (A), Fig. 1 (B), Fig. 1 (C), Fig. 1 (D), Fig. 1 (E), and Fig. 1 (F) each illustrate an adhesive support and device A schematic cross-sectional view of the wafer temporarily showing a state in which the device wafer temporarily attached to the adhesive support is thinned, a state in which the adhesive support and the device wafer are peeled off, and an adhesive support and device wafer A schematic cross-sectional view of the state after the surface is washed.

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

The subsequent support precursor 100 contains a polymerizable monomer and/or a polymerizable oligomer.

As shown in FIG. 1(B), the composition for forming a precursor layer of the precursor layer is adjusted to a polymerization rate of 10 to 70% by irradiation of active light or radiation or heat. Before the agent layer Drive 13 Further, the storage layer precursor has a storage elastic modulus at 25 ° C, preferably 10 MPA or more and less than 1 GPa. When the adjustment is within this range, the strong adhesion at the time of thinning the device wafer to be described later and the easy peelability at the time of separation of the device wafer can coexist.

The polymerization rate of the monomer is controlled by adjusting the amount of the photoinitiator, the amount of the thermal initiator, or the energy of the active light or radiation or heat.

The polymerization rate of the monomer can be measured by Fourier transform infrared spectroscopy (FT-IR), and the peak area of σ _{= CH} (the surface vibration angle of the vinyl CH) at 820-800 cm ^{-1 is} measured. The peak area of the state before the active light or the radiation or the heat is regarded as 0%, and the state in which the peak completely disappears is calculated as 100%. As the Fourier transform type infrared spectrometer, for example, EXCALIBUR FTS-3000 manufactured by DIGILAB Co., Ltd. can be used.

When a protective layer to be described later is provided on the support 12, it can be applied to (preferably, apply) the surface of the protective layer, and secondarily by drying (baking). Drying can be carried out, for example, at 60 to 150 ° C for 10 seconds to 2 minutes.

Next, the adhesive support 100' having the support and the adhesive layer precursor, the temporary connection with the device wafer 60 (the processed member) having the protective layer, the thinning of the device wafer, and the subsequent support will be described in detail. The separation of the body from the device wafer.

As shown in FIG. 1(B), the device wafer 60 (processed member) is formed by providing a plurality of structures (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 to 1200 μm. The device wafer 62, for example, a metal structure, preferably has a height in the range of 10 to 100 μm.

When the protective layer 71 is provided on the surface 61a, it can be applied on the surface of the protective layer (preferably coating), and secondarily by drying (baking). Drying can be carried out, for example, at 60 to 150 ° C for 10 seconds to 2 minutes. The protective layer 71 preferably completely covers the device wafer 62. When the height of the device wafer is X μm and the thickness of the protective layer is Y μm, it is preferably expressed by X + 100 ≧ Y > X.

In this manner, the protective layer 71 completely covers the device wafer 62, and is effective for thinning the device wafer 60 temporarily attached via the adhesive support 100' to obtain a TTV (Total Thickness Variation) of the thin device wafer. Further reductions (ie, situations where the flatness of the thin device wafer is to be further improved).

That is, in the case where the device wafer 60 temporarily attached via the adhesive support 100 is thinned, the uneven shape of the device wafer 60 formed by the plurality of device wafers 62 is transferred to the thin device wafer 60. The tendency of 'back 61b' may become a major factor in the increase of TTV.

On the other hand, in the case where the device wafer to which the protective layer is temporarily attached via the adhesive support 100' is thinned, first, the device is attached to the protective layer by protecting the plurality of device wafers 62 by the protective layer. In the contact surface of the wafer with the adhesive support 100', there is almost no uneven shape. Therefore, even if the device wafer having such a protective layer is thinned in a state of being supported by the adhesive support 100', the shape of transferring the device wafer 62 derived from the plurality to the protective layer can be reduced. After the back side 61b of the device wafer, the TTV of the resulting thin device wafer can be further reduced.

Continuing, as shown in FIG. 1(C), provided on the surface 61a In the case of the protective layer 71, the protective layer 71 is then pressed against the adhesive layer precursor 13 of the adhesive support 100'. Thereby, the protective layer 71 and the adhesive layer precursor 13 are followed by the adhesive support 100' and the device wafer 60 are temporarily followed.

Then, if necessary, the adhesive body of the adhesive support 100' and the device wafer 60 may be heated (irradiation heat) to make the adhesion of the adhesive layer precursor a stronger adhesive layer. Thereby, the anchoring effect at the interface between the adhesive support and the member to be processed can be promoted, and the cohesive failure of the adhesive layer which is likely to occur at the time of mechanical or chemical treatment to be described later of the donor wafer 60 can be suppressed. Therefore, the adhesion of the adhesive support 100' is improved, and the peeling property at the time of separation of the device wafer can be improved because the elastic modulus of the adhesive layer is further increased.

The heating temperature at this time is preferably from 150 ° C to 300 ° C, more preferably from 170 ° C to 250 ° C, and particularly preferably from 180 ° C to 220 ° C.

The heating time at this time is preferably from 20 seconds to 10 minutes, more preferably from 30 seconds to 5 minutes, and particularly preferably from 40 seconds to 3 minutes.

Next, as shown in FIG. 1(D), the back surface 61b of the ruthenium substrate 61 is subjected to mechanical or chemical treatment, specifically, thin film processing such as sliding or chemical mechanical polishing (CMP), and the ruthenium substrate 61 is used. The thickness is reduced (for example, to a thickness of 1 to 200 μm) to obtain a thin device wafer 60'.

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

Next, as shown in Figure 1 (E), the self-adhesive support The 100' adhesive layer is detached from the surface 61a of the thin device wafer 60'.

The method of detachment is not particularly limited, but it is preferable that the end portion of the thin device wafer 60' is pulled up and peeled off in a direction perpendicular to the device wafer, without any treatment.

<Peeling liquid>

Hereinafter, the peeling liquid will be described in detail.

As the peeling liquid, water and a solvent (organic solvent) can be used. Further, as the stripping liquid, an organic solvent in which the protective layer 71 is dissolved is preferable. Examples of the organic solvent include aliphatic hydrocarbons (hexane, heptane, Isopar E, H, G (manufactured by ESSO Chemical Co., Ltd.), aromatic hydrocarbons (toluene, xylene, etc.), and halogenated hydrocarbons. (dichloromethane, dichloroethane, trichloroethylene, monochlorobenzene, etc.), polar solvent. Examples of the polar solvent include alcohols (methanol, ethanol, propanol, isopropanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-octanol). , 2-ethyl-1-hexanol, 1-nonanol, 1-nonanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethyl Glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl Ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, methyl phenyl carbitol, n-pentanol, methyl pentanol, etc.), ketones (acetone, methyl Ethyl ketone, ethyl butyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, methyl lactate, Butyl lactate, ethylene glycol monobutyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol acetate, diethyl phthalate, butyl acetonate, etc.), other (phosphoric acid Triethyl ester, tricresyl phosphate, N-phenylethanolamine, N-phenyldiethanolamine , N-methyldiethanolamine, N-ethyldiethanolamine, 4-(2-hydroxyethyl) Oresine, N,N-dimethylacetamide, N-methylpyrrolidone, etc.).

Further, the release liquid may contain a base, an acid, and a surfactant from the viewpoint of peelability. When these components are blended, the blending amount is preferably from 0.1 to 5.0% by mass based on the stripping liquid.

Further, from the viewpoint of the releasability, a form in which two or more kinds of organic solvents and water, two or more kinds of bases, an acid, and a surfactant are mixed is also preferable.

As the base, for example, sodium third phosphate, potassium third phosphate, ammonium tertiary phosphate, sodium second phosphate, potassium second potassium phosphate, ammonium second ammonium phosphate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogencarbonate, or carbonic acid can be used. An inorganic alkali agent such as potassium hydrogen, ammonium hydrogencarbonate, sodium borate, potassium borate, ammonium borate, sodium hydroxide, ammonium hydroxide, potassium hydroxide or lithium hydroxide, or monomethylamine, dimethylamine or trimethylamine Amine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, An organic alkaline agent such as monoisopropylamine, diisopropylamine, ethylenediamine, ethylenediamine, pyridine or tetramethylammonium hydroxide. These alkaline agents may be used alone or in combination of two or more.

As the acid, an inorganic acid such as hydrogen halide, sulfuric acid, nitric acid, phosphoric acid or boric acid, or methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, acetic acid, citric acid or formic acid can be used. An organic acid such as gluconic acid, lactic acid, oxalic acid or tartaric acid.

As the surfactant, an anionic, cationic, nonionic or zwitterionic surfactant can be used. In this case, the content of the surfactant is preferably from 1 to 20 with respect to the total amount of the aqueous alkali solution. The mass% is more preferably 1 to 10% by mass.

When the content of the surfactant is within the above range, the peeling property of the adhesive support 100' and the thin device wafer 60' can be further improved.

The anionic surfactant is not particularly limited, and examples thereof include fatty acid salts, rosin acid salts, hydroxyalkanesulfonates, alkanesulfonates, dialkyl sulfosuccinates, and straight Alkenyl benzene sulfonates, branched alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl diphenyl ethers (di) sulfonates, alkyl phenoxy polyoxyethylenes Sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-alkyl-N-oleyl taurosodium salts, N-alkyl sulfosuccinate monodecylamine disodium salt, petroleum Sulfonates, sulfated castor oil, sulfated tallow oil, sulfate esters of fatty acid alkyl esters, alkyl sulfate salts, polyoxyethylene alkyl ether sulfate salts, fatty acid monoglyceride sulfate salts , polyoxyethylene alkyl phenyl ether sulfate salts, polyoxyethylene styryl phenyl ether sulfate salts, alkyl phosphate salts, polyoxyethylene alkyl ether phosphate salts, polyoxyethylene Alkyl phenyl ether phosphate salts, partial saponifications of styrene-maleic anhydride copolymers, partial saponates of olefin-maleic anhydride copolymers, naphthalene sulfonate Salt formalin condensates and the like. Among them, alkylbenzenesulfonates, alkylnaphthalenesulfonates, and alkyldiphenylether (di)sulfonate are particularly preferably used.

The cationic surfactant is not particularly limited, and a conventional one can be used. For example, alkylamine salts, quaternary ammonium salts, alkylimidazolium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives can be given.

The nonionic surfactant is not particularly limited, and examples thereof include a polyethylene glycol type higher alcohol ethylene oxide adduct, an alkylphenol ethylene oxide adduct, and an alkyl naphthol epoxy. Ethane adduct, phenol ethylene oxide adduct, naphthol ethylene oxide adduct, fatty acid ethylene oxide adduct, polyol fatty acid ester ethylene oxide adduct, higher alkyl Amine oxirane adduct, fatty acid decylamine ethylene oxide adduct, ethylene oxide adduct of fats and oils, polypropylene glycol ethylene oxide adduct, dimethyl decane-epoxy Alkane block copolymer, dimethyloxane-(propylene oxide-ethylene oxide) block copolymer, fatty acid ester of glycerol of polyol, fatty acid ester of pentaerythritol, sorbitol and sorbitol A fatty acid ester of an anhydride, a fatty acid ester of sucrose, an alkyl ether of a polyhydric alcohol, a fatty acid decylamine of an alkanolamine, or the like. Among them, preferred are those having an aromatic ring and an ethylene oxide chain, more preferably an alkyl-substituted or unsubstituted phenol ethylene oxide adduct or an alkyl-substituted or unsubstituted naphthol epoxy ethylene adduct. .

The zwitterionic surfactant is not particularly limited, and examples thereof include an amine oxide system such as an alkyl dimethylamine oxide, a betaine such as an alkylbetaine, and an alkylamino fatty acid sodium. Amino acid system. In particular, an alkyldimethylamine oxide which may have a substituent, an alkylcarboxybetaine which may have a substituent, an alkylsulfobetaine which may have a substituent, is preferably used. Specifically, a compound represented by the formula (2) of paragraph No. [0256] of JP-A-2008-203359, and a formula (I) and a formula (II) of paragraph number [0028] of JP-A-2008-276166 can be used. And a compound represented by the formula (VI), and a compound represented by paragraphs [0022] to [0029] of JP-A-2009-47927.

In addition, as needed, it can also contain softeners such as defoamers and hard water. Additive for the agent.

Next, as shown in Fig. 1(F), a thin device wafer can be obtained by removing the protective layer 71 on the device wafer surface 61a. As a method of removing the protective layer 71, a method of directly removing a film, a method of dissolving and dissolving in an aqueous solution or an organic solvent, and a method of dissolving and vaporizing by active light, radiation, or heat may be mentioned. However, it is preferred to use a method of dissolving and dissolving in an organic solvent. The aqueous solution or the organic solvent may be used arbitrarily as long as it is a solution capable of dissolving and removing the protective layer. Specifically, the above-mentioned peeling liquid capable of dissolving and removing the protective layer can be preferably used, and a more preferable aspect is also the same as the peeling liquid.

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

Further, as shown in Fig. 1(F), the support can be regenerated by removing the adhesive layer on the support. As a method of removing the adhesive layer, a method of physically removing the film directly by spraying with a brush, an ultrasonic wave, an ice particle or an aerosol, and dissolving it in an aqueous solution or an organic solvent to dissolve and remove it is exemplified. A chemical removal method such as a method of decomposing or vaporizing by irradiation with active light, radiation, or heat can be carried out by a conventionally known cleaning method in accordance with the support.

For example, when a ruthenium substrate is used, a conventionally known ruthenium wafer cleaning method can be used, for example, an aqueous solution or an organic solvent which can be used as a chemical removal, and examples thereof include a strong acid, a strong alkali, a strong oxidizing agent or the like. Specific examples of the mixture include acids such as sulfuric acid, hydrochloric acid, hydrofluoric acid, nitric acid, and organic acids, alkalis such as tetramethylammonium, ammonia, and organic bases, and peroxygen. An oxidizing agent such as hydrogen or a mixture of ammonia and hydrogen peroxide, a mixture of hydrochloric acid and hydrogen peroxide, a mixture of sulfuric acid and hydrogen peroxide, a mixture of hydrofluoric acid and hydrogen peroxide, a mixture of hydrofluoric acid and ammonium fluoride, and the like.

From the viewpoint of the adhesion when using the regenerated support, the following substrate cleaning solution is preferred.

The substrate cleaning solution preferably contains an acid having a pKa of less than 0 and hydrogen peroxide. The acid having a pKa of less than 0 may be selected from inorganic acids such as hydrogen iodide, perchloric acid, hydrogen bromide, hydrogen chloride, nitric acid, sulfuric acid, or the like, or an organic acid such as an alkylsulfonic acid or an arylsulfonic acid. From the viewpoint of the detergency of the adhesive layer on the substrate, a mineral acid is preferred, and sulfuric acid is preferred.

As the hydrogen peroxide, 30 w/v% hydrogen peroxide is preferably used, and the mixture of the above strong acid and 30 w/v% hydrogen peroxide is preferably 0.1:1 to 100:1, more preferably 1:1 to 10:1, and most preferably 3:1~5:1.

Next, the conventional embodiment will be described.

Fig. 2 is a schematic cross-sectional view showing the release of the temporary state of the conventional adhesive support and the device wafer.

In the conventional embodiment, as shown in FIG. 2, as the adhesive support, an adhesive support in which the adhesive layer 11' formed of a conventional temporary adhesive is provided on the support 12 is used. In the same manner as described with reference to FIGS. 1(A) and 1(B), the adhesive support 100' is temporarily attached to the device wafer to perform the ruthenium substrate in the device wafer. The thin film processing is followed by peeling off the thin device wafer 60' from the adhesive support 100' in the same manner as the above procedure.

However, it is difficult to temporarily support the member to be processed by a high adhesion force by the conventional temporary adhesive agent, and the processing is not performed. The damage is caused by the pieces, and the temporary support for the treated members is easily released. For example, in order to make the temporary contact between the device wafer and the support sufficiently sufficient, if the adhesion is high in the conventional temporary adhesive, the temporary orientation of the device wafer and the support tends to be too strong. Therefore, in order to release this excessively strong temporary, for example, as shown in FIG. 2, a tape (for example, a dicing tape) is adhered to the back surface 61b' of the thin device wafer 60', and the thin device is peeled off from the adhesive support 100'. In the case of the wafer 60', it is easy to cause the structure 63 to be detached from the device wafer 62 in which the structure (bump) 63 is provided, and the device wafer 62 is broken.

On the other hand, in the conventional temporary adhesive, if the adhesion is low, the temporary support for the processed member can be easily released, but the temporary connection between the device wafer and the carrier substrate is weak and easy to occur. The carrier substrate cannot reliably support the device wafer.

However, the adhesive layer formed of the adhesive layer precursor of the present invention exhibits sufficient adhesion while easily releasing the temporary attachment of the wafer 60 and the adhesive support 100'. That is, with the laminated body of the present invention, the device wafer 60 can be temporarily supported with a high adhesion force, and the thin device wafer 60' can be prevented from being damaged, and the temporary support for the thin device wafer 60' can be easily released.

The method for forming a laminate and the method for producing a semiconductor device of the present invention are not limited to the above embodiments, and suitable modifications, improvements, and the like are possible.

In the above embodiment, the adhesive layer formed of the adhesive layer precursor of the present invention constitutes an adhesive support by being provided on the support before the temporary mounting of the device wafer. First, it is placed on a member to be processed such as a device wafer, and then the member to be treated in which the adhesive layer is provided is temporarily brought back to the support.

Further, in the above embodiment, the adhesive layer precursor and the adhesive layer have a single layer structure, but the adhesive layer precursor and the adhesive layer may have a multilayer structure. As a method of forming the adhesive layer of the multilayer structure, a method of applying a temporary adhesive agent in stages by the aforementioned conventional method, or after irradiating active light, radiation or heat, before irradiating active light, radiation or heat, A method of applying a temporary adhesive or the like by the aforementioned conventional method.

Further, in the above-described embodiment, the substrate to be processed supported by the adhesive support is not limited thereto, and may be mechanically or chemically treated in the method of manufacturing the semiconductor device. Any of the processed components.

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

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 present invention is not limited thereto. Any processing necessary in the method of manufacturing the semiconductor device can also be cited.

The shape, size, number, arrangement place, and the like of the device wafer in the device wafer may be arbitrarily and unrestricted as long as it is cost-effective.

[Examples]

Hereinafter, the present invention will be more specifically described by the examples, but the present invention should not be construed as limited to In addition, "parts" and "%" are based on quality unless otherwise specified.

<Formation of Support Body Having Composition Layer for Adhesive Layer Precursor Formation>

The composition for forming an adhesive layer precursor described below was applied onto a 200 mm Si wafer by a spin coater, and then baked at 120 ° C for 30 seconds to form a composition layer for forming an adhesive precursor having a thickness of 0.2 μm. Wafer. For a wafer provided with a composition layer for an adhesive precursor formation, σ _{= CH} (vinyl CH) is measured in the vicinity of 820-800 cm ^-1 using a Fourier transform infrared spectrometer (EXCALIBUR FTS-3000). The angular area of the angular vibration band).

<Substituent composition for forming an adhesive layer precursor>

‧Polymerizable monomer or oligomer (b-1) The mass parts described in the following table

‧ Polymerizable monomer or oligomer (b-1') The mass parts described in the following table

‧Photoradical polymerization initiator (b-2) The mass parts described in the following table

‧ Thermal radical polymerization initiator (b-3) The mass parts described in the following table

‧ Polymer compound (b-4) The mass parts described in the following table

‧Polymerization inhibitor (p-methoxyphenol, manufactured by Tokyo Chemical Industry Co., Ltd.) 0.008 parts by mass

‧ Surfactant (PF6320, manufactured by OMNOVA) 0.032 parts by mass

‧ solvent (propylene glycol monopropyl ether acetate) 94.96 parts by mass

The compounds described in Table 1 are as follows.

[(b-1) polymerizable monomer or oligomer]

(b-1-1) Blemmer PME400 (Nippon Oil Co., Ltd.)

(b-1-2) NK Ester A-BPE-4 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

(b-1-3) NK Ester A-BPE-10 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

(b-1-4) Divinylbenzene (Wako Pure Chemical Industries, Ltd.)

(b-1-5) Light Acrylate TMP-A (Kyoeisha Chemical Co., Ltd.)

(b-1-6) NK Ester A-TMP-3EO (New Nakamura Chemical Industry Co., Ltd.)

(b-1-7) NK Ester AD-TMP (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

(b-1-8) NK Ester A-DPH (New Nakamura Chemical Industry Co., Ltd.)

(b-1-9) Triallyl isocyanurate (Tokyo Chemical Industry Co., Ltd.)

(b-1-10) RS-76-E (fluorine-based oligomer, manufactured by DIC)

(b-1-11) RS-72-K (fluorine-based oligomer, manufactured by DIC)

(b-1-12) Optool DAC-HP (fluorine-based oligomer, manufactured by DAIKIN Industries Co., Ltd.)

(b-1-13) X-22-164 (lanthanum oligomer, 2-functional monomer, manufactured by Shin-Etsu Chemical Co., Ltd.)

(b-1-14) Fluorine monomer of the following structure

[(b-2) Photoradical polymerization initiator]

(b-2-1) IRGACURE OXE 02 (manufactured by BASF Corporation)

(b-2-2) Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.)

[(b-3) Thermal Radical Polymerization Initiator]

(b-3-1) Perbutyl Z (tertiary butyl peroxybenzoate, decomposition temperature (10-hour half-life temperature = 104 ° C), manufactured by Nippon Oil Co., Ltd.)

(b-3-2) Perhexa 22 (2,2-di-(t-butylperoxy)butane, decomposition temperature (10-hour half-life temperature = 103 ° C), manufactured by Nippon Oil Co., Ltd.)

[(b-4) polymer compound]

(b-4-1) Estyrene MS600 (Methyl Methacrylate-Styrene Copolymerized Resin, Nippon Steel & Sumitomo Chemical Co., Ltd.)

(b-4-2) Polymethyl methacrylate (made by Aldrich, Mw: 120,000)

[Compound (b-5) having a fluorine atom]

(b-5-1) Daifree FB-962 (DAIKIN Industrial Co., Ltd.)

<Production of processed components>

As a member to be processed, a composition for forming a protective layer described in the following table was applied onto a 200 mm Si wafer with a bump of Cu having a height of 10 μm by a spin coater, and then under the conditions described in the following table. Baking is performed twice or twice to form a wafer having a protective layer having a thickness of 20 μm.

<Composition of a composition for forming a protective layer>

‧Resin component The mass parts described in the following table

‧Solvents The mass parts described in the following table

The compounds described in Table 2 are as follows.

[resin composition]

(C-1-1) ultrason E6020P (polyether oxime resin, manufactured by BASF Corporation)

(C-1-2) PCZ-300 (polycarbonate resin, Mitsubishi Gas Chemical Co., Ltd.)

(C-1-3) Estyrene MS200NT (polystyrene resin, Nippon Steel Chemical Co., Ltd.)

(C-1-4) TOPAS 5013 (hydrocarbon resin, manufactured by POLYPLASTICS)

[solvent]

(C-2-1) N-methyl-2-pyrrolidone (NMP) (made by Wako Pure Chemical Industries, Ltd.)

(C-2-2) Anisole (made by Wako Pure Chemical Industries, Ltd.)

(C-2-3) Propylene Glycol Monomethyl Ether Acetate (PGMEA) (made by Wako Pure Chemical Industries, Ltd.)

(C-2-4) Limonene (made by Kanto Chemical Co., Ltd.)

[Compound (C-3) having a fluorine atom]

(C-3-1) Daifree FB-962 (DAIKIN Industrial Co., Ltd.)

<Production of laminated body>

Next, as described in the table, a wafer having a composition layer for forming an adhesive layer precursor and a member to be treated having a protective layer are pressed under vacuum at 120 ° C under a pressure of 1000 N for 3 minutes to obtain A laminate of a wafer, an adhesive layer precursor, a protective layer, and a member to be processed. The obtained laminate is stretched in the vertical direction of the layer, and is divided into a wafer having an adhesive precursor and a member to be processed having a protective layer. For a wafer having an adhesive precursor, a Fourier transform infrared spectrometer is used. (EXCALIBUR FTS-3000), the peak area of σ _{= CH} (external angular vibration band of vinyl CH) in the vicinity of 820-800 cm ^{-1 was} measured.

Calculating the reduction rate of the peak area value before and after the bonding, and calculating the aggregation of the polymerizable monomer or oligomer in the adhesive precursor before and after heating or light irradiation Combination rate.

Further, as described in the table, a wafer having a composition layer for forming an adhesive layer precursor and a member to be treated having a protective layer are pressed under vacuum at 120 ° C under a pressure of 1000 N for 3 minutes, thereby obtaining A laminate of a wafer, an adhesive layer precursor, a protective layer, and a member to be processed.

Further, the film was heated at 200 ° C for 3 minutes under normal pressure, and the adhesive layer precursor was used as an adhesive layer to obtain an adhesive test piece.

<Measurement of adhesion force of adhesive test piece>

Using a tensile tester (IMADA (digital) dynamometer, type: ZP-50N), the film was stretched in the direction of the surface of the adhesive layer at 250 mm/min, and the conditions described in the following table were measured. The shearing force of the test piece produced below was evaluated by the following criteria.

A: Strong to the extent of wafer rupture

B: peeling off with a force of more than 10N and less than 50N

C: peeling off with a force of 10N or less

<peelability>

The test piece prepared under the conditions described in the following table was stretched in the vertical direction of the adhesive layer under conditions of 250 mm/min. Confirm the peelability. Furthermore, the test piece produced was heated at 250 ° C for 30 minutes, and then stretched in the vertical direction of the adhesive layer under the conditions of 250 mm/min in the same manner, and the peeling property after hot working was confirmed, and the evaluation was performed based on the following criteria. Furthermore, it was visually confirmed whether or not the Si wafer was damaged.

AA: peelable with a maximum peel force of less than 10N

A: peelable at a maximum peeling force of 10 N or more and less than 20 N

B: peelable at a maximum peeling force of 20 N or more and less than 30 N

C: peelable at a maximum peeling force of 30 N or more and less than 50 N

D: The maximum peeling force is 50N or more or the wafer is damaged.

<TTV: Total Thickness Variation>

For the bonded wafer, a back side of the joint surface of the member to be processed was thinned using a DISCO 8560 grinding machine (DFG8560) until the film thickness of the member to be processed became 100 μm. Then, the layer thickness of the member to be processed was measured using a semiconductor substrate surface inspection apparatus (SemDex300) manufactured by ISIS, and the difference between the minimum value and the maximum value of the thickness was determined and evaluated by the following criteria.

A: the difference between the minimum value and the maximum value is 5 μm or less

B: the difference between the minimum value and the maximum value exceeds 5 μm

<washing removal>

After the peeling test was completed, the 200 mm wafer (exposed to the heat resistance test condition) attached to the dicing frame via a dicing tape was placed, and the adhesive layer was placed on the spin coater, and the following table was used. The solvent was used as a washing solvent, and after spraying for 5 minutes, isopropyl alcohol (IPA) was sprayed while rotating the wafer. Then, the appearance was observed, and the presence or absence of the residual adhesive resin was visually checked and evaluated by the following criteria.

A: I didn't see the resin remaining.

B: I saw the residual resin.

As described above, it is understood that the (B) adhesive layer precursor, the (C) protective layer, and the (D) device wafer are sequentially provided on the (A) support, and the (B) adhesive layer precursor includes (b-1). In the examples in which the polymerization ratio of the polymerizable monomer or oligomer is from 10 to 70%, not only the adhesion and the release property are good, but also the TTV and the detergency are excellent.

On the other hand, in Comparative Example 1 in which the polymerization rate of the polymerizable monomer was less than 10%, the peelability was inferior to that of the examples. In Comparative Example 2 in which the polymerization rate of the polymerizable monomer exceeded 70%, the adhesion was worse than that of the examples. Further, it is understood that Comparative Examples 3 to 4 which do not have any of the adhesive layer precursor and the protective layer are inferior to the examples in terms of adhesion and TTV.

In addition, when the radical polymerizable monomer having a trifunctional or higher functional group and/or a radical polymerizable monomer having a fluorine atom is contained in the adhesive layer precursor, the peeling property is further improved (Examples 8 and 10 to 12, 14~30, 33).

In addition, when a radical polymerizable compound having a fluorine atom is contained in the precursor of the adhesive layer, and a non-polymerizable compound having a fluorine atom is contained in the adhesive layer precursor or the protective layer, the peeling property is further improved. (Examples 35, 36, 39 to 48)).

Claims (24)

A laminate comprising (B) an adhesive layer precursor, (C) a protective layer, and (D) a device wafer on the (A) support, the (B) adhesive layer precursor comprising (b) -1) a polymerizable monomer and/or a polymerizable oligomer, and a polymerization ratio of a polymerizable monomer and/or a polymerizable oligomer is 10 to 70%, and the support is a ruthenium substrate, a glass substrate or a metal substrate. The adhesive layer precursor is in contact with the support. The layered product of claim 1, wherein the (b-1) polymerizable monomer and/or the polymerizable oligomer contains at least one of three or more functional groups of a radical polymerizable monomer. The laminate according to claim 1 or 2, wherein the (b-1) polymerizable monomer and/or the polymerizable oligomer contains at least one radical polymerizable compound having a fluorine atom and/or a ruthenium atom. The laminate according to claim 1 or 2, wherein the (b-1) polymerizable monomer and/or the polymerizable oligomer contains a bifunctional or less radical polymerizable monomer and a trifunctional or higher radical polymerizable monomer. . The laminate of claim 1 or 2, wherein the adhesive layer precursor further comprises (b-2) a photoradical initiator. The laminate of claim 1 or 2, wherein the adhesive layer precursor further comprises (b-3) a thermal radical initiator. The laminate of claim 1 or 2, wherein the adhesive layer precursor further contains (b-4) a polymer compound. The laminate according to claim 1 or 2, wherein the adhesive layer precursor has a storage elastic modulus at 25 ° C of 10 MPa or more and less than 1 GPa. A laminate comprising (B2) an adhesive layer, (C) a protective layer, and (D) a device wafer on a (A) support, the (B2) adhesive layer being an adhesive layer precursor a cured product, the adhesive layer precursor comprising (b-1) a polymerizable monomer and/or a polymerizable oligomer, and a polymerization ratio of the polymerizable monomer and/or the polymerizable oligomer is 10 to 70%. The support is a tantalum substrate, a glass substrate or a metal substrate, and the adhesive layer precursor is in contact with the support. The laminate according to claim 9, wherein the adhesive layer precursor has a storage elastic modulus at 25 ° C of 10 MPa or more and less than 1 GPa. The laminate of claim 1 or 9, wherein the softening point of the (C) protective layer is 170 ° C or more and 250 ° C or less. The laminate of claim 1 or 9, wherein the (C) protective layer is a thermoplastic resin. The laminate according to claim 1 or 9, wherein the (C) protective layer comprises a polyether oxime resin, a polyimide resin, a polyester resin, a polybenzimidazole resin, a polyamide amide resin, a polycarbonate At least one thermoplastic resin selected from the group consisting of a resin, a polystyrene resin, and a polyetheretherketone resin. The laminate according to claim 1 or 9, wherein the (D) device wafer has a structure having a height of 1 μm or more and 150 μm or less on the surface. A protective layer forming composition which is a protective layer forming composition for a protective layer of a laminate according to any one of claims 1 to 14, which comprises a resin and a solvent, and the resin has a softening point of 170 ° C. Above 250 ° C. A composition for producing an adhesive layer precursor of the laminate of any one of claims 1 to 8 and 10 to 14 or a composition for an adhesive layer of claim 9, and comprising a solvent and (b) -1) a polymerizable monomer and/or a polymerizable oligomer. The composition of claim 16, wherein the (b-1) polymerizable monomer and/or the polymerizable oligomer contains at least one of three or more functional groups of a radical polymerizable monomer. The composition of claim 16 or 17, wherein the (b-1) polymerizable monomer and/or the polymerizable oligomer comprises at least one radical polymerizable compound having a fluorine atom and/or a ruthenium atom. The composition of claim 16 or 17, wherein (b-1) the polymerizable monomer and/or the polymerizable oligomer contains a bifunctional or less radical polymerizable monomer and a trifunctional or higher radical polymerizable monomer . The composition of claim 16 or 17, which further comprises (b-2) a photoradical initiator. The composition of claim 16 or 17, further comprising (b-3) a thermal free radical initiator. The composition of claim 16 or 17, which further comprises (b-4) a polymer compound. A kit for manufacturing a laminate according to any one of claims 1 to 14, comprising: a protective layer-forming composition containing a resin and a solvent; and a solvent and a polymerizable monomer; / or an adhesive layer precursor of a polymerizable oligomer or a composition for forming an adhesive layer. The kit of claim 23, wherein the adhesive layer precursor has a storage elastic modulus at 25 ° C of 10 MPa or more and less than 1 GPa.