TWI557202B - And a temporary fixing agent composition - Google Patents

Description

Temporary fixing adhesive composition

The present invention relates to a method of temporarily fixing a member when processing various members, or a composition and an adhesive suitable for the method. The present invention relates to a method of temporarily fixing a member, for example, when a silicon wafer is processed by a silicon block, and an acrylic temporary fixing adhesive composition suitable for the use.

A double-sided tape, a hot-melt adhesive-based adhesive, or an epoxy-based adhesive is used as a temporary fixing adhesive for a semiconductor package or the like. After the member joined or laminated with the above-mentioned adhesive is cut into a predetermined shape, the adhesive is removed, and the processed member is produced. For example, in the case of a semiconductor package component, the components are fixed to a substrate by a double-sided tape, and then cut into a desired component, and the double-sided tape is further irradiated with ultraviolet light to be peeled off from the component. In the case of a hot melt adhesive-based adhesive, the members are joined, and the adhesive is allowed to permeate into the gap by heating, and then cut into a desired element, and the adhesive is peeled off in an organic solvent. In the case of an epoxy-based adhesive, the main component and the curing agent are metered, mixed, and joined to a member, and then cut into a desired element, and the adhesive is peeled off in an organic solvent.

However, the double-sided tape has a problem that it is difficult to produce thickness precision or that the joint strength is weak and it is impossible to peel off during processing of the component. The double-sided tape has a problem that it cannot be peeled off unless it is heated to 100 ° C or more. When the double-sided tape is peeled off by ultraviolet irradiation, if the penetration property of the bonded object is insufficient, there is a problem that peeling cannot be performed.

The hot-melt adhesive-based adhesive can be bonded without being heated to 100 ° C or more at the time of joining, and is limited in the usable members. Hot melt adhesive-based adhesive An organic solvent is used for the peeling, and the cleaning step of the alkaline solvent and the halogen-based organic solvent is cumbersome, and causes problems in the working environment.

When the epoxy-based adhesive is insufficient in the measurement and mixing of the main agent and the curing agent, the bonding property may be remarkably lowered. The epoxy-based adhesive is similar to the hot-melt adhesive-based adhesive, and it is necessary to use an organic solvent at the time of peeling. The cleaning step of the alkaline solvent of the epoxy-based adhesive and the halogen-based organic solvent is cumbersome, and causes problems in the working environment. The curing speed of the epoxy-based adhesive is slow, and it is necessary to retain a sufficient hardening time until hardening.

In order to solve such problems, Patent Documents 1 to 3 have proposed a photocuring type or heat curing type adhesive for temporarily fixing a water-soluble compound such as a water-soluble ethylene monomer. Although the above-mentioned adhesive composition solves the peeling property in water, there is a problem that the joint strength at the time of fixing the component is relatively low, and the dimensional precision of the member at the time of the cutting process is lacking. In the case of a photocurable adhesive, the use thereof is limited to a penetrating adherend, and when it is a heat-curing adhesive, its use is limited to a heat-resistant adherend.

Prior Technical Literature Patent Literature

[Patent Document 1] Japanese Patent Laid-Open No. Hei 6-116534

[Patent Document 2] Japanese Patent Laid-Open No. Hei 11-71553

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2001-226641

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2010-248395

[Patent Document 5] International Publication WO2008/018252

[Patent Document 6] Japanese Patent Laid-Open No. 7-153724

[Patent Document 7] Japanese Patent Laid-Open No. Hei 11-60400

However, even if the proposals according to Patent Documents 1 to 3 are still insufficient, in order to solve the above problems, a two-component acrylic adhesive has been proposed which has high joint strength and is excellent in peelability in water, and is peeled off due to peeling. In the form of a film, no residue remains on the member, and it is excellent both in terms of environment and workability (Patent Document 4). However, even if the processing conditions are not particularly limited, there is no description about "the chipping does not occur on the processed wafer". If the wafer is peeled off, there is a flaw in the wafer due to its use as a base point.

Patent Document 5 describes an adhesive composition containing spherical cerium oxide as a particulate matter, but the amount thereof used is 20 parts by mass or less, which is different from the amount used in the present invention.

As a result of various investigations to solve the above problems, the inventors have found that the inorganic filler is filled in the above-mentioned adhesive, and the peeling of the processed wafer can be reduced, and the present invention has been achieved.

That is, the present invention is:

A temporary fixing adhesive composition comprising the following components: (1) 100 parts by mass of a monomer and/or oligomer having a (meth) acrylonitrile group, (2) a polymerization initiator, (3) β -diketone chelate and/or β -ketoester, and (4) 25 to 300 parts by mass of an inorganic filler.

2. The temporary fixing adhesive composition according to Item 1, which further comprises (5) an elastomer component.

3. The temporary fixing adhesive composition according to the first aspect, wherein (4) the inorganic filler is one or more selected from the group consisting of cerium oxide, quartz, alumina, and talc.

4. The temporary fixing adhesive composition according to any one of items 1 to 3, wherein (1) the monomer and/or oligomer having a (meth)acrylinyl group comprises: (1-2) (meth)acrylic acid monomer having a bisphenol skeleton, (1-4) (meth)acrylate having an aromatic group, and (1-5) hydroxyalkyl (meth)acrylate.

5. The temporary fixing adhesive composition according to item 4, wherein, in the total of 100 parts by mass of the component (1-2), the component (1-4), and the component (1-5), the component (1-2) The content ratio of the component (1-4) and the component (1-5) is a component (1-2) by mass ratio: component (1-4): component (1-5) = 1 to 20: 20 to 60. : 30~70.

6. The temporary fixing adhesive composition according to any one of items 1 to 3, wherein the monomer and/or oligomer having a (meth)acrylinyl group comprises: (1-1) (methyl An alkyl acrylate, (1-2) a (meth)acrylic monomer having a bisphenol skeleton, (1-4) a (meth) acrylate having an aromatic group, and (1-5) (meth)acrylic acid Hydroxyalkyl ester.

7. The temporary fixing adhesive composition according to item 6, wherein the total amount of the component (1-1), the component (1-2), the component (1-4), and the component (1-5) is 100 parts by mass. The content ratio of the component (1-1), the component (1-2), the component (1-4), and the component (1-5) is a component (1-1) by mass ratio: component (1-2): Ingredients (1-4): Ingredients (1-5) = 5 to 35: 1 to 30: 20 to 50: 15 to 45.

8. The temporary fixing adhesive composition according to any one of items 1 to 7, wherein the (3) β-diketone chelate and/or the β-ketoester comprises vanadium acetonate, naphthenate One or more of the group consisting of copper acid and cobalt octoate.

A two-part type temporary fixing adhesive composition comprising an adhesive agent which is obtained by dividing the temporary fixing adhesive composition according to any one of items 1 to 8 into a first agent and a second agent. A composition wherein the first agent contains at least component (2) and the second agent contains at least component (3).

10. The temporary fixing adhesive composition according to any one of items 1 to 9, which It further contains olefins.

The temporary fixing adhesive composition according to any one of items 1 to 10, which further comprises a polymerization inhibitor.

The temporary fixing adhesive composition according to any one of items 1 to 11, which further comprises a phosphate.

The temporary fixing adhesive composition according to any one of items 1 to 12, which is used in the group consisting of sputum cutting, sapphire cutting, glass cutting, and resin cutting. One or two or more.

A temporary fixing method of a member, characterized in that the member is temporarily fixed by using the temporary fixing adhesive composition according to any one of items 1 to 13, and the temporary fixing adhesive is composed of The material is hardened, the temporarily fixed member is processed, and the processed member is immersed in water to remove the hardened body of the temporary fixing adhesive composition.

15. The method of temporarily fixing a member according to item 14, wherein the water is warm water.

A method of producing a tantalum wafer, characterized in that the temporary fixing adhesive composition according to any one of claims 1 to 13 is used, and the tantalum block is bonded to the substrate to be temporarily fixed, and then cut. The germanium wafer is fabricated by cutting the germanium wafer, and the germanium wafer is immersed in water and the germanium wafer is removed from the substrate.

17. The method of manufacturing a wafer according to claim 16 wherein the water is warm water.

A joined body obtained by joining the joined body using the temporary fixing adhesive composition according to any one of items 1 to 13.

19. The joined body according to Item 18, wherein the joined body is one or more selected from the group consisting of ruthenium, sapphire, resin, and glass.

The present invention has effects such as the following. The temporary fixing adhesive composition of the present invention increases the hardness by including an inorganic filler, whereby the peeling of the member to be processed can be suppressed.

The invention is described in detail below.

The monomer (1) having a (meth) acrylonitrile group used in the present invention and/or an oligomer may be exemplified below.

(1-1) alkyl (meth)acrylate

The alkyl (meth)acrylate may, for example, be a (meth)acrylic monomer represented by the general formula (A).

General formula (A) ZOR ₁

(wherein Z represents a (meth)acrylonitrile group, and R ₁ represents an alkyl group having 1 to 20 carbon atoms).

R ₁ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 6 to 12 carbon atoms. When the carbon number exceeds 20, the surface hardenability is lowered to exhibit viscosity, and the curing rate is lowered.

Examples of such a (meth)acrylic monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. Butyl acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate One or two or more of these may be used. Among these, 2-ethylhexyl (meth)acrylate is preferred from the viewpoint of good adhesion.

(1-2) (meth)acrylic monomer having a bisphenol skeleton

The (meth)acrylic monomer having a bisphenol skeleton can be exemplified by the general formula (B) The (meth)acrylic monomer shown and the like.

General formula (B) ZO-(R ₂ O) _p -C ₆ H ₄ -C(R ₃ )(R ₃ ')-C ₆ H ₄ -O-(R ₂ 'O) _P' -Z'

(wherein Z and Z' represent a (meth)acrylinyl group; and R ₂ and R ₂ ' represent -C ₂ H ₄ -, -C ₃ H ₆ -, -CH ₂ CH(CH ₃ )-, -C ₄ H ₈ - or -C ₆ H ₁₂ -; R ₃ , R ₃ ' represents hydrogen or an alkyl group having 1 to 4 carbon atoms; p, p' represents an integer of 0 to 8)

Examples of such a (meth)acrylic monomer include 2,2-bis(4-(methyl)propenyloxyphenyl)propane and 2,2-bis(4-(methyl)propene oxime. Ethylethoxyphenyl)propane, 2,2-bis(4-(methyl)propenyloxydiethoxyphenyl)propane, 2,2-bis(4-(methyl)propenyloxyl Tetraethoxyphenyl)propane, 2,2-bis(4-(methyl)propenyloxypolyethoxyphenyl)propane, 2,2-bis(4-(methyl)propenyloxyl One type or two or more kinds of these may be used as the propoxyphenyl)propane. Among these, 2,2-bis(4-(methyl)propenyloxypolyethoxyphenyl)propane is preferred from the viewpoint of a large effect. Preferably, p and p' are 1 or more.

(1-3) Dicyclopentenyloxyalkyl (meth) acrylate

The dicyclopenteneoxyalkylene (meth) acrylate may, for example, be a (meth)acrylic monomer represented by the general formula (C).

(wherein Z represents (meth)acrylinyl; R ₄ represents an alkylene group having 1 to 12 carbon atoms; and q represents an integer of 1 to 20)

Examples of such a (meth)acrylic monomer include dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyloxy diethylene glycol (meth) acrylate, and dicyclopentene. One or two or more kinds of these may be used, such as oxytriethylene glycol (meth) acrylate and dicyclopentenyloxy propylene glycol (meth) acrylate. Among these, dicyclopentenyloxyethyl (meth) acrylate is preferable from the viewpoint of excellent surface hardenability and easy availability. R _{4 is} preferably an alkyl group having 1 to 4 carbon atoms and more preferably an ethyl group in view of the strength of the resin. q From the viewpoint of the resin strength of the cured product, it is preferably from 1 to 3, more preferably from 1.

(1-4) (meth) acrylate having an aromatic group

Examples of the (meth)acrylic acid ester having an aromatic group include a (meth)acrylic monomer represented by the general formula (D).

General formula (D) ZO-(R ₅ O) _r -R ₆

(wherein Z represents (meth)acrylinyl; R ₅ represents -C ₂ H ₄ -, -C ₃ H ₆ -, -CH ₂ CH(CH ₃ )-, -C ₄ H ₈ - or -C ₆ H ₁₂ -; R ₆ represents a phenyl group or a phenyl group having an alkyl group having 1 to 3 carbon atoms; r represents an integer of 1 to 10)

Examples of such a (meth)acrylic monomer include phenoxyethyl (meth)acrylate, phenoxy diethylene glycol (meth) acrylate, and phenoxy polyethylene glycol (meth) acrylate. The ester, the phenoxypropyl (meth) acrylate, the phenoxy dipropylene glycol (meth) acrylate, and the phenoxy polypropylene glycol (meth) acrylate may be used alone or in combination of two or more. Among these, phenoxyethyl (meth)acrylate is preferred from the viewpoint of high effect.

(1-5) (meth)acrylic monomer having a hydroxyl group (hydroxyalkyl (meth)acrylate)

The (meth)acrylic monomer having a hydroxyl group may, for example, be a (meth)acrylic monomer represented by the general formula (E).

General formula (E) ZO-(R ₇ O) _s -H

(wherein Z represents (meth)acrylinyl; R ₇ represents -C ₂ H ₄ -, -C ₃ H ₆ -, -CH ₂ CH(CH ₃ )-, -C ₄ H ₈ - or -C ₆ H ₁₂ -; s represents an integer from 1 to 10)

Examples of such a (meth)acrylic monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate. One or two or more kinds of these may be used as the hydroxyalkyl acrylate or the like. Among these, 2-hydroxyethyl (meth)acrylate and/or 2-hydroxypropyl (meth)acrylate are preferred from the viewpoint of being inexpensive and having good bonding properties.

(1-6) Poly (meth) acrylate

Examples of the (meth) acrylate of the polyhydric alcohol include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,9-nonanediol. Di(meth)acrylate, tripropylene glycol di(meth)acrylate, and the like. Among these, it is preferable to use 1,9-nonanediol di(meth)acrylate and/or tripropylene glycol di(meth)acrylate from the viewpoint of low skin irritation.

(1-7) oligomer having (meth) acrylonitrile group

The oligomer having a (meth) acrylonitrile group may, for example, be a 1,2-poly-butadiene terminal (meth)acrylic acid urethane (for example, "TE-2000" manufactured by Japan Soda Corporation, "TEA-1000"), its hydride (for example, "TEAI-1000" manufactured by Nippon Soda Co., Ltd.), 1,4-polybutadiene terminal (meth) acrylate (for example: Osaka Organic Chemistry) "BAC-45" manufactured by the company, polyisoprene terminal (meth) acrylate, polyester (meth) acrylate urethane (for example, "UV-3000B" manufactured by Nippon Synthetic Co., Ltd.) Polyether (meth) acrylate, polyester (meth) acrylate, bisphenol A (meth) acrylate epoxy (for example, "VISCOAT #540" manufactured by Osaka Organic Chemical Co., Ltd.) ), "VISCOAT VR-77" manufactured by Showa Polymer Co., Ltd.).

Among the (meth)acrylic monoesters, it is preferred to contain (1-5) a (meth)acrylic monomer having a hydroxyl group from the viewpoint of having a large effect. (1-5) (meth)acrylic monomer having a hydroxyl group in the (meth)acrylic monomer The ratio is preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass, per 100 parts by mass of the (meth)acrylic monomer.

Among the (meth)acrylic monomers, a combination of the following (X) or (Y) is preferred from the viewpoint of having a large effect.

(X) is a (meth)acrylic acid monomer having a bisphenol skeleton, (1-4) a (meth) acrylate having an aromatic group, and (1-5) a hydroxyl group of (meth) acrylate a combination of alkyl esters. The content ratio of the component (1-2), the component (1-4), and the component (1-5) is 100 parts by mass in total of the component (1-2), the component (1-4), and the component (1-5). In terms of mass ratio, the composition is (1-2): component (1-4): component (1-5) = 1 to 20: 20 to 60: 30 to 70, preferably 5 to 15:30. ~55:35~60 is better.

(Y) is (1-1) alkyl (meth)acrylate, (1-2) (meth)acrylic monomer having a bisphenol skeleton, (1-4) (meth)acrylic acid having an aromatic group A combination of an ester and (1-5) hydroxyalkyl (meth) acrylate. The content ratio of the component (1-1), the component (1-2), the component (1-4), and the component (1-5) is in the component (1-1), the component (1-2), and the component (1). 4) and 100 parts by mass of the total of the components (1-5), in terms of mass ratio, the component (1-1): component (1-2): component (1-4): component (1-5) =5~35:1~30:20~50:15~45 is better, and 10~30:5~25:25~45:20~40 is better.

The (2) polymerization initiator used in the present invention is cumene hydroperoxide, hydroperoxide p-menthane, t-butyl hydroperoxide, dicumyl dihydroperoxide, methyl ethyl ketone peroxide, An organic peroxide such as benzamidine peroxide or a third butyl peroxybenzoate is preferable, and one type or two or more types may be used. Among these, cumene hydroperoxide is preferred from the viewpoint of reactivity with the component (1) or the component (3) to be described later.

The amount of the component (2) used in the present invention is not particularly limited, and is preferably 0.5 to 10 parts by mass, and 1 to 7 based on 100 parts by mass of the component (1). The mass portion is better. If the amount of the component (2) used is too small, the curing rate may be slow. On the other hand, if the amount is too large, the storage stability may be poor.

Use of the present invention, (3) β - diketone chelating agent and / or a β - keto ester, include such as: β - diketone chelating agent and / or a β - keto ester. Examples of the β -diketone chelating agent include vanadium acetonate, cobalt acetonide, and copper acetonitrile. Examples of the β -ketoester include vanadium naphthenate, vanadium stearate, copper naphthenate or cobalt octoate. One type or two or more types may be used. Among these, a metal salt having a reducing property is preferred from the viewpoint of reactivity with the component (2), and one of a group consisting of vanadium acetonate vanadium, copper naphthenate, and cobalt octoate. Two or more kinds are more preferable, and vanadium acetone is preferred.

The amount of the component (3) to be used is not particularly limited, and is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the component (1). When the amount of the component (3) used is too small, the curing rate may be slow and the bonding property may be small. On the other hand, if the amount is too large, unreacted components may remain and the bondability may be lowered.

(4) The inorganic filler used in the present invention may be a glass powder composed of quartz, quartz glass, molten cerium oxide, a composite oxide, cerium oxide powder such as spherical cerium oxide, or the like, or spherical oxidation. Oxides such as aluminum, crushed alumina, magnesia, yttria, and titania; nitrides such as boron nitride, tantalum nitride, and aluminum nitride; carbides such as tantalum carbide, aluminum hydroxide, and hydroxide A hydroxide such as magnesium, a metal or an alloy such as copper, silver, iron, aluminum, nickel or titanium, a carbon-based filler such as diamond or carbon, talc or calcium carbonate. These may be used alone or in combination of two or more. In the cerium oxide, molten cerium oxide is preferred. Among the aluminas, alumina is preferred, and spherical alumina is more preferred. Among these, the cutting is effectively distributed In view of the heat generated in the member, one or two or more of the group consisting of cerium oxide, quartz, alumina, and talc are preferred; in terms of heat dissipation, quartz and oxidation are used. Any one or two of aluminum is more preferable.

The amount of the component (4) to be used is preferably from 25 to 300 parts by mass, more preferably from 50 to 200 parts by weight, per 100 parts by mass of the component (1). If the amount of the component (4) used is too small, it may be difficult to obtain an effect of improving the hardness. On the other hand, if the amount is too large, the viscosity may be too high, which may cause inconvenience in handling or decrease in peelability in water. situation.

The average particle diameter of the component (4) according to the laser diffraction scattering method is preferably 1 to 100 μm, more preferably 3 to 20 μm. If the average particle diameter is too small, the amount of increase in viscosity increases and it is difficult to perform high filling. On the other hand, if it is too large, the inorganic filler may settle. The particle size distribution was measured by a laser diffraction type particle size distribution measuring apparatus (laser diffraction scattering method).

In the present invention, in order to improve the peel strength and the impact strength, it is preferred to use (5) an elastomer component.

The (5) elastomer component used in the present invention may, for example, be an acrylonitrile-butadiene-methacrylic acid copolymer, an acrylonitrile-butadiene-methacrylate copolymer, or a methyl methacrylate-butyl group. Diene-styrene copolymer, acrylonitrile-styrene-butadiene copolymer; and acrylonitrile-butadiene rubber, linear polyurethane, styrene-butadiene rubber, chloroprene Various synthetic rubbers such as rubber and butadiene rubber; natural rubber, styrene-based thermoplastic elastomer of styrene-polybutadiene-styrene-based synthetic rubber, olefin-based thermoplastic elastomer of polyethylene-EPDM synthetic rubber, and Polyester-based thermoplastic elastomers of caprolactone type, adipate type and PTMG type urethane-based thermoplastic elastomer, polybutylene terephthalate-polytetramethylene glycol multi-block polymer body, A polyamide-polyol block copolymer, a polyamine-based thermoplastic elastomer, a 1,2-polybutadiene-based thermoplastic elastomer, and a polyvinyl chloride-based thermoplastic elastomer. When the compatibility of the above-mentioned elastomer components is good, one type or two or more types can be used.

Further, polybutadiene modified with terminal methacrylic acid can also be used.

Among these, methyl methacrylate-butadiene-styrene copolymer and/or acrylonitrile-butadiene rubber are used in view of solubility and bonding property to a (meth)acrylic monomer. It is better to use it as a better one. In the case of an acrylonitrile-butadiene rubber, the acrylonitrile content (nitrile content) is preferably 36 to 45% by mass.

The amount of the component (5) to be used is preferably 5 to 35 parts by mass, more preferably 10 to 30 parts by mass, per 100 parts by mass of the component (1). If the amount of the component (5) used is too small, the viscosity and the bondability may be lowered. On the other hand, if the amount is too large, the viscosity may be too high, which may cause inconvenience in handling.

In the acrylic-based temporary fixing adhesive composition of the present invention, various alkanes can be used in order to rapidly cure the portion in contact with air. Examples of the alkane include paraffin wax, microcrystalline wax, palm wax, beeswax, lanolin, cetyl wax, ceresin, and candelilla wax. One type or two or more types may be used.

The amount of the alkane to be used is preferably 0.1 to 5 parts by mass, more preferably 0.3 to 2.5 parts by mass, per 100 parts by mass of the component (1). When the amount of the alkane used is too small, the hardening of the portion in contact with air may be deteriorated. On the other hand, if the amount exceeds 5 parts by mass, the joint strength may be lowered.

The acrylic-based temporary fixing adhesive composition of the present invention can be used for the purpose of improving storage stability, and a polymerization inhibitor can be used. The polymerization inhibitor may, for example, be hydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tributyl) Phenol), triphenyl phosphate, phenothiazine and N-isopropyl-N'-phenyl-p-phenylenediamine and the like. One type or two or more types may be used. The polymerization inhibitor system also contains an antioxidant.

When the polymerization initiator is added, the amount of the polymerization initiator to be used is preferably 0.001 to 3 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the component (1). If the amount of the polymerization initiator used is too small, there is no effect; on the other hand, if the amount is too large, the joint strength may be lowered.

In the composition for temporary fixing of the present invention, phosphate can be used for the purpose of improving the bonding property.

The phosphate may, for example, be a compound represented by the general formula (F).

(wherein R ₈ represents CH ₂ =CR ₉ CO(OR ₁₀ ) _u - group (except that R ₉ represents hydrogen or methyl; R ₁₀ represents -C ₂ H ₄ -, -C ₃ H ₆ -, -CH ₂ CH(CH ₃ )-, -C ₄ H ₈ -, -C ₆ H ₁₂ - or ;u represents an integer from 1 to 10; t represents an integer of 1 or 2.)

The phosphate may, for example, be an acid phosphinomethoxyethyl (meth) acrylate, an acid phosphinopropyl propyl (meth) acrylate or a bis (2-(methyl) propylene oxyethyl) Phosphate and the like. One type or two or more types may be used. Among these In view of the effect, the acid phosphinomethoxyethyl (meth) acrylate is preferred.

When the phosphate is added, the amount of the phosphate to be used is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 1.0 part by mass, per 100 parts by mass of the component (1). If the amount of the phosphate used is too small, the joint strength may be lowered, and if it is too large, the joint strength may be lowered.

Further, in addition to these, a conventional substance such as a coupling agent, a plasticizer, a coloring agent, and a preservative can be used as needed.

Further, for the purpose of adjusting the viscosity and the fluidity, a thermoplastic polymer such as chlorosulfonated polyethylene, polyurethane, styrene-acrylonitrile copolymer or polymethyl methacrylate may be used.

The embodiment of the present invention can be used as a composition of an adhesive for a two-part type. Regarding the two dosage forms, in the storage of the adhesive composition of the present invention, the essential components are not completely mixed, but the adhesive composition is divided into the first agent and the second agent, and at least the component (2) is One dose, at least the second agent of the component (3), is separately stored. Preferably, the phosphate is stored in the second dose. In this case, two or more doses are applied to the material to be joined at the same time or separately, and can be used as a two-part type temporary fixing adhesive composition by contact and hardening.

In another embodiment, the monomer and/or oligomer having a (meth)acrylinyl group or any other optional component is included in advance in either or both of the first agent and the second agent. Further, when they are mixed at the time of use, they can be used as a one-part temporary fixing adhesive composition.

In the above embodiments, it is preferable to use it as a two-part type temporary fixing adhesive composition from the viewpoint of excellent storage stability.

The method of using the composition for temporarily fixing the adhesive of the present invention may be, for example, coating on a joint surface of a member or a support substrate which is fixed. An appropriate amount of the adhesive is applied, followed by a method of laminating the other member; or a plurality of temporarily fixed members are laminated in advance, and the adhesive is applied between the slits, and the adhesive is applied in this manner to temporarily fix A method in which the adhesive composition is hardened, and the members are temporarily fixed to each other.

The temporary fixing adhesive composition of the present invention is preferably obtained by using two doses in substantially equal amounts, but it is not necessary to correctly measure the two doses, and in the case of incomplete metering or mixing, only two doses are contacted. It can be hardened at room temperature. The curing of the temporary fixing adhesive composition of the present invention does not require ultraviolet rays. The composition for temporary fixing of the adhesive of the present invention is excellent in workability.

The temporary fixing adhesive composition of the present invention is obtained by temporarily fixing various objects to be joined, cutting the member into a desired shape, and performing processing such as grinding, polishing, etc., and then immersing the member in water. The composition is peeled off from the member.

For the method of temporarily fixing, the temporary fixing adhesive composition of the present invention is used, and the member is temporarily bonded and fixed, and the cured body of the temporary fixing adhesive composition is produced, and the temporarily fixed member is processed. The processed member is immersed in water, and the hardened body of the temporary fixing adhesive composition is removed.

In the temporary fixing method of the present invention, as the water for removing the hardened body, it is preferred to use warm water of moderate heating, for example, warm water of 90 ° C or less, to be removed in water in a short time. The requirement is better in terms of productivity improvement. The method of contacting the hardened body of the temporary fixing adhesive composition with water is preferably a method of immersing each joined body in water from the viewpoint of simplicity. The temperature of the warm water is preferably from 30 to 100 ° C, more preferably from 50 to 95 ° C.

After the member is fixed by the above method, in the present invention, the member to be temporarily fixed is cut into a desired shape, and subjected to grinding, grinding, opening, etc., and then the member is immersed in water, preferably. In order to be immersed in warm water, the hardened body of the adhesive can be peeled off from the member.

The composition for temporary fixing of the present invention can be used for joining one or more of a group consisting of ruthenium, a resin, carbon, a metal, sapphire, and glass. When it is used for joining one or more of a group of enamel, sapphire, glass, and resin, it has a larger effect. It has the greatest effect when used to join the crucible.

When used for joining tantalum, the acrylic temporary fixing adhesive composition of the present invention has a great effect particularly when the tantalum wafer is formed into a tantalum wafer.

The method for producing the tantalum wafer may be, for example, using the temporary fixing adhesive composition of the present invention, temporarily bonding the tantalum block to the substrate, and then cutting the tantalum block into a tantalum wafer to immerse the tantalum wafer in the wafer. In the water, the method of removing the wafer from the substrate, and the like.

The crucible block can be obtained by a method of melting and solidifying a solid crucible in a heating furnace. The block can be cut with a wire saw or the like. The wire saw can be exemplified by a piano wire or the like (see Patent Documents 6 and 7). Silicon wafers are used in solar cells and semiconductors.

[Examples]

The present invention will be described in detail by the following examples, but the invention is not limited thereto. Moreover, the unit of use of each material used is expressed in parts by mass.

(Example 1)

Mix the materials used in the composition of Table 1, and prepare the first agent and the first A temporary fixing adhesive composition composed of two doses. The results are presented in Table 1.

(using materials)

2-Hydroxyethyl methacrylate: Commercial product

2-hydroxypropyl methacrylate: commercial product

Phenyloxyethyl methacrylate: commercial product

2,2-bis[4-(methacryloxypolyethoxy)phenyl]propane: a commercially available product, in the general formula (B), p=5, p'=5

Cumene hydroperoxide: commercial products

Acrylonitrile-butadiene rubber (AN-BD rubber): commercially available, high nitrile NBR, nitrile content 41% by mass

Quartz: average particle size 12μm, commercial products

Cerium dioxide: molten cerium oxide, average particle size 3 μm, commercial product

Alkanes: Commercial products, paraffin

Polymerization inhibitor: hydroquinone monomethyl ether, commercial product

Acetylacetone vanadium: commercial products

Phosphate: Commercial product, acid phosphinomethoxyethyl methacrylate

SPCC: Commercial product, SPCC-D sandblasted steel plate

矽 wafer (Si wafer): commercial products

Block (Si block): Commercial product

The physical properties were determined as follows.

[fixing time]

According to JIS K-6856, the first agent and the second agent are mixed in equal amounts on one side of the test piece (100 mm × 25 mm × 1.6 mmt, SPCC-D blasting treatment), and then immediately overlapped on the other side. The test piece was used as a sample for the fitter. The fixing time of the sample (unit: minute) is at a temperature of 23 ° C, humidity In a 50% RH environment, the time from the stretching and the bonding to a strength of 0.4 MPa or more was measured by a push pull gauge.

[Si wafer/glass tensile shear strength]

According to JIS K-6856, the first agent and the second agent are mixed in equal amounts on one side of the test piece (25 mm × 25 mm × 0.3 mmt, Si wafer), and then the test piece on the other side is immediately superposed. (The heat-resistant PYREX (registered trademark) glass (25 mm × 25 mm × 2.0 mmt)) was prepared by hardening at room temperature for 24 hours. The tensile shear strength (unit: MPa) of the sample was measured at a tensile speed of 10 mm/min in an environment of a temperature of 23 ° C and a humidity of 50% RH.

[warm water peel test]

Applying the first agent to the second agent in an equal amount on the heat-resistant PYREX (registered trademark) glass, and then bonding the Si wafer directly to the 90° direction, and then curing at room temperature for 24 hours as Sample. The obtained sample was immersed in warm water (90 ° C), and the peeling time (90 ° C warm water peeling time) of the heat-resistant PYREX (registered trademark) glass and the Si wafer was measured. The peeling state (peeling state) was also observed. From the viewpoint of reducing the bonding strength by contact with water, recovering the film from the member in a film form, and being excellent in workability, it is preferable that the peeling state is interfacial damage.

[矽块加工试验]

The first and second agents were mixed in an equal amount, and a Si block of 125 mm × 125 mm × 400 mm was bonded and hardened with soda lime glass (125 mm × 400 mm × 20 mmt). Only the Si block portion of the bonded test piece was cut into a thickness of 200 μm using a wire saw device. The presence or absence of the dropping of the Si block at the time of cutting was observed (Si block processing test (shedding state)). Then, the bonded test piece obtained by cutting only the Si block was immersed in warm water of 90 ° C, and the peeling time of the Si block and the soda lime glass (90 ° C warm water peeling time) was measured, that is, (Si block processing test (90 ° C temperature) Water stripping time)).

[Exfoliation size]

The end face of the Si wafer obtained in the Si block processing test was observed with a System Industrial Microscope BX51 manufactured by Olympus Co., Ltd., and the size of the peeling was measured. The peeling system measures 10 places per wafer, and takes the average value of 5 wafers as the peeling size.

(Examples 2 to 11)

A temporary fixing adhesive composition was produced in the same manner as in Example 1 except that the materials shown in Table 1 were used in the compositions shown in Table 1. The obtained temporary fixing adhesive composition was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

(using materials)

2-ethylhexyl methacrylate: commercial product

Methyl methacrylate-butadiene-styrene copolymer (MMA-BD-ST copolymer): commercial product

1,2-polybutadiene terminal methacrylate urethane: "TE-2000" manufactured by Japan Soda Corporation

Alumina: spherical alumina oxide, average particle size 5μm, commercial product

Talc: average particle size 1.6μm, commercial product

(Comparative examples 1 to 4)

A temporary fixing adhesive composition was produced in the same manner as in Example 1 except that the materials shown in Table 2 were used in the composition shown in Table 2. The obtained temporary fixing adhesive composition was evaluated in the same manner as in Example 1, and the results are shown in Table 2.

It can be seen from Tables 1 to 2 that in Examples 1 to 7, and 9 to 11, the size of the peeling can be reduced by 10 to 20% by adding an inorganic filler. Even if an inorganic filler is added, the joint strength hardly changes, showing that it can withstand the processing of the block. There was no influence on the warm water peeling time, and it was confirmed that it was peeled off by immersion in warm water after the wafer processing.

Even if the elastomer was not used, it can be seen from Table 1 that the size of the peeling can be reduced by adding the inorganic filler (Example 8 and Comparative Example 4).

The present invention has the following effects, for example.

By using the acrylic temporary fixing adhesive of the present invention The material can reduce the size of the peeling when cutting the wafer. The temporary fixing adhesive composition of the present invention can exhibit high bonding strength in a short time of hardening. The cured product can reduce the bonding strength by contact with water and reduce the bonding force between the members or the bonding force between the member and the mold, so that the member can be easily recovered. The temporary fixing adhesive composition of the present invention accelerates peeling by being immersed in water. When the tantalum wafer is cut using the temporary fixing adhesive composition of the present invention, the tantalum block does not peel off, showing good workability.

Since the present invention can be hardened in a short period of time by mixing two agents, it is remarkably excellent in terms of workability and shortening of work time as compared with an epoxy-based adhesive. In the composition for temporary fixing of the present invention, the cured product is swollen by contact with water at 90 ° C or lower, and can be recovered from the member in the form of a film, so that workability is excellent.

Claims (19)

A temporary fixing adhesive composition comprising the following components: (1) 100 parts by mass of a monomer and/or oligomer having a (meth) acrylonitrile group, (2) a polymerization initiator, (3) An β -diketone chelate compound and/or a β -ketoester, and (4) an inorganic filler in an amount of more than 50 parts by mass and not more than 300 parts by mass. The temporary fixing adhesive composition according to claim 1, further comprising (5) an elastomer component. The temporary fixing adhesive composition according to the first aspect of the invention, wherein the (4) inorganic filler is one or more selected from the group consisting of cerium oxide, quartz, alumina, and talc. The temporary fixing adhesive composition according to claim 1, wherein (1) the monomer and/or oligomer having a (meth)acryl fluorenyl group comprises: (1-2) a bisphenol skeleton; (meth)acrylic acid monomer, (1-4) (meth) acrylate having an aromatic group, and (1-5) hydroxyalkyl (meth) acrylate. The temporary fixing adhesive composition of claim 4, wherein the component (1-2), the component (1-4), and the component (1-5) are 100 parts by mass in total, the component (1-2) The content ratio of the component (1-4) and the component (1-5) is a component (1-2) by mass ratio: component (1-4): component (1-5) = 1 to 20: 20~ 60:30~70. The temporary fixing adhesive composition according to claim 1, wherein the monomer and/or oligomer having a (meth) acrylonitrile group comprises: (1-1) an alkyl (meth) acrylate, (1-2) (meth)acrylic acid monomer having a bisphenol skeleton, (1-4) (meth) acrylate having an aromatic group, and (1-5) hydroxyalkyl (meth) acrylate. The temporary fixing adhesive composition of claim 6, wherein the total amount of the component (1-1), the component (1-2), the component (1-4), and the component (1-5) is 100 parts by mass. Medium, component (1-1), component (1-2), component (1-4), and component (1-5) The content ratio is based on the mass ratio (1-1): component (1-2): component (1-4): component (1-5) = 5 to 35: 1 to 30: 20 to 50: 15 to 45 . The temporary fixing adhesive composition of claim 1, wherein the (3) β-diketone chelate and/or β-ketoester comprises vanadium acetonate, copper naphthenate and cobalt octoate One or two or more of the grouped groups. A two-component temporary fixing adhesive composition comprising an adhesive composition comprising the first fixing agent and the second agent according to the first fixing adhesive composition of the first aspect of the patent application, wherein One dose contains at least component (2) and the second dose contains at least component (3). The temporary fixing adhesive composition according to any one of claims 1 to 9, which further comprises an olefin. The temporary fixing adhesive composition according to any one of claims 1 to 9, which further comprises a polymerization inhibitor. The temporary fixing adhesive composition according to any one of claims 1 to 9, which further comprises a phosphate. The temporary fixing adhesive composition according to any one of claims 1 to 9, which is used in the group consisting of dicing, sapphire cutting, glass cutting, and resin cutting. One or two or more. A temporary fixing method of a member, characterized in that the member is temporarily fixed by using a temporary fixing adhesive composition according to any one of claims 1 to 13, and the temporary fixing adhesive is used The composition is hardened, the temporarily fixed member is processed, and the processed member is immersed in water to remove the hardened body of the temporary fixing adhesive composition. For example, the temporary fixing method of the component of claim 14 wherein the water is warm water. A method for producing a tantalum wafer, characterized in that the temporary fixing adhesive composition according to any one of claims 1 to 13 is used, and the tantalum block is bonded to the substrate to be temporarily fixed, and then cut. The silicon wafer is fabricated by dicing, and the germanium wafer is immersed in water and the germanium wafer is removed from the substrate. For example, the method for manufacturing a wafer according to claim 16 wherein the water is warm water. A bonded body obtained by joining the bonded body using the temporary fixing adhesive composition according to any one of claims 1 to 13. The bonded body of claim 18, wherein the joined body is one or more selected from the group consisting of ruthenium, sapphire, resin, and glass.