JP2023099535A - Adhesive for temporary stopping water system, manufacturing method of adhesive for temporary stopping water system, and manufacturing method of various members or components using the adhesive for temporary stopping water system - Google Patents

Abstract

To provide an adhesive for temporary stopping a water system containing at least (A) a thermoplastic rein having a hydroxyl group, having excellent temporary stopping performance, as well as coating performance and cissing prevention performance, an adhesive for temporary stopping the water system having function reduction suppression performance of various members and components used for an optical device, an electronic device or the like, an adhesive for temporary stopping a water system having excellent temporary stopping performance as well as coating performance and safety performance, and low in load to environment, and a manufacturing method of members or components using the adhesive for temporary stopping the water system.SOLUTION: There are provided an adhesive for temporary stopping a water system (i) containing (A) a thermoplastic resin or the like having a hydroxyl group and having prescribed melting point, (ii) containing at least the (A) thermoplastic resin having the hydroxyl group, and containing a prescribed metal ion at prescribed content, or (iii) containing the (A) thermoplastic resin having the hydroxyl group and (B) a solvent containing water, and having content of water in the solvent of 95 mass% or more, and prescribed surface tension and adhesive strength at 25°C, and a manufacturing method of members or components using the adhesive for temporary stopping the water system.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a water-based temporary fixing adhesive.

Adhesives are used for home use, as well as various members and parts (hereinafter referred to as " It is used in a variety of applications, including various industrial applications such as the manufacture of adhesives. Needless to say, the performance originally required for adhesives is adhesion performance, but depending on the application, it exhibits adhesion performance when temporarily fixing one or more members or parts, and then peels off. In some cases, performance that exhibits peelability (hereinafter sometimes referred to as “temporary fixing performance”) is required. For example, an optical lens used in an optical device is temporarily fixed to a support and subjected to various mechanical processes such as cutting, polishing, cutting, grinding, drilling, etc. to obtain a predetermined shape and surface properties, The adhesive used in the production of the optical lens, which is then peeled off from the support, is required to have temporary fixing performance.

In the mechanical processing of a member such as a wafer, which is a member for a semiconductor device used in electronic equipment, etc., the member is temporarily fixed to a support, cut, polished, and cut in the same manner as in the manufacture of the optical lens described above. , Various mechanical processes such as grinding, drilling, etc. are applied to obtain a predetermined shape and surface properties, and then peeled from the support to produce a method (for example, Patent Document 1). The adhesive used is also required to have temporary fixing performance. In addition to optical lenses, wafers, etc., various machines such as cutting, polishing, cutting, grinding, drilling, etc. for sapphire, gallium arsenide, crystal, magnetic members, metal members, glass members, resin members, semiconductor device members, etc. Adhesives having temporary fixing performance (hereinafter sometimes referred to as "temporary fixing adhesives") may also be used in mechanical processing.

Since the temporary fixing adhesive described in Patent Document 1 is an organic solvent-based adhesive containing a cycloolefin polymer and an ultraviolet absorber, it is removed using another organic solvent when the adherend is peeled off. Otherwise, it will be necessary to remove it using an oxidizing cleaning agent such as a strong acid. However, with the increasing awareness of the environment and safety in recent years, adhesives that use as little organic solvent as possible are becoming popular from the viewpoint of reducing the burden on the natural environment such as air pollution and the environment such as working environments, and from the viewpoint of safety. Therefore, there is a demand for a water-based temporary fixing adhesive that does not contain an organic solvent like the adhesive described in Patent Document 1 (for example, Patent Document 2). Patent Document 2 describes a water-releasable energy ray-curable adhesive containing a water-soluble resin or the like having an oxirane ring with photo-cationically polymerizable properties. The adherend can be easily peeled off by immersing it in water or hot water.

In recent years, improvements such as thinning, miniaturization, weight reduction, etc. of the above-mentioned various devices have been promoted, and similar improvements are required for various members and parts used in various devices. Higher precision is now required for various mechanical processes such as drilling. However, although the water-based adhesive described in Patent Document 2 is a preferable adhesive in that it has a low impact on the environment such as the natural environment and the working environment, Due to the minute foreign matter in the adhesive, the adhesive cannot be applied to the outer edge of the adherend, and even if it can be applied to the outer edge of the adherend, it is partially repelled (the adhesive repels and the coating film has holes or dents. The problem that uniform coating is not possible due to the occurrence of a phenomenon in which the coating material can be applied is becoming more apparent. If the temporary fixing adhesive cannot be applied to the outer edge of the adherend, or if repelling occurs, the temporary fixing of the outer edge or the part where repelling occurs will be insufficient during mechanical processing, resulting in a decrease in processing accuracy. problems are more likely to occur. Therefore, the water-based temporary bonding adhesive is required not only to have temporary bonding performance, but also to have application performance that can be applied to the outer edge of the adherend, and partially repelling prevention performance that does not cause repelling.

In addition, the temporary fixing adhesive used for temporary fixing of various members and parts such as optical lenses, wafers, etc. incorporated in optical equipment, electronic equipment, etc., does not contain contamination due to raw materials, adhesive manufacturing processes, etc. Substances such as particles, metal ions, corrosive ions, and organics may be included. As a result, there have been cases where the reliability of various members and parts has decreased and the manufacturing yield has decreased, but the frequency of such occurrences has been extremely low so far and has not been a serious problem. However, as various members and parts are becoming thinner, smaller, and lighter, along with the recent trend toward thinner, smaller, and lighter portable devices such as mobile phones, the influence of these contaminants becomes greater. For example, in members such as wafers, deterioration in the characteristics of semiconductor devices due to metal ion contamination and corrosive ions causes the problem of pn junction leakage, and the deterioration in reliability of various members and parts is remarkable. ing. However, the adhesives described in Patent Documents 1 and 2 are not considered to reduce the contaminants contained in the adhesive, and not only the temporary fixing performance but also the content of contaminants, especially metal ions. There is a demand for the development of adhesives that also focus on

JP 2013-33814 A JP-A-2004-35866

The present invention was made under such circumstances, and various members and parts used for optical equipment, electronic equipment, etc. A water-based temporary fixing adhesive that has a function deterioration suppression performance, a water-based temporary fixing adhesive that has excellent temporary fixing performance, application performance and safety performance, and has a low environmental load, and the water-based temporary fixing adhesive. It is an object of the present invention to provide a method for manufacturing various members or parts that have been used.

As a result of extensive research in order to solve the above problems, the present inventors have found that a thermoplastic resin having a hydroxyl group can be used as a water-based adhesive, and exhibits temporary fixing performance that combines adhesive performance and peeling performance. The present inventors have found that the above problems can be solved by an invention relating to a water-based temporary fixing adhesive containing at least (A) a thermoplastic resin having a hydroxyl group. That is, the present invention provides a water-based temporary fixing adhesive or the like having the following constitution.

1. A water-based temporary fixing adhesive containing (A) a thermoplastic resin having a hydroxyl group, (B) a surface conditioner, and (C) a compatibilizer, and having a melting point of 30°C or higher as measured according to JIS K0064:1992.
2. At least (A) contains a thermoplastic resin having a hydroxyl group, and the total content of sodium metal ions, aluminum metal ions, iron metal ions, zinc metal ions, copper metal ions, nickel metal ions, chromium metal ions and lead metal ions is 3000 ppb. and a sodium metal ion, iron metal ion, zinc metal ion and copper metal ion content of 1000 ppb or less each.
3. (A) a thermoplastic resin having a hydroxyl group; and (B) a solvent containing water, wherein the water content in the solvent is 95% by mass or more, and the surface tension at 25°C is 20 mN/m or more and 55 mN /m or less and an adhesive strength of 0.1 MPa or more and 20 MPa or less.
4. Temporary bonding step of temporarily bonding a precursor of a member or part and a processing substrate using the water-based temporary bonding adhesive according to any one of 1 to 3 above, mechanically processing the precursor to perform a member or A method for manufacturing a member or part having a processing step for manufacturing the part.

According to the present invention, along with excellent temporary fixing performance, a water-based temporary fixing adhesive that has both coating performance and repelling prevention performance, optical equipment, water-based temporary fixing performance that suppresses functional deterioration of various members and parts used in electronic equipment, etc. A water-based temporary fixing adhesive that has excellent temporary fixing performance, application performance and safety performance, and has a low environmental load, and a method for manufacturing various members or parts using the water-based temporary fixing adhesive. can provide.

Hereinafter, the water-based temporary fixing adhesive of the present invention will be described in detail. In this specification, the upper and lower limits of "more than", "less than", and "to" regarding the description of numerical ranges are numerical values that can be arbitrarily combined, and the numerical values in the examples are the upper and lower limits. can do.

[Water-based temporary adhesive]
The water-based temporary fixing adhesive of the present invention can be used as a water-based adhesive, and exhibits a temporary fixing performance that combines adhesive performance and peeling performance (A). The following first to third water-based temporary fixing adhesives are characterized by having excellent temporary fixing performance despite being an adhesive of.
- First water-based temporary fixing adhesive: (A) a thermoplastic resin having a hydroxyl group, (B) a surface conditioner, and (C) a compatibilizer, and has a melting point of 30 as measured according to JIS K0064: 1992 A water-based temporary adhesive that has a temperature of ℃ or higher.
- Second water-based temporary adhesive: contains at least (A) a thermoplastic resin having a hydroxyl group, sodium metal ion, aluminum metal ion, iron metal ion, zinc metal ion, copper metal ion, nickel metal ion, chromium metal ion and a total content of lead metal ions is 3000 ppb or less, and the content of each of sodium metal ions, iron metal ions, zinc metal ions and copper metal ions is 1000 ppb or less.
- Third water-based temporary fixing adhesive: (A) a thermoplastic resin having a hydroxyl group, and (B) a solvent containing water, wherein the water content in the solvent is 95% by mass or more, and 25 A water-based temporary fixing adhesive having a surface tension at °C of 20 mN/m or more and 55 mN/m or less and an adhesive strength of 0.1 MPa or more and 20 MPa or less.
The first water-based temporary fixing adhesive will be described below.

<First water-based temporary fixing adhesive>
The first water-based temporary fixing adhesive of the present invention contains (A) a thermoplastic resin having a hydroxyl group, (B) a surface conditioner, and (C) a compatibilizer, and is measured in accordance with JIS K0064: 1992. It has a melting point of 30° C. or higher. (A) A thermoplastic resin having a hydroxyl group (hereinafter sometimes referred to as "(A) component") is a component that exhibits temporary fixing performance mainly having adhesive performance and peeling performance, and (B) The surface conditioner (hereinafter sometimes referred to as "(B) component") is a component that mainly expresses coating performance, and (C) the compatibilizer (hereinafter sometimes referred to as "(C) component"). ) is a component that develops anti-repellency performance mainly by improving the compatibility between the components (A) and (B). In the present invention, by combining the above three components, component (A), component (B), and component (C), it is possible to simultaneously satisfy not only excellent temporary fixing performance, but also coating performance and anti-repellency performance. and In addition, by combining these three components and setting the melting point to 30 ° C. or higher, the coating performance resulting from compatibility due to differences in materials, surface characteristics, etc. between the temporary adhesive and the adherend. , By improving the heat resistance against heat generated during mechanical processing, it suppresses the occurrence of displacement and peeling of the adherend from the support during processing, improving the adhesion performance. Versatility that can correspond to stopping is also obtained.

((A) Thermoplastic resin having a hydroxyl group)
The (A) thermoplastic resin having a hydroxyl group contained in the first water-based temporary bonding adhesive of the present invention is a component that exhibits temporary bonding performance mainly having adhesive performance and peeling performance. The resin contained in (A) the thermoplastic resin having a hydroxyl group is not particularly limited as long as it is a thermoplastic resin having a hydroxyl group in the molecule, but one having a melting point of 30° C. or higher is preferable. (A) When the melting point of the resin contained in the thermoplastic resin having a hydroxyl group is 30 ° C. or higher, the melting point of the first water-based temporary fixing adhesive of the present invention tends to be 30 ° C. or higher, and together with the temporary fixing performance, general purpose sexuality is also improved. From the same point of view, the melting point of the resin contained in (A) the thermoplastic resin having a hydroxyl group is more preferably 35°C or higher, more preferably 37°C, even more preferably 40°C or higher, and particularly preferably 43°C. That's it. The upper limit is preferably 200°C or lower, more preferably 180°C or lower, still more preferably 160°C or lower, still more preferably 120°C or lower, and particularly preferably 100°C or lower. When the upper limit of the melting point of the component (A) is 200° C. or less, the temporary fixing performance is improved by improving the peeling performance of the first water-based temporary fixing adhesive of the present invention, and the application performance and versatility are also improved. . As used herein, the melting point of component (A) means the melting end point measured according to JIS K0064:1992. The specific measurement will be described later.

(A) The number average molecular weight of the resin contained in the thermoplastic resin having a hydroxyl group is preferably 800 or more, more preferably 1,000 or more, and more preferably 1,000 or more, from the viewpoint of improving the temporary fixing performance as well as the coating performance and the anti-repellency performance. It is preferably 1,200 or more, particularly preferably 1,400 or more, and the upper limit is preferably 25,000 or less, more preferably 20,000 or less, still more preferably 15,000 or less, and particularly preferably 10,000 or less. be. As used herein, the number average molecular weight is measured by gel permeation chromatography (GPC method) using polystyrene as a standard substance.

As the resin contained in (A) the thermoplastic resin having a hydroxyl group having the above properties, a thermoplastic resin having an oxyalkylene group is preferably mentioned from the viewpoint of obtaining a more excellent temporary fixing performance, and a kind of oxyalkylene group It is more preferable that the resin is a constituent unit.

The oxyalkylene group preferably has 1 or more carbon atoms, more preferably 2 or more carbon atoms, and the upper limit is 12 or less, more preferably 8 or less, and still more preferably 4 or less, Particularly preferably, those having 3 or less are mentioned.
Further, the number of repeating units of the oxyalkylene group is preferably 10 or more, more preferably 30 or more, still more preferably 50 or more, and the upper limit is preferably 500 or less, more preferably 300 or less, and still more preferably 150 or less. .

More specifically, the thermoplastic resin having an oxyalkylene group preferably includes polyalkylene glycol, polyoxyalkylene ester, polyoxyalkylene alkyl ether, and polyoxyalkylene alkylaryl ether, more preferably polyalkylene glycol, They are polyoxyalkylene esters and polyoxyalkylene alkyl ethers, more preferably polyalkylene glycols and polyoxyalkylene esters, and particularly preferably polyalkylene glycols. These thermoplastic resins can be used alone or in combination.

Polyalkylene glycol preferably includes polyethylene glycol, polypropylene glycol, polybutylene glycol, etc., more preferably polyethylene glycol and polypropylene glycol, and still more preferably polyethylene glycol.
Polyoxyalkylene esters preferably include esters of fatty acids having 12 to 24 carbon atoms, more specifically polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, polypropylene glycol mono Polyoxyalkylene monoesters such as laurate, polypropylene glycol monostearate and polypropylene glycol monooleate, and polyoxyalkylene diesters such as polyethylene glycol distearate and polyethylene glycol dioleate are preferred. More preferred are polyoxyethylene monoesters, and particularly preferred is polyoxyethylene monostearate.

The polyoxyalkylene alkyl ether preferably includes those having an alkyl group having 12 to 24 carbon atoms, more specifically, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxypropylene oleyl ether, Polyoxypropylene lauryl ether and the like are preferred.
The polyoxyalkylene alkylaryl ether preferably includes those having an alkylaryl group having 12 to 24 carbon atoms, more specifically, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Propylene octylphenyl ether, polyoxypropylene nonylphenyl ether and the like are preferred.
In the present invention, the (A) thermoplastic resin having a hydroxyl group includes a resin having a predetermined melting point and number average molecular weight as exemplified above, a resin having an oxyalkylene group, and a type of oxyalkylene group as a constituent unit. It is preferable that at least a resin or the like to be contained is included, and that resins other than the resins exemplified above may be included, but it is preferable that all the resins contained are the resins exemplified above.

In the present invention, from the viewpoint of improving coating performance and repelling prevention performance as well as temporary fixing performance, (A) a thermoplastic resin having a hydroxyl group may be a type of thermoplastic resin, or two thermoplastic resins having different number average molecular weights. It is also possible to use more than one type of thermoplastic resin, such as two or more types of polyalkylene glycols with different number average molecular weights. In this case, a polyalkylene glycol having a number average molecular weight of 800 or more and less than 5,000 (hereinafter sometimes referred to as "polyalkylene glycol A") and a polyalkylene having a number average molecular weight of 5,000 or more and 10,000 or less It is preferable to combine a glycol (hereinafter sometimes referred to as "polyalkylene glycol B"), a polyethylene glycol having a number average molecular weight of 800 or more and less than 5,000, and a number average molecular weight of 5,000 or more and 10, 000 or less polyethylene glycol is more preferable.

The mixing ratio (mass ratio) of polyalkylene glycol A and polyalkylene glycol B is preferably 10:90 to 90:10, more preferably 15:85 to 85:15, still more preferably 20:80 to 80:20. is. When the blending ratio is within the above range, it becomes easier to secure the film thickness of the coating film of the water-based temporary fixing adhesive, so that more stable adhesion performance is obtained, so the temporary fixing performance is improved. Prevention performance is also improved.

The content of (A) the thermoplastic resin having a hydroxyl group in the water-based temporary fixing adhesive is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 12% by mass or more, and particularly preferably 15% by mass. The upper limit is preferably 50% by mass or less, more preferably 47% by mass or less, still more preferably 45% by mass or less, and particularly preferably 42% by mass or less. When the content of the thermoplastic resin is within the above range, it becomes easier to ensure the film thickness of the coating film of the water-based temporary fixing adhesive, so that more stable adhesion performance is obtained, thereby improving the temporary fixing performance.

((B) surface conditioner)
The (B) surface conditioner contained in the first water-based temporary fixing adhesive of the present invention is a component that mainly exhibits coating performance, especially coating performance for adherends such as wafers. (B) Surface conditioners generally include surface conditioners and leveling agents that have the ability to eliminate coating film defects caused by changes in viscosity, changes in surface tension, and generation of bubbles associated with high molecular weight. , wetting agents, antifoaming agents, etc., can be used without particular limitation. Examples include acrylic, vinyl, silicone, fluorine, cellulose, natural wax, water-soluble organic In addition to various surface conditioners such as solvents, leveling agents, wetting agents, antifoaming agents, and the like, surfactants are also preferred, and among them, surfactants, especially nonionic surfactants, are preferred.

As nonionic surfactants, more specifically, acetylene surfactants having acetylene bonds such as acetylene alcohol surfactants and acetylene glycol surfactants, fluorine surfactants, fatty acid monoglycerides, sorbitan fatty acid esters. , sucrose fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene-added acetylene glycol. Among these, acetylenic surfactants having an acetylene bond, such as acetylene alcohol surfactants and acetylene glycol surfactants, and fluorine surfactants are preferred, and acetylene surfactants are more preferred. In the present invention, as (B) the surface conditioner, the above-mentioned agents can be used alone or in combination.

Acetylene alcohol-based surfactants, acetylene glycol-based surfactants, and other acetylene-based surfactants having an acetylene bond include, more specifically, acetylene alcohol-based surfactants represented by the following general formula (1): and acetylene glycol-based surfactants represented by general formula (2).

In general formula (1), R ¹¹ and R ¹² each independently represent a hydrocarbon group having 1 to 8 carbon atoms, and A ₁₁ represents a single bond or an oxyalkylene group having 1 to 30 repeating units. In general formula (2), R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrocarbon group having 1 to 8 carbon atoms, and A ₂₁ and A ₂₂ each independently represent a single bond or repeating It represents an oxyalkylene group having 1 or more and 30 or less units.
Preferred examples of the hydrocarbon groups for R ¹¹ , R ¹² , R ²¹ , R ²² , R ²³ and R ²⁴ include alkyl groups and alkenyl groups, more preferably alkyl groups. It may be branched. Moreover, as an upper limit of carbon number, 6 or less are preferable and 4 or less are more preferable.

Further, when A ₁₁ , A ₂₁ and A ₂₂ are oxyalkylene groups having repeating units of 1 to 30, the acetylene alcohol-based surfactant represented by the general formula (1) becomes an alkylene oxide adduct of acetylene alcohol. , the acetylene glycol-based surfactant represented by the general formula (2) is an alkylene oxide adduct of acetylene glycol.
The number of repeating units of A ₁₁ , A ₂₁ and A ₂₂ is preferably 2 or more, more preferably 3 or more, and the upper limit is preferably 24 or less, more preferably 12 or less, still more preferably 8 or less, and particularly preferably 6 or less.

The oxyalkylene group for A ₁₁ , A ₂₁ and A ₂₂ preferably has 1 or more carbon atoms, more preferably 2 or more carbon atoms, and the upper limit is 12 or less carbon atoms, more preferably 8 or less, more preferably 4 or less, particularly preferably 3 or less. Alkylene groups may be linear or branched.
Moreover, when the number of repeating units of A ₁₁ , A ₂₁ and A ₂₂ is 2 or more, a plurality of A ₁₁ , A ₂₁ and A ₂₂ may be the same or different. For example, A ₁₁ may be one in which an oxyethylene group and an oxypropylene group are linked, and the same applies to A ₂₁ and A ₂₂ .

In the present invention, among acetylene-based surfactants, acetylene glycol-based surfactants represented by the general formula (2) are preferable, and at least one of A ₂₁ and A ₂₂ is an oxyalkylene group having a repeating unit number of 1 to 30. A certain alkylene oxide adduct of acetylene glycol is more preferable, and an alkylene oxide adduct of acetylene glycol in which A ₂₁ and A ₂₂ are oxyalkylene groups having 1 to 30 repeating units is even more preferable.

Examples of the acetylenic surfactant include Surfynol 104E, 104H, 104A, 104PA, 104PG-50, 104S, 420, 440, 465, 485, SE, SE-F, PSA-336, DF-110, DF37 , Olfin E1004, E1006, E1010, E1020, E1030W, EXP.4001, EXP.4200, EXP.4300, PD-002W, SPC, AF-103, AK-02 (manufactured by Nissin Chemical Industry Co., Ltd.), etc. It is available as a commercial product.

Examples of fluorine-based surfactants include fluorine-containing group/lipophilic group-containing oligomers and fluorine-containing group/hydrophilic group/lipophilic group-containing oligomers. As the fluorine-containing group/lipophilic group-containing oligomer, for example, MEGAFACE F-569, F-574 (manufactured by DIC Corporation) and the like are available as commercial products, and fluorine-containing group/hydrophilic group/lipophilic Group-containing oligomers are available as commercial products such as Megafac F-477, F-553, F-556, R-94 and F-559 (manufactured by DIC Corporation).

Examples of fluorosurfactants include partially fluorinated alcohol-substituted glycols represented by the following general formula (3). Such fluorine-based surfactants are available as commercial products such as Capstone FS-3100, FS-30, FS-31, FS-34 and FS-35 (manufactured by Dupont).
_{C6F13 - CH2CH2O} ( _CH2CH2O ) _nH ( _{3 )}
(In the formula, n is an integer of 1 or more and 40 or less.)

Examples of fluorine-based surfactants include partially fluorinated alcohols, which are available as commercial products such as Capstone FS-65 (manufactured by Dupont).

As the (B) surface conditioner, a surface conditioner such as an acrylic surface conditioner is also preferably used. Examples of acrylic surface conditioners include acrylic copolymers such as poly(meth)acrylate and modified poly(meth)acrylate. (manufactured by Co., Ltd.).

(B) As the surface conditioner, acetylene-based surfactants having an acetylene bond such as acetylene alcohol-based surfactants and acetylene glycol-based surfactants are used from the viewpoint of improving coating performance and anti-repellency performance as well as temporary fixing performance. , fluorine-based surfactants and acrylic surface-controlling agents are preferable, acetylenic surfactants, fluorine-based surfactants and acrylic surface-controlling agents are more preferable, and acetylenic surfactants are still more preferable. In addition to nonionic fluorine-based surfactants, amphoteric surfactants also exist, but nonionic surfactants are preferred from the viewpoint of improving coating performance and anti-repellency performance as well as temporary bonding performance.
In the present invention, the (B) surface conditioner preferably contains at least the surface conditioners exemplified above, and may contain other than those exemplified above, but all of the contained The surface conditioners exemplified above are preferred.

The content of the surface conditioner (B) in the water-based temporary adhesive is preferably 0.01% by mass or more, more preferably 0.03, from the viewpoint of improving the coating performance and repelling prevention performance as well as the temporary bonding performance. % by mass or more, more preferably 0.05% by mass or more, particularly preferably 0.10% by mass or more, and the upper limit is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1.5% by mass. % or less, particularly preferably 1 mass % or less.

((C) compatibilizer)
The (C) compatibilizer contained in the first water-based temporary fixing adhesive of the present invention mainly improves the compatibility between (A) the thermoplastic resin having a hydroxyl group and (B) the surface conditioner, It is a component that expresses repelling prevention performance. Since the above component (A) contains hydroxyl groups, it exhibits hydrophilicity, while the surface conditioner (B) tends to exhibit hydrophobicity. It cannot be said. Therefore, when the component (A) and the component (B) are used together, the amount of the adhesive applied due to repelling is particularly small in a part of the coating film of the adhesive, or a repelling portion that is not applied tends to occur. It becomes difficult to apply uniformly to adherends such as. Therefore, in the present invention, by using the (C) compatibilizer, the compatibility between the (A) component and the (B) component is improved, and excellent temporary fixing performance, coating performance and repelling prevention performance are improved. making it possible to obtain

The compatibilizer (C) is not particularly limited as long as it is a compound having a compatibilizing ability to improve the compatibility between the hydrophilic component (A) and the hydrophobic component (B). It is preferable to use a compound having a hydrophilic portion and a hydrophobic portion therein. Preferred examples of such compounds include copolymers of alkylene oxides. The alkylene oxide preferably has 2 to 8 carbon atoms, more preferably 2 to 4 carbon atoms, such as ethylene oxide, 1,2-propylene oxide, 1,3-propylene oxide and 1,2-butylene. Oxide, 2,3-butylene oxide, 1,3-butylene oxide, tetrahydrofuran, etc., and among them, a combination of ethylene oxide and propylene oxide is preferred.
The alkylene oxide copolymer may be of random type, block type, or graft type, but from the viewpoint of exhibiting better compatibilization performance and improving repelling performance, it is block type. is preferred.

Among the above alkylene oxide copolymers, copolymers of ethylene oxide and propylene oxide (hereinafter also referred to as "ethylene oxide-propylene oxide copolymers") are preferred, and block copolymers of ethylene oxide and propylene oxide (hereinafter , Also referred to as "ethylene oxide-propylene oxide block copolymer".) is more preferable, and among ethylene oxide-propylene oxide block copolymers, triblock copolymers having a propylene oxide chain as a main chain and ethylene oxide chains at both ends are particularly preferred. coalescence (hereinafter also referred to as "ethylene oxide-propylene oxide-ethylene oxide triblock copolymer"), a triblock copolymer having an ethylene oxide chain as a main chain and propylene oxide chains at both ends (hereinafter referred to as "propylene oxide-ethylene oxide - propylene oxide triblock copolymers") are preferred. Ethylene oxide-propylene oxide block copolymers, especially ethylene oxide-propylene oxide-ethylene oxide triblock copolymers, propylene oxide-ethylene oxide-propylene oxide triblock copolymers, are characterized in that the ethylene oxide chains are hydrophilic and the propylene oxide chains are hydrophobic. Therefore, the compatibilizing performance for improving the compatibility between the hydrophilic component (A) and the hydrophobic component (B) is exhibited more remarkably, and a more excellent repelling prevention performance can be obtained.

As the ethylene oxide-propylene oxide block copolymer, a diblock copolymer of ethylene oxide and propylene oxide (also referred to as "ethylene oxide-propylene oxide diblock copolymer") is also preferred. Similar to the above triblock copolymer, the ethylene oxide chain exhibits hydrophilicity and the propylene oxide chain exhibits hydrophobicity. The compatibilization performance to be improved is more remarkably expressed, and a more excellent anti-repellency performance is obtained.

Alkylene oxide copolymers such as the ethylene oxide-propylene oxide-ethylene oxide triblock copolymers and propylene oxide-ethylene oxide-propylene oxide triblock copolymers are, for example, Niupol PE61, 62, 64, 68, 71, 74, 75, 78, 108, 128 (manufactured by Sanyo Chemical Industries, Ltd.), Pluronic P85, F88, F108 (manufactured by ADEKA Corporation), Unilube 70DP-600B, 70DP-950B, Pronon #208, Pronon #238, Pronon #357 (manufactured by NOF Corporation), Epan 485, Epan 680, Epan 785, Epan U-108 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), etc. are also available as commercial products. be.

In the ethylene oxide-propylene oxide copolymer, the ratio of propylene oxide to ethylene oxide is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more, and the upper limit is preferably 300% by mass. % or less, more preferably 200 mass % or less, and still more preferably 100 mass % or less. When the ratio of ethylene oxide and propylene oxide is within the above range, better compatibilization can be obtained, and as a result, better anti-repellency performance can be obtained.

(C) When the compatibilizer is an alkylene oxide copolymer, its number average molecular weight is preferably 5,000 or more, more preferably 6,000 or more, still more preferably 7,000 or more, and particularly preferably 8, 000 or more, and the upper limit is preferably 500,000 or less, more preferably 250,000 or less, even more preferably 100,000 or less, and particularly preferably 50,000 or less.
In the present invention, the (C) compatibilizing agent preferably contains at least the alkylene oxide copolymers exemplified above, and may contain other than the alkylene oxide copolymers exemplified above. , are preferably copolymers of the alkylene oxides exemplified above.

The ethylene oxide-propylene oxide copolymer can be prepared by a known method. For example, in the case of an ethylene oxide-propylene oxide-ethylene oxide triblock copolymer, a propylene oxide chain is used as a main chain, and ethylene oxide is attached to both ends thereof. A block copolymer having a chain is polymerized by blowing ethylene oxide into propylene glycol under pressure and temperature in the presence of an alkali catalyst to prepare polypropylene oxide. It can be prepared by polymerizing ethylene oxide using both ends of the polypropylene oxide as polymerization bases.

The content of the (C) compatibilizer in the water-based temporary adhesive is preferably 0.1% by mass or more, more preferably 0.3, from the viewpoint of improving the coating performance and repelling prevention performance as well as the temporary fixing performance. % by mass or more, more preferably 0.5% by mass or more, and the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

(solvent)
The first water-based temporary fixing adhesive of the present invention can be used by dissolving the above components (A), (B) and (C) in a solvent. Water is used as the solvent, and for example, ion-exchanged water may be used. In the present invention, a solvent other than water, such as various organic solvents, may be included as a solvent, but considering the reduction of the load on the environment such as the natural environment and the working environment, safety, etc., it is preferable not to include the organic solvent. preferable. That is, the first water-based temporary fixing adhesive of the present invention is a substantially completely water-based temporary fixing adhesive that does not contain an organic solvent. Here, "not containing an organic solvent" means that the content of the organic solvent is 0% by mass, and that no organic solvent is intentionally used, for example, the above components (A), (B) and The content of an organic solvent that may inevitably be contained in component (C) is allowed, and in this case, the content of the organic solvent contained in all solvents is preferably 1% by mass or less, more preferably 0.5% by mass or less. , and more preferably 0.1% by mass or less.

(Other additives)
If desired, the first water-based temporary fixing adhesive of the present invention may contain other additives other than the above components, such as antifoaming agents, leveling agents, silane coupling agents, crystal nucleating agents, plasticizers, preservatives, and the like. may be included.

(Various properties of the first water-based temporary fixing adhesive)
The first water-based temporary fixing adhesive of the present invention must have a melting point of 30° C. or higher. If the melting point is not 30 ° C. or higher, it is not possible to suppress the reduction in coating performance due to compatibility between the temporary adhesive and the adherend due to differences in materials, surface characteristics, etc., and against heat generation during mechanical processing. Due to the improvement in heat resistance, it is not possible to suppress the occurrence of misalignment of the adherend with respect to the support during processing, peeling, etc., so excellent temporary fixing performance (especially adhesion performance) cannot be obtained. Also, versatility capable of coping with temporary fixation of adherends cannot be obtained. The melting point of the water-based temporary fixing adhesive is preferably 30°C or higher, more preferably 35°C or higher, still more preferably 37°C or higher, even more preferably 40°C or higher, and particularly preferably 43°C or higher. The upper limit is preferably 200°C or lower, more preferably 180°C or lower, still more preferably 160°C or lower, still more preferably 120°C or lower, and particularly preferably 100°C or lower. When the melting point of the water-based temporary fixing adhesive is within the above range, not only the adhesive performance of the first water-based temporary fixing adhesive of the present invention but also the peeling performance are improved, thereby improving the temporary fixing performance and versatility. improves.
As used herein, the melting point means the melting end point measured in accordance with JIS K0064:1992 (Method for measuring melting point and melting range of chemical products), as described above. Specifically, the first water-based temporary fixing adhesive of the present invention is heated and melted (temperature condition: 30 to 90 ° C.), cooled (temperature condition: -20 to 30 ° C.) and finely divided (maximum particle size: 300 μm) powder, and dried for 24 hours in a desiccator as necessary based on “4. Melting range measuring method” specified in JIS K0064: 1992 (Method for measuring melting point and melting range of chemical products). as a sample, this is filled in a capillary tube (made of glass, inner diameter 0.8 to 1.2 mm, thickness: 0.2 to 0.3 mm, length: 150 mm), and the temperature is increased at a rate of 1 ° C./min. The temperature was raised under the conditions, and the melting temperature at which no solid was observed by visual observation (the temperature at which the powdery solid sample was completely liquefied) was taken as the melting point of the first water-based temporary fixing adhesive of the present invention. .

(Use of the first water-based temporary fixing adhesive)
The first water-based temporary fixing adhesive of the present invention has excellent temporary fixing performance, coating performance and repelling prevention performance, and is water-based, so it reduces the load on the environment such as the natural environment and the working environment. It is a highly safe adhesive. Therefore, the first water-based temporary fixing adhesive of the present invention is used for applications where temporary fixing performance is required as an adhesive, such as OA equipment, information equipment, various electronic equipment such as home appliances, optical equipment, medical equipment, Various members and parts used in various devices such as automobile devices, such as wafers such as silicon wafers, optical lenses, sapphire, gallium arsenide, crystal, magnetic members, metal members, glass members, resin members, semiconductor device members It is suitably used for temporary fixing (temporary fixing) to a support during various mechanical processes such as cutting, polishing, cutting, grinding, drilling, etc.

Among the mechanical processing of the various members and parts described above, a typical example of a method of polishing the surface of a wafer such as a silicon wafer, which is a semiconductor device member used in electronic equipment and the like, will be described.
First, the first water-based temporary fixing adhesive of the present invention is uniformly applied to the entire surface of one surface of the wafer by a coating method such as a spin coater method, a spray method, a die coat method, an ink jet method, a dip coat method, a roll coat method, or the like. to form a coating film of the adhesive. After the adhesive coating is dried as necessary, the wafer and the platen of the polishing machine are heat-pressed, usually at a temperature of 50 to 140° C., to fix the wafer on the platen of the polishing machine. Then, the wafer surface is polished by a polishing machine. After finishing the polishing process, the wafer may be peeled off from the surface plate of the polishing machine by using a razor or by heating and melting. The method of applying the adhesive is not particularly limited. The method of (2) is not particularly limited, and can be appropriately selected according to the shape of the wafer and the like.
Further, if necessary, after peeling off the wafer, it is possible to wash the wafer by using water or warm water to remove the residue of the temporary fixing adhesive on the wafer. Since the first water-based temporary fixing adhesive of the present invention is water-based, it also has the advantage that it can be easily removed from the adherend by washing with water or warm water.

The first water-based temporary fixing adhesive of the present invention exhibits adhesion performance that prevents the wafer from peeling off or being displaced from the surface plate during polishing. To enable easy peeling from the disc. In addition, since the coating film of the adhesive is uniformly present on the entire surface of the wafer without repelling, the first water-based temporary fixing adhesive of the present invention can meet high precision requirements such as mechanical processing. It becomes possible. In addition, the first water-based temporary fixing adhesive of the present invention exhibits the same effect not only in the polishing process of the wafer, but also in the mechanical processing of other various members and parts, and responds to high precision requirements. is possible.

<Second water-based temporary fixing adhesive>
The second water-based temporary fixing adhesive of the present invention contains at least (A) a thermoplastic resin having a hydroxyl group, and contains sodium metal ions, aluminum metal ions, iron metal ions, zinc metal ions, copper metal ions, nickel metal ions, The total content of chromium metal ions and lead metal ions is 3000 ppb or less, and the content of sodium metal ions, iron metal ions, zinc metal ions and copper metal ions is each 1000 ppb or less. be.

((A) Thermoplastic resin having a hydroxyl group)
The (A) thermoplastic resin having a hydroxyl group contained in the second water-based temporary bonding adhesive of the present invention is a component that exhibits temporary bonding performance mainly having adhesive performance and peeling performance, and generally various Since the content of metal ions tends to be small, it is also advantageous in terms of improving the performance of suppressing functional deterioration of various members and parts used in optical equipment, electronic equipment, and the like.
The resin contained in (A) the thermoplastic resin having a hydroxyl group is not particularly limited as long as it is a thermoplastic resin having a hydroxyl group in the molecule, but one having a melting point of 30° C. or higher is preferable. (A) When the melting point of the resin contained in the thermoplastic resin having a hydroxyl group is 30 ° C. or higher, the melting point of the water-based temporary fixing adhesive of the present invention tends to be 30 ° C. or higher, and the temporary fixing performance is improved. sexuality is also improved. From the same point of view, the melting point of the resin contained in (A) the thermoplastic resin having a hydroxyl group is more preferably 35° C. or higher, still more preferably 37° C. or higher, even more preferably 40° C. or higher, and particularly preferably 43° C. °C or higher. The upper limit is preferably 200°C or lower, more preferably 180°C or lower, still more preferably 160°C or lower, still more preferably 120°C or lower, and particularly preferably 100°C or lower. When the upper limit of the melting point of the component (A) is 200° C. or less, the release performance of the second water-based temporary bonding adhesive of the present invention is improved, thereby improving the temporary bonding performance and versatility. As used herein, the melting point means the melting end point measured according to JIS K0064:1992. The specific measurement will be described later.

(A) The number average molecular weight of the resin contained in the thermoplastic resin having a hydroxyl group is preferably 800 or more, more preferably 1,000 or more, still more preferably 1,200 or more, from the viewpoint of improving the temporary fixing performance. It is preferably 1,400 or more, and the upper limit is preferably 25,000 or less, more preferably 20,000 or less, even more preferably 15,000 or less, and particularly preferably 10,000 or less. Further, when the number average molecular weight is within the above range, versatility is also improved. As used herein, the number average molecular weight is measured by gel permeation chromatography (GPC method) using polystyrene as a standard substance.

As the resin contained in (A) the thermoplastic resin having a hydroxyl group having the above properties, a thermoplastic resin having an oxyalkylene group is preferably mentioned from the viewpoint of obtaining a more excellent temporary fixing performance, and a kind of oxyalkylene group It is more preferable that the resin is a constituent unit.
The carbon number of the oxyalkylene group and the number of repeating units of the oxyalkylene group are the same as those of the oxyalkylene group of the component (A) of the first water-based temporary fixing adhesive.

More specifically, the thermoplastic resin having an oxyalkylene group preferably includes polyalkylene glycol, polyoxyalkylene ester, polyoxyalkylene alkyl ether, and polyoxyalkylene alkylaryl ether, more preferably polyalkylene glycol, Polyoxyalkylene esters and polyoxyalkylene alkyl ethers, more preferably polyalkylene glycols and polyoxyalkylene esters, which have a small content of various metal ions and are excellent various members used in optical devices, electronic devices, etc. And polyalkylene glycol is particularly preferable from the viewpoint of obtaining performance for suppressing functional deterioration of parts. These thermoplastic resins can be used alone or in combination.

Further, more specific examples of polyalkylene glycol, polyoxyalkylene ester, polyoxyalkylene alkyl ether and polyoxyalkylene alkyl aryl ether are those exemplified as the component (A) of the first water-based temporary fixing adhesive. The same can be mentioned.

In the second water-based temporary bonding adhesive of the present invention, from the viewpoint of improving the temporary bonding performance, (A) a thermoplastic resin having a hydroxyl group may be a thermoplastic resin of a type having a number average molecular weight. Two or more different thermoplastic resins, such as two or more polyalkylene glycols with different number average molecular weights, can also be used. In this case, a polyalkylene glycol having a number average molecular weight of 800 or more and less than 5,000 (hereinafter sometimes referred to as "polyalkylene glycol A") and a polyalkylene having a number average molecular weight of 5,000 or more and 10,000 or less It is preferable to combine a glycol (hereinafter sometimes referred to as "polyalkylene glycol B"), a polyethylene glycol having a number average molecular weight of 800 or more and less than 5,000, and a number average molecular weight of 5,000 or more and 10, 000 or less polyethylene glycol is more preferable.

The mixing ratio (mass ratio) of polyalkylene glycol A and polyalkylene glycol B is preferably 10:90 to 90:10, more preferably 15:85 to 85:15, still more preferably 20:80 to 80:20. is. When the blending ratio is within the above range, it becomes easier to ensure the film thickness of the coating film of the water-based temporary fixing adhesive, so that more stable adhesion performance is obtained, resulting in improved temporary fixing performance.

The content of (A) the thermoplastic resin having a hydroxyl group in the second water-based temporary fixing adhesive is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably, from the viewpoint of improving the temporary fixing performance. is 12% by mass or more, particularly preferably 15% by mass or more, and the upper limit is preferably 50% by mass or less, more preferably 47% by mass or less, further preferably 45% by mass or less, and particularly preferably 42% by mass or less. is. When the content of the thermoplastic resin is within the above range, it becomes easier to ensure the film thickness of the coating film of the water-based temporary fixing adhesive, so that more stable adhesion performance is obtained, thereby improving the temporary fixing performance.

((B) various metal ions)
The second water-based temporary fixing adhesive of the present invention contains various metal ions such as sodium metal ions, aluminum metal ions, iron metal ions, zinc metal ions, copper metal ions, nickel metal ions, chromium metal ions and lead metal ions (hereinafter , sometimes simply referred to as "component (B)")) is 3000 ppb or less, and the content of sodium metal ions, iron metal ions, zinc metal ions and copper metal ions is 1000 ppb or less each. . In this specification, "ppb" means "mass ppb" unless otherwise specified. (B) If the total content of various metal ions is more than 3000 ppb, the reliability of the member is likely to be lowered, such as the problem of pn junction leakage due to the deterioration of the characteristics of the member such as a silicon wafer, and the manufacturing yield is reduced. tend to increase rapidly. The same applies when the content of sodium metal ions, iron metal ions, zinc metal ions and copper metal ions exceeds 1000 ppb.

In the second water-based temporary fixing adhesive of the present invention, from the viewpoint of further improving the performance of suppressing functional deterioration of various members and parts used in optical equipment, electronic equipment, etc., that is, further suppressing functional deterioration of various members and parts. (B) The content of various metal ions is preferably as low as possible, preferably 2500 ppb or less, more preferably 2000 ppb or less, still more preferably 1000 ppb or less, even more preferably 500 ppb or less, particularly preferably 200 ppb or less, and most preferably It is preferably 100 ppb or less. In addition, (B) the lower limit of the content of various metal ions is preferably 0 ppb, that is, no metal ions are contained, but practically it is usually about 0.5 ppb or more. In addition, the content of sodium metal ions, iron metal ions, zinc metal ions, and copper metal ions is preferably 950 ppb or less, more preferably 750 ppb or less, still more preferably 600 ppb or less, and particularly preferably 450 ppb or less. is 0 ppb, and practically is usually 0.5 ppb or more. In the second water-based temporary fixing adhesive of the present invention, (B) the content of various metal ions is a measured value measured by an appropriate analysis method according to the type of various metal ions. Measured by the method described in .

In the second water-based temporary fixing adhesive of the present invention, (B) the content of various metal ions can be reduced, for example, by selecting the type of (A) the thermoplastic resin having a hydroxyl group. As a resin component used for adhesives that are water-based and have temporary fixing performance, salt types using metal salts of resins such as sodium salts of resins such as acrylic resins, emulsions of acrylic resins, vinyl acetate resins, etc. In some cases, emulsion types containing The content of contaminants such as metal ions tends to be high due to reasons such as erosion. The salt-type resin component itself contains (B) various metal ions, which is extremely high, and the emulsion-type resin component has (B) various metal ions incorporated in the particles of the emulsion. It is difficult to try to remove various metal ions. In addition to the above resin components, for example, a thermoplastic resin having a sulfonic acid group (--SO ₃ H) or a carboxyl group (--COOH) may be employed. Since the resin has a higher affinity for water than these resins, stability as a water-based temporary fixing adhesive can be obtained. In the second water-based temporary fixing adhesive of the present invention, (A) a thermoplastic resin having a hydroxyl group is used, and (B) various metal ions are removed by (B) a treatment for removing various metal ions, which will be described later. The amount can be easily reduced, and the content of (B) various metal ions in the adhesive can be extremely reduced.

(Other components: (C) surface conditioner)
The second water-based temporary fixing adhesive of the present invention may contain (C) a surface conditioner as another component in addition to (A) the thermoplastic resin having a hydroxyl group and (B) various metal ions. (C) The surface conditioner is a component that mainly improves the application performance of the adhesive, particularly the application performance to various electronic members such as wafers. When applying an adhesive to various members and parts used in optical devices, electronic devices, etc., the adhesive may spread to the outer edges of the various members and parts due to differences in the materials of the adhesive and the various members and parts. It cannot be applied and may not be applied to the entire surface. In such a case, by using (A) a thermoplastic resin having a hydroxyl group and (C) a surface conditioner, it is possible to obtain excellent coating performance regardless of differences in the materials of various members and parts. become.

(C) Surface conditioners generally include surface conditioners and leveling agents that have the ability to eliminate coating film defects caused by changes in viscosity, changes in surface tension, and generation of bubbles associated with high molecular weight. , wetting agents, antifoaming agents, etc., can be used without particular limitation. Examples include acrylic, vinyl, silicone, fluorine, cellulose, natural wax, water-soluble organic In addition to various surface conditioners such as solvents, leveling agents, wetting agents, antifoaming agents and the like, surfactants are also preferred, and nonionic surfactants are particularly preferred.

(C) Acetylene surfactants having acetylene bonds such as nonionic surfactants, acetylene alcohol surfactants, and acetylene glycol surfactants used as surface conditioners, fluorine surfactants, and acrylic surface conditioners Examples of surface conditioners such as agents are the same as those described as those that can be used as the (B) surface conditioner in the first water-based temporary fixing adhesive.

(C) As a surface conditioner, acetylene-based surfactants having acetylene bonds, such as acetylene alcohol-based surfactants and acetylene glycol-based surfactants, are used from the viewpoint of improving coating performance and anti-repellency performance as well as temporary fixing performance. , fluorine-based surfactants and acrylic surface-controlling agents are preferable, acetylenic surfactants, fluorine-based surfactants and acrylic surface-controlling agents are more preferable, and acetylenic surfactants are still more preferable. In particular, from the viewpoint of metal removal, a nonionic one is preferable.
In the second water-based temporary fixing adhesive of the present invention, the (C) surface conditioner preferably contains at least the surface conditioners exemplified above, and may contain other than those exemplified above. However, it is preferable that all of them are surface conditioners exemplified above.

The content of the surface conditioner (C) in the second water-based temporary fixing adhesive is preferably 0.01% by mass or more, more preferably 0.03% by mass, from the viewpoint of improving coating performance as well as temporary fixing performance. % or more, more preferably 0.05% by mass or more, particularly preferably 0.10% by mass or more, and the upper limit is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1.5% by mass. or less, and particularly preferably 1% by mass or less.

(Other components: (D) compatibilizer)
The second water-based temporary fixing adhesive of the present invention may contain (D) a compatibilizer (hereinafter sometimes referred to as "(D) component") as another component. (D) The compatibilizer, when the (C) surface conditioner is used, mainly improves the compatibility between the (A) thermoplastic resin having a hydroxyl group and the (C) surface conditioner to prevent repelling. It is a component that expresses performance. The (A) thermoplastic resin having a hydroxyl group exhibits hydrophilicity because it contains a hydroxyl group, while the (C) surface conditioner tends to exhibit hydrophobicity. It cannot be said that the solubility is high. Therefore, when component (A) and component (C) are used in combination, the amount of adhesive applied due to repelling is particularly small in a part of the coating film of the adhesive, or a repelling portion that is not applied tends to occur, and the adhesive is removed from the wafer. It may be difficult to apply uniformly to various members and parts such as. When (C) a surface conditioner is used in the (A) thermoplastic resin having a hydroxyl group, the use of (D) a compatibilizer can reduce the occurrence of repelling, which is the second aspect of the present invention. The water-based temporary fixing adhesive has excellent temporary fixing performance and performance for suppressing functional deterioration of various members and parts used in optical devices, electronic devices, etc., as well as excellent coating performance and repelling prevention performance.

The (D) compatibilizing agent that can be used in the second water-based temporary fixing adhesive of the present invention is the same as the (C) compatibilizing agent used in the first water-based temporary fixing adhesive, and the alkylene oxide co- Polymers are preferably used. Specific examples of the alkylene oxide copolymer are the same as the (C) compatibilizing agent used in the first water-based temporary fixing adhesive, and such a copolymer has hydrophilicity in the ethylene oxide chain and propylene Since the oxide chain exhibits hydrophobicity, the compatibilizing performance for improving the compatibility between the hydrophilic component (A) and the hydrophobic component (C) is exhibited more remarkably, resulting in better repellency. Preventive performance is obtained. In addition, these alkylene oxide copolymers themselves do not contain metal ions, or do not contain metal ions in the raw materials and manufacturing processes of these copolymers, and are used in optical devices, electronic devices, etc. It is effective in improving the performance of suppressing functional deterioration of various members.

For commercial products of alkylene oxide copolymers such as the above ethylene oxide-propylene oxide-ethylene oxide triblock copolymer and propylene oxide-ethylene oxide-propylene oxide triblock copolymer, in the first water-based temporary fixing adhesive The same as the exemplified commercial products can be mentioned.

In the ethylene oxide-propylene oxide copolymer, the ratio of propylene oxide to ethylene oxide, the number average molecular weight when the (D) compatibilizer is an alkylene oxide copolymer, and the ethylene oxide-propylene oxide copolymer are known. The preparation method in the method of is the same as the content described in the first water-based temporary fixing adhesive.

The content of the (D) compatibilizing agent in the second water-based temporary fixing adhesive is preferably 0.1% by mass or more, more preferably, from the viewpoint of improving the coating performance and repelling prevention performance as well as the temporary fixing performance. It is 0.3% by mass or more, more preferably 0.5% by mass or more, and the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less.

(solvent)
The second water-based temporary fixing adhesive of the present invention can be used by dissolving it in a solvent. Water is used as the solvent, and for example, ion-exchanged water may be used. When water is used as the solvent, the content of the solvent is preferably 50% by mass or more, more preferably 55% by mass, in consideration of the characteristics of the second temporary fixing adhesive of the present invention, which is water-based, ease of handling, etc. % or more, more preferably 60 mass % or more, and the upper limit is preferably 95 mass % or less, more preferably 90 mass % or less, and still more preferably 85 mass % or less.

In the second water-based temporary fixing adhesive of the present invention, a solvent other than water, such as various organic solvents, may be included as a solvent. , preferably does not contain the organic solvent. That is, the second water-based temporary fixing adhesive of the present invention is a substantially completely water-based temporary fixing adhesive that does not contain an organic solvent. Here, the term "not containing an organic solvent" means that the content of the organic solvent is 0% by mass, and that no organic solvent is intentionally used, for example, the above components (A) to (D) The inclusion of an organic solvent that may be unavoidably included is allowed, and in this case, the content of the organic solvent included in all the solvents is preferably 5% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass. Hereafter, it means that it is more preferably 0.5% by mass or less, particularly preferably 0.1% by mass or less. That is, the content of water contained in the total solvent is preferably 95% by mass or more, more preferably 98% by mass or more, still more preferably 99% by mass or more, still more preferably 99.5% by mass or more, particularly preferably It is 99.9% by mass or more. In the second water-based temporary fixing adhesive of the present invention, the solvent other than water and the organic solvent include the components (A) to Components other than the component (D) (contained as impurities) are also included.

(Other additives)
If desired, the second water-based temporary fixing adhesive of the present invention may contain other additives other than the above components, such as antifoaming agents, leveling agents, silane coupling agents, crystal nucleating agents, plasticizers, preservatives, and the like. may be included.

(Various properties of the second water-based temporary fixing adhesive)
The second water-based temporary fixing adhesive of the present invention preferably has a melting point of 30° C. or higher. When the melting point is 30° C. or higher, it is possible to suppress the decrease in coating performance due to compatibility between the temporary adhesive and the adherend due to differences in materials, surface characteristics, etc., and heat resistance against heat generated during mechanical processing. By improving it, it is possible to suppress the occurrence of positional deviation and peeling of the adherend from the support during processing, so excellent temporary fixing performance (especially adhesion performance) can be obtained, and various adherends can be used. Versatility that can be used for temporary fixing can also be obtained. From the same point of view, the melting point of the second water-based temporary fixing adhesive is more preferably 35° C. or higher, still more preferably 37° C. or higher, still more preferably 40° C. or higher, and particularly preferably 43° C. or higher. The upper limit is preferably 200°C or lower, more preferably 180°C or lower, still more preferably 160°C or lower, still more preferably 120°C or lower, and particularly preferably 100°C or lower.
The melting point is measured by the same method as the melting point of the first water-based temporary fixing adhesive.

(Use of the second water-based temporary fixing adhesive)
The second water-based temporary bonding adhesive of the present invention has excellent temporary bonding performance and has a low content of various metal ions, so it has the ability to suppress functional deterioration of various members and parts used in optical devices, electronic devices, etc. Moreover, since it is a water-based adhesive, it can reduce the burden on the environment such as the natural environment and the working environment, and is also excellent in safety. Therefore, the second water-based temporary bonding adhesive of the present invention is used for applications where temporary bonding performance is required as an adhesive, such as OA equipment, information equipment, various electronic equipment such as home appliances, optical equipment, medical equipment, Various members and parts used in various devices such as automobile devices, such as wafers such as silicon wafers, optical lenses, sapphire, gallium arsenide, crystal, magnetic members, metal members, glass members, resin members, semiconductor device members It is suitably used for temporary fixing (temporary fixing) to a support during various mechanical processes such as cutting, polishing, cutting, grinding, drilling, etc.

The second water-based temporary fixing adhesive of the present invention exhibits adhesion performance that prevents various members and parts from peeling off or being displaced from the processing substrate (surface plate, etc.) during mechanical processing, and polishing processing is completed. After that, the various members and parts can be easily peeled off from the processing substrate (surface plate, etc.) by using a razor or the like or by heating and melting. In addition, since the coating film of the adhesive is uniformly present on the entire surface of various members and parts without repelling, the second water-based temporary fixing adhesive of the present invention can meet high precision requirements such as mechanical processing. It becomes possible to Therefore, the second water-based temporary fixing adhesive of the present invention is particularly suitable for mechanical processing that requires high precision, such as wafers such as silicon wafers, optical lenses, semiconductor device members, and especially the surface of wafers such as silicon wafers. Suitable for polishing.

[Method for producing second water-based temporary fixing adhesive]
The second method for producing a water-based temporary bonding adhesive of the present invention includes (A) bringing a composition containing a thermoplastic resin having a hydroxyl group and metal ions into contact with an ion exchanger to obtain sodium metal ions, aluminum metal ions, The total content of iron metal ions, zinc metal ions, copper metal ions, nickel metal ions, chromium metal ions and lead metal ions is 3000 ppb or less, and contains sodium metal ions, iron metal ions, zinc metal ions and copper metal ions 1000 ppb or less for each.

(Ion exchanger)
Examples of the ion exchanger used in the second water-based temporary bonding adhesive production method of the present invention include organic ion exchangers such as ion exchange resins and inorganic ion exchangers, and (B) various metal ions From the viewpoint of further reducing the content of, an organic ion exchanger such as an ion exchange resin is preferred, and one having a cation trapping performance is preferred.

Examples of inorganic ion exchangers having cation trapping properties include zirconium phosphate, zirconium tungstate, zirconium molybdate, zirconium tungstate, zirconium antimonate, zirconium selenate, zirconium tellurate, zirconium silicate, Metal oxides such as zirconium phosphate and zirconium polyphosphate are included. These inorganic ion exchangers can be used alone or in combination.

As the organic ion exchanger, one using a cation exchange resin having cation trapping performance is preferable.
Cation exchange resins include strongly acidic cation exchange resins such as sulfonic acid-type strongly acidic cation exchange resins having sulfonic acid groups (RSO ₃ ⁻ H ⁺ ) as acidic groups; carboxylic acid groups (R-COO ^- H ⁺ ), phosphonic acid groups (R-P(O)(O ^- H ⁺ ) ₂ ), phosphinic acid groups (R-PH(O)(O ^- H ⁺ )), etc. etc. may be used. In addition, the ionic type of the cation exchange resin is preferably a hydrogen type or an ammonia type, and (B) from the viewpoint of further reducing the content of various metal ions, a hydrogen type cation exchange resin is more preferable. . These organic ion exchangers can be used alone or in combination.
The form of the organic ion exchanger is not particularly limited, and may be, for example, particulate, fibrous, liquid, or gel. A type decorated with exchange resin may be used.

In addition, for the second water-based temporary adhesive, (A) a thermoplastic resin having a hydroxyl group, (B) various metal ions, and optionally (C) a surface conditioner, (D) a compatibilizer, The contents of these and other additives are the same as those described for each component that can be contained in the second water-based temporary fixing adhesive, and the description thereof will be omitted.

Although the method for producing the second water-based temporary fixing adhesive of the present invention is not particularly limited, it is preferably produced by the above-described method for producing the second water-based temporary fixing adhesive of the present invention. According to the second method for producing a water-based temporary bonding adhesive of the present invention, a water-based temporary bonding adhesive having excellent temporary bonding performance and performance for suppressing functional deterioration of various members and parts used in optical equipment, electronic equipment, etc. can be easily obtained. In addition, the second water-based temporary fixing adhesive of the present invention is manufactured by selecting (A) a thermoplastic resin having a hydroxyl group, etc., which is a component contained in the adhesive, and making it a predetermined metal ion content. It is also possible to This production method was described as a method for producing the second water-based temporary fixing adhesive, but in the production of the first water-based temporary fixing adhesive and the third water-based temporary fixing adhesive described later, (A) hydroxyl groups When using a composition containing a resin and metal ions, it is also possible to produce using an ion exchanger according to this production method.

[Manufacturing method of member or part]
The method for manufacturing a member or part of the present invention includes a temporary fixing step of temporarily fixing a precursor of the member or part and a processing substrate using the second water-based temporary fixing adhesive of the present invention; It has a processing step of applying mechanical processing to produce a member or part. The temporary fixing process and the working process will be described in detail below. In the description of the method for manufacturing a member or part of the present invention, the water-based temporary fixing adhesive used is the second water-based temporary fixing adhesive, but the first water-based temporary fixing adhesive and the third water-based adhesive described later. It is also possible to use a temporary adhesive.

The temporary bonding step is a step of temporarily bonding the precursor of the member or part and the processing substrate using the second water-based temporary bonding adhesive of the present invention, more specifically, the precursor and the processing substrate. A coating film of the water-based temporary bonding adhesive of the present invention is formed between and temporarily bonding the precursor and the substrate for processing. As a method of forming a coating film and temporarily fixing it, a temporary fixing adhesive is applied to one surface of the precursor to form a coating film, and the surface provided with the coating film is used as an attachment surface to a substrate for processing. Method (i) for temporarily fixing the precursor, by applying a temporary fixing adhesive to a processing substrate to form a coating film, and placing the precursor on the coating film, through the coating film Any of the methods (ii) of temporarily fixing the precursor to the substrate for processing may be used.

For example, in the above method (i), as a method for applying the second water-based temporary fixing adhesive, a spin coating method, a spray method, a die coating method, an inkjet method, a dip coating method, a roll coating method, or the like can be used. mentioned. The amount of the second water-based temporary fixing adhesive to be applied depends on the surface area of the precursor to be temporarily fixed, but for example, about 1 to 3 mL is applied to the precursor of the wafer member such as a 4-inch silicon wafer. do it.
Thereafter, while the coating film provided on the precursor faces the substrate for processing, the precursor is placed at a predetermined position on the substrate for processing and temporarily fixed. At this time, it is preferable to temporarily bond the precursor and the substrate for processing by thermocompression bonding at a temperature of usually 50 to 140° C., because the temporary bonding can be performed more reliably.
The surface of the precursor may be roughly polished with an abrasive or the like and, if necessary, subjected to surface treatment by chemical etching before being temporarily attached to the substrate for processing.

The processing step is a step of processing the processed surface of the precursor temporarily fixed to the substrate for processing in the temporary fixing step. Processing in the production method of the present invention includes various mechanical processing such as cutting, polishing, cutting, grinding, and drilling, and these processings alone or in combination may be used.

The processing in the processing steps in the manufacturing method of the present invention is roughly divided into general processing that does not require special precision and precision processing that requires high precision. For example, precision processing is required for mechanical processing of wafers such as silicon wafers, optical lenses, and members for semiconductor devices, and particularly polishing processing of the surface of wafers such as silicon wafers. In the production method of the present invention, since the water-based temporary fixing adhesive of the present invention having excellent temporary fixing performance is used, the precursor can be temporarily fixed to the substrate for processing without tilting, and the adhesive The in-plane film thickness difference of the coating film is small, and the non-adhesion area is very small. Therefore, in the processing step, the pressure applied from the jig for mechanical processing to the surface of the precursor to be processed can be substantially uniform with respect to the surface to be processed of the precursor. As a result, the precursor can be processed with high accuracy, so that high-quality members or parts can be manufactured.

According to the manufacturing method of the present invention, high-precision processing is possible even under severe mechanical processing conditions. As a method for manufacturing these various wafers, it is particularly suitable as a method for manufacturing wafers having a Mohs degree of 9 or more (for example, sapphire wafers, etc.).

The method for manufacturing a member or component of the present invention may have a peeling step of peeling off the mechanically processed member or component from the processing substrate after the processing step. For peeling, a member or component such as a wafer may be peeled from the substrate for processing by using a razor, a scraper, or the like, or by heating and melting.
Further, if necessary, after the member or part is peeled off, it is possible to wash the member or part by using water or warm water to remove the residue of the temporary fixing adhesive on the member or part. Since the water-based temporary fixing adhesive of the present invention is water-based, it also has the advantage that it can be easily removed from the adherend by washing with water or warm water.

The members and parts obtained by the method for producing the members or parts of the present invention include, for example, OA equipment, information equipment, various electronic devices such as home appliances, optical devices, medical devices, and various devices such as automobile devices. Various members and parts used, more specifically, wafers such as silicon wafers, optical lenses, sapphire, gallium arsenide, crystal, magnetic members, metal members, glass members, resin members, semiconductor device members, etc. . In addition to silicon wafers, various wafers made of wafer materials such as sapphire, gallium phosphide, or gallium nitride, optical lenses, and semiconductor device members are preferable in consideration of the features of the method for producing members or components of the present invention. Among them, various wafers are preferable.

<Third water-based temporary fixing adhesive>
The third water-based temporary fixing adhesive of the present invention contains (A) a thermoplastic resin having a hydroxyl group, and (B) a solvent containing water, and the water content in the solvent is 95% by mass or more. It is characterized by having a surface tension of 20 mN/m or more and 55 mN/m or less at 25° C. and an adhesive strength of 0.1 MPa or more and 20 MPa or less. (A) A thermoplastic resin having a hydroxyl group (hereinafter sometimes referred to as "(A) component") is a component that exhibits temporary fixing performance mainly having adhesive performance and peeling performance. By setting the surface tension to 20 mN/m or more and 55 mN/m or less and the adhesive strength to 0.1 MPa or more and 20 MPa or less, excellent application performance as well as temporary fixing performance can be obtained. In addition, since the solvent contains water in an amount of 95% by mass or more and is water-based, the adhesive has high safety performance and low environmental load.

((A) Thermoplastic resin having a hydroxyl group)
The resin contained in (A) the thermoplastic resin having a hydroxyl group is not particularly limited as long as it is a thermoplastic resin having a hydroxyl group in the molecule, but one having a melting point of 30° C. or higher is preferable. (A) When the melting point of the resin contained in the thermoplastic resin having a hydroxyl group is 30° C. or higher, the temporary fixing performance and coating performance are improved, and versatility is also improved. (A) The melting point of the resin contained in the thermoplastic resin having a hydroxyl group is more preferably 35°C or higher, still more preferably 37°C or higher, still more preferably 40°C or higher, and particularly preferably 43°C. The upper limit is preferably 200°C or lower, more preferably 180°C or lower, still more preferably 160°C or lower, even more preferably 120°C or lower, and particularly preferably 100°C or lower. When the upper limit of the melting point of the component (A) is 200° C. or less, the release performance of the third water-based temporary bonding adhesive of the present invention is improved, thereby improving the temporary bonding performance and versatility. As used herein, the melting point means the melting end point measured according to JIS K0064:1992. The specific measurement will be described later.

(A) The number average molecular weight of the thermoplastic resin having a hydroxyl group is preferably 800 or more, more preferably 1,000 or more, still more preferably 2,000 or more, from the viewpoint of improving the coating performance as well as the temporary fixing performance. It is preferably 3,000 or more, and the upper limit is preferably 25,000 or less, more preferably 20,000 or less, even more preferably 15,000 or less, and particularly preferably 10,000 or less. Further, when the number average molecular weight is within the above range, versatility is also improved. As used herein, the number average molecular weight is measured by gel permeation chromatography (GPC method) using polystyrene as a standard substance.

As the (A) thermoplastic resin having a hydroxyl group having the above properties, a thermoplastic resin having an oxyalkylene group is preferably mentioned from the viewpoint of temporary fixing performance, and a type of oxyalkylene group is used as a structural unit. is more preferable.
The carbon number of the oxyalkylene group and the number of repeating units of the oxyalkylene group are the same as those of the oxyalkylene group of the component (A) of the first water-based temporary fixing adhesive.

Specific examples of the thermoplastic resin having an oxyalkylene group include the same thermoplastic resin having an oxyalkylene group as the component (A) of the first water-based temporary fixing adhesive. From the viewpoint of improving the polyalkylene glycol is particularly preferred.
Further, more specific examples of polyalkylene glycol, polyoxyalkylene ester, polyoxyalkylene alkyl ether and polyoxyalkylene alkyl aryl ether are those exemplified as the component (A) of the first water-based temporary fixing adhesive. The same can be mentioned.

In the third water-based temporary fixing adhesive, from the viewpoint of improving the coating performance as well as the temporary fixing performance, (A) the thermoplastic resin having a hydroxyl group may be a type of thermoplastic resin, and the number average molecular weight It is also possible to use two or more thermoplastic resins with different molecular weights, for example, two or more polyalkylene glycols with different number average molecular weights. In this case, a polyalkylene glycol having a number average molecular weight of 800 or more and less than 5,000 (hereinafter sometimes referred to as "polyalkylene glycol A") and a polyalkylene having a number average molecular weight of 5,000 or more and 10,000 or less It is preferable to combine a glycol (hereinafter sometimes referred to as "polyalkylene glycol B"), a polyethylene glycol having a number average molecular weight of 800 or more and less than 5,000, and a number average molecular weight of 5,000 or more and 10, 000 or less polyethylene glycol is more preferable.

The mixing ratio (mass ratio) of polyalkylene glycol A and polyalkylene glycol B is preferably 10:90 to 90:10, more preferably 15:85 to 85:15, still more preferably 20:80 to 80:20. is. When the blending ratio is within the above range, it becomes easier to ensure the film thickness of the coating film of the water-based temporary fixing adhesive, so that more stable adhesion performance is obtained, resulting in improved temporary fixing performance.

Moreover, shellac resin can also be used as (A) the thermoplastic resin having a hydroxyl group. Shellac resin is obtained by purifying a resinous substance secreted by lactoid bugs by a known solution extraction method, soda method, or the like. natural shellac resin or synthetic shellac resin containing an ester compound as a main component, and specifically, purified shellac resin, bleached shellac resin, decolorized shellac resin, and the like. Ammonium neutralized products of these shellac resins may also be used.

The content of (A) the thermoplastic resin having a hydroxyl group in the third water-based temporary fixing adhesive is preferably 5% by mass or more, more preferably 10% by mass, from the viewpoint of improving the coating performance as well as the temporary fixing performance. Above, more preferably 12% by mass or more, particularly preferably 15% by mass or more, and the upper limit is preferably 50% by mass or less, more preferably 47% by mass or less, further preferably 45% by mass or less, and particularly preferably It is 42% by mass or less. When the content of the thermoplastic resin is within the above range, it becomes easier to ensure the film thickness of the coating film of the water-based temporary fixing adhesive, so that more stable adhesion performance is obtained, thereby improving the temporary fixing performance.

((B) solvent containing water)
The third water-based temporary fixing adhesive of the present invention is a solvent containing water (hereinafter sometimes referred to as "(B) component"), and the content of water in the solvent is 95% by mass or more. contains a solvent that is
(B) As the water used in the solvent containing water, for example, ion-exchanged water may be used. In addition, in the third water-based temporary fixing adhesive of the present invention, solvents other than water, such as various organic solvents, may be included as a solvent. Considering this, it is preferable that the content of the organic solvent is as small as possible. (B) The content of water in the solvent containing water must be 95% by mass or more. By reducing the content of solvents other than water in this way, excellent safety performance can be obtained, and the burden on the environment can be reduced.
From the same point of view, the content of water in the solvent containing water (B) is preferably 96% by mass or more, more preferably 98% by mass or more, and still more preferably substantially completely free of organic solvents. A water-based temporary fixing adhesive is preferred. Here, the phrase "not containing an organic solvent" means that the content of the organic solvent is 0% by mass, and that the organic solvent is not intentionally used, for example, the above component (A), and (C ) component and (D) component may contain an organic solvent that may be unavoidably contained. In this case, the content of the organic solvent contained in all solvents is preferably 1% by mass or less, more preferably 0.5 % by mass or less, more preferably 0.1 mass % or less. That is, in the present invention, "not containing an organic solvent" means that the content of water in the total solvent is preferably 99% by mass or more, more preferably 99.5% by mass or more, and still more preferably 99.9% by mass. % or more.

The content of the water-containing solvent (B) in the third water-based temporary fixing adhesive is appropriately changed according to the content of the above component (A) and other components described later. It is 50% by mass or more and about 95% by mass.

(Other components: (C) surface conditioner)
The third water-based temporary fixing adhesive of the present invention may contain (C) a surface conditioner as another component other than (A) the thermoplastic resin having a hydroxyl group and (B) the solvent containing water. . (C) The surface conditioner is a component that mainly improves the application performance of the adhesive, particularly the application performance to various electronic components such as wafers. When applying adhesive to various parts such as optical equipment and electronic parts, the adhesive cannot be applied to the outer edges of the various parts due to differences in the materials of the adhesive and the various parts, and the entire surface of the parts must be coated. Sometimes I can't. In such a case, (A) a thermoplastic resin having a hydroxyl group and (C) a surface conditioner are used to adjust the surface tension of the third water-based temporary fixing adhesive of the present invention, and the materials of various parts, etc. Excellent coating performance can be obtained irrespective of the difference in .

(C) Surface conditioners generally include surface conditioners and leveling agents that have the ability to eliminate coating film defects caused by changes in viscosity, changes in surface tension, and generation of bubbles associated with high molecular weight. , wetting agents, antifoaming agents, etc., can be used without particular limitation. Examples include acrylic, vinyl, silicone, fluorine, cellulose, natural wax, water-soluble organic Various surface conditioners such as solvents, leveling agents, wetting agents, antifoaming agents and the like are preferably used. Moreover, as (C) the surface conditioner, a surfactant is also preferably mentioned, and a nonionic surfactant is preferable.

(C) Acetylene surfactants having acetylene bonds such as nonionic surfactants, acetylene alcohol surfactants, and acetylene glycol surfactants used as surface conditioners, fluorine surfactants, and acrylic surface conditioners Examples of surface conditioners such as agents are the same as those described as those that can be used as the (B) surface conditioner in the first water-based temporary fixing adhesive.

(C) As a surface conditioner, acetylene-based surfactants having acetylene bonds, such as acetylene alcohol-based surfactants and acetylene glycol-based surfactants, are used from the viewpoint of improving coating performance and anti-repellency performance as well as temporary fixing performance. , fluorine-based surfactants and acrylic surface-controlling agents are preferable, acetylenic surfactants, fluorine-based surfactants and acrylic surface-controlling agents are more preferable, and acetylenic surfactants are still more preferable. In addition to nonionic fluorine-based surfactants, amphoteric surfactants also exist, but nonionic surfactants are preferred from the viewpoint of improving coating performance and anti-repellency performance as well as temporary bonding performance.
In the third water-based temporary fixing adhesive of the present invention, the (C) surface conditioner preferably contains at least the surface conditioners exemplified above, and may contain other than those exemplified above. However, it is preferable that all of them are surface conditioners exemplified above.

The content of the surface conditioner (C) in the third water-based temporary bonding agent is preferable from the viewpoint of improving the temporary bonding performance, the performance of suppressing functional deterioration of various parts such as optical devices and electronic components, and the coating performance. is 0.01% by mass or more, more preferably 0.03% by mass or more, still more preferably 0.05% by mass or more, particularly preferably 0.10% by mass or more, and the upper limit is preferably 5% by mass or less, more The content is preferably 3% by mass or less, more preferably 1.5% by mass or less, and particularly preferably 1% by mass or less.

(Other components: (D) compatibilizer)
The third water-based temporary fixing adhesive of the present invention may contain (D) a compatibilizer (hereinafter sometimes referred to as "(D) component") as another component. (D) Compatibilizer, when using the above (C) surface conditioner, mainly due to the compatibility between the above (A) thermoplastic resin having a hydroxyl group and the (C) surface conditioner, the Even if the third temporary fixing adhesive can be applied to the outer edges of various parts, repelling may occur in some parts and the adhesive cannot be uniformly applied, that is, so-called repelling may occur. When repelling occurs, the compatibility between (A) the thermoplastic resin having a hydroxyl group and (C) the surface conditioner is improved by using (D) a compatibilizer, thereby improving repelling prevention performance. becomes possible.

Since (A) a thermoplastic resin having a hydroxyl group exhibits hydrophilicity because it contains a hydroxyl group, (C) a surface conditioner tends to exhibit hydrophobicity, so components (A) and (C) are compatible with each other. is not high. Therefore, when component (A) and component (C) are used in combination, the amount of adhesive applied due to repelling is particularly small in a part of the coating film of the adhesive, or a repelling portion that is not applied tends to occur, and the adhesive is removed from the wafer. It may be difficult to apply uniformly to various members and parts such as. When (C) a surface conditioner is used in (A) a thermoplastic resin having a hydroxyl group, the use of (D) a compatibilizing agent can reduce the occurrence of repelling. The water-based temporary fixing adhesive has not only excellent temporary fixing performance, but also application performance and anti-repellency performance.

The (D) compatibilizing agent that can be used in the third water-based temporary fixing adhesive is the same as the (C) compatibilizing agent used in the first water-based temporary fixing adhesive, and the alkylene oxide copolymer is It is preferably used. Specific examples of the alkylene oxide copolymer are the same as the (C) compatibilizing agent used in the first water-based temporary fixing adhesive, and such a copolymer has hydrophilicity in the ethylene oxide chain and propylene Since the oxide chain exhibits hydrophobicity, the compatibilizing performance for improving the compatibility between the hydrophilic component (A) and the hydrophobic component (C) is exhibited more remarkably, resulting in better repellency. Preventive performance is obtained.

For commercial products of alkylene oxide copolymers such as the above ethylene oxide-propylene oxide-ethylene oxide triblock copolymer and propylene oxide-ethylene oxide-propylene oxide triblock copolymer, in the first water-based temporary fixing adhesive The same as the exemplified commercial products can be mentioned.

In the ethylene oxide-propylene oxide copolymer, the ratio of propylene oxide to ethylene oxide, the number average molecular weight when the (D) compatibilizer is an alkylene oxide copolymer, and the ethylene oxide-propylene oxide copolymer are known. The preparation method in the method of is the same as the content described in the first water-based temporary fixing adhesive.

The content of the (D) compatibilizer in the third water-based temporary bonding adhesive is preferably 0.1% by mass or more, more preferably 0.1% by mass or more, from the viewpoint of improving the coating performance and anti-repellency performance as well as the temporary bonding performance. It is 0.3% by mass or more, more preferably 0.5% by mass or more, and the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less.

(Other additives)
If desired, the third water-based temporary fixing adhesive of the present invention may contain other additives other than the above components, such as antifoaming agents, leveling agents, silane coupling agents, crystal nucleating agents, plasticizers, preservatives, and the like. may be included.

(Various properties of water-based temporary fixing adhesive)
The third water-based temporary fixing adhesive of the present invention is required to have a surface tension of 20 mN/m or more and 55 mN/m or less at 25°C. If the surface tension at 25°C is not within the above range, excellent temporary fixing performance and coating performance cannot be obtained. From the viewpoint of improving coating performance as well as temporary bonding performance, the surface tension at 25° C. of the third water-based temporary bonding adhesive of the present invention is preferably 20 mN/m or more, more preferably 22 mN/m or more, and still more preferably It is 25 mN/m or more, and the upper limit is preferably 55 mN/m or less, more preferably 50 mN/m or less, and still more preferably 45 mN/m or less. In the present invention, the surface tension at 25° C. can be adjusted by (A) the type and content of the thermoplastic resin having a hydroxyl group, or (C) by using a surface conditioner. .
As used herein, the surface tension at 25°C is a value measured by the Wolhelmy method at a measurement temperature of 25°C. is a value that can be measured using

The third water-based temporary fixing adhesive of the present invention is required to have an adhesive strength of 0.1 MPa or more and 20 MPa or less. If the adhesive strength is not within the above range, excellent temporary fixing performance cannot be obtained. From the viewpoint of improving the temporary fixing performance, the adhesive strength of the third water-based temporary fixing adhesive of the present invention is preferably 0.15 Pa or more, more preferably 0.2 MPa or more, and still more preferably 0.5 MPa or more. , the upper limit is preferably 15 MPa or less, more preferably 10 MPa or less, still more preferably 7 MPa or less, and even more preferably 5 MPa or less.
In this specification, the adhesive strength is measured by dropping 5 drops on one stainless steel substrate, drying by heating at 100° C. for 20 minutes, bonding to the other stainless substrate, cooling to room temperature, and cooling to room temperature for 20 minutes. , The shear force of the laminated substrate is defined as the shear force measured using a tensile strength tester according to the "test method for tensile shear bond strength" specified in JIS K6850:1999.

Moreover, the third water-based temporary fixing adhesive of the present invention preferably has a melting point of 30° C. or higher. When the melting point is 30° C. or higher, excellent versatility can be obtained along with temporary fixing performance. From the viewpoint of improving coating performance and versatility as well as temporary bonding performance, the melting point of the third water-based temporary bonding adhesive is more preferably 35° C. or higher, still more preferably 37° C. or higher, and even more preferably 40° C. It is particularly preferably 43° C. or higher, and the upper limit is preferably 200° C. or lower, more preferably 180° C. or lower, still more preferably 160° C. or lower, still more preferably 120° C., and particularly preferably 100° C. or lower.
The melting point is measured by the same method as the melting point of the first water-based temporary fixing adhesive.

(Use of the third water-based temporary fixing adhesive)
The third water-based temporary bonding adhesive of the present invention is an adhesive having excellent temporary bonding performance, application performance and safety performance, and low environmental load. Therefore, the third water-based temporary bonding adhesive of the present invention is used for applications where temporary bonding performance is required as an adhesive, such as optical equipment, OA equipment, information equipment, various electronic equipment such as home appliances, medical equipment, Various members and parts used in various devices such as automobile devices, such as wafers such as silicon wafers, optical lenses, sapphire, gallium arsenide, crystal, magnetic members, metal members, glass members, resin members, semiconductor device members It is suitably used for temporary fixation (temporary fixation) during various mechanical processes such as cutting, polishing, cutting, grinding, drilling, etc.

Among the mechanical processing of electronic parts, a typical example of a method of polishing the surface of a wafer such as a silicon wafer, which is a member for semiconductor devices used in electronic equipment and the like, will be described.
First, the third water-based temporary fixing adhesive of the present invention is uniformly applied to the entire surface of one surface of the wafer by a coating method such as a spin coater method, a spray method, a die coat method, an ink jet method, a dip coat method, a roll coat method, or the like. to form a coating film of the adhesive. After the adhesive coating is dried as necessary, the wafer and the platen of the polishing machine are heat-pressed, usually at a temperature of 50 to 140° C., to fix the wafer on the platen of the polishing machine. Then, the wafer surface is polished by a polishing machine. After finishing the polishing process, the wafer may be peeled off from the surface plate of the polishing machine by using a razor or by heating and melting. The method of applying the adhesive is not particularly limited. The method of (2) is not particularly limited, and can be appropriately selected according to the shape of the wafer and the like.
Further, if necessary, after peeling off the wafer, it is possible to wash the wafer by using water or warm water to remove the residue of the temporary fixing adhesive on the wafer. Since the third water-based temporary fixing adhesive of the present invention is water-based, it also has the advantage that it can be easily removed from the adherend by washing with water or warm water.

The third water-based temporary fixing adhesive of the present invention exhibits adhesion performance that prevents the wafer from peeling off from the surface plate during polishing, and after finishing the polishing process, the wafer can be easily removed from the surface plate using a razor or the like. It is possible to peel it off. In addition, since the coating film of the adhesive is uniformly present on the entire surface of the wafer without repelling, the water-based temporary fixing adhesive of the present invention can, for example, meet high precision requirements such as mechanical processing. . In addition, the third water-based temporary fixing adhesive of the present invention exhibits the same effect not only in the polishing process of the wafer, but also in the mechanical processing of other various members and parts, and responds to high precision requirements. is possible.

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited by these examples.

(Evaluation and measurement method: first water-based temporary fixing adhesive)
(1-1) Measurement of Melting Point The melting points of the adhesives obtained in Examples and Comparative Examples were measured according to JIS K0064:1992. Specifically, a sample obtained by drying the moisture contained in the adhesive obtained in each example and comparative example (2 ml of the adhesive was placed in a small petri dish with an inner diameter of 40 mm, and was placed in a clean oven without a lid. Samples dried under conditions of 120 ° C. for 60 minutes at 120 ° C.) and A-PEG 1 to 5 and A-PPGS used in these examples are heated and melted (temperature conditions: 30 to 90 ° C.) and cooled (temperature conditions: −20 to 30 ° C.) to make a fine powder (maximum particle size: 300 μm), which is applied to a capillary tube (made of glass, inner diameter 0.8 to 1.2 mm, thickness: 0.2 to 0.3 mm, length height: 150 mm), and the temperature was raised at a temperature elevation rate of 1 ° C./min, and the melting temperature at which no solid was observed by visual observation (the temperature at which the powdery solid sample was completely liquefied ) was taken as the melting point.
(2-1) Evaluation of coating performance The adhesive obtained in each example and comparative example was coated on a silicon wafer (size: φ150 mm, thickness: 3000 rpm, coating time: 3 seconds) using a spin coater. thickness: 625 μm), and the ratio of the coating film area of the adhesive to the entire surface of the silicon wafer was visually confirmed and evaluated according to the following criteria. In this example, if the evaluation was B or higher, it was regarded as a pass.
A: The coating film area reached 100%.
B: The coating area was 80% or more and less than 100%.
C: The coating area was less than 80%.
(3-1) Evaluation of repelling prevention performance The adhesive obtained in each example and comparative example was coated on a silicon wafer (size: φ150 mm, Thickness: 625 μm), and the ratio of the area of the repellent portion in the coating film of the adhesive to the entire surface of the silicon wafer was visually confirmed and evaluated according to the following criteria. In this example, if the evaluation was B or higher, it was regarded as a pass.
A: The area of the repelling portion was 0%.
B: The area of the repelling portion was more than 0% and 10% or less.
C: The area of the repelling portion exceeded 10%.
(4-1) Evaluation of adhesive performance Five drops of the adhesive obtained in each example and comparative example were dropped on one stainless steel substrate, dried by heating at 100 ° C. for 20 minutes, and then the other stainless steel After 20 minutes of cooling to room temperature, the shear force of the laminated substrate is measured using a tensile strength measuring instrument according to the "test method for tensile shear adhesive strength" specified in JIS K6850: 1999. It was measured and evaluated according to the following criteria. In this example, if the evaluation was B or higher, it was regarded as a pass.
A: The shear force was 0.5 MPa or more.
B: The shear force was 0.1 MPa or more and less than 0.5 MPa.
C: The shear force was less than 0.1 MPa.
(5-1) Evaluation of peeling performance The adhesive obtained in each example and comparative example was coated on a silicon wafer (size: φ150 mm, thickness: 3000 rpm, coating time: 3 seconds) using a spin coater thickness: 625 μm), and the silicon wafer was heat-pressed to a ceramic surface plate at a temperature of 70°C. Next, after cooling to room temperature and temporarily fixing, the razor was fixed to a jig that can be installed so that the tip is inclined by 15°, and the tip was inserted between the silicon wafer and the surface plate, and the insertion amount ( mm), it was evaluated according to the following criteria. In this example, if the evaluation was B or higher, it was regarded as a pass.
A: The silicon wafer was peeled off from the surface plate when the insertion amount was less than 10 mm.
B: The silicon wafer was peeled off from the surface plate when the insertion amount was 10 mm or more and less than 15 mm.
C: The silicon wafer was peeled off from the surface plate when the insertion amount was 15 mm or more.

Examples 1-1 to 17-1, Comparative Examples 1-1 to 4-1: First Water-based Temporary Fixing Adhesives Adhesives were prepared in amounts (% by mass) shown in Table 1-1. The resulting adhesive was evaluated for application performance, anti-repellency performance, and temporary fixing performance (adhesion performance and peeling performance) by the methods (1-1) to (5-1) above. Evaluation results are shown in Table 1-1.

註）本実施例で用いた第１－１表に示される各成分の詳細は以下の通りである。
・Ａ－ＰＥＧ１：ポリエチレングリコール（数平均分子量：１，０００、融点：４０℃）
・Ａ－ＰＥＧ２：ポリエチレングリコール（数平均分子量：３，１００、融点：５５℃）
・Ａ－ＰＥＧ３：ポリエチレングリコール（数平均分子量：８，８００、融点：６０℃）
・Ａ－ＰＥＧ４：ポリエチレングリコール（数平均分子量：２０，０００、融点：６５℃）
・Ａ－ＰＥＧ５：ポリエチレングリコール（数平均分子量：６００、融点：１８～２３℃）
・Ａ－ＰＰＧＳ：ポリプロピレングリコールモノステアレート（オキシエチレン基繰り返し単位数：１４０、融点：５６．５～６１．５℃）
・Ｂ－１：アセチレングリコール系界面活性剤（上記一般式（２）において、Ｒ^２１及びＲ^２３がメチル基、Ｒ^２２及びＲ^２４がイソブチル基、Ａ_２１及びＡ_２２が単結合である、２，４，７，９－テトラメチル－５－デシン－４，７－ジオールのエチレンオキサイド付加物（オキシエチレン基繰り返し単位数：４））
・Ｂ－２：フッ素系界面活性剤（部分フッ素化アルコール置換グリコール、商品名「Ｃａｐｓｔｏｎｅ ＦＳ－３４」、Ｄｕｐｏｎｔ社製）
・Ｂ－３：アクリル系界面活性剤（商品名「ＢＹＫ－３４４０」、ビックケミー社製）
・Ｃ－１：アルキレンオキシドのブロック共重合体（エチレンオキシド－プロピレンオキシド－エチレンオキシドトリブロック共重合体（ＨＯ－（ＥＯ）_ａ－（ＰＯ）_５５－（ＥＯ）_ｂ－Ｈ（ａ＋ｂ＝３００）で示される共重合体（ＥＯ：エチレンオキシド、ＰＯ：プロピレンオキシド））、数平均分子量：１６５００、エチレンオキシド：プロピレンオキシド（モル比）＝３００：５５）
・Ｃ－２：アルキレンオキシドのブロック共重合体（エチレングリコール５．２質量部に、酸化エチレン９９５重量部をアルカリ触媒の存在下で加圧、加温状態で吹き込み重合させて、ポリエチレングリコール（数平均分子量：１２，０００）を作製し、金属アルコラート触媒を用いて、該ポリエチレングリコールと酸化プロピレン１，０００重量部とを重合させて、ポリエチレングリコールを主鎖として、その両端にポリプロピレングリコールが１００質量％部分付加重合された、プロピレンオキシド－エチレンオキシド－プロピレンオキシドトリブロック共重合体）

Note) Details of each component shown in Table 1-1 used in this example are as follows.
· A-PEG1: polyethylene glycol (number average molecular weight: 1,000, melting point: 40 ° C.)
· A-PEG2: polyethylene glycol (number average molecular weight: 3,100, melting point: 55 ° C.)
· A-PEG3: polyethylene glycol (number average molecular weight: 8,800, melting point: 60 ° C.)
· A-PEG4: polyethylene glycol (number average molecular weight: 20,000, melting point: 65 ° C.)
· A-PEG5: polyethylene glycol (number average molecular weight: 600, melting point: 18-23°C)
- A-PPGS: polypropylene glycol monostearate (oxyethylene group repeating unit number: 140, melting point: 56.5 to 61.5 ° C.)
B-1: Acetylene glycol-based surfactant (in general formula (2) above, R ²¹ and R ²³ are methyl groups, R ²² and R ²⁴ are isobutyl groups, A ₂₁ and A ₂₂ are single bonds, 2 ,4,7,9-tetramethyl-5-decyne-4,7-diol with ethylene oxide adduct (oxyethylene group repeating unit number: 4))
・B-2: Fluorinated surfactant (partially fluorinated alcohol-substituted glycol, trade name “Capstone FS-34”, manufactured by Dupont)
・ B-3: Acrylic surfactant (trade name “BYK-3440”, manufactured by BYK-Chemie)
C-1: Alkylene oxide block copolymer (ethylene oxide-propylene oxide-ethylene oxide triblock copolymer (HO-(EO) _a- (PO) _55- (EO) _b -H (a+b=300) copolymer (EO: ethylene oxide, PO: propylene oxide), number average molecular weight: 16500, ethylene oxide: propylene oxide (molar ratio) = 300: 55)
・C-2: Block copolymer of alkylene oxide (5.2 parts by mass of ethylene glycol is polymerized by blowing 995 parts by weight of ethylene oxide under pressure and heating in the presence of an alkali catalyst to obtain polyethylene glycol (number The polyethylene glycol and 1,000 parts by weight of propylene oxide are polymerized using a metal alcoholate catalyst to form a main chain of polyethylene glycol and 100 parts by mass of polypropylene glycol at both ends. % partially addition polymerized propylene oxide-ethylene oxide-propylene oxide triblock copolymer)

From the results of Examples, the first water-based temporary fixing adhesive of the present invention has excellent temporary fixing performance that combines adhesive performance and peeling performance, and is also excellent in coating performance and repelling prevention performance. As a result, a highly accurate silicon wafer was obtained. In addition, since the adhesive of the present invention is a water-based adhesive that does not substantially contain an organic solvent, it can reduce the burden on the environment such as the natural environment and the working environment, and is excellent in safety. be.
On the other hand, the adhesive of Comparative Example 1-1, which did not contain component (A), was inferior in application performance and did not exhibit adhesion performance. The adhesive of Comparative Example 2-1, which does not contain component (C), is inferior in anti-repellent performance, and the adhesive of Comparative Example 3-1, which does not contain component (B), is inferior in coating performance. rice field. In addition, the adhesive of Comparative Example 4-1, which had a melting point of less than 30° C., could not be adhered because the adhesive did not harden, and the performance could not be evaluated.
The adhesives of Examples 10-1 to 13-1 containing one (A) component and the adhesives containing two (A) components of other Examples (especially Examples 1-1 to 3-1 From the comparison with adhesives), it was confirmed that the temporary fixing performance, coating performance, and repelling prevention performance are equivalent or improved by using two or more resins as the component (A).

Examples 18-1 to 22-1: First Water-Based Temporary Bonding Adhesives Adhesives were prepared in amounts (% by mass) shown in Table 2-1. The resulting adhesive was evaluated for application performance, anti-repellency performance, and temporary fixing performance (adhesion performance and peeling performance) by the methods (1-1) to (5-1) above. Evaluation results are shown in Table 2-1.

註）本実施例で用いた第２－１表に示される各成分の詳細は以下の通りである。
・Ａ－ＰＥＧ６：ポリエチレングリコール（数平均分子量：１，５４０、融点：４５℃）
・Ａ－ＰＥＧ７：ポリエチレングリコール（数平均分子量：２，０００、融点：５０℃）
・Ｃ－３：アルキレンオキシドのブロック共重合体（エチレンオキシド－プロピレンオキシドトリブロック共重合体（ＨＯ－（ＥＯ）_ａ－（ＰＯ）_３５－（ＥＯ）_ｂ－Ｈ（ａ+ｂ=１５０）で示される共重合体（ＥＯ：エチレンオキシド、ＰＯ：プロピレンオキシド））、数平均分子量：９，４００、エチレンオキシド：プロピレンオキシド（モル比）＝１５０：３５）

Note) Details of each component shown in Table 2-1 used in this example are as follows.
· A-PEG6: polyethylene glycol (number average molecular weight: 1,540, melting point: 45 ° C.)
· A-PEG7: polyethylene glycol (number average molecular weight: 2,000, melting point: 50 ° C.)
・C-3: Alkylene oxide block copolymer (ethylene oxide-propylene oxide triblock copolymer (HO-(EO) _a- (PO) _35- (EO) _b -H (a+b=150) copolymer (EO: ethylene oxide, PO: propylene oxide), number average molecular weight: 9,400, ethylene oxide: propylene oxide (molar ratio) = 150: 35)

From Examples 18-1 to 22-1, the first water-based temporary fixing adhesive has both adhesive performance and peeling performance, and has excellent temporary fixing performance, and also has excellent coating performance and repelling prevention performance. As a result, a highly accurate silicon wafer was obtained. In addition, since the adhesive of the present invention is a water-based adhesive that does not substantially contain an organic solvent, it can reduce the burden on the environment such as the natural environment and the working environment, and is excellent in safety. be.

(Evaluation and measurement method: second water-based temporary fixing adhesive)
(1-2) Measurement of Contents of Various Metal Ions The adhesives obtained in each of the examples and comparative examples were weighed in a platinum container and heated and ashed in an electric furnace at a heating temperature of 550°C. After treating this with dilute hydrochloric acid, it was dissolved in dilute nitric acid to a constant volume. The obtained solution was measured for the content of sodium metal ions by atomic absorption spectrometry using a polarized Zeeman atomic absorption spectrophotometer ("180-80 (model number)", manufactured by Hitachi, Ltd.), and an ICP mass spectrometer ( The content of aluminum metal ions, zinc metal ions, nickel metal ions, and chromium metal ions is measured by ICP mass spectrometry using "SPQ6500 (model number)" manufactured by Seiko Electronics Industry Co., Ltd.), and polarized Zeeman atomic absorption spectrophotometry is used. The content of copper metal ions is measured by frameless atomic absorption spectrometry using a meter ("Z8270 (model number)", manufactured by Hitachi, Ltd.), and a sequential ICP emission spectrometer ("SPS4000 (model number)", Seiko (manufactured by Denshi Kogyo Co., Ltd.) was used to measure the content of iron metal ions by ICP emission spectroscopic analysis.
Also, the adhesive obtained in each example and comparative example was weighed in a Teflon (registered trademark) beaker, thermally decomposed with sulfuric acid, nitric acid and perchloric acid, and then dissolved in dilute nitric acid to a constant volume. . The resulting solution was subjected to measurement of the content of lead metal ions by ICP mass spectrometry using an ICP mass spectrometer ("SPQ6500 (model number)", manufactured by Seiko Instruments Inc.). The measured contents (ppb) of various metal ions are shown in Table 1-2.
(2-2) Measurement of Melting Point The melting points of the adhesives obtained in Examples and Comparative Examples were measured according to JIS K0064:1992. Specifically, a sample obtained by drying the moisture contained in the adhesive obtained in each example and comparative example (2 ml of the adhesive was placed in a small petri dish with an inner diameter of 40 mm and placed in a clean oven without a lid. 120° C. for 60 minutes) and A-PEG1 used in these examples were heated and melted (temperature condition: 30 to 130° C.) and cooled (temperature condition: −20 to 30° C.). A fine powder (maximum particle size: 300 μm) was dried in a desiccator for 24 hours, and the sample was placed in a capillary tube (made of glass, inner diameter: 0.8 to 1.2 mm, thickness: 0.2 mm). ~ 0.3 mm, length: 150 mm), and the temperature was raised at a temperature elevation rate of 1 ° C./min. ) was taken as the melting point.

(3-2) Evaluation of Adhesive Performance Evaluation was performed using the same method and criteria as in "(4-1) Evaluation of Adhesive Performance" above. In this example, if the evaluation was B or higher, it was regarded as a pass.
(4-2) Evaluation of peeling performance Evaluation was performed using the same method and criteria as in “(5-1) Evaluation of peeling performance” above. In this example, if the evaluation was B or higher, it was regarded as a pass.

Examples 1-2 to 6-2, Comparative Examples 1-2 to 6-2: Second water-based temporary adhesive Adhesive was prepared in the amount (% by mass) shown in Table 1-2, and the first -2 Metal ions were removed according to the method for removing metal ions in Table 2, and the adhesives of each example and comparative example were obtained. The method for removing metal ions was as follows. For the obtained adhesive, the content of various metal ions was measured by the method (1-2) above, the melting point was measured by the method (2-2) above, and the above (3-2) and (4) were measured. -2) The temporary fixing performance was evaluated by the method. Evaluation results are shown in Table 1-2.
(Method for removing metal ions)
A: A hydrogen-type cation exchange resin (“ORLITE DS-4 (product number)”, acidic group: sulfonic acid group, manufactured by Organo Co., Ltd.) was used as an ion exchanger and treated from an adhesive.
B: As an ion exchanger, an ammonia-type cation exchange resin (a resin column (diameter: 13 cm, height: 50 cm) is filled with 4 L of "Orlite DS-4 (product number)" (manufactured by Organo Co., Ltd.), and 10 % ammonia water was flowed down at a linear velocity of 1 cm/min and washed with ion-exchanged water until the effluent became neutral.
-: Metal ion removal was not performed.

註）表中、各種金属イオン欄の「－」は測定不可、又は各種金属イオンの含有量が低減しなかったことを示す。また、本実施例で用いた第１－２表に示される各成分の詳細は以下の通りである。
・Ａ－ＰＥＧ１：ポリエチレングリコール（ポリエチレングリコール１（数平均分子量：３，１００、融点：５５℃）５０質量部とポリエチレングリコール２（数平均分子量：８，８００、融点：６０℃）５０質量部との混合物）
・Ａ－エステル：ポリエチレングリコールモノステアレート（オキシエチレン基繰り返し単位数：１４０、融点：５６．５～６１．５℃）
・Ａ－塩：ロジン系熱可塑樹脂のナトリウム塩（「Ｖｉｎｓｏｌ ＮＶＸ（商品名）」、Ｐｉｎｏｖａ社製）
・Ａ－エマルション：ロジン系樹脂（「スーパーエステルＮＳ－１２１（商品名）」、荒川化学工業株式会社製）
・Ｃ－１：アセチレングリコール系界面活性剤（上記一般式（２）において、Ｒ^２１及びＲ^２３がメチル基、Ｒ^２２及びＲ^２４がイソブチル基、Ａ_２１及びＡ_２２が単結合である、２，４，７，９－テトラメチル－５－デシン－４，７－ジオールのエチレンオキサイド付加物（オキシエチレン基繰り返し単位数：４））
・Ｄ－１：アルキレンオキシドのブロック共重合体（エチレンオキシド－プロピレンオキシド－エチレンオキシドトリブロック共重合体（ＨＯ－（ＥＯ）_ａ（ＰＯ）_５５－（ＥＯ）_ｂ－Ｈ（ａ＋ｂ＝３００）で示される共重合体（ＥＯ：エチレンオキシド、ＰＯ：プロピレンオキシド））、数平均分子量：１６５００、エチレンオキシド：プロピレンオキシド（モル比）＝３００：５５））

Note) In the table, "-" in the column of various metal ions indicates that the measurement was impossible or that the content of various metal ions did not decrease. Further, the details of each component shown in Table 1-2 used in this example are as follows.
· A-PEG1: polyethylene glycol (polyethylene glycol 1 (number average molecular weight: 3,100, melting point: 55 ° C.) 50 parts by mass and polyethylene glycol 2 (number average molecular weight: 8,800, melting point: 60 ° C.) 50 parts by mass mixture)
· A-ester: polyethylene glycol monostearate (oxyethylene group repeating unit number: 140, melting point: 56.5 to 61.5 ° C.)
・ A-salt: sodium salt of rosin-based thermoplastic resin (“Vinsol NVX (trade name)”, manufactured by Pinova)
・ A-emulsion: rosin-based resin ("Super Ester NS-121 (trade name)", manufactured by Arakawa Chemical Industries, Ltd.)
C-1: Acetylene glycol-based surfactant (in general formula (2) above, R ²¹ and R ²³ are methyl groups, R ²² and R ²⁴ are isobutyl groups, A ₂₁ and A ₂₂ are single bonds, 2 ,4,7,9-tetramethyl-5-decyne-4,7-diol with ethylene oxide adduct (oxyethylene group repeating unit number: 4))
D-1: Alkylene oxide block copolymer (ethylene oxide-propylene oxide-ethylene oxide triblock copolymer (HO-(EO) _a (PO) ₅₅ -(EO) _b -H (a+b = 300) Copolymer (EO: ethylene oxide, PO: propylene oxide)), number average molecular weight: 16500, ethylene oxide: propylene oxide (molar ratio) = 300:55))

From the results of Examples, the second water-based temporary bonding adhesive of the present invention has excellent temporary bonding performance that combines adhesion performance and peeling performance, and has a low content of various metal ions, It is excellent in suppressing functional deterioration of various members and parts used in optical equipment, electronic equipment, and the like. In addition, by adopting (A) a thermoplastic resin having a hydroxyl group as the resin component, the content of various metal ions can be within a predetermined range without performing various metal ion removal treatments, and furthermore, the ion exchanger By performing various metal ion removal treatments using It can be an excellent adhesive.
From the results of Examples 1-2 and 4-2, the second water-based temporary fixing adhesive of the present invention has various metal ions depending on the selection of the component ((A) thermoplastic resin having a hydroxyl group) contained in the adhesive. can be set within a predetermined range, and (A) the thermoplastic resin having a hydroxyl group has a high affinity for water, so stability as a water-based temporary fixing adhesive can be obtained. In addition, when the content of various metal ions is further reduced and used, metal ion removal treatment may be performed as shown in Examples 2-2, 3-2, 5-2 and 6-2. A) By using a thermoplastic resin having a hydroxyl group, it becomes possible to more easily reduce the content of metal ions.

On the other hand, from the results of Comparative Examples 1-2 and 4-2, the total content of various metal ions cannot be 3000 ppb or less unless (A) a thermoplastic resin having a hydroxyl group is used as the resin component. An attempt was made to reduce the content of various metal ions in the adhesives of Comparative Examples 1-2 and 4-2 by using an ion exchanger, but the content of sodium metal ions in the adhesive of Comparative Example 1-2 was too high. It could not be reduced to the predetermined content (Comparative Examples 2-2 and 3-2). The content of the adhesive of Comparative Example 2-2 could not be measured because the ion-exchange resin precipitated. In addition, although the adhesive of Comparative Example 4-2 uses an emulsion type resin component, various metal ions are incorporated in the emulsion, so the content could not be reduced to the predetermined content (Comparative Examples 5-2 and 6-2).

Examples 7-2 to 15-2: Second Water-Based Temporary Bonding Adhesives Adhesives were prepared in amounts (% by mass) shown in Table 2-2. Regarding the obtained adhesive, the content of various metal ions was measured by the method (1-2) above, the melting point was measured by the method (2-2) above, and the above ( Temporary fixing performance was evaluated by the methods of 3-2) and (4-2). Evaluation results are shown in Table 2-2.

註）本実施例で用いた第２－２表に示される各成分の詳細は以下の通りである。
・Ａ－ＰＥＧ２：ポリエチレングリコール（数平均分子量：１，５４０、融点：４５℃）
・Ｄ－２：アルキレンオキシドのブロック共重合体（エチレンオキシド－プロピレンオキシドトリブロック共重合体（ＨＯ－（ＥＯ）_ａ－（ＰＯ）_３５－（ＥＯ）_ｂ－Ｈ（ａ＋ｂ＝１５０）で示される共重合体（ＥＯ：エチレンオキシド、ＰＯ：プロピレンオキシド））、数平均分子量：９，４００、エチレンオキシド：プロピレンオキシド（モル比）＝１５０：３５）

Note) Details of each component shown in Table 2-2 used in this example are as follows.
· A-PEG2: polyethylene glycol (number average molecular weight: 1,540, melting point: 45 ° C.)
D-2: block copolymer of alkylene oxide (ethylene oxide-propylene oxide triblock copolymer (HO-(EO) _a -(PO) ₃₅ -(EO) _b -H (a+b=150) Polymer (EO: ethylene oxide, PO: propylene oxide), number average molecular weight: 9,400, ethylene oxide: propylene oxide (molar ratio) = 150:35)

From the results of Examples 7-2 to 15-2, the second water-based temporary fixing adhesive has both adhesive performance and peeling performance, and has excellent temporary fixing performance, and contains various metal ions. It has a small amount and is excellent in suppressing functional deterioration of various members and parts used in optical equipment, electronic equipment, and the like. In addition, by adopting (A) a thermoplastic resin having a hydroxyl group as the resin component, the content of various metal ions can be within a predetermined range without performing various metal ion removal treatments, and furthermore, the ion exchanger By performing various metal ion removal treatments using It can be an excellent adhesive.

(Evaluation and measurement method: third water-based temporary fixing adhesive)
(1-3) Measurement of Surface Tension at 25° C. The melting points of the adhesives obtained in Examples and Comparative Examples were measured according to JIS K0064:1992. Specifically, a sample obtained by drying the moisture contained in the adhesive obtained in each example and comparative example (2 ml of the adhesive was placed in a small petri dish with an inner diameter of 40 mm and placed in a clean oven without a lid. 120° C. for 60 minutes) and A-PEG1 used in these examples were heated and melted (temperature condition: 30 to 90° C.) and cooled (temperature condition: −20 to 30° C.). A fine powder (maximum particle size: 300 μm) was dried in a desiccator for 24 hours, and the sample was placed in a capillary tube (made of glass, inner diameter: 0.8 to 1.2 mm, thickness: 0.2 mm). ~ 0.3 mm, length: 150 mm), and the temperature was raised at a temperature elevation rate of 1 ° C./min. ) was taken as the melting point.

(2-3) Measurement of Melting Point The melting points of the adhesives obtained in Examples and Comparative Examples were measured by the same method as in "(1-1) Measurement of Melting Point" above.

(3-3) Measurement of adhesive strength Five drops of the adhesive obtained in each example and comparative example were dropped on one stainless steel substrate, dried by heating at 100 ° C. for 20 minutes, and then the other After 20 minutes of cooling to room temperature, the shear force of the laminated substrate was measured using a tensile strength measuring instrument according to the "test method for tensile shear adhesive strength" specified in JIS K6850: 1999. measured by

(4-3) Evaluation of Coating Performance Evaluation was performed using the same method and criteria as in “(2-1) Evaluation of coating performance” above. In this example, if the evaluation was B or higher, it was regarded as a pass.
(5-3) Evaluation of anti-repellency performance Evaluation was performed using the same method and criteria as in "(3-1) Evaluation of coating performance" above. In this example, if the evaluation was B or higher, it was regarded as a pass.
(6-3) Evaluation of adhesive performance Regarding the adhesive strength measured based on "(3-3) Measurement of adhesive strength" above, the same method and standard as "(4-1) Evaluation of adhesive performance" evaluated. In this example, if the evaluation was B or higher, it was regarded as a pass.
(7-3) Evaluation of peeling performance Evaluation was performed using the same method and criteria as in “(5-1) Evaluation of peeling performance” above. In this example, if the evaluation was B or higher, it was regarded as a pass.

Examples 1-3 to 14-3, Comparative Examples 1-3 to 4-3
Adhesives were prepared with the blending amounts (% by mass) shown in Table 1-3. As the solvent containing water (B), ionized water was used (the water content in the solvent was 100% by mass). For the obtained adhesive, the surface tension was measured by the method (1-3) above, the melting point was measured by the method (2-3) above, and the adhesive strength was measured by the method (3-3) above. Also, various performances were evaluated by the methods (4-3) to (7-3) above. The measurement results and evaluation results are shown in Table 1-3.

Note) Details of each component shown in Table 1-3 used in this example are as follows.
· A-PEG1: polyethylene glycol (number average molecular weight: 1,000, melting point: 40 ° C., surface tension at 25 ° C.: 56 mN / m [20% aqueous solution])
· A-PEG2: polyethylene glycol (number average molecular weight: 3,100, melting point: 55 ° C., surface tension at 25 ° C.: 56 mN / m [20% aqueous solution])
· A-PEG3: polyethylene glycol (number average molecular weight: 8,800, melting point: 60 ° C., surface tension at 25 ° C.: 55 mN / m [20% aqueous solution])
· A-PEG4: polyethylene glycol (number average molecular weight: 20,000, melting point: 65 ° C., surface tension at 25 ° C.: 54 mN / m [20% aqueous solution])
・ Resin component 1: Ammonium neutralized shellac resin (surface tension at 25 ° C.: 45 mN / m [20% aqueous solution], “Shellac KTA (trade name)” manufactured by Koyo Chemical) ・ Resin component 2: Styrene maleic acid Resin water solution (30 mass%) (Surface tension at 25 ° C.: 41 mN / m [20% aqueous solution], "Alastor 703S (trade name)", manufactured by Arakawa Chemical Industries)
C-1: Acetylene glycol-based surfactant (in general formula (2) above, R ₂₁ and R ₂₃ are methyl groups, R ₂₂ and R ₂₄ are isobutyl groups, A ₂₁ and A ₂₂ are single bonds, 2 ,4,7,9-tetramethyl-5-decyne-4,7-diol with ethylene oxide adduct (oxyethylene group repeating unit number: 4))
・ C-2: fluorine-based surfactant (“FS-31 (trade name)”, manufactured by Dupont)
D-1: Block copolymer of alkylene oxide (ethylene oxide-propylene oxide-ethylene oxide triblock copolymer (HO-(EO) _a -(PO) ₅₅ -(EO) _b -H (a+b = 300) copolymer (EO: ethylene oxide, PO: propylene oxide)), number average molecular weight: 16,500, ethylene oxide: propylene oxide (molar ratio) = 300: 55))

From the results of the examples, the third water-based temporary fixing adhesive of the present invention has a predetermined surface tension and adhesive strength, so that it is an excellent temporary fixing adhesive having both adhesive performance and peeling performance. In addition, it was confirmed that the coating performance was excellent, and as a result, a highly accurate silicon wafer was obtained. In addition, since the third water-based temporary fixing adhesive is a water-based adhesive that does not substantially contain an organic solvent, it can reduce the burden on the environment such as the natural environment and the work environment, and is excellent in safety. It is a thing.
On the other hand, in Comparative Examples 1-3 to 4-3, the surface tension was large or small, and the adhesive strength was small. became.

The water-based temporary fixing adhesive of the present invention is a water-based temporary fixing adhesive that has excellent temporary fixing performance as well as coating performance and repelling prevention performance, and performance of suppressing functional deterioration of various members and parts used in optical devices, electronic devices, etc. It is a water-based temporary fixing adhesive that has excellent temporary fixing performance, application performance and safety performance, and has a low environmental load. It is an adhesive that can reduce the burden on the environment such as, and is also excellent in safety. Therefore, the water-based temporary fixing adhesive of the present invention is used for applications where temporary fixing performance is required as an adhesive, such as OA equipment, information equipment, various electronic devices such as home appliances, optical equipment, medical equipment, and automotive equipment. For example, wafers such as silicon wafers, optical lenses, sapphire, gallium arsenide, crystal, magnetic members, metal members, glass members, resin members, semiconductor device members, etc. , polishing, cutting, grinding, drilling, etc., for temporary fixation (temporary fixation).

Claims (26)

A water-based temporary fixing adhesive containing (A) a thermoplastic resin having a hydroxyl group, (B) a surface conditioner, and (C) a compatibilizer, and having a melting point of 30°C or higher as measured according to JIS K0064:1992. The water-based temporary fixing adhesive according to claim 1, wherein the melting point is 30°C or higher and 200°C or lower. 3. The water-based temporary fixing adhesive according to claim 1 or 2, wherein the surface conditioner (B) contains at least one selected from acetylenic surfactants, fluorosurfactants and acrylic surface conditioners. Claims 1 to 1, wherein the acetylenic surfactant of the surface conditioner (B) contains at least one selected from acetylene alcohol represented by the following general formula (1) and acetylene glycol represented by the following general formula (2). 4. The water-based temporary fixing adhesive according to any one of 3.

(In Formula (1), R ¹¹ and R ¹² each independently represent a hydrocarbon group having 1 to 8 carbon atoms, and A ₁₁ represents a single bond or an oxyalkylene group having 1 to 30 repeating units. , in formula (2), R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrocarbon group having 1 to 8 carbon atoms, A ₂₁ and A ₂₂ each independently represent a single bond or the number of repeating units 1 or more and 30 or less oxyalkylene groups.) The water-based temporary fixing adhesive according to any one of claims 1 to 4, wherein the (C) compatibilizer contains at least an alkylene oxide copolymer. The water-based temporary fixing adhesive according to claim 5, wherein the alkylene oxide copolymer contains at least an ethylene oxide-propylene oxide block copolymer. The water-based temporary fixing adhesive according to any one of claims 1 to 6, further comprising water as a solvent. The water-based temporary fixing adhesive according to claim 7, wherein the solvent does not contain an organic solvent. The content of (A) the thermoplastic resin having a hydroxyl group, (B) the surface conditioner, and (C) the compatibilizer based on the total amount of the composition is 5% by mass or more and 50% by mass or less, and 0.01% by mass. The water-based temporary fixing adhesive according to any one of claims 1 to 8, which is 3 mass% or more and 0.1 mass% or more and 15 mass% or less. At least (A) contains a thermoplastic resin having a hydroxyl group, and the total content of sodium metal ions, aluminum metal ions, iron metal ions, zinc metal ions, copper metal ions, nickel metal ions, chromium metal ions and lead metal ions is 3000 ppb. and a sodium metal ion, iron metal ion, zinc metal ion and copper metal ion content of 1000 ppb or less each. The water-based temporary fixing adhesive according to claim 10, wherein the content of (A) the thermoplastic resin having a hydroxyl group is 5% by mass or more and 50% by mass or less based on the total amount of the composition. The water-based temporary fixing adhesive according to claim 10 or 11, further comprising water as a solvent. The water-based temporary fixing adhesive according to claim 12, wherein the solvent does not contain an organic solvent. (A) a thermoplastic resin having a hydroxyl group; and (B) a solvent containing water, wherein the water content in the solvent is 95% by mass or more, and the surface tension at 25°C is 20 mN/m or more and 55 mN /m or less and an adhesive strength of 0.1 MPa or more and 20 MPa or less. 15. The water-based temporary fixing adhesive according to claim 14, wherein the (B) solvent containing water does not contain an organic solvent. The water-based temporary fixing adhesive according to claim 14 or 15, wherein the content of (A) the thermoplastic resin having a hydroxyl group is 5% by mass or more and 50% by mass or less based on the total amount of the composition. The water-based temporary fixing adhesive according to any one of claims 1 to 16, which contains at least a resin having a melting point of 30 ° C. or higher as measured in accordance with JIS K0064:1992 for the (A) thermoplastic resin having a hydroxyl group. The water-based temporary fixing adhesive according to any one of claims 1 to 17, wherein (A) the thermoplastic resin having a hydroxyl group contains at least a resin having an oxyalkylene group. The water-based temporary fixing adhesive according to any one of claims 1 to 18, wherein (A) the thermoplastic resin having a hydroxyl group contains at least one selected from polyalkylene glycol and polyalkylene glycol ester. The water-based temporary fixing adhesive according to any one of claims 1 to 19, which is used for processing members or parts used in electronic equipment. 21. The water-based temporary fixing adhesive according to claim 20, wherein the processing of the members or parts used in the electronic device is polishing of the wafer surface. (A) A composition containing a thermoplastic resin having a hydroxyl group and metal ions is brought into contact with an ion exchanger to obtain sodium metal ions, aluminum metal ions, iron metal ions, zinc metal ions, copper metal ions, nickel metal ions, A method for producing a water-based temporary fixing adhesive, wherein the total content of chromium metal ions and lead metal ions is 3000 ppb or less, and the content of each of sodium metal ions, iron metal ions, zinc metal ions and copper metal ions is 1000 ppb or less. . 23. The method for producing a water-based temporary fixing adhesive according to claim 22, wherein the ion exchanger uses an ion exchange resin. A temporary fixing step of temporarily fixing a member or part precursor and a processing substrate using the water-based temporary fixing adhesive according to any one of claims 1 to 21, and subjecting the precursor to mechanical processing. A method for manufacturing a member or component, which includes a processing step for manufacturing the member or component. 25. The method of manufacturing a member or component according to claim 24, wherein the precursor of the member or component is a precursor of a member or component used in an electronic device. 25. The method of manufacturing a member or part according to claim 24, wherein said member or part used in said electronic equipment is a wafer, and said mechanical processing is polishing of said wafer surface.