JP2019163485A - 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

  The present invention relates to an aqueous temporary adhesive.

  Adhesives include various members and parts used in various devices such as home appliances, various electronic devices such as OA devices, information devices, and home appliances, optical devices, medical devices, and automotive devices (hereinafter referred to as “ It may be referred to as an “adhered object”). Needless to say, the performance originally required for the adhesive is adhesive performance, but depending on the application, it may exhibit adhesive performance when temporarily fixing one or more members or parts, and then peel off. There is a case where performance (hereinafter, sometimes referred to as “temporary fixing performance”) that exhibits peeling performance is required. For example, for an optical lens used in an optical device, temporarily fix it to a support, and perform various mechanical processing such as cutting, polishing, cutting, grinding, drilling, etc. to obtain a predetermined shape and surface property, Next, the adhesive used in the production of an optical lens that is peeled off from the support is required to have a temporary fixing performance.

  Also in the mechanical processing of a member such as a wafer, which is a member for a semiconductor device used in electronic equipment, etc., as in the production of the optical lens, the member is temporarily fixed to a support, and cutting, polishing and cutting are performed. In this method, various mechanical processes such as grinding, drilling, etc. are performed to obtain a predetermined shape and surface property, and then peeled off from the support (for example, Patent Document 1). The adhesive to be used is also required to have a temporary fixing performance. In addition to optical lenses, wafers, etc., various machines for cutting, polishing, cutting, grinding, drilling, etc. for sapphire, gallium arsenide, crystal, magnetic members, metal members, glass members, resin members, semiconductor device members, etc. Also in the processing, an adhesive having temporary fixing performance (hereinafter sometimes referred to as “temporary adhesive”) may be used.

  Since the adhesive for temporary fixing 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. Need to be removed using an oxidizing detergent such as a strong acid. However, with the recent increase in awareness of the environment and safety, adhesives that refrain from using organic solvents as much as possible from the viewpoint of reducing the burden on the natural environment such as air pollution and the environment such as the work environment, safety, etc. There is a demand for water-based temporary fixing adhesives instead of containing 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 having an oxirane ring having photocationic polymerizability, and using such an aqueous temporary fixing adhesive, The adherend can be easily peeled by immersing in water or warm water.

  In recent years, improvements such as thinning, downsizing, and weight reduction of the above-described various devices have been promoted, and various improvements in the various members and parts used in various devices are also required. Higher precision is required for various mechanical processes such as drilling. However, although the water-based adhesive described in Patent Document 2 is a preferable adhesive in terms of low load on the environment such as the natural environment and the working environment, it is compatible with the adherend and adheres to the adherend surface. Even if it can be applied to the outer edge of the adherend due to minute foreign matter, etc., even if it can be applied to the outer edge of the adherend, it will partially repel (the adhesive will repel and there will be holes or dents in the coating. The phenomenon that a uniform phenomenon cannot be applied due to a phenomenon that can occur is becoming more apparent. If the temporary adhesive cannot be applied to the outer edge of the adherend, or if repelling occurs, temporary fixing of the outer edge or the part where the repelling occurs is insufficient during mechanical processing, resulting in reduced processing accuracy. Such a problem is likely to occur. For this reason, water-based temporary fixing adhesives are required to have not only temporary fixing performance but also coating performance that can be applied up to the outer edge of the object to be bonded, and repellency prevention performance that does not cause any repellency.

  In addition, the temporary fixing adhesive used for temporary fixing of various components and parts such as optical lenses and wafers incorporated in optical devices and electronic devices is contaminated due to raw material, adhesive manufacturing process, etc. Substances such as particles, metal ions, corrosive ions, and organic substances may be included. For this reason, the reliability of various members and parts may be reduced and the manufacturing yield may be reduced. However, until now, the frequency has been extremely small and has not been a major problem. However, the influence of these pollutants becomes more significant as various members and parts become thinner, smaller, lighter, etc. as mobile devices such as mobile phones become thinner, smaller and lighter in recent years. For example, in the case of a member such as a wafer, the reliability of various members and parts is significantly reduced, such as a problem of pn junction leakage caused by metal ion contamination and characteristic deterioration of a semiconductor device due to corrosive ions. ing. However, the adhesives described in Patent Documents 1 and 2 do not take into account the reduction of contaminants contained in the adhesive, but reduce not only the temporary fixing performance but also the content of contaminants, particularly metal ions. The development of adhesives that pay attention to these issues is also required.

JP 2013-33814 A JP 2004-35866 A

  The present invention has been made under such circumstances, and various members and parts used in water-based temporary fixing adhesives, optical devices, electronic devices, etc. that have excellent temporary fixing performance and coating performance and repellency prevention performance. Water-based temporary fixing adhesive that has the ability to suppress degradation of function, water-based temporary fixing adhesive that has excellent temporary fixing performance, application performance and safety performance, and low environmental impact, and water-based temporary fixing adhesive It is an object of the present invention to provide a method for manufacturing various members or parts.

  As a result of intensive research to solve the above-mentioned problems, the present inventor can use a thermoplastic resin having a hydroxyl group as a water-based adhesive, and exhibits temporary fixing performance that combines adhesive performance and peeling performance. In view of the above, the present inventors have found that the above-described problems can be solved by an invention relating to an aqueous temporary fixing adhesive containing a thermoplastic resin having at least (A) a hydroxyl group. That is, this invention provides the water-system temporary fix adhesive etc. which have the following structure.

1. (A) A water-based temporary fixing adhesive containing 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 measured according to JIS K0064: 1992.
2. (A) It contains a thermoplastic resin having at least a hydroxyl group, and the total content of sodium metal ion, aluminum metal ion, iron metal ion, zinc metal ion, copper metal ion, nickel metal ion, chromium metal ion and lead metal ion is 3000 ppb A water-based temporary fixing adhesive having a content of sodium metal ions, iron metal ions, zinc metal ions and copper metal ions of 1000 ppb or less.
3. (A) a thermoplastic resin having a hydroxyl group, and (B) a solvent containing water, 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. An aqueous temporary fixing adhesive having an adhesive strength of 0.1 MPa to 20 MPa.
4). A temporary fixing step of temporarily fixing a member or a component precursor and a processing substrate using the water-based temporary fixing adhesive according to any one of the above 1 to 3, a mechanical processing on the precursor, or a member or A method of manufacturing a member or component having a processing step for producing the component.

  According to the present invention, a water-based temporary holding performance that suppresses deterioration in functions of various members and parts used in water-based temporary fixing adhesives, optical equipment, electronic equipment, etc., which has excellent temporary fastening performance and coating performance and repellency prevention performance. A water-based temporary fixing adhesive that has application performance and safety performance as well as a temporary adhesive, excellent temporary fixing performance, and a low environmental load, and a method for manufacturing various members or parts using the aqueous temporary fixing adhesive Can be provided.

  Hereinafter, the water-based temporary fixing adhesive of the present invention will be described in detail. In addition, in the present specification, the numerical values of the upper limit and the lower limit relating to the description of the numerical ranges are arbitrarily combined, and the numerical values in Examples are referred to as the upper limit and the lower limit. can do.

[Water-based temporary adhesive]
The aqueous temporary fixing adhesive of the present invention can be used as an aqueous adhesive, and includes (A) a thermoplastic resin having a hydroxyl group that exhibits temporary fixing performance having both adhesive performance and peeling performance. It is the following 1st-3rd water-system temporary fix adhesives characterized by having the outstanding temporary fix performance in spite of being an adhesive of these.
First aqueous temporary adhesive: (A) a thermoplastic resin having a hydroxyl group, (B) a surface conditioner, and (C) a compatibilizing agent, having a melting point of 30 measured according to JIS K0064: 1992 Water-based temporary fixing adhesive that is above ℃
Second water-based temporary adhesive: 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 the total content of lead metal ions is 3000 ppb or less, and the contents of sodium metal ions, iron metal ions, zinc metal ions, and copper metal ions are each 1000 ppb or less.
Third water-based temporary fixing adhesive: (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, 25 An aqueous temporary fixing adhesive having a surface tension at 20 ° C. of 20 mN / m to 55 mN / m and an adhesive strength of 0.1 MPa to 20 MPa.
Hereinafter, the first water-based temporary fixing adhesive will be described.

<First aqueous temporary adhesive>
The first water-based temporary fixing adhesive of the present invention includes (A) a thermoplastic resin having a hydroxyl group, (B) a surface conditioner, and (C) a compatibilizing agent, and is measured according to JIS K0064: 1992. The melting point is 30 ° C. or higher. (A) A thermoplastic resin having a hydroxyl group (hereinafter sometimes referred to as “component (A)”) is a component that expresses temporary fixing performance mainly having adhesion performance and peeling performance, and (B) A surface conditioner (hereinafter sometimes referred to as “component (B)”) is a component that mainly exhibits coating performance, and is referred to as (C) a compatibilizer (hereinafter referred to as “component (C)”). Is a component that expresses anti-repellency performance mainly by improving the compatibility between the component (A) and the component (B). In the present invention, by combining the above three components (A), (B), and (C), it is possible to satisfy both the application performance and the anti-repellency performance together with excellent temporary fixing performance. It is said. In addition, by combining these three components and having a melting point of 30 ° C. or higher, the coating performance resulting from the compatibility of the temporary adhesive and the adherend due to differences in materials, surface characteristics, etc. The heat resistance against heat generation during mechanical processing is improved, so that the bonding performance is improved by suppressing the occurrence of displacement, peeling, etc. of the bonded object to the support during processing, and the temporary bonding of various bonded objects. Versatility that can cope with 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 fixing adhesive of the present invention is a component that exhibits temporary fixing performance mainly having adhesion performance and peeling performance. (A) The resin contained in 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 a resin 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. Also improves. From the same viewpoint, the melting point of the resin contained in the thermoplastic resin having a hydroxyl group (A) is more preferably 35 ° C or higher, still more preferably 37 ° C, still more preferably 40 ° C or higher, 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 aqueous temporary fixing adhesive of the present invention, and the coating performance and versatility are also improved. . In the present specification, the melting point of the component (A) means the end point of melting 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, further from the viewpoint of improving the coating performance and the anti-repelling performance together with the temporary fixing performance. Preferably, it is 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. is there. In this specification, the number average molecular weight is measured by gel permeation chromatography (GPC method) using polystyrene as a standard substance.

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

The oxyalkylene group preferably has 1 or more carbon atoms, more preferably 2 or more, and the upper limit is 12 or less, more preferably 8 or less, and still more preferably 4 or less. Particularly preferred are those having 3 or less.
The number of repeating units of the oxyalkylene group is preferably 10 or more, more preferably 30 or more, and further preferably 50 or more. 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 is preferably a polyalkylene glycol, a polyoxyalkylene ester, a polyoxyalkylene alkyl ether, or a polyoxyalkylene alkyl aryl ether, more preferably a polyalkylene glycol, Polyoxyalkylene esters and polyoxyalkylene alkyl ethers are preferred, polyalkylene glycols and polyoxyalkylene esters are more preferred, and polyalkylene glycols are particularly preferred. These thermoplastic resins can be used alone or in combination of two or more.

Preferred examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol, polybutylene glycol, etc., polyethylene glycol and polypropylene glycol are more preferred, and polyethylene glycol is even more preferred.
The polyoxyalkylene ester is preferably an ester of a fatty acid having 12 to 24 carbon atoms, and more specifically, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, polypropylene glycol monoester. Preferred examples include polyoxyalkylene monoesters such as laurate, polypropylene glycol monostearate and polypropylene glycol monooleate, and polyoxyalkylene diesters such as polyethylene glycol distearate and polyethylene glycol dioleate. More preferred are polyoxyethylene monoesters, and particularly preferred is polyoxyethylene monostearate.

Examples of the polyoxyalkylene alkyl ether include those having an alkyl group having 12 to 24 carbon atoms. More specifically, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxypropylene oleyl ether, Preferred examples include polyoxypropylene lauryl ether.
Examples of the polyoxyalkylene alkyl aryl ether preferably include those having an alkyl aryl group having 12 to 24 carbon atoms, and more specifically, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene Preferred examples include propylene octyl phenyl ether and polyoxypropylene nonyl phenyl ether.
In the present invention, (A) the thermoplastic resin having a hydroxyl group includes a resin having the predetermined melting point and number average molecular weight exemplified above, a resin having an oxyalkylene group, and a kind of oxyalkylene group as a structural unit. It is preferable to include at least a resin to be used, and a resin other than the above-exemplified resins may be included, but it is preferable that all of the included resins are the above-exemplified resins.

  In the present invention, from the viewpoint of improving coating performance and repellency prevention performance as well as temporary fixing performance, (A) a kind of thermoplastic resin may be used as the thermoplastic resin having a hydroxyl group, and the number average molecular weight is different. It is also possible to use two or more kinds of thermoplastic resins, for example, two or more kinds of polyalkylene glycols having 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. Glycol (hereinafter sometimes referred to as “polyalkylene glycol B”) is preferably combined, and 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, More preferably, it is combined with polyethylene glycol of 000 or less.

  The blending 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, and still more preferably 20:80 to 80:20. It is. When the blending ratio is within the above range, it becomes easy to secure the film thickness of the water-based temporary fixing adhesive film, so that more stable adhesive performance can be obtained. The prevention performance is also improved.

  The content of the thermoplastic resin having a hydroxyl group (A) in the aqueous temporary 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 easy to secure the film thickness of the coating film of the water-based temporary fixing adhesive, so that more stable adhesive performance can be obtained, so that the temporary fixing performance is improved.

((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 application performance, particularly application performance to an adherend such as a wafer. (B) As a surface conditioner, generally, a surface conditioner or leveling agent having a performance capable of eliminating coating film defects caused by changes in viscosity, surface tension, and generation of bubbles due to an increase in molecular weight. , Wetting agents, antifoaming agents, etc., can be used without particular limitation, for example, 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, among which surfactants, among which nonionic surfactants are preferred.

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

  As an acetylene surfactant having an acetylene bond such as an acetylene alcohol surfactant and an acetylene glycol surfactant, more specifically, an acetylene alcohol surfactant represented by the following general formula (1), An acetylene glycol surfactant represented by the general formula (2) is preferred.

In the 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 the 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 are each independently a single bond or a repeating group. An oxyalkylene group having 1 to 30 units is shown.
Preferred examples of the hydrocarbon group for R ¹¹ , R ¹² , R ²¹ , R ²² , R ²³ and R ²⁴ include an alkyl group and an alkenyl group, more preferred is an alkyl group, and these hydrocarbon groups may be linear. It may be branched. Moreover, as an upper limit of carbon number, 6 or less is preferable and 4 or less is more preferable.

When A ₁₁ , A ₂₁ and A ₂₂ are oxyalkylene groups having 1 to 30 repeating units, the acetylene alcohol surfactant represented by the general formula (1) is an alkylene oxide adduct of acetylene alcohol. The acetylene glycol 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, particularly preferably. 6 or less.

The oxyalkylene group of A ₁₁ , A ₂₁ and A ₂₂ preferably has 1 or more carbon atoms, more preferably 2 or more carbon atoms, and has an upper limit of 12 or less carbon atoms, more preferably Those having 8 or less, more preferably 4 or less, and particularly preferably 3 or less are mentioned. The alkylene group may be linear or branched.
In _addition, when A _{11, A 21} and the number of repeating units _{A 22} is 2 or more, plural _{A 11, A 21} and _{A 22} may be the same or different. For example, A ₁₁ may be an oxyethylene group and an oxypropylene group linked together, and A ₂₁ and A ₂₂ are the same.

In the present invention, among the acetylene surfactants, the acetylene glycol surfactant represented by the general formula (2) is preferable, and at least one of A ₂₁ and A _{22 is} an oxyalkylene group having 1 to 30 repeating units. A certain alkylene oxide adduct of acetylene glycol is more preferable, and an alkylene oxide adduct of acetylene glycol having an oxyalkylene group in which A ₂₁ and A ₂₂ have 1 to 30 repeating units is more preferable.

  Examples of the acetylene surfactants include Surfinol 104E, 104H, 104A, 104PA, 104PG-50, 104S, 420, 440, 465, 485, SE, SE-F, PSA-336, DF-110, and 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.) It is available as a commercial product.

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

Examples of the fluorosurfactant include partially fluorinated alcohol-substituted glycols represented by the following general formula (3). As such a fluorosurfactant, commercially available products such as Capstone FS-3100, FS-30, FS-31, FS-34, and FS-35 (manufactured by Dupont) are available.
_{C 6 F 13 -CH 2 CH 2} O (CH 2 CH 2 O) n H ··· (3)
(In the formula, n is an integer of 1 to 40.)

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

  Further, as the (B) surface conditioner, a surface conditioner such as an acrylic surface conditioner is also preferably used. Examples of the acrylic surface conditioner include acrylic copolymers such as poly (meth) acrylate and modified poly (meth) acrylate. For example, BYK-381, BYK-3440, BYK-3441 (above, Big Chemie Japan) Available as a commercial product.

(B) As a surface conditioner, from the viewpoint of improving coating performance and repellency prevention performance as well as temporary fixing performance, an acetylene surfactant having an acetylene bond such as an acetylene alcohol surfactant and an acetylene glycol surfactant. Surface modifiers such as fluorine surfactants and acrylic surface modifiers are preferred, acetylene surfactants, fluorine surfactants and acrylic surface modifiers are more preferred, and acetylene surfactants are even more preferred. In addition to nonionic surfactants, there are amphoteric and other fluorine surfactants, but nonionic surfactants are preferred from the viewpoint of improving application performance and repellency prevention performance as well as temporary fixing performance.
In the present invention, (B) the surface conditioner preferably includes at least the above-exemplified surface conditioner, and may include other than those exemplified above. The surface conditioner exemplified above is preferable.

  The content of the (B) surface conditioner in the water-based temporary fixing adhesive is preferably 0.01% by mass or more, more preferably 0.03, from the viewpoint of improving the application performance and the anti-flicking performance together with the temporary fixing 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, still more preferably 1.5% by mass. % Or less, and particularly preferably 1% by mass or less.

((C) compatibilizer)
The (C) compatibilizing agent contained in the first water-based temporary fixing adhesive of the present invention mainly improves the compatibility between the thermoplastic resin having the hydroxyl group (A) and the surface conditioning agent (B), It is a component that exhibits repellency prevention performance. The component (A) contains a hydroxyl group and thus exhibits hydrophilicity. On the other hand, since the (B) surface conditioner tends to exhibit hydrophobicity, the components (A) and (B) are highly compatible with each other. It can't be said. Therefore, when the component (A) and the component (B) are used in combination, the amount of the adhesive applied by repelling is small, or the repelling part that is not applied is likely to occur on a part of the coating film of the adhesive. It becomes difficult to apply uniformly to the adherend such as. Therefore, in the present invention, by using the (C) compatibilizing agent, the compatibility between the component (A) and the component (B) is improved, and the coating performance and the anti-repellency performance are achieved along with excellent temporary fixing performance. It is possible to get.

The (C) compatibilizer is not particularly limited as long as it is a compound having a compatibilizing performance that improves 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. As such a compound, an alkylene oxide copolymer is preferably mentioned. The alkylene oxide is preferably an alkylene oxide having 2 to 8 carbon atoms, more preferably 2 to 4 carbon atoms, such as ethylene oxide, 1,2-propylene oxide, 1,3-propylene oxide, 1,2-butylene. Examples thereof include oxide, 2,3-butylene oxide, 1,3-butylene oxide, tetrahydrofuran and the like, and among them, a combination of ethylene oxide and propylene oxide is preferable.
Further, the alkylene oxide copolymer may be any of a random type, a block type, and a graft type, but is a block type from the viewpoint of expressing better compatibilization performance and improving repelling performance. It is preferable.

  Among the copolymers of alkylene oxide, a copolymer of ethylene oxide and propylene oxide (hereinafter also referred to as “ethylene oxide-propylene oxide copolymer”) is preferable, and a block copolymer of ethylene oxide and propylene oxide (hereinafter referred to as “ethylene oxide-propylene oxide copolymer”). , Also referred to as “ethylene oxide-propylene oxide block copolymer”), and among the ethylene oxide-propylene oxide block copolymers, a triblock copolymer having a propylene oxide chain as a main chain and ethylene oxide chains at both ends thereof is particularly preferred. Copolymer (hereinafter also referred to as “ethylene oxide-propylene oxide-ethylene oxide triblock copolymer”), triblock copolymer having an ethylene oxide chain as a main chain and propylene oxide chains at both ends thereof Body (hereinafter., Also referred to as "propylene oxide - - ethylene oxide-propylene oxide triblock copolymer") is preferable. Ethylene oxide-propylene oxide block copolymers, especially ethylene oxide-propylene oxide-ethylene oxide triblock copolymers, propylene oxide-ethylene oxide-propylene oxide triblock copolymers, have ethylene oxide chains that are hydrophilic and propylene oxide chains that are hydrophobic. Therefore, the compatibilization performance for improving the compatibility between the hydrophilic component (A) and the hydrophobic component (B) is more remarkably exhibited, and a more excellent repellency prevention performance is 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 preferable. Similar to the above triblock copolymer, since the ethylene oxide chain is hydrophilic and the propylene oxide chain is hydrophobic, the compatibility between the hydrophilic component (A) and the hydrophobic component (B) is improved. The compatibilizing performance to be improved is more remarkably exhibited, and more excellent repelling prevention performance is obtained.

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

  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, still more preferably 20% by mass or more, and the upper limit is preferably 300% by mass. % Or less, More preferably, it is 200 mass% or less, More preferably, it is 100 mass% or less. When the ratio of ethylene oxide to propylene oxide is within the above range, better compatibilization can be obtained, and as a result, better repelling performance can be obtained.

When the (C) compatibilizer is an alkylene oxide copolymer, the 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, The upper limit is preferably 500,000 or less, more preferably 250,000 or less, still 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 above-exemplified alkylene oxide copolymer, and may contain other than the above-exemplified alkylene oxide copolymer. It is preferable that all of them be a copolymer of the alkylene oxide 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 as a main chain and ethylene oxide at both ends thereof. A block copolymer having a chain is prepared by polymerizing propylene glycol by blowing ethylene oxide under pressure and in a heated state in the presence of an alkali catalyst to prepare polypropylene oxide, and then, for example, in the presence of a metal alcoholate catalyst. Ethylene oxide can be prepared by polymerizing both ends of the polypropylene oxide as polymerization bases.

  The content of the (C) compatibilizer in the water-based temporary fixing adhesive is preferably 0.1% by mass or more, more preferably 0.3%, from the viewpoint of improving the application performance and the anti-repelling performance together with the temporary fixing performance. 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 first water-based temporary fixing adhesive of the present invention can be used by dissolving the above component (A), component (B) and component (C) in a solvent. As the solvent, water is used. For example, ion exchange water may be used. In the present invention, a solvent other than water, for example, various organic solvents may be included as a solvent. However, in consideration of reduction of environmental load such as natural environment and work environment, safety, etc., the organic solvent may not be included. preferable. That is, the first aqueous temporary adhesive of the present invention is a substantially complete aqueous temporary 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 the organic solvent is not intentionally used, for example, the component (A), the component (B), and The content of the organic solvent that can be inevitably contained in the component (C) is allowed. In this case, the content of the organic solvent contained in the total solvent is preferably 1% by mass or less, more preferably 0.5% by mass or less. More preferably, it means 0.1% by mass or less.

(Other additives)
In the first water-based temporary fixing adhesive of the present invention, an antifoaming agent, a leveling agent, a silane coupling agent, a crystal nucleating agent, a plasticizer, a preservative, etc., as other additives other than the above components, as desired. May be included.

(Various properties of the first aqueous temporary adhesive)
The first water-based temporary fixing adhesive of the present invention needs to 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 the compatibility between the temporary adhesive and the adherend due to differences in materials, surface characteristics, etc., and against the heat generated during mechanical processing As the heat resistance is improved, it is not possible to suppress the occurrence of misalignment or peeling of the adherend to the support during processing, so excellent temporary fixing performance (particularly adhesive performance) cannot be obtained, and various The versatility which can respond to the temporary fixing of the adherend is not 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, 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. When the melting point of the aqueous temporary fixing adhesive is within the above range, the temporary fixing performance is improved by improving not only the adhesive performance of the first aqueous temporary adhesive of the present invention but also the peeling performance. improves.
In this specification, melting | fusing point means the melting end point measured based on JISK0064: 1992 (melting | fusing point and melting range measurement method of a chemical product) as above-mentioned. Specifically, the first water-based temporary fixing adhesive of the present invention is heated and melted (temperature condition: 30 to 90 ° C.), and cooled (temperature condition: −20 to 30 ° C.). 300 μm) powder and dried in a desiccator for 24 hours as required based on “4. Melting range measurement method” defined in JIS K0064: 1992 (Measuring point of melting point and melting range of chemical products) Was filled into a capillary (made of glass, inner diameter 0.8 to 1.2 mm, thickness: 0.2 to 0.3 mm, length: 150 mm), and this was heated at a heating rate of 1 ° C./min. The melting temperature of the first aqueous temporary fixing adhesive of the present invention was defined as the melting temperature at which the temperature was raised under conditions and no solid was observed by visual observation (the temperature at which the powdery solid sample was completely liquefied). .

(Use of first water-based temporary adhesive)
The first water-based temporary fixing adhesive of the present invention has excellent temporary fixing performance, coating performance and repellency prevention performance, and is water-based, thus reducing the load on the environment such as natural environment and work environment. It is an adhesive that is excellent in safety. Therefore, the first water-based temporary fixing adhesive of the present invention is used in applications where temporary fixing performance is required as an adhesive, for example, various electronic devices such as OA equipment, information equipment, home appliances, optical equipment, medical equipment, Various members and parts used in various devices such as automotive devices, for example, 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 in various mechanical processing such as cutting, polishing, cutting, grinding, drilling and the like.

A typical example of a method for polishing a surface of a wafer such as a silicon wafer, which is a member for a semiconductor device used in an electronic device or the like, among the above-described mechanical processing of various members and components will be described.
First, the first aqueous 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 coating method, an ink jet method, a dip coating method, or a roll coating method. It is applied to form an adhesive coating film. The coating film of the adhesive is dried as necessary, and the wafer and the surface plate of the polishing machine are thermocompression bonded at a temperature of usually 50 to 140 ° C. to fix the wafer on the surface plate of the polishing machine. Next, the wafer surface is polished by a polishing machine. After the polishing process is completed, the wafer may be peeled off from the surface plate of the polishing machine using a razor or by heat melting. The method for applying the adhesive is not particularly limited. For example, the adhesive may be applied to an adherend such as a wafer, may be applied to a support, or may be peeled off after polishing. The method is not particularly limited, and can be appropriately selected according to the shape of the wafer.
Further, if necessary, after the wafer is peeled off, cleaning for removing the residue of the temporary fixing adhesive on the wafer using water or warm water can be performed. Since the first water-based temporary fixing adhesive of the present invention is water-based, it also has an 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 an adhesive performance that prevents the wafer from being peeled or displaced from the surface plate during polishing, and after the polishing is completed, the wafer is fixed using a razor or the like. It can be easily peeled from the board. Further, since the adhesive coating film is uniformly present on the entire surface of the wafer, the first water-based temporary fixing adhesive of the present invention can meet high accuracy requirements such as mechanical processing. It becomes possible. In addition, the first water-based temporary fixing adhesive of the present invention is not limited to the polishing process of the wafer, but also exhibits the same effect in the mechanical processing of other various members and parts, and responds to high accuracy requirements. Is possible.

<Second aqueous temporary adhesive>
The second water-based temporary adhesive of the present invention includes at least (A) a thermoplastic resin having a hydroxyl group, and includes 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 contents of sodium metal ions, iron metal ions, zinc metal ions and copper metal ions are each 1000 ppb or less. is there.

((A) Thermoplastic resin having a hydroxyl group)
The (A) hydroxyl group-containing thermoplastic resin contained in the second aqueous temporary fixing adhesive of the present invention is a component that exhibits temporary fixing performance mainly having adhesion performance and peeling performance, and generally has various types. Since the content of metal ions tends to be small, it is advantageous also in terms of improving the function deterioration suppressing performance of various members and parts used in optical devices and electronic devices.
(A) The resin contained in 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 a resin 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 aqueous temporary fixing adhesive of the present invention tends to be 30 ° C. or higher, and the temporary fixing performance is improved. Also improves. From the same viewpoint, the melting point of the resin contained in the thermoplastic resin having a hydroxyl group (A) is more preferably 35 ° C. or higher, still more preferably 37 ° C. or higher, still more preferably 40 ° C. or higher, particularly preferably 43 It is above ℃. 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 second aqueous temporary fixing adhesive of the present invention, and the versatility is also improved. In the present specification, the melting point means the melting end point measured in accordance with 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, particularly from the viewpoint of improving the temporary fixing performance. The upper limit is preferably 1,400 or more, and 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. Moreover, versatility will also improve that a number average molecular weight is in the said range. In this specification, the number average molecular weight is measured by gel permeation chromatography (GPC method) using polystyrene as a standard substance.

As the resin contained in the thermoplastic resin having a hydroxyl group (A) having the above properties, a thermoplastic resin having an oxyalkylene group is preferably mentioned from the viewpoint of obtaining superior temporary fixing performance, and a kind of oxyalkylene group. It is more preferable that the resin be a structural unit.
The number of carbon atoms of the oxyalkylene group and the number of repeating units of the oxyalkylene group are the same as the oxyalkylene group of the component (A) of the first aqueous temporary tacking adhesive.

  More specifically, the thermoplastic resin having an oxyalkylene group is preferably a polyalkylene glycol, a polyoxyalkylene ester, a polyoxyalkylene alkyl ether, or a polyoxyalkylene alkyl aryl ether, more preferably a 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 used for more excellent optical and electronic devices. And from the viewpoint of obtaining the function deterioration suppressing performance of the parts, polyalkylene glycol is particularly preferable. These thermoplastic resins can be used alone or in combination of two or more.

  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 aqueous temporary tacking adhesive. The same can be mentioned.

  In the second aqueous temporary fixing adhesive of the present invention, from the viewpoint of improving the temporary fixing performance, (A) as the thermoplastic resin having a hydroxyl group, a kind of thermoplastic resin may be used, and the number average molecular weight Two or more different thermoplastic resins, for example, two or more polyalkylene glycols having different number average molecular weights may 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. Glycol (hereinafter sometimes referred to as “polyalkylene glycol B”) is preferably combined, and 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, More preferably, it is combined with polyethylene glycol of 000 or less.

  The blending 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, and still more preferably 20:80 to 80:20. It is. When the blending ratio is within the above range, the film thickness of the water-based temporary fixing adhesive film can be easily secured, so that more stable adhesive performance can be obtained, so that temporary fixing performance is improved.

  The content of the thermoplastic resin having a hydroxyl group (A) in the second aqueous temporary adhesive is preferably 5% by mass or more, more preferably 10% by mass or more, and still 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, still more preferably 45% by mass or less, and particularly preferably 42% by mass or less. It is. When the content of the thermoplastic resin is within the above range, it becomes easy to secure the film thickness of the coating film of the water-based temporary fixing adhesive, so that more stable adhesive performance can be obtained, so that the temporary fixing performance is improved.

((B) Various metal ions)
The second water-based temporary adhesive of the present invention includes various metal ions (hereinafter referred to 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). The total content of “(B) component” may be 3000 ppb or less, and the content of sodium metal ions, iron metal ions, zinc metal ions, and copper metal ions may be 1000 ppb or less. . In the present specification, “ppb” means “mass ppb” unless otherwise specified. (B) If the total content of various metal ions is greater than 3000 ppb, the reliability of the member is liable to decrease, such as a problem of pn junction leakage due to deterioration of the characteristics of the member such as a silicon wafer, and the manufacturing yield. Is likely to increase rapidly. The same applies to the case where each content of sodium metal ion, iron metal ion, zinc metal ion and copper metal ion is greater than 1000 ppb.

  In the second water-based temporary fixing adhesive of the present invention, the function deterioration suppressing performance of various members and parts used in optical equipment, electronic equipment, etc. is further improved, that is, from the viewpoint of further suppressing the functional deterioration of various members and parts. (B) The content of various metal ions is preferably as small 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. Preferably it is 100 ppb or less. Moreover, (B) About the lower limit of content of various metal ions, it is desirable that 0 ppb, that is, various metal ions are not included, but in reality, it is generally about 0.5 ppb or more. Further, the content of sodium metal ion, iron metal ion, zinc metal ion and copper metal ion is preferably 950 ppb or less, more preferably 750 ppb or less, further preferably 600 ppb or less, particularly preferably 450 ppb or less. Is 0 ppb, practically 0.5 ppb or more. In the second water-based temporary fixing adhesive of the present invention, the content of (B) various metal ions is a measured value measured by an appropriate analysis method according to the type of various metal ions. It is set as the measured value measured by the method of description.

In the second water-based temporary fixing adhesive of the present invention, (B) the content of various metal ions can be reduced by, for example, selecting the type of the thermoplastic resin (A) having a hydroxyl group. As a resin component used for adhesives that are water-based and have temporary fixing performance, a salt type using a resin metal salt such as a sodium salt of an acrylic resin or the like, an emulsion such as an acrylic resin or a vinyl acetate resin In some cases, the emulsion type is also used, but the resin components used in these salt types and emulsion types contain metal ions themselves or are included in the raw materials of these resin components in the production process. For this reason, the content of contaminants such as metal ions tends to be large. The salt-type resin component contains (B) various metal ions contained in itself, and the emulsion-type resin component contains (B) various metal ions in the emulsion particles. It is difficult 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. (A) Thermoplastic having a hydroxyl group Since the resin has higher affinity with water than these resins, stability as an aqueous temporary fixing adhesive can be obtained. In the 2nd water-system temporary fix | bonding adhesive of this invention, by using the thermoplastic resin which has (A) hydroxyl group, by the removal process of (B) various metal ions mentioned later, (B) containing various metal ions It is possible to easily reduce the amount, and it is possible to extremely reduce the content of (B) various metal ions in the adhesive.

(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 other than (A) the thermoplastic resin having a hydroxyl group and (B) various metal ions. (C) The surface conditioner is a component mainly improving the coating performance of the adhesive, particularly the coating performance of various electronic members such as a wafer. When applying adhesive to various members and parts used in optical equipment, electronic equipment, etc., due to the difference in the adhesive and the materials of various members and parts, the adhesive extends to the outer edges of the various members and parts. It cannot be applied and may not be applied to the entire surface. In such a case, by using the (A) surface conditioning agent together with the thermoplastic resin having a hydroxyl group (A), it is possible to obtain excellent coating performance regardless of the difference in materials of various members and parts. become.

  (C) As a surface conditioner, generally, a surface conditioner or leveling agent having a performance capable of eliminating a coating film defect caused by a change in viscosity, a change in surface tension, and generation of bubbles due to an increase in molecular weight. , Wetting agents, antifoaming agents, etc., can be used without particular limitation, for example, 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, nonionic surfactants are preferred.

  (C) Nonionic surfactants, acetylene alcohol surfactants, acetylene glycol surfactants, and other acetylene surfactants having acetylene bonds, fluorine surfactants, and acrylic surface modifiers that are used as surface modifiers Examples of the surface conditioner such as an agent are the same as those described as those that can be used as the (B) surface conditioner in the first aqueous temporary fixing adhesive.

(C) As a surface conditioner, from the viewpoint of improving coating performance and repellency prevention performance as well as temporary fixing performance, an acetylene surfactant having an acetylene bond such as an acetylene alcohol surfactant and an acetylene glycol surfactant. Surface modifiers such as fluorine surfactants and acrylic surface modifiers are preferred, acetylene surfactants, fluorine surfactants and acrylic surface modifiers are more preferred, and acetylene surfactants are even more preferred. Further, nonionic ones are particularly preferable from the viewpoint of metal removal.
In the second water-based temporary fixing adhesive of the present invention, (C) the surface conditioner preferably includes at least the surface conditioner exemplified above, and may include those other than those exemplified above. However, it is preferable that all of them are the surface conditioning agents exemplified above.

  The content of the (C) surface conditioner 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 the application performance together with the 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 compatibilizing agent (hereinafter sometimes referred to as “(D) component”) as another component. (D) When the above-mentioned (C) surface conditioner is used, the (D) compatibilizer mainly improves the compatibility between the (A) thermoplastic resin having a hydroxyl group and the (C) surface conditioner, and prevents repelling. It is a component that expresses performance. The thermoplastic resin having a hydroxyl group (A) is hydrophilic because it contains a hydroxyl group, while the (C) surface conditioner tends to exhibit hydrophobicity, so that the component (A) and the component (C) are mutually compatible. 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 by repelling is small, or a repelling part that is not applied tends to occur, especially on a part of the adhesive coating film. It may become difficult to apply uniformly to various members and parts. When (C) a surface conditioner is used for the thermoplastic resin having a hydroxyl group (A), the occurrence of repellency can be reduced by using the (D) compatibilizing agent. The water-based temporary fixing adhesive has excellent application performance and repellency prevention performance as well as excellent temporary fixing performance and performance deterioration suppressing performance of various members and parts used in optical equipment, electronic equipment and the like.

  The (D) compatibilizing agent that can be used in the second water-based temporary tacking adhesive of the present invention is the same as the (C) compatibilizing agent used in the first water-based temporary tacking adhesive and is a co-agent of alkylene oxide. A polymer is preferably used. Specific examples of the copolymer of alkylene oxide are the same as the (C) compatibilizer used in the first water-based temporary fixing adhesive. Such a copolymer has an ethylene oxide chain that is hydrophilic. Since the oxide chain exhibits hydrophobicity, the compatibility between the hydrophilic component (A) and the hydrophobic component (C) is improved and the compatibility is improved more significantly. Prevention performance is obtained. Further, these alkylene oxide copolymers do not contain metal ions themselves, or are contained in the raw materials and production processes of these copolymers, and are used in optical equipment, electronic equipment, and the like. It is effective in improving the performance deterioration suppressing performance of various members.

  Regarding the commercial products of alkylene oxide copolymers such as the ethylene oxide-propylene oxide-ethylene oxide triblock copolymer and the propylene oxide-ethylene oxide-propylene oxide triblock copolymer, The same thing as the commercial item illustrated can be mentioned.

  In the ethylene oxide-propylene oxide copolymer, the ratio of propylene oxide to ethylene oxide, (D) when the compatibilizer is an alkylene oxide copolymer, its number average molecular weight, the ethylene oxide-propylene oxide copolymer is known. The preparation method is the same as that described in the first aqueous temporary adhesive.

  The content of the (D) compatibilizer in the second aqueous temporary fixing adhesive is preferably 0.1% by mass or more, more preferably from the viewpoint of improving the application performance and the anti-flicking performance together with the temporary fixing performance. It is 0.3 mass% or more, More preferably, it is 0.5 mass% or more, Preferably it is 20 mass% or less as an upper limit, More preferably, it is 15 mass% or less, More preferably, it is 10 mass% or less.

(solvent)
The second water-based temporary fixing adhesive of the present invention can be used after being dissolved in a solvent. As the solvent, water is used. For example, ion exchange water may be used. In the case of using water as the solvent, the content of the solvent is preferably 50% by mass or more, more preferably 55% by mass considering the characteristics of the second temporary fixing adhesive of the present invention which is an aqueous system, ease of handling, and the like. % Or more, more preferably 60% by mass or more, and the upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less.

  In the second water-based temporary fixing adhesive of the present invention, a solvent other than water, for example, various organic solvents may be included as a solvent. However, in consideration of reduction of environmental load such as natural environment and work environment, safety and the like. The organic solvent is preferably not contained. That is, the second aqueous temporary adhesive of the present invention is a substantially complete aqueous temporary adhesive that does not contain an organic solvent. Here, “not containing an organic solvent” means that the organic solvent content is 0% by mass and that the organic solvent is not intentionally used, for example, the above components (A) to (D) Inclusion of an organic solvent that can be unavoidably included is allowed. In this case, the content of the organic solvent contained in the total solvent is preferably 5% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass. In the following, 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, and particularly preferably. It is 99.9 mass% or more. In the second water-based temporary fixing adhesive of the present invention, the solvent (A) other than water and the organic solvent may be inevitably contained in the components (A) to (D). Components other than the component (D) (included as impurities) are also included.

(Other additives)
In the second water-based temporary adhesive of the present invention, an antifoaming agent, a leveling agent, a silane coupling agent, a crystal nucleating agent, a plasticizer, a preservative, etc., as other additives other than the above components, if desired. May be included.

(Various properties of the second water-based temporary adhesive)
The second aqueous 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 a reduction in coating performance due to the difference in materials, surface characteristics, etc. between the temporary fixing adhesive and the adherend, and heat resistance against heat generation during mechanical processing. By improving, it is possible to suppress the occurrence of misalignment, peeling, etc. of the adherend to the support during processing, so excellent temporary fixing performance (especially adhesive performance) can be obtained, and various adherends Versatility that can cope with temporary fixing is also obtained. From the same viewpoint, 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 aqueous temporary fixing adhesive.

(Use of second water-based temporary adhesive)
The second water-based temporary fixing adhesive of the present invention has excellent temporary fixing performance and has a small content of various metal ions, so that the function deterioration suppressing performance of various members and parts used in optical equipment, electronic equipment, etc. In addition, since it is water-based, it is an adhesive that can reduce the burden on the environment such as the natural environment and work environment, and is excellent in safety. Therefore, the second water-based temporary fixing adhesive of the present invention is used in applications where temporary fixing performance is required as an adhesive, for example, various electronic devices such as OA equipment, information equipment, home appliances, optical equipment, medical equipment, Various members and parts used in various devices such as automotive devices, for example, 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 in various mechanical processing such as cutting, polishing, cutting, grinding, drilling and the like.

  The second water-based temporary fixing adhesive of the present invention exhibits an adhesive performance in which various members and parts are not peeled or displaced from a processing substrate (such as a surface plate) during mechanical processing, and the polishing process is completed. After that, various members and parts can be easily separated from the processing substrate (such as a surface plate) by using a razor or the like or by heating and melting. In addition, since the adhesive coating film is uniformly present on the entire surface of various members and parts, the second water-based temporary fixing adhesive of the present invention also meets high accuracy requirements such as mechanical processing. It becomes possible to do. Therefore, the second water-based temporary fixing adhesive of the present invention is used for mechanical processing that requires particularly high precision, for example, a wafer such as a silicon wafer, an optical lens, a member for a semiconductor device, particularly a surface of a wafer such as a silicon wafer. It is suitably used for polishing.

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

(Ion exchanger)
Examples of the ion exchanger used in the second aqueous temporary fixing 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 the organic ion exchanger, an organic ion exchanger such as an ion exchange resin is preferable, and one having a cation capturing performance is preferable.

  As the inorganic ion exchanger, those having cation scavenging performance, for example, zirconium phosphate, zirconium tungstate, zirconium molybdate, zirconium tungstate, zirconium antimonate, zirconium selenate, zirconium tellurate, zirconium silicate, Examples thereof include metal oxides such as zirconium phosphosilicate and zirconium polyphosphate. These inorganic ion exchangers can be used alone or in combination.

As an organic ion exchanger, what used the cation exchange resin which has cation capture | acquisition performance is preferable.
The cation exchange resins, sulfonic acid group as the acidic group (RSO 3 _- ^{H +)} strongly acidic cation-exchange resin such as sulfonic acid type strongly acidic cation-exchange resin having; carboxylic acid as an acidic group (R-COO ^- H ^+), a phosphonic acid group ^{(R-P (O) (} O - H +) 2), phosphinic acid group ^{(R-PH (O) (} O - H +)) weakly acidic cation exchange resin having such Any of these may be used. In addition, examples of the ion type of the cation exchange resin preferably include hydrogen type and 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 any of particulate, fiber, liquid, gel, and the like, and for example, organic ions may be applied to resin fibers such as acrylic resin and styrene resin. A type in which an exchange resin is decorated 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 (C) a surface conditioning agent, (D) a compatibilizing agent, which are included as necessary, And about these content, other additives, etc., it is the same as the description regarding each component which may be contained in the said 2nd water-system temporary fixing adhesive, The description is abbreviate | omitted.

  Although there is no restriction | limiting in particular in the manufacturing method, the 2nd water based temporary fix | bonding adhesive of this invention is preferably manufactured with the manufacturing method of the said 2nd water based temporary fix adhesive of this invention. According to the second method for producing a water-based temporary fixing adhesive of the present invention, the water-based temporary fixing adhesive having excellent temporary fixing performance and performance deterioration suppressing performance of various members and parts used in optical equipment, electronic equipment and the like. Can be easily obtained. Further, the second water-based temporary fixing adhesive of the present invention is manufactured by selecting (A) a thermoplastic resin having a hydroxyl group, which is a component contained in the adhesive, and setting it to a predetermined metal ion content. It is also possible to do. Although this manufacturing method was demonstrated as a manufacturing method of the 2nd water-system temporary fix adhesive, in manufacturing the said 1st water-system temporary fix adhesive and the 3rd water-system temporary fix adhesive mentioned later, (A) A hydroxyl group is used. In the case of using a resin-containing composition and a metal ion-containing composition, it can be produced using an ion exchanger according to this production method.

[Manufacturing method of member or part]
The member or component manufacturing method of the present invention includes a temporary fixing step in which the precursor of the member or component and the processing substrate are temporarily fixed using the second aqueous temporary fixing adhesive of the present invention. It has a processing step of producing a member or a part by subjecting it to mechanical processing. Hereinafter, the temporary fixing process and the processing process will be described in detail. In the description of the method for producing 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, a third aqueous system described later, is used. It is also possible to use a temporary fixing adhesive.

  The temporary fixing step is a step of temporarily fixing the precursor of the member or component and the processing substrate using the second aqueous temporary fixing adhesive of the present invention, more specifically, the precursor and the processing substrate. In this process, a coating film of the water-based temporary fixing adhesive of the present invention is formed, and the precursor and the processing substrate are temporarily fixed. As a method for forming and temporarily fixing the coating film, 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 a bonding surface on the processing substrate. Method (i) of temporarily fixing the precursor, applying a temporary fixing adhesive to a processing substrate to form a coating film, and placing the precursor on the coating film, Any of the methods (ii) for temporarily fixing the precursor to a processing substrate may be used.

For example, in the above method (i), the second water-based temporary fixing adhesive may be applied by a spin coating method, a spray method, a die coating method, an ink jet method, a dip coating method, a roll coating method, or the like. Can be mentioned. The application amount of the second water-based temporary fixing adhesive is, for example, about 1 to 3 mL applied to the precursor of a wafer member such as a 4-inch silicon wafer, although it depends on the area of the surface to which the precursor is temporarily fixed. do it.
Thereafter, the precursor is placed at a predetermined position on the processing substrate and temporarily fixed while the coating film provided on the precursor is opposed to the processing substrate. At this time, it is preferable to temporarily fix the precursor and the processing substrate by thermocompression bonding at a temperature of 50 to 140 ° C. because temporary fixing can be more reliably performed.
The precursor may be roughened with a polishing agent or the like before being temporarily fixed to the processing substrate, and surface treatment may be performed by chemical etching as necessary.

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

  The processing in the processing step of the manufacturing method of the present invention is roughly classified into general processing that does not require special precision and precision processing that requires high precision. For example, mechanical processing of a wafer such as a silicon wafer, an optical lens, and a semiconductor device member, particularly polishing of the surface of a wafer such as a silicon wafer, requires processing by precision processing. 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 adhesive can be temporarily fixed to the processing substrate without inclining the precursor. The in-plane film thickness difference of the coating film is small, and the non-contact area is very small. For this reason, in the processing step, the pressure applied to the precursor from the jig for mechanical processing can be made substantially uniform with respect to the surface to be processed of the precursor. As a result, since the precursor can be processed with high accuracy, a high-quality member or component 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 wafer, in addition to a silicon wafer, a wafer material such as sapphire, gallium phosphide, or gallium nitride can be used. These wafers are suitable as a method for producing these various wafers, particularly as a method for producing a wafer having a Mohs altitude of 9 or more (for example, a sapphire wafer).

The manufacturing method of the member or component of this invention may have the peeling process which peels the member or component in which the mechanical processing was given after the said process process from the board | substrate for a process. For peeling, for example, a member such as a wafer or a part may be peeled from the processing substrate using a razor, a scraper, or the like, or by heating and melting.
Moreover, after peeling a member or a part as needed, the washing | cleaning which removes the residue of the temporary fix | stop adhesive on this member or a part using water or warm water etc. can also be performed. Since the water-based temporary fixing adhesive of the present invention is water-based, it also has an advantage that it can be easily removed from the adherend by washing with water or warm water.

  Examples of members and parts obtained by the member or part manufacturing method of the present invention include various electronic devices such as OA equipment, information equipment, and home appliances, optical equipment, medical equipment, and various equipment such as automobile equipment. 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, and the like. . In addition, in consideration of the characteristics of the member or component manufacturing method of the present invention, 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. Of these, various wafers are preferable.

<Third aqueous temporary adhesive>
The third water-based temporary fixing adhesive of the present invention includes (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. The surface tension at 25 ° C. is 20 mN / m or more and 55 mN / m or less, and the adhesive strength is 0.1 MPa or more and 20 MPa or less. (A) A thermoplastic resin having a hydroxyl group (hereinafter sometimes referred to as “component (A)”) is a component that exhibits temporary fixing performance mainly having adhesion performance and peeling performance at 25 ° C. 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 water content in the solvent is 95% by mass or more, the adhesive has high safety performance and low environmental load.

((A) Thermoplastic resin having a hydroxyl group)
(A) The resin contained in 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 a resin 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 more, the temporary fixing performance and coating performance are improved, and versatility is also improved. (A) Melting | fusing point of resin contained in the thermoplastic resin which has a hydroxyl group becomes like this. More preferably, it is 35 degreeC or more, More preferably, it is 37 degreeC or more, More preferably, it is 40 degreeC or more, Especially preferably, it is 43 degreeC. The upper limit is preferably 200 ° C. or less, more preferably 180 ° C. or less, still more preferably 160 ° C. or less, still more preferably 120 ° C., and particularly preferably 100 ° C. or less. 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 third aqueous temporary fixing adhesive of the present invention, and the versatility is also improved. In the present specification, the melting point means the melting end point measured in accordance with 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, particularly from the viewpoint of improving the coating performance together with the temporary fixing performance. The upper limit is preferably 3,000 or more, and 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. Moreover, versatility will also improve that a number average molecular weight is in the said range. In this specification, the number average molecular weight is measured by gel permeation chromatography (GPC method) using polystyrene as a standard substance.

The thermoplastic resin having a hydroxyl group (A) having the above properties is preferably a thermoplastic resin having an oxyalkylene group from the viewpoint of temporary fixing performance, and has a kind of oxyalkylene group as a constituent unit. It is more preferable.
The number of carbon atoms of the oxyalkylene group and the number of repeating units of the oxyalkylene group are the same as the oxyalkylene group of the component (A) of the first aqueous temporary tacking adhesive.

Specific examples of the thermoplastic resin having an oxyalkylene group include the same ones as the thermoplastic resin having an oxyalkylene group as the component (A) of the first aqueous temporary tacking adhesive. From the viewpoint of improving the viscosity, polyalkylene glycol is particularly preferable.
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 aqueous temporary tacking 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) as the thermoplastic resin having a hydroxyl group, a kind of thermoplastic resin may be used, and the number average molecular weight may be used. Two or more types of thermoplastic resins having different numbers, for example, two or more types of polyalkylene glycols having different number average molecular weights may 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. Glycol (hereinafter sometimes referred to as “polyalkylene glycol B”) is preferably combined, and 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, More preferably, it is combined with polyethylene glycol of 000 or less.

  The blending 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, and still more preferably 20:80 to 80:20. It is. When the blending ratio is within the above range, the film thickness of the water-based temporary fixing adhesive film can be easily secured, so that more stable adhesive performance can be obtained, so that temporary fixing performance is improved.

  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 the shellworm by a known solution extraction method, soda method, etc., and the resin content is a resin acid such as alleuritic acid, jarlaric acid, laxialaric acid, etc. And natural shellac resin or synthetic shellac resin mainly composed of an ester compound. Specific examples include purified shellac resin, bleached shellac resin, and decolorized shellac resin. Further, neutralized ammonium products of these shellac resins may be used.

  The content of the thermoplastic resin having a hydroxyl group (A) 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 application performance together with the temporary fixing performance. More preferably, it 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, 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 easy to secure the film thickness of the coating film of the water-based temporary fixing adhesive, so that more stable adhesive performance can be obtained, so that the temporary fixing performance is improved.

((B) Solvent containing water)
The third aqueous temporary fixing adhesive of the present invention is a solvent containing water (hereinafter sometimes referred to as “component (B)”), and the water content in the solvent is 95% by mass or more. Containing a solvent.
(B) As water used for the solvent containing water, ion-exchange water may be used, for example. Further, in the third water-based temporary fixing adhesive of the present invention, a solvent other than water, for example, various organic solvents may be included as a solvent. However, the load on the environment such as the natural environment and the work environment is reduced, and safety is improved. In consideration, the smaller the content of the organic solvent, the better. (B) Content of water in the solvent containing water needs to be 95 mass% or more. Thus, by reducing the content of solvents other than water, excellent safety performance can be obtained, and the load on the environment can be reduced.
From the same viewpoint, the content of water in the solvent containing (B) water is preferably 96% by mass or more, more preferably 98% by mass or more, and further preferably no organic solvent. A water-based temporary adhesive is preferable. Here, “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 component (A) described above, and (C ) And the organic solvent that can be inevitably contained in the component (D) are allowed. In this case, the content of the organic solvent in the total solvent is preferably 1% by mass or less, more preferably 0.5%. It means that it is not more than mass%, more preferably not more than 0.1 mass%. 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 further preferably 99.9% by mass. It means that it is more than%.

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

(Other components: (C) surface conditioner)
The third aqueous 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) a solvent containing water. . (C) The surface conditioner is a component that mainly improves the coating performance of adhesives, particularly coating performance of various electronic parts 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 the difference in material between the adhesive and the various parts, and applied to the entire surface. There are things that cannot be done. In such a case, the surface tension of the third water-based temporary fixing adhesive of the present invention is adjusted by using (C) a surface conditioning agent together with (A) a hydroxyl group-containing thermoplastic resin, and materials for various parts, etc. Regardless of the difference, excellent coating performance can be obtained.

  (C) As a surface conditioner, generally, a surface conditioner or leveling agent having a performance capable of eliminating a coating film defect caused by a change in viscosity, a change in surface tension, and generation of bubbles due to an increase in molecular weight. , Wetting agents, antifoaming agents, etc., can be used without particular limitation, for example, acrylic, vinyl, silicone, fluorine, cellulose, natural wax, water-soluble organic Preferable examples include various surface conditioners such as solvents, leveling agents, wetting agents, and antifoaming agents. Moreover, as (C) surface conditioning agent, surfactant is also mentioned preferably, Nonionic surface activity is preferable.

  (C) Nonionic surfactants, acetylene alcohol surfactants, acetylene glycol surfactants, and other acetylene surfactants having acetylene bonds, fluorine surfactants, and acrylic surface modifiers that are used as surface modifiers Examples of the surface conditioner such as an agent are the same as those described as those that can be used as the (B) surface conditioner in the first aqueous temporary fixing adhesive.

(C) As a surface conditioner, from the viewpoint of improving coating performance and repellency prevention performance as well as temporary fixing performance, an acetylene surfactant having an acetylene bond such as an acetylene alcohol surfactant and an acetylene glycol surfactant. Surface modifiers such as fluorine surfactants and acrylic surface modifiers are preferred, acetylene surfactants, fluorine surfactants and acrylic surface modifiers are more preferred, and acetylene surfactants are even more preferred. In addition to nonionic surfactants, there are amphoteric and other fluorine surfactants, but nonionic surfactants are preferred from the viewpoint of improving application performance and repellency prevention performance as well as temporary fixing performance.
In the third water-based temporary fixing adhesive of the present invention, (C) the surface conditioner preferably includes at least the above-exemplified surface conditioner, and may include other than those exemplified above. However, it is preferable that all of them are the surface conditioning agents exemplified above.

  The content of the (C) surface conditioner in the third water-based temporary fixing adhesive is preferably from the viewpoint of improving the function deterioration suppressing performance and coating performance of various parts such as optical equipment and electronic parts, together with the temporary fixing 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. Preferably it is 3 mass% or less, More preferably, it is 1.5 mass% or less, Most preferably, it is 1 mass% or less.

(Other components: (D) compatibilizer)
The third water-based temporary fixing adhesive of the present invention may contain (D) a compatibilizing agent (hereinafter sometimes referred to as “(D) component”) as another component. (D) When the above-mentioned (C) surface conditioner is used, the (D) compatibilizer is mainly derived from the compatibility between the (A) thermoplastic resin having a hydroxyl group and the (C) surface conditioner. Even if the third temporary fixing adhesive can be applied to the outer edges of various parts, repelling may occur in part and the so-called repelling may not occur evenly. When repelling occurs, (D) using a compatibilizing agent improves the compatibility between the (A) thermoplastic resin having a hydroxyl group and (C) the surface conditioner, thereby improving repelling prevention performance. It becomes possible.

  (A) Since the thermoplastic resin having a hydroxyl group contains a hydroxyl group, it exhibits hydrophilicity, while (C) the surface conditioner tends to exhibit hydrophobicity, so that the component (A) and the component (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 by repelling is small, or a repelling part that is not applied tends to occur, especially on a part of the adhesive coating film. It may become difficult to apply uniformly to various members and parts. When (C) a surface conditioner is used for the thermoplastic resin having a hydroxyl group (A), the occurrence of repellency can be reduced by using the (D) compatibilizing agent. The water-based temporary fixing adhesive has excellent temporary fixing performance as well as coating performance and repellency prevention performance.

  The (D) compatibilizing agent that can be used in the third aqueous temporary fixing adhesive is the same as the (C) compatibilizing agent used in the first aqueous temporary fixing adhesive, and an alkylene oxide copolymer is used. Preferably used. Specific examples of the copolymer of alkylene oxide are the same as the (C) compatibilizer used in the first water-based temporary fixing adhesive. Such a copolymer has an ethylene oxide chain that is hydrophilic. Since the oxide chain exhibits hydrophobicity, the compatibility between the hydrophilic component (A) and the hydrophobic component (C) is improved and the compatibility is improved more significantly. Prevention performance is obtained.

  Regarding the commercial products of alkylene oxide copolymers such as the ethylene oxide-propylene oxide-ethylene oxide triblock copolymer and the propylene oxide-ethylene oxide-propylene oxide triblock copolymer, The same thing as the commercial item illustrated can be mentioned.

  In the ethylene oxide-propylene oxide copolymer, the ratio of propylene oxide to ethylene oxide, (D) when the compatibilizer is an alkylene oxide copolymer, its number average molecular weight, the ethylene oxide-propylene oxide copolymer is known. The preparation method is the same as that described in the first aqueous temporary adhesive.

  The content of the (D) compatibilizing agent in the third aqueous temporary fixing adhesive is preferably 0.1% by mass or more, more preferably from the viewpoint of improving the application performance and the anti-repelling performance together with the temporary fixing performance. It is 0.3 mass% or more, More preferably, it is 0.5 mass% or more, Preferably it is 20 mass% or less as an upper limit, More preferably, it is 15 mass% or less, More preferably, it is 10 mass% or less.

(Other additives)
In the third water-based temporary fixing adhesive of the present invention, an antifoaming agent, a leveling agent, a silane coupling agent, a crystal nucleating agent, a plasticizer, a preservative, etc., as other additives other than the above components, if desired. May be included.

(Various properties of water-based temporary adhesive)
The third water-based temporary fixing adhesive of the present invention is required to have a surface tension at 25 ° C. of 20 mN / m or more and 55 mN / m or less. If the surface tension at 25 ° C. is not within the above range, application performance cannot be obtained together with excellent temporary fixing performance. From the viewpoint of improving the coating performance as well as the temporary fixing performance, the surface tension at 25 ° C. of the third aqueous temporary fixing adhesive of the present invention is preferably 20 mN / m or more, more preferably 22 mN / m or more, and still more preferably. 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 of thermoplastic resin having a hydroxyl group and its content, and can also be adjusted by using (C) a surface conditioner. .
In this specification, the surface tension at 25 ° C. is a value measured by the Wolhelmy method at a measurement temperature of 25 ° C., for example, a surface tension meter (“CBVP-Z (model number)”, manufactured by Kyowa Interface Chemical Co., Ltd.). It is a value which can be measured using etc.

The third water-based temporary fixing adhesive of the present invention needs 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 aqueous temporary fixing adhesive of the present invention is preferably 0.15 Pa or higher, more preferably 0.2 MPa or higher, still more preferably 0.5 MPa or higher. The upper limit is preferably 15 MPa or less, more preferably 10 MPa or less, still more preferably 7 MPa or less, and still more preferably 5 MPa or less.
In this specification, the adhesive strength is determined by dropping 5 drops on one stainless steel substrate, heating and drying at 100 ° C. for 20 minutes, bonding to the other stainless steel substrate, cooling to room temperature, and 20 minutes later. The shearing force of the bonded substrate is a shearing force measured in accordance with “Tensile Shear Bond Strength Test Method” defined in JIS K6850: 1999 using a tensile strength measuring instrument.

Moreover, it is preferable that melting | fusing point of the 3rd water-system temporary fixing adhesive of this invention is 30 degreeC or more. When the melting point is 30 ° C. or higher, excellent versatility is obtained along with temporary fixing performance. From the viewpoint of improving the application performance and further versatility together with the temporary fixing performance, the melting point of the third aqueous temporary fixing adhesive is more preferably 35 ° C. or higher, more preferably 37 ° C. or higher, still more preferably 40 ° C., The upper limit 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 aqueous temporary fixing adhesive.

(Use of third water-based temporary adhesive)
The third water-based temporary fixing adhesive of the present invention is an adhesive having excellent temporary fixing performance, application performance and safety performance, and low load on the environment. Therefore, the third water-based temporary fixing adhesive of the present invention is used for applications requiring temporary fixing performance as an adhesive, for example, various electronic devices such as optical devices, OA devices, information devices, home appliances, medical devices, Various members and parts used in various devices such as automotive devices, for example, 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) in various mechanical processing such as cutting, polishing, cutting, grinding, drilling and the like.

A typical example of a method for polishing a surface of a wafer such as a silicon wafer, which is a member for a semiconductor device used in an electronic device or the like, among mechanical processing of an electronic component will be described.
First, the third aqueous 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 coating method, an ink jet method, a dip coating method, or a roll coating method. It is applied to form an adhesive coating film. The coating film of the adhesive is dried as necessary, and the wafer and the surface plate of the polishing machine are thermocompression bonded at a temperature of usually 50 to 140 ° C. to fix the wafer on the surface plate of the polishing machine. Next, the wafer surface is polished by a polishing machine. After the polishing process is completed, the wafer may be peeled off from the surface plate of the polishing machine using a razor or by heat melting. The method for applying the adhesive is not particularly limited. For example, the adhesive may be applied to an adherend such as a wafer, may be applied to a support, or may be peeled off after polishing. The method is not particularly limited, and can be appropriately selected according to the shape of the wafer.
Further, if necessary, after the wafer is peeled off, cleaning for removing the residue of the temporary fixing adhesive on the wafer using water or warm water can be performed. Since the third water-based temporary fixing adhesive of the present invention is water-based, it has an 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 an adhesive performance in which the wafer does not peel off from the surface plate during polishing, and the wafer is easily removed from the surface plate using a razor or the like after finishing the polishing. It is possible to peel off. In addition, since the adhesive coating film is uniformly present on the entire surface of the wafer, the water-based temporary fixing adhesive of the present invention can meet high accuracy requirements such as mechanical processing. . Moreover, the third water-based temporary fixing adhesive of the present invention is not limited to the polishing process of the wafer, but also exhibits the same effect in the mechanical processing of other various members and parts, and responds to high accuracy requirements. Is possible.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example.

(Evaluation and measurement method: first water-based temporary fixing adhesive)
(1-1) Measurement of melting | fusing point About the adhesive agent obtained by each Example and the comparative example, melting | fusing point was measured based on JISK0064: 1992. Specifically, a sample obtained by drying moisture contained in the adhesives obtained in each of the examples and comparative examples (2 ml of the adhesive was put in a small petri dish having an inner diameter of 40 mm and a clean oven without a lid. Samples dried at 120 ° C. for 60 minutes) and A-PEG1-5 and A-PPGS used in these examples were heated and melted (temperature conditions: 30 to 90 ° C.) and cooled (temperature conditions: -20 to 30 ° C) is made into a fine (maximum particle size: 300 µm) powder, and this is a capillary (made of glass, inner diameter 0.8 to 1.2 mm, thickness: 0.2 to 0.3 mm, long The melting temperature at which the solid was not recognized by visual observation (the temperature at which the powdered solid sample was completely liquefied) ) As the melting point.
(2-1) Evaluation of coating performance The adhesive obtained in each of the examples and the comparative examples was subjected to a silicon wafer (size: φ150 mm, thickness) using a spin coater (rotation speed: 3000 rpm, coating time: 3 seconds). 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, it was determined to be acceptable if it was B or higher.
A: The coating area was 100%.
B: The coating film area was 80% or more and less than 100%.
C: The coating film area was less than 80%.
(3-1) Evaluation of repellency prevention performance The adhesive obtained in each of the examples and the comparative examples is a silicon wafer (size: φ150 mm, using a spin coater (rotation speed: 3000 rpm, application time: 3 seconds)). The thickness was applied to one surface of 625 μm), the ratio of the area of the repelling part of the adhesive coating film to the entire surface of the silicon wafer was visually confirmed, and evaluated according to the following criteria. In this example, it was determined to be acceptable if it was B or higher.
A: The area of the repelling part was 0%.
B: The area of the repelling part was more than 0% and 10% or less.
C: The area of the repelling part exceeded 10%.
(4-1) Evaluation of adhesive performance Five drops of the adhesive obtained in each of the examples and comparative examples were dropped on one stainless steel substrate, dried by heating at 100 ° C. for 20 minutes, and then the other stainless steel. After bonding to the substrate and cooling to room temperature, the shear force of the bonded substrate was measured in accordance with the “Tensile Shear Bond Strength Test Method” defined in JIS K6850: 1999 using a tensile strength measuring instrument. Measured and evaluated according to the following criteria. In this example, it was determined to be acceptable if it was B or higher.
A: The shearing force was 0.5 MPa or more.
B: The shearing force was 0.1 MPa or more and less than 0.5 MPa.
C: Shear force was less than 0.1 MPa.
(5-1) Evaluation of Peeling Performance The adhesive obtained in each of the examples and comparative examples is a silicon wafer (size: φ150 mm, thickness) using a spin coater (rotation speed: 3000 rpm, coating time: 3 seconds). The silicon wafer was heat-pressed on a ceramic surface plate under a temperature condition of 70 ° C. Next, after cooling to room temperature and temporarily fixing, the razor is fixed to a jig that can be installed so that its tip is inclined by 15 °, and the tip is inserted between a silicon wafer and a surface plate, and the amount of insertion ( mm), and evaluated according to the following criteria. In this example, it was determined to be acceptable if it was B or higher.
A: The insertion amount was less than 10 mm, and the silicon wafer was peeled from the surface plate.
B: The insertion amount was 10 mm or more and less than 15 mm, and the silicon wafer was peeled from the surface plate.
C: The silicon wafer 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 Aqueous Temporary Adhesive Adhesives Adhesives were prepared in amounts (mass%) shown in Table 1-1. About the obtained adhesive agent, application | coating performance, the repellency prevention performance, and temporary fix | stop performance (adhesion performance and peeling performance) were evaluated by the method of said (1-1)-(5-1). The evaluation results are shown in Table 1-1.

I) 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: 56.5-61.5 ° C.)
B-1: Acetylene glycol surfactant (in the above general formula (2), R ²¹ and R ²³ are methyl groups, R ²² and R ²⁴ are isobutyl groups, and A ₂₁ and A ₂₂ are single bonds 2 , 4,7,9-Tetramethyl-5-decyne-4,7-diol ethylene oxide adduct (oxyethylene group repeating unit number: 4))
B-2: Fluorosurfactant (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: a block copolymer of alkylene oxide (ethylene oxide - indicated by (EO) b -H (a + b = 300) - propylene oxide - ethylene oxide triblock copolymer _{(HO- (EO) a - (} PO) 55 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 (by polymerization of polyethylene glycol (several 95.2 parts by weight of ethylene oxide in the presence of an alkali catalyst) under pressure and warm conditions. Average molecular weight: 12,000), and using a metal alcoholate catalyst, the polyethylene glycol and 1,000 parts by weight of propylene oxide are polymerized to have polyethylene glycol as a main chain, and 100 mass of polypropylene glycol at both ends thereof. % Partial addition polymerization, propylene oxide-ethylene oxide-propylene oxide triblock copolymer)

From the results of the examples, the first water-based temporary fixing adhesive of the present invention has excellent temporary fixing performance that has both adhesive performance and peeling performance, and is also excellent in coating performance and repellency 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 work environment, and is excellent in safety. is there.
On the other hand, the adhesive of Comparative Example 1-1 containing no component (A) was inferior in coating performance and did not exhibit adhesive performance. (C) The adhesive of Comparative Example 2-1 containing no component is inferior in repelling prevention performance, and the adhesive of Comparative Example 3-1 not containing (B) component is inferior in coating performance. It was. Further, the adhesive of Comparative Example 4-1 having a melting point of less than 30 ° C. could not be bonded because the adhesive did not harden, and performance evaluation could not be performed.
An adhesive of Examples 10-1 to 13-1 containing one kind of component (A) and an adhesive containing two kinds of (A) components of other examples (particularly Examples 1-1 to 3-1. From the comparison with (adhesive agent), it was confirmed that by using two or more kinds of resins together as the component (A), the temporary fixing performance, coating performance, and anti-repellency performance are equivalent or improved.

Examples 18-1 to 22-1: First water-based temporary fixing adhesive An adhesive was prepared with a blending amount (% by mass) shown in Table 2-1. About the obtained adhesive agent, application | coating performance, the repellency prevention performance, and temporary fix | stop performance (adhesion performance and peeling performance) were evaluated by the method of said (1-1)-(5-1). The evaluation results are shown in Table 2-1.

I) 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: block copolymers of alkylene oxides (ethylene oxide - indicated by _{(EO) b -H (a +} b = 150) - propylene oxide triblock copolymer _{(HO- (EO) a - (} PO) 35 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 excellent temporary fixing performance, which has both adhesive performance and peeling performance, and also has an application performance and a repellency prevention performance. As a result, a silicon wafer with high accuracy 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 work environment, and is excellent in safety. is there.

(Evaluation and measurement method: second water-based temporary adhesive)
(1-2) Measurement of content of various metal ions The adhesives obtained in each of the examples and comparative examples were weighed in a platinum container and heated and incinerated at a heating temperature of 550 ° C. in an electric furnace. This was treated with dilute hydrochloric acid and then dissolved in dilute nitric acid to make 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 was measured by ICP mass spectrometry using “SPQ6500 (model number)” manufactured by Seiko Denshi Kogyo Co., Ltd. Measurement of copper metal ion content by flameless atomic absorption spectrometry using a meter (“Z8270 (model number)”, manufactured by Hitachi, Ltd.), a sequential ICP emission spectroscopic analyzer (“SPS4000 (model number)”, Seiko) The content of iron metal ions was measured by ICP emission spectroscopic analysis using an electronic industry).
In addition, the adhesives obtained in each Example and Comparative Example were weighed into a Teflon (registered trademark) beaker, thermally decomposed with sulfuric acid, nitric acid and perchloric acid, and then dissolved in dilute nitric acid to obtain a constant volume. . About the obtained solution, the content of lead metal ions was measured by ICP mass spectrometry using an ICP mass spectrometer (“SPQ6500 (model number)”, manufactured by Seiko Denshi Kogyo Co., Ltd.). Table 1-2 shows the measured content (ppb) of various metal ions.
(2-2) Measurement of melting | fusing point About the adhesive agent obtained by each Example and the comparative example, melting | fusing point was measured based on JISK0064: 1992. Specifically, a sample obtained by drying moisture contained in the adhesives obtained in each of the examples and comparative examples (2 ml of the adhesive was put in a small petri dish having an inner diameter of 40 mm, and a clean oven was used without a lid. Samples dried at 120 ° C. for 60 minutes) and A-PEG1 used in these examples were heated and melted (temperature conditions: 30 to 130 ° C.) and cooled (temperature conditions: −20 to 30 ° C.). A fine powder (maximum particle size: 300 μm) is made into a powder and dried in a desiccator for 24 hours. The sample is a capillary (made of glass, inner diameter 0.8 to 1.2 mm, thickness: 0.2). -0.3 mm, length: 150 mm), heated at a heating rate of 1 ° C./min, and a melting temperature at which no solid was observed by visual observation (a powdered solid sample was completely Liquefied temperature) Was the point.

(3-2) Evaluation of Adhesion Performance Evaluation was performed by the same method and the same standard as the above “(4-1) Evaluation of Adhesion Performance”. In this example, it was determined to be acceptable if it was B or higher.
(4-2) Evaluation of peeling performance The same method and the same standard as the above "(5-1) Evaluation of peeling performance" were used. In this example, it was determined to be acceptable if it was B or higher.

Examples 1-2 to 6-2, Comparative Examples 1-2 to 6-2: Second Aqueous Temporary Fixing Adhesive An adhesive was prepared with a blending amount (% by mass) shown in Table 1-2. -2 Metal ions were removed in accordance with the method for removing metal ions in Table, and adhesives of Examples and Comparative Examples were obtained. The metal ion removal method was performed by the following method. About the obtained adhesive, content of various metal ions is measured by the method (1-2), the melting point is measured by the method (2-2), and the above (3-2) and (4). -2) The temporary fixing performance was evaluated. The evaluation results are shown in Table 1-2.
(Metal ion removal method)
A: A hydrogen type cation exchange resin (“Allite DS-4 (product number)”, acidic group: sulfonic acid group, manufactured by Organo Corporation) was used as an ion exchanger, and then treated with an adhesive.
B: As an ion exchanger, an ammonia type cation exchange resin (resin column (diameter: 13 cm, height: 50 cm) was charged with 4 L of “Orlite DS-4 (product number)” (manufactured by Organo Corporation). 4 L% ammonia water was flowed down at a linear velocity of 1 cm / min, and was treated with an adhesive using ammonia type cation exchange resin washed with ion exchange water until the effluent became neutral.
-: Metal ion removal was not performed.

I) In the table, "-" in the column of various metal ions indicates that measurement is not possible or the content of various metal ions has not been reduced. Moreover, the detail of each component shown by Table 1-2 used by the present Example is 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 A mixture of
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 thermoplastic resin (“Vinsol NVX (trade name)”, manufactured by Pinova)
-A-emulsion: rosin resin ("Superester NS-121 (trade name)", manufactured by Arakawa Chemical Industries, Ltd.)
C-1: Acetylene glycol surfactant (in the general formula (2), R ²¹ and R ²³ are methyl groups, R ²² and R ²⁴ are isobutyl groups, and A ₂₁ and A ₂₂ are single bonds) , 4,7,9-Tetramethyl-5-decyne-4,7-diol ethylene oxide adduct (oxyethylene group repeating unit number: 4))
· D-1: a block copolymer of alkylene oxide (ethylene oxide - represented by (EO) b -H (a + b = 300) - propylene oxide - ethylene oxide triblock copolymer _{(HO- (EO) a (PO} ) 55 Copolymer (EO: ethylene oxide, PO: propylene oxide)), number average molecular weight: 16500, ethylene oxide: propylene oxide (molar ratio) = 300: 55))

From the results of the examples, the second water-based temporary fixing adhesive of the present invention has excellent temporary fixing performance, which has both adhesive performance and peeling performance, and has a small content of various metal ions, It is excellent in the function deterioration suppressing performance of various members and parts used in optical equipment, electronic equipment, and the like. Further, by adopting a thermoplastic resin having a hydroxyl group (A) as a resin component, the content of various metal ions can be within a predetermined range without performing various metal ion removal treatments, and further, an ion exchanger. By carrying out various metal ion removal treatments using various types of metal ions, the content of various metal ions can be reduced to a very small amount, and the function deterioration suppressing performance of various members and parts used in optical equipment and electronic equipment can be reduced. An extremely excellent adhesive can be obtained.
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 by selecting the component ((A) thermoplastic resin having a hydroxyl group) contained in the adhesive. Since the thermoplastic resin having a hydroxyl group (A) has a high affinity with water, stability as an aqueous temporary fixing adhesive can be obtained. Moreover, when using it, reducing content of various metal ions more, as shown in Example 2-2, 3-2, 5-2, and 6-2, metal ion removal processing may be performed. A) By using a thermoplastic resin having a hydroxyl group, the content of metal ions can be more easily reduced.

  On the other hand, from the results of Comparative Examples 1-2 and 4-2, if the thermoplastic resin (A) having a hydroxyl group is not used as a resin component, the total content of various metal ions cannot be 3000 ppb or less. The adhesives of Comparative Examples 1-2 and 4-2 were tried to reduce the content of various metal ions by an ion exchanger, but the adhesive of Comparative Example 1-2 had too much sodium metal ion content. It could not be reduced to a predetermined content (Comparative Examples 2-2 and 3-2). In addition, since the ion exchange resin deposited the adhesive of Comparative Example 2-2, the content could not be measured. Moreover, although the adhesive type of Comparative Example 4-2 uses an emulsion type as a resin component, since various metal ions were taken in the emulsion, it could not be reduced to a predetermined content (Comparative Examples 5-2 and 6-2).

Examples 7-2 to 15-2: Second water-based temporary fixing adhesive An adhesive was prepared with a blending amount (% by mass) shown in Table 2-2. About the obtained adhesive, about the obtained adhesive, content of various metal ions is measured by the method of the above (1-2), melting | fusing point is measured by the method of the above (2-2), The temporary fixing performance was evaluated by the methods 3-2) and (4-2). The evaluation results are shown in Table 2-2.

I) 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 copolymers of alkylene oxides (ethylene oxide - propylene oxide triblock copolymer _{(HO- (EO) a - (} PO) 35 - (EO) co represented by 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 excellent temporary fixing performance, which has both adhesive performance and peeling performance, and contains various metal ions. The amount is small, and it is excellent in performance deterioration suppressing performance of various members and parts used in optical equipment, electronic equipment and the like. Further, by adopting a thermoplastic resin having a hydroxyl group (A) as a resin component, the content of various metal ions can be within a predetermined range without performing various metal ion removal treatments, and further, an ion exchanger. By carrying out various metal ion removal treatments using various types of metal ions, the content of various metal ions can be reduced to a very small amount, and the function deterioration suppressing performance of various members and parts used in optical equipment and electronic equipment can be reduced. An extremely excellent adhesive can be obtained.

(Evaluation and measurement method: third water-based temporary adhesive)
(1-3) Measurement of surface tension at 25 ° C. The melting points of the adhesives obtained in each Example and Comparative Example were measured according to JIS K0064: 1992. Specifically, a sample obtained by drying moisture contained in the adhesives obtained in each of the examples and comparative examples (2 ml of the adhesive was put in a small petri dish having an inner diameter of 40 mm, and a clean oven was used without a lid. Samples dried at 120 ° C. for 60 minutes) and A-PEG1 used in these examples were heated and melted (temperature conditions: 30 to 90 ° C.) and cooled (temperature conditions: −20 to 30 ° C.). A fine powder (maximum particle size: 300 μm) is made into a powder and dried in a desiccator for 24 hours. The sample is a capillary (made of glass, inner diameter 0.8 to 1.2 mm, thickness: 0.2). -0.3 mm, length: 150 mm), heated at a heating rate of 1 ° C./min, and a melting temperature at which no solid was observed by visual observation (a powdered solid sample was completely Liquefied temperature) And the.

(2-3) Measurement of Melting Point The melting point of the adhesive obtained in each of Examples and Comparative Examples was measured by the same method as the above “(1-1) Measurement of melting point”.

(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 and dried at 100 ° C. for 20 minutes. After bonding to a stainless steel substrate and cooling to room temperature, 20 minutes later, the shear force of the bonded substrate was measured in accordance with JIS K6850: 1999 “Tensile shear bond strength test method” using a tensile strength measuring instrument. Measured.

(4-3) Evaluation of coating performance The evaluation was performed by the same method and the same standard as the above "(2-1) Evaluation of coating performance". In this example, it was determined to be acceptable if it was B or higher.
(5-3) Evaluation of repelling prevention performance The evaluation was performed by the same method and the same standard as the above "(3-1) Evaluation of coating performance". In this example, it was determined to be acceptable if it was B or higher.
(6-3) Evaluation of Adhesive Performance Regarding the adhesive strength measured based on the above “(3-3) Measurement of Adhesive Strength”, the same method and the same standard as the above “(4-1) Evaluation of Adhesive Performance”. evaluated. In this example, it was determined to be acceptable if it was B or higher.
(7-3) Evaluation of Peeling Performance Evaluation was performed by the same method and the same standard as the above “(5-1) Evaluation of Peeling Performance”. In this example, it was determined to be acceptable if it was B or higher.

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

I) 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: Shellac resin (surface tension at 25 ° C .: 45 mN / m [20% aqueous solution], “Serak KTA (trade name)”, manufactured by Koyo Chemical Co., Ltd.) Ammonium neutralized product Resin component 2: Styrene maleic acid Resin water solution (30% by 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 surfactant (in the general formula (2), R ₂₁ and R ₂₃ are methyl groups, R ₂₂ and R ₂₄ are isobutyl groups, and A ₂₁ and A ₂₂ are single bonds) , 4,7,9-Tetramethyl-5-decyne-4,7-diol ethylene oxide adduct (oxyethylene group repeating unit number: 4))
C-2: Fluorosurfactant (“FS-31 (trade name)”, manufactured by Dupont)
· D-1: a block copolymer of alkylene oxide (ethylene oxide - indicated by (EO) b -H (a + b = 300) - propylene oxide - ethylene oxide triblock copolymer _{(HO- (EO) a - (} PO) 55 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 has an adhesive strength, and thus has excellent temporary fixing that has both adhesive performance and peeling performance. It was confirmed that the film had excellent performance and coating performance, and as a result, a highly accurate silicon wafer was obtained. In addition, since the third water-based temporary 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 work environment, and is excellent in safety. It is a thing.
On the other hand, in Comparative Examples 1-3 to 4-3, since the surface tension is large or small and the adhesive strength is small, excellent coating performance cannot be obtained, and the function for temporarily fixing a silicon wafer is not achieved. It became.

  The water-based temporary fixing adhesive of the present invention has excellent temporary fixing performance, as well as water-based temporary fixing adhesive that has both coating performance and repellency prevention performance, optical device, function deterioration suppression performance of various components and parts used in electronic devices, etc. Water-based temporary fixing adhesive with excellent temporary fixing performance, application performance and safety performance, water-based temporary fixing adhesive with low environmental impact, and because it is water-based, natural environment, work environment It is an adhesive that can reduce the burden on the environment such as, and is excellent in safety. Therefore, the water-based temporary fixing adhesive of the present invention is used for applications that require temporary fixing performance as an adhesive, for example, various electronic devices such as OA equipment, information equipment, home appliances, optical equipment, medical equipment, and automotive equipment. Various members and parts used in various 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, etc. It is suitably used for temporary fixing (temporary fixing) in various mechanical processes such as polishing, cutting, grinding, and drilling.

Claims (26)

  (A) A water-based temporary fixing adhesive containing 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 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.   The aqueous temporary fixing adhesive according to claim 1 or 2, wherein the (B) surface conditioner includes at least one selected from an acetylene surfactant, a fluorine surfactant and an acrylic surface conditioner. The acetylene surfactant of the (B) surface conditioner 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 aqueous temporary fixing adhesive according to any one of 3 above.

(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, and A ₂₁ and A ₂₂ each independently represent a single bond or the number of repeating units. 1 to 30 oxyalkylene groups.)   The water-based temporary fixing adhesive according to any one of claims 1 to 4, wherein the (C) compatibilizing agent includes at least an alkylene oxide copolymer.   The water-based temporary fixing adhesive according to claim 5, wherein the copolymer of alkylene oxide includes 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, which does not contain an organic solvent as the solvent.   The above-mentioned (A) hydroxyl group-containing thermoplastic resin, (B) surface conditioner, and (C) compatibilizer content based on the total amount of the composition are 5% by mass to 50% by mass, 0.01% by mass, respectively. The water-based temporary fixing adhesive according to any one of claims 1 to 8, which is 3% by mass or less and 0.1% by mass or more and 15% by mass or less.   (A) It contains a thermoplastic resin having at least a hydroxyl group, and the total content of sodium metal ion, aluminum metal ion, iron metal ion, zinc metal ion, copper metal ion, nickel metal ion, chromium metal ion and lead metal ion is 3000 ppb A water-based temporary fixing adhesive having a content of sodium metal ions, iron metal ions, zinc metal ions and copper metal ions of 1000 ppb or less.   The water-based temporary fixing adhesive according to claim 10, wherein the content of the (A) hydroxyl group-containing thermoplastic resin based on the total amount of the composition is 5% by mass or more and 50% by mass or less.   The water-based temporary fixing adhesive according to claim 10 or 11, further comprising water as a solvent.   The aqueous temporary fixing adhesive according to claim 12, which does not contain an organic solvent as the solvent.   (A) a thermoplastic resin having a hydroxyl group, and (B) a solvent containing water, 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. A water-based temporary fixing adhesive having an adhesive strength of 0.1 MPa or more and 20 MPa or less.   The aqueous temporary fixing adhesive according to claim 14, wherein the solvent containing (B) water does not contain an organic solvent.   The water-based temporary fixing adhesive according to claim 14 or 15, wherein the content of the thermoplastic resin having a hydroxyl group (A) based on the total amount of the composition is 5% by mass or more and 50% by mass or less.   The water-based temporary fixing adhesive according to any one of claims 1 to 16, comprising at least a resin having a melting point measured in accordance with JIS K0064: 1992 of the thermoplastic resin having a hydroxyl group (A) of 30 ° C or higher.   The water-based temporary fixing adhesive according to any one of claims 1 to 17, wherein the thermoplastic resin (A) having a hydroxyl group includes at least a resin of a resin having an oxyalkylene group.   The water-based temporary fixing adhesive according to any one of claims 1 to 18, wherein the thermoplastic resin (A) 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 a member or a part used in an electronic device.   21. The water-based temporary fixing adhesive according to claim 20, wherein the processing of the member or component used in the electronic device is polishing of the wafer surface.   (A) A composition containing a thermoplastic resin having a hydroxyl group and a metal ion is brought into contact with an ion exchanger, sodium metal ion, aluminum metal ion, iron metal ion, zinc metal ion, copper metal ion, nickel metal ion, A method for producing an aqueous temporary fixing adhesive, wherein the total content of chromium metal ions and lead metal ions is 3000 ppb or less, and the contents of sodium metal ions, iron metal ions, zinc metal ions and copper metal ions are each 1000 ppb or less. .   The method for producing an aqueous temporary fixing adhesive according to claim 22, wherein the ion exchanger uses an ion exchange resin.   A temporary fixing step of temporarily fixing a precursor of a member or a part and a processing substrate using the aqueous 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 a component, which includes a processing step for producing the member or the component.   The method of manufacturing a member or part according to claim 24, wherein the precursor of the member or part is a precursor of a member or part used in an electronic device.   The method of manufacturing a member or part according to claim 24, wherein the member or part used in the electronic device is a wafer, and the mechanical processing is polishing of the wafer surface.