WO2006028227A1

WO2006028227A1 - Adhesive

Info

Publication number: WO2006028227A1
Application number: PCT/JP2005/016667
Authority: WO
Inventors: Kazuya Tsukamoto; Shigeto Shigematsu; Hideto Matsuoka; Yuichi Itou; Yasushi Mizuta
Original assignee: Mitsui Chemicals, Inc.
Priority date: 2004-09-10
Filing date: 2005-09-09
Publication date: 2006-03-16
Also published as: JPWO2006028227A1; TW200617129A

Abstract

An adhesive having an excellent strength of adhesion to fluoropolymers; and a pellicle which has an adhesive layer formed from the adhesive and retains durability sufficient for practical pellicle use. For producing the pellicle, use is made of a fluoropolymer adhesive which contains no solvents and comprises a fluororubber, a polyvalent (meth)acrylate compound having two or more (meth)acryloyl groups per molecule, and a monovalent (meth)acrylate compound.

Description

Specification

adhesive

Technical field

TECHNICAL FIELD [0001] The present invention relates to a pellicle, a method for manufacturing a pellicle, and an adhesive, and in particular, dust on a mask or reticle (hereinafter simply referred to as a mask) used in a lithography process in an integrated circuit or liquid crystal display manufacturing process. The present invention relates to a pellicle used for the purpose of preventing adhesion of a pellicle, a method for manufacturing a pellicle, and an adhesive for pellicle.

Background art

[0002] Hydrocarbon polymers such as cellulose and fluorine-based polymers are used for pellicle membranes used for pellicles. Although a pellicle film made of a fluorine-based polymer is particularly excellent in light resistance and durability, it is also excellent in releasability, that is, hardly adhesive, and it is difficult to bond the pellicle film to the pellicle frame. In addition, masks used in the manufacture of liquid crystal displays are becoming larger than conventional ones as represented by liquid crystal televisions, and the adhesion strength between the pellicle film and the pellicle frame is further increased in the large pellicles mounted on these masks. The necessity is increasing.

[0003] In order to solve the problem of the pellicle film adhesive that also has a fluorine-based polymer force, there is also a pellicle formed by bonding a pellicle film made of a fluorine-based organic substance to the pellicle frame with the same fluorine-based organic substance adhesive. It has been proposed (JP-A-6-67409). However, with this adhesive, it is necessary to air dry for 3 hours after applying an organic solvent dissolved in a solvent on the frame. It is necessary to heat to C or higher. For this reason, there is a problem that the bonding process takes time, and further, the members such as the frame are distorted due to the application of heat.

[0004] Japanese Patent Application Laid-Open No. 2002-258465 discloses a technique in which an adhesive containing a fluorine-based polymer and an ultraviolet-curing fluorine-based (meth) attareito toy compound is sandwiched between a pellicle film and a pellicle frame and cured by ultraviolet curing. Is disclosed.

While this method can provide a pellicle with extremely good durability, the viscosity of the adhesive is so high that it can be diluted with a solvent when the adhesive is applied to the pellicle frame. However, the solvent must be volatilized before UV curing, which complicates the pellicle manufacturing process and takes time. In addition, there is a problem that the workability in the bonding process is poor in that the adhesive is difficult to spread over the entire pellicle frame after the adhesive is sandwiched between the pellicle film and the pellicle frame.

Patent Document 1: Japanese Patent Laid-Open No. 6-67409

Patent Document 2: JP 2002-258465 A

Disclosure of the invention

Problems to be solved by the invention

[0006] The main object of the present invention is to provide an adhesive having excellent adhesive strength to a fluorine-based polymer and an adhesive layer using such an adhesive while maintaining durability sufficient for practical use of the pellicle. It is to provide a pellicle and a method for manufacturing the pellicle.

Means for solving the problem

[0007] As a result of intensive investigations to achieve the above-mentioned problems, the present inventors have found that an adhesive comprising a fluororubber, a polyvalent (meth) atarylate compound, and a monovalent (meth) ataretoy compound. The pellicle was found to have good workability while maintaining practically sufficient durability, and to exhibit excellent adhesiveness to the fluorine-based polymer, thereby completing the present invention.

That is, the present invention includes a polyvalent (meth) acrylate compound having no solvent, a fluororubber and two or more (meth) atalyloyl groups in one molecule, and the following formula (1):

[0008] [Chemical 1]

[Wherein R is a hydrogen atom or a methyl group, R is a hydrogen atom substituted with a fluorine atom,

1 2

Or a hydrocarbon group having 1 to 12 carbon atoms. The present invention provides a fluorine-based polymer adhesive comprising a monovalent (meth) atrelate toy compound represented by (1).

The ultraviolet curable adhesive obtained in the present invention is an ultraviolet curable adhesive obtained by further blending a photoinitiator with the adhesive. [0010] Further, the present application is that the polyvalent (meth) atrelate toy compound is selected from the group consisting of a divalent (meth) arylate compound compound force represented by the following formula (2): In one preferred embodiment of the present invention, the formula (2) is

[0011] [Chemical 2]

^ 1 Ri

H2C C C, CH2

|] ° II ^L

I! II

0 0

(In the formula, R is a hydrogen atom or a methyl group, and R is an alkylene group having 1 to 12 carbon atoms.

13

Is an alicyclic hydrocarbon group, an alkylene ether group represented by the following formula (3), or a fluorine-containing group represented by the following formula (4):

[0013] [Chemical 3]

[0014] In the above formula (3), R represents an alkylene group having 2 to 4 carbon atoms, n represents an integer of 1 to 20,

Four

[0015] [Chemical 4]

—— CH ₂ — Rf—— CH ₂ —— (4)

In the above formula (4), Rf represents a perfluoroalkylene group having 1 to 12 carbon atoms or a perfluoroalkylene ether group represented by the following formula (5),

[0017] [Chemical 5]

In the above formula (5), Rf ¹ represents a perfluoroalkylene group having 2 to 4 carbon atoms, and n represents an integer of 1 to 20. ).

And as the monovalent (meth) ataretoy compound represented by the above formula (1) used in the present invention, a compound in which R is an alkyl group having 4 to 8 carbon atoms is preferable.

2

In addition, the glass transition temperature (Tg) of the cured adhesive product obtained by curing the adhesive of the present invention (measurement frequency: 1 Hz, measurement mode: tensile mode) is −40 to 20 ° C. A range is preferable.

The adhesive of the present invention can be used for an adhesive layer between a pellicle film and a pellicle frame that supports the pellicle film.

The glass transition temperature (Tg) of the adhesive layer of the pellicle using the adhesive of the present invention is preferably in the range of -40 to 20 ° C by the viscoelasticity test! /.

According to the present invention, the pellicle is manufactured through the step of bonding the pellicle film and the pellicle frame that supports the pellicle film using the adhesive.

The invention's effect

[0020] According to the present invention, it is possible to provide an adhesive having excellent adhesion to a fluorine-based polymer, having good workability and excellent durability against ultraviolet rays. Brief Description of Drawings

[0021] [Fig. 1] E ', E ", tan obtained by measuring viscoelasticity of the cured adhesive produced in Example 1

It is a chart of δ.

BEST MODE FOR CARRYING OUT THE INVENTION

[0022] The present invention is described in detail below.

(Solvent)

In the present invention, the solvent is a known organic compound that does not have a polymerizable unsaturated group. For example, aliphatic solvents such as hexane, nonane, decane, etc. described in the solvent handbook, Halogen solvents such as methylene chloride and chloroform, alcohol solvents such as methanol, ethanol, propanol and butanol, ketone solvents such as acetone, methyl ethyl ketone and methyl i butyl ketone, esters such as ethyl acetate and butyl acetate Illustrative are organic solvents, ether solvents such as diethyl ether and tetrahydrofuran, aromatic solvents such as benzene, toluene and xylene, dimethyl sulfoxide, dimethylformamide and the like.

[0023] (Fluoro rubber)

As long as the fluororubber contained in the adhesive used in the present invention has a fluorine atom in the molecular skeleton and has rubber elasticity, any known fluororubber without any restriction on the structure can be used. For example, a binary copolymer of vinylidene fluoride and hexafluoropropylene Terpolymer of tetrafluoroethylene, vinylidene fluoride and hexafluoropropylene, terpolymer of vinylidene fluoride, perfluoro (alkyl butyl ether) and tetrafluoroethylene Polymer, binary copolymer of tetrafluoroethylene and perfluoro (alkyl butyl ether), binary copolymer of tetrafluoroethylene and propylene, ternary copolymer of tetrafluoroethylene, propylene and vinylidene fluoride Examples of the polymer include a tetrafluoroethylene propylene copolymer and a tetrafluoroethylene propylene-vinylidene fluoride copolymer.

[0024] The molecular weight of fluororubber is related to the intrinsic viscosity of tetrahydrofuran solution at 30 ° C [7?], And the force related to adhesiveness [7?] Is 0.2 ~ 0. A molecular weight of 8 dlZg is preferred. The adhesive strength after curing may be low at less than 0.2 dlZg, and sometimes the adhesive layer may be deformed due to the tension of the film, while at 0.8 dlZg or more, the adhesive frame when the film is pasted. The spread at the top will be worse and it may be difficult to adhere with good appearance.

[0025] (Multivalent (meta) ata relay toy compound)

The polyvalent (meth) acrylate compound contained in the adhesive of the present invention is not particularly limited as long as it has two or more (meth) attalyloyl groups in one molecule. A rate-i compound can be used. Among these compounds, from the viewpoint of adhesiveness, R is a hydrogen atom in the formula (2) in which the divalent (meth) attale toy compound represented by the following formula (2) is more preferable.

More preferred is a divalent atalyte toy compound having one atom.

Here, the equation (2) is

[0027] [Chemical 6]

HY ⁰ヽ. To (2)

o II o II

[0028] In the above formula (2), R is a hydrogen atom or a methyl group, and R is an alkyl group having 1 to 12 carbon atoms.

13

A xylene or alicyclic hydrocarbon group, an alkylene ether group represented by the following formula (3), or a fluorine-containing group represented by the following formula (4): [0029] [Chemical 7]

[0030] In the above formula (3), R represents an alkylene group having 2 to 4 carbon atoms, n represents an integer of 1 to 20,

Four

[0031] [Chemical 8]

—— CH ₂ —— Rf—— CH ₂ —— (4)

In the above formula (4), Rf represents a perfluoroalkylene group having 1 to 12 carbon atoms or the following formula (

5) represents a perfluoroalkylene ether group represented by

[0033] [Chemical 9]

—— Rf ¹ and so on. One Rf ¹ (5)

[0034] In the above formula (5),! /, Rf ¹ represents a perfluoroalkylene group having 2 to 4 carbon atoms, and n represents an integer of 1 to 20.

Among these polyvalent (meth) acrylate compounds, R is a (meth) alkyl represented by the above formula (4).

Three

It is preferable to be a relay toy compound (meth) atta relay toy compound represented by the above formula (4) and Rf is a perfluoroalkylene group having 1 to 12 carbon atoms is more preferable. More preferred is an attaleuto compound represented by the above formula (4), wherein Rf is a perfluoroalkylene group having 1 to 12 carbon atoms.

[0035] Examples of the polyvalent (meth) ataretoy compound include 2, 2, 3, 3, 4, 4, 5, 5-octafluoro 1,6 hexanediol ditalylate, 2 , 2, 3, 3, 4, 4, 5, 5—Octafluoro 1,6 hexanediol dimetatalylate, 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7 Dodecafluo mouth 1,8-octanediol ditalitalate, 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7 Dodecafluoro-1,8 octanediol dimetatalylate It is out.

Among these polyvalent (meth) atalylate compounds, 2, 2, 3, 3, 4, 4, 5, 5—octafluoro 1,6 hexanediol ditalylate, 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7 Dodecafluoro-1,8 octanediol ditalylate is preferred.

In the case where the polyvalent (meth) ataretoy compound is the above compound, the reactivity is high, so Less monomer remains in the reaction, and less residue volatilizes when the pellicle is used.

[0037] (Monovalent (meta) atta relay toy compound)

The monovalent (meth) acrylate compound contained in the adhesive used in the present invention has one (meth) attalyloyl group in one molecule and is represented by the following formula (1).

[0038] [Chemical 10]

I)

In the above formula (1), R is a hydrogen atom or a methyl group, R is a hydrogen atom substituted with a fluorine atom

1 2

And a hydrocarbon group having 1 to 12 carbon atoms. R is an alkyl group,

2

Examples of the compound represented by the above formula (1) include an alicyclic hydrocarbon group, a fluorinated alkyl group, a fluorinated alicyclic hydrocarbon group, and the like. R is an alkyl group having 1 to 12 carbon atoms or an alicyclic ring.

2

A compound that is a hydrocarbon group is preferred. R is an alkyl group having 1 to 10 carbon atoms or an alicyclic group.

2

Compounds in which hydrocarbon groups are preferred are compounds in which R is an alkyl group having 4 to 8 carbon atoms.

2

More preferred are.

[0040] Examples of the monovalent (meth) atalytoi compound include methyl acrylate, ethyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, 2-ethyl hexyl acrylate. Rate, lauryl acrylate, i-stearyl acrylate, cyclohexyl acrylate, etc., talate toy compounds, methyl methacrylate, ethyl methacrylate, i propyl methacrylate, n butyl methacrylate, i Mention may be made of methacrylate compounds such as butyl metatalylate, 2-ethylhexyl metatalylate, lauryl metatalylate and the like, and among these compounds, attareito toy compounds are preferred. Most preferred are n-butyl acrylate, i-butyl acrylate, 2-ethylhexyl Ta relays, etc.

[0041] When the monovalent (meth) atreatoy compound is the preferred compound, it tends to be excellent in compatibility with the fluororubber and the polyvalent (meth) atalytoid compound. For example, fluororubber is vinyl fluoride-lidene-tetrafluoroethylene propylene copolymer, and polyvalent (meth) atalylate compound is 2, 2, 3, 3, 4, 4, 5, 5—octafluoro- In the case of 1,6-hexanediol ditalylate, it tends to be excellent in compatibility with n-butyl acrylate, i-butyl acrylate, 2-ethyl hexyl acrylate, and lauryl acrylate. It tends to be inferior in compatibility with other monovalent (meth) attale toy compounds.

[0042] (Formulation of adhesive)

The adhesive according to the present invention includes the above-mentioned fluoro rubber, a polyvalent (meth) ata relay toy compound and a monovalent (meth) atta relay toy compound. It is preferable that the compound is a (meth) atareto toy compound containing fluorine, at least one of the above monovalent (meth) atareto toy compounds.

[0043] When at least one of the polyvalent (meth) attareito toy compound and the monovalent (meth) attareito toy compound is the above compound, the compatibility with the fluororubber is excellent.

The adhesive of the present invention does not contain a solvent that contains the above-mentioned fluororubber, polyvalent (meth) atreatoi compound, and monovalent (meth) atreatoi compound. Here, in the present invention, “containing a solvent” means a stage of application to an adherend such as a pellicle frame or a pellicle film, and is 1% by weight, preferably 0.5% by weight with respect to the adhesive. %, More preferably more than 0.1% by weight of solvent is included.

[0044] Accordingly, when the adhesive of the present invention is blended, a solvent may be used in combination with the fluororubber, the polyvalent (meth) attareito toy compound, and the monovalent (meth) atetale toy compound. In that case, however, the residual solvent amount of the adhesive is reduced to 1% by weight or less, preferably 0.5% by weight of the adhesive by solvent removal treatment such as air drying, heating, and decompression before being applied to the adherend. % Or less, more preferably 0.1% by weight or less.

[0045] When a solvent exceeding the above range remains in the adhesive when applied to the adherend, a solvent removal treatment is required to remove the residual solvent. For example, the efficiency of the pellicle manufacturing process is improved. It tends to decrease.

Also, for example, if the bonding process between the pellicle frame and the pellicle film is proceeded with the solvent exceeding the above range remaining in the adhesive, the adhesive strength tends to decrease. When actually used in the lithography process, the residual solvent volatilizes and deposits as foreign matter on a mask or the like, which tends to greatly reduce the yield of semiconductor elements.

[0046] (Adhesive mixing ratio)

The preferred ratio of fluororubber, polyvalent (meth) atalylate compound and monovalent (meth) atalylate compound contained in the adhesive is as follows: fluororubber: polyvalent (meth) ataretoy compound: monovalent ( meth) § Tarireto compound = 15 to 40: 5 to 40: 20 to 60 (wt ^_0/0). That is, fluorine rubber and, based on the total weight of the polyvalent (meth) Atari Rate compound and a monovalent (meth) adhesive comprising a Atari rate Lee匕合thereof, fluororubber is 15 to 40 weight ^_0/0 range, It is preferable that the polyvalent (meth) acrylate compound is in the range of 5 to 40% by weight, and the monovalent (meth) acrylate compound is in the range of 20 to 60% by weight.

[0047] If the amount of the polyvalent (meth) attareito toy compound is less than the above range, the curability of the adhesive may be lowered and the adhesive strength may be lowered. If the amount is more than the above range, The Tg after curing may increase and the adhesive strength may decrease. If the amount of monovalent (meth) talate toy compound is less than the above range, the adhesive may not spread well on the frame when the film is attached, and it may be difficult to adhere with good appearance. If the amount is larger than the above range, the strength of the adhesive itself after curing is lowered, and the adhesive strength may be lowered.

[0048] Further, more preferredヽproportion of the compound, based on the total weight of the adhesive, the range fluorine rubber is 15 to 35 weight ^_0/0, a polyvalent (meth) Atari rate compound 10-40 weight range ^_0/0, monovalent (meth) Atari rate b匕合product is in the range of 25 to 60 wt%, more preferred percentage is based on the total weight of the adhesive, a fluorine rubber is 20 to 30 weight range ^_0/0, a polyvalent (meth) range Atari rate compound is 15 to 35 wt%, monovalent (meth) Atari rate compound is in the range of 35-6 0% by weight.

[0049] When the blending amount of the fluororubber is more than the above range, the spreadability of the adhesive tends to deteriorate, and when it is less than the above range, the adhesive strength tends to be insufficient.

When the blending amount of the polyvalent (meth) attalei toy compound is within the above range, the adhesive has sufficient curability, and the Tg does not become high after curing, so that the adhesive strength is more excellent.

When the blending amount of the monovalent (meta) talate toy compound is within the above range, the adhesive spreads better on the frame when the film is attached, so that it can be bonded with better appearance. In addition, the adhesive strength is also excellent.

[0050] The adhesive of the present invention adjusts the viscosity of the adhesive as appropriate by changing the ratio of the fluororubber, the polyvalent (meth) acrylate compound, and the monovalent (meth) acrylate compound within the above range. be able to.

Especially when the width of the pellicle frame exceeds 10 mm, the viscosity of the adhesive is 15000 mPa · S or less, more preferably ί or 8000 mPa · S or less, more preferably ί or 2000 to 6000 mPa · s. In the bonding process, the spreadability of the adhesive (hereinafter referred to as the spreadability of the adhesive) after interposing the adhesive between the pellicle film and the pellicle frame can be improved.

[0051] (Adhesive usage)

The adhesive of the present invention can be prepared by dissolving fluorine-based rubber in a mixture of a polyvalent (meth) acrylate compound and a monovalent (meth) ateryl compound. There is no particular limitation on the method of dissolving, but it can be prepared under the condition of being heated to room temperature or a temperature not higher than the boiling point of the (meth) atalytoi compound. In particular, when dissolved by heating, it is preferable to add an appropriate amount of a polymerization inhibitor or carry out air publishing in order to prevent polymerization of the (meth) attale toy compound.

[0052] In addition, the adhesive of the present invention is prepared by mixing a fluorine-based rubber, a polyvalent (meth) talate toy compound, a monovalent (meth) acrylate, and a solvent, and then evaporating the solvent, for example. It can be used as an adhesive without solvent.

(Pellicle)

In the present invention, the pellicle is also a force between the pellicle frame and the pellicle film. The pellicle film is bonded to one side end surface of the pellicle frame via a film adhesive, and the end surface on the side of the pellicle frame opposite to the film adhesive layer. It is used by being attached to a mask via a frame adhesive.

[0053] The adhesive used to bond the pellicle film to the pellicle frame includes the above-described fluororubber, a polyvalent (meth) acrylate compound, and a monovalent (meth) ate larito toy compound, Therefore, since these ratios can be changed and the viscosity of the adhesive can be adjusted according to the width of the pellicle frame, an adhesive with excellent workability can be obtained.

(Curing method) The adhesive of the present invention can be used by curing the above adhesive. There are no particular restrictions on the means for curing, but for example, a photoinitiator may be further blended with the above adhesive, followed by polymerization and curing with ultraviolet rays.

[0054] Further, the adhesive used to bond the pellicle film to the pellicle frame includes the above-described adhesive containing a fluorine rubber, a polyvalent (meth) acrylate compound, and a monovalent (meth) acrylate compound. By using a photoinitiator or a sensitizer in combination, it is possible to rapidly perform polymerization and curing by ultraviolet rays, and it is possible to improve the adhesive strength by increasing the degree of polymerization.

As a photoinitiator, power capable of using all known photoinitiators is preferable. 2,2-Diethoxyacetophenone, Darocur 1173 (Darocur 1173; manufactured by Chinoku "Specialty" Chemicals Co., Ltd.), Irgacure 369 (Irgacure 369; Chinoku's Specialty Chemicals Co., Ltd.), Irgacure 819 (Irgacure 819; Chinoku's Specialty Chemicals Co., Ltd.), Irgacure 1700 (Irgacure 1700; Chiba's Specialty Chemicals Co., Ltd.) Irgacure 1850 (Irugacure 1850; manufactured by Chinoku 'Specialty' Chemicals Co., Ltd.) and Irgacure 184 (Irgacure 184; manufactured by Chinoku 'Specialty Chemicals Co., Ltd.) are used.

[0055] When the photoinitiator is dissolved in the adhesive, it is usually performed at room temperature or lower.

As the sensitizer, benzoin, benzoin ether and benzoin isopropyl ether can be preferably used.

A cured product obtained by curing the adhesive of the present invention using a photoinitiator as described above is a glass defined by a peak temperature of tan δ by a viscoelasticity test (measurement frequency: 1 Hz, measurement mode: tensile mode). Transition temperature (Tg) force is preferably in the range of 40 to 20 ° C, more preferably in the range of 40 to 0 ° C. Depending on the cured product, a plurality of peak temperatures of tan δ may be observed. In that case, it is preferable that the plurality of peak temperatures be within the above range.

[0056] When the glass transition temperature of the cured product is in the above range, both spreadability and adhesive strength can be achieved.

Normally, a cured product having a glass transition temperature in the above range can be obtained by blending the above preferred compound in a suitable blending amount and curing.

(Pellicle membrane) The pellicle membrane used for the pellicle is preferably made of a fluorine-based polymer. Specifically, the pellicle membrane is made of a fluoropolymer (trade name: Cytop) manufactured by Asahi Glass Co., Ltd. or a fluoropolymer (trade name) manufactured by DuPont. : Teflon (registered trademark) AF) and the like.

[0057] The pellicle membrane having the fluorine polymer power can be produced by using the fluorine polymer as a fluorine solvent, particularly a perfluoro organic solvent such as perfluoro (2-ptyltetrahydrofuran), perfluoro (2-propyltetrahydrofuran), After being dissolved to a concentration of 0.1 to 20% by weight, particularly 0.3 to 15% by weight using fluorohydrofuran, perfluorooctane or the like, a casting film forming method known per se, for example, spin It can be performed by a coating method, a knife coating method, etc., and a resin solution is generally cast on a smooth substrate surface such as a glass plate to form a thin film, which is dried by means such as hot air or infrared irradiation to remove residual solvent. It is better to remove it. The thickness of the thin film to be formed can be easily changed by changing the solution viscosity, the rotation speed of the substrate, etc., and generally has a transmittance in the range of 0.05 to 10 m with respect to the wavelength of the light source used. Thus, the thickness can be set.

[0058] In addition to the pellicle film itself having a fluoropolymer force, a pellicle film in which an antireflection layer made of a fluoropolymer is laminated on a thin film having a conventionally known pellicle film material force such as nitrocellulose is also preferably used. can do. Even in this case, even if the part in contact with the adhesive is an antireflective layer having a fluorine-based polymer force, the above-mentioned adhesive comprising fluororubber and a (meth) acrylate compound exhibits excellent adhesion, and fluorine The same effect as when a pellicle film made of a polymer is adhered can be obtained.

[0059] (Pellicle frame)

As the pellicle frame, all conventionally known ones can be used, and those made of metal such as aluminum, aluminum alloy, stainless steel, synthetic resin, or ceramic are preferable. Can be used. In the pellicle of the present invention, the pellicle film is stretched on one side of the pellicle frame via the above-mentioned adhesive, and an adhesive is applied to the other side, or a double-sided tape is adhered to the mask. Example that can be mounted on

[0060] Hereinafter, the present invention will be described in more detail with reference to production examples, examples, and comparative examples. Ming is below

It is not limited to the examples described above.

(Example 1)

(Preparation of adhesive)

2.8 g of vinylidene fluoride / tetrafluoroethylene / propylene copolymer (intrinsic viscosity: [r?]: = 0.30 ~ 0.45dl / g manufactured by Asahi Glass Co., Ltd.) 4.7 g of 2-ethylhexyl acrylate and polyvalent (meth) ateryl as a toy compound 2.5 g 2, 2, 3, 3, 4, 4, 5, 5 years old Kutafunole uni 1, 6 hexane It was heated and dissolved in a mixture of diol diatalylate while air publishing. After cooling to room temperature, 0.13 g of Irgacure 369 (Irgacure 369; manufactured by Ciba 'Specialty' Chemicals Co., Ltd.), 0.13 g of 2,2 diethoxyacetophenone was added as a photoinitiator and stirred and dissolved. An adhesive was prepared.

[0061] As the characteristic values of the adhesive thus obtained, the viscosity and Tg of the cured adhesive were measured by the following methods, and the results are shown in Table 1.

(Adhesive viscosity)

The viscosity of the adhesive obtained in Example 1 at 25 ° C. was measured with a Brookfield viscometer.

[0062] (Tg measurement of cured adhesive)

The adhesive obtained in Example 1 was sandwiched between glass plates to a thickness of 100 m, and irradiated with ultraviolet rays having an illuminance of 28 OmW / cm ² for 15 seconds to obtain a cured adhesive. Carefully peel off the cured adhesive from the glass plate, cut it to an appropriate size, and plot viscoelasticity under the following conditions, plotting E ', E ", and tan δ against temperature. The peak temperature of tan δ at this time is 7 ° C, and this is Tg.

Measuring device ； RSA— Π (Smoked)

Measurement mode Tensile mode

Measurement temperature — 70-100. C

Temperature increase rate 3 ° CZ min

Measurement frequency: 1Hz (Preparation of pellicle film)

Cyclic Par Full O b Cytop is a perfluorinated榭脂having an ether group (Asahi Glass Co., Ltd. trade name) of fluorinated solvent IL- 263 was dissolved in (Tokuyama Co., Ltd.) 6 wt ^_0/0 A solution was prepared, and a pellicle film having a thickness of 0.8 μm was prepared by spin coating.

[0063] The spreadability of the adhesive (adhesive spreadability) after the adhesive was sandwiched between the pellicle film and the pellicle frame in the bonding process was evaluated by the following method.

Aluminum alloy pellicle frame (length 149mm x width 122mm, height 5.8mm, width 10mm), outer diameter 1.4mm0> Z inner diameter 1. もと πιπιΦ dispense needle 1.2gZ The adhesive was applied onto the adhesive surface of the pellicle frame at a coating speed of 20 mmZ seconds. Immediately after the application was completed, the prepared pellicle film was affixed so that the edge of the pellicle film was 1 mm below the adhesive surface, and the time for the adhesive to spread over the entire mold was visually measured and shown in Table 1.

[0064] (Preparation of pellicle)

Pelicle frame made of aluminum alloy (length 149mm x width 122mm, height 5.8mm, width 2mm), outer diameter 1.4mm0> Z inner diameter 1. 吐出 πιπιΦ dispense needle 0.0g The adhesive was applied onto the adhesive surface of the pellicle frame at a coating speed of 2 OmmZ seconds. Immediately after the application, the prepared pellicle film was attached, and then irradiated for 90 seconds with a UV irradiation device (Toshiba Lighting & Technology Corp .; M2000L / 8 IN (80 W / cm): spectral range 220 to 600 nm). The agent was cured. Subsequently, the excess film on the outside of the pellicle frame was cut with a cutter to produce a pellicle.

The prepared pellicle was subjected to the following durability evaluation in order to evaluate the adhesion strength of the pellicle film, the appearance evaluation, and the durability of the pellicle itself by the method shown below, and the results are shown in Table 1.

(Pellicle film adhesive strength)

Outer diameter 1. Using a needle with ΟπιπιΦΖ inner diameter 0.665πιπιΦ, the pellicle film is adhered to the pellicle film surface at a distance of 10mm, angle 45 °, pressure 0.2MPa at a speed of about 2mmZ seconds ヽAfter spraying along the inside of the pellicle frame, the interface between the pellicle film and the adhesive was visually observed to evaluate the presence or absence of peeling. If there is no peeling as a result of the evaluation, the air pressure is increased in increments of 0. OlMPa and the same operation is repeated, and peeling is observed. The maximum pressure that was not used was defined as the inner blow adhesive strength. Similarly, after spraying along the inside of the pellicle frame where the pellicle film adheres at a speed of about 2 mmZ seconds, air at a distance of 10 mm, an angle of 65 °, and a pressure of 0.2 MPa from the surface of the pellicle film without the pellicle frame Then, the interface between the pellicle film and the adhesive was observed visually and under microscopic conditions to evaluate the presence or absence of peeling. After two rounds of the inner periphery of the pellicle frame, if there was no peeling, the air pressure was increased in increments of 0. OlMPa and the same operation was repeated, and the maximum pressure at which no peeling was observed was taken as the outer blow adhesive strength.

[0066] (Appearance evaluation)

Visually observe and evaluate the appearance of the manufactured pellicle. If there is no abnormality in the appearance or film surface, the result is shown in Table 1 as X when there is an abnormality that causes problems in use such as discoloration on the appearance or film surface. showed that.

(Durability evaluation)

The prepared pellicle is attached to a quartz glass substrate, a mercury lamp (wavelength 300 to 600 nm) is irradiated to the center of the film surface at 200,000 jZcm ^2, and the film surface is visually observed for cloudiness while illuminated by a projector. The results are shown in Table 1. The results are shown as 〇 if no clouding has occurred and X if clouding has occurred.

[0067] (Examples 2 to 9)

Except for changing the amount of fluororubber, polyvalent (meth) atrelate toy compound, monovalent (meth) atarire one toy compound and photoinitiator to be blended as adhesives as shown in Table 1. Prepare an adhesive in the same way as in Example 1, measure the viscosity and Tg of the cured adhesive as characteristic values of the adhesive, evaluate the spread of the adhesive, prepare a separate pellicle, and bond the pellicle film The strength, appearance and durability were evaluated, and the results are shown in Table 1.

(Comparative Example 1)

(Preparation of adhesive)

CYTOP CTX A type (trade name, manufactured by Asahi Glass Co., Ltd.) is dissolved in the solvent CTsolvl60 (perfluorotrialkylamine (a chemical formula: (C F) N); product name, manufactured by Asahi Glass Co., Ltd.)

n 2n + l 3

The concentration was adjusted to 9 wt%.

[0068] (Preparation of pellicle film)

Cytop (Asahi Glass Co., Ltd.), a fully fluorinated resin having a cyclic perfluoroether group Trade name) Ltd. A solution of 6 wt ^_0/0 was prepared by dissolving the IL- 263 fluorinated solvent (manufactured by Tokuyama Corporation), the pellicle film having a thickness 0. 8 mu m by spin coating Produced.

(Pellicle production)

Pelicle frame made of aluminum alloy (length 149mm x width 122mm, height 5.8mm, width 2mm), outer diameter 1.4mm0> Z inner diameter 1. 吐出 πιπιΦ dispense needle 0.0g The adhesive was applied onto the adhesive surface of the pellicle frame at a coating speed of 2 OmmZ seconds. 3 hours after air drying, place this aluminum frame on a 130 ° C hot plate with the adhesive applied surface facing up, and after 5 minutes, place the prepared film on the adhesive applied surface for adhesion did. Subsequently, an excess film outside the pellicle frame was cut with a cutter to produce a pellicle.

[0069] (Adhesive strength, appearance evaluation and durability evaluation of pellicle film)

The prepared pellicle was evaluated in the same manner as in Example 1 for the adhesive strength, appearance, and durability of the pellicle film, and the results are shown in Table 1.

(Comparative Example 2)

(Preparation of adhesive)

Fluoro rubber as a solvent in 1.7g of vinylidene fluoride / tetrafluoroethylene / propylene copolymer (Intrinsic viscosity: [r?] = 0.30 ~ 0.45dlZg Asahi Glass Co., Ltd.) As a monovalent acrylate compound, 0.85 g of 2- (perfluorooctyl) ethyl acrylate was dissolved. After dissolution, Darocur 1173 (Darocur 1173; Chinoku 'Specialty' Chemicals Co., Ltd.) 0.06 g was added as a photoinitiator to dissolve uniformly to prepare an adhesive.

[0070] The spreadability of the adhesive was evaluated by the following method.

Aluminum alloy pellicle frame (length 149mm x width 122mm, height 5.8mm, width 10mm), outer diameter 1.4mm0> Z inner diameter 1. もと πιπιΦ dispense needle 1.2gZ The adhesive was applied onto the adhesive surface of the pellicle frame at a coating speed of 20 mmZ seconds. After coating, the solvent, butyl acetate, is removed by air-drying, and then the pellicle film is pasted so that the edge of the pellicle film is 1 mm below the bonding surface, and the adhesive spreads over the entire mold. The time was measured visually and shown in Table 1.

[0071] (Preparation of pellicle) Pelicle frame made of aluminum alloy (length 149mm x width 122mm, height 5.8mm, width 2mm), outer diameter 1.4mm0> Z inner diameter 1. 吐出 πιπιΦ dispense needle 0.0g The adhesive was applied onto the adhesive surface of the pellicle frame at a coating speed of 2 OmmZ seconds. After coating is completed, the solvent, butyl acetate, is removed by air-drying, and the prepared pellicle film is attached. Then, a UV irradiation device (manufactured by Toshiba Lighting & Technology Corporation; M2000LZ81N (80WZcm): spectral range 220-600nm) Was irradiated for 90 seconds, and then the excess film outside the pellicle frame was cut with a cutter to produce a pellicle.

(Adhesive strength, appearance evaluation and durability evaluation of pellicle film)

The prepared pellicle was evaluated in the same manner as in Example 1 for the adhesion strength, appearance evaluation and durability evaluation of the pellicle film, and the results are shown in Table 1.

(Comparative Example 3)

Comparative example except that the amounts of fluororubber, polyvalent (meth) atrelate toy compound, monovalent (meth) acrylate compound, solvent, and photoinitiator to be blended as adhesives were changed as shown in Table 1. In the same manner as in 2, the spread of the adhesive was evaluated, and a pellicle was prepared separately, and the adhesion strength, appearance, and durability of the pellicle film were evaluated. The results are shown in Table 1.

[0073] [Table 1]

Table 1. Adhesive formulation, characteristic values and adhesion strength of pellicle film, appearance evaluation, durability evaluation results

Example 1 Example 2 Example 3 Actual 4 Example 5 Example 6 Example 7 Example 8 Example 9 Comparative Example 1 Comparative Example 2 Comparative Example 3 Fluoro rubber g g Vinylidene fluoride 亍 trafluid 2.8 2.8 2.8 2.1 2.5 2.8 2.8 2.8 3.0 1.7 2.2 Ethylene monopropylene copolymer

Multivalent relay 2 3, 3, 4, 4, 5, 5-to Octafluoro 1, 6-

2.5 1.5 3.5 2.2 2.5 1.5 2.5 1.5 2.3 3.3 Soot Compound Zg Xanthdiol Diacrylate

2-Ethylhexyl acrylate 4 5,7 3.7 5.7 5.0 4.7 4.7

Acrylate

n-Butyl acrylate 4.7 5.7

Compound Zg

2- (Perful-born Roctil)

Contact 1.0 0.85

Etylacrylate

Arrival

Agent Butyl acetate 7.4 Solvent

Ethyl acetate 4.7 Irgacure 369 0.13 0.13 0.13 0.15 0.13 0.13 0.13 0.05 Irgacure 369 0.28 0.28

Photoinitiator g

2.2 -Jetoxycetophenone 0.13 0.13 0.13 0.15 0.13 0,13 0.13 0.05 Darocur 1 1 73 0.06 Special adhesive viscosity mPa'S 4100 3900 5700 2100 3200 3700 4000 3800 5900

Sex

Value Glass transition temperature -7 -9, -31 -4 -9, -18 -7 -6 -9. -22 -7

Adhesive width is y / min 0.S 0.8 1.1 0.7 0.8 0.8 0.9 0.9 1.5 10 or more 10 or more Inner blow bond strength / MPa 0.35 or more 0.35 or more 0.3 0.35 0.35 or more 0.35 or more 0.35 or more 0.35 or more 0.34 0.35 or more 0.2Β 0.26 Adhesive strength

External blow bond strength / MPa 0.35 0.36 0.35 0.28 0.32 0.28 0.35 0.35 0.32 0.40 or more 0.26 0.24

Result

Fruit appearance evaluation ○ ○ O ○ O ○ ○ ○ ○ ○ ○ Durability evaluation ○ 0 O o O 0 0 0 0 0 ○ ○ ○

In Examples 2, 4, 6 and 8, two tan δ peaks (= glass transition temperature) were observed. An inner blow bond strength of 0.35 MPa or more indicates that the pellicle film was broken and could not be measured.

The adhesive of the present invention has extremely good adhesive strength and spreadability as compared with conventional adhesives while having sufficient durability for practical use of the pellicle.

[0075] In Examples 1 to 9, it was possible to apply a film immediately after applying the adhesive. However, in Comparative Examples 2 and 3, it took time and labor to air-dry the solvent, and It turns out that it is inferior in spreading.

From the results in Table 1, it can be seen that the adhesive of Comparative Example 1 requires damage to the film because it requires a high temperature to be bonded. Furthermore, it took a lot of time and work to produce a pellicle.

Industrial applicability

[0076] According to the present invention, it is possible to provide an adhesive that is excellent in adhesion to a fluorine-based polymer, and that is excellent in durability against ultraviolet rays. Therefore, the paricle film is interposed between the adhesive layers. A pellicle characterized by being adhered to the pellicle frame and a method for manufacturing the pellicle can be provided.

Claims

Claims [1] Solvent-free fluoro rubber, a polyvalent (meth) acrylate compound having two or more (meth) attalyloyl groups in one molecule, and a monovalent compound represented by the following formula (1) An adhesive comprising a (meth) acrylate compound.

[Chemical 1]

HZY ⁰ヽ)

I!

0

Wherein R is a hydrogen atom or a methyl group,

1

R is a hydrocarbon group having 1 to 12 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom.

2

is there. )

[2] At least one of the polyvalent (meth) atta relay toy compound and the monovalent (meth) atta relay toy compound is a (meth) atta relay toy compound containing fluorine. The adhesive according to claim 1.

[3] The adhesive according to claim 1 or 2, wherein the polyvalent (meth) atreatoy compound is selected from the group consisting of a (meth) atalytoy compound represented by the following formula (2): Agent.

[Chemical 2]

R Ri

_H Z 丫.ヽ To ヽ (2)

0 II o II

13

[Chemical 3]

In the above formula (3), R represents an alkylene group having 2 to 4 carbon atoms, n represents an integer of 1 to 20, [Chemical 4]

—— CH ₂ ― Rf— CH ₂ —— (4)

[Chemical 5]

—— Rf 0— Rf ¹ (5) In the above formula (5), Rf ¹ represents a perfluoroalkylene group having 2 to 4 carbon atoms, and n represents an integer of 1 to 20. )

[4] Based on the total weight of the adhesive, the fluororubber is in the range of 15 to 40% by weight, the polyvalent (meth) atrelate toy compound is in the range of 5 to 40% by weight, and the monovalent ( The adhesive according to any one of claims 1 to 3, wherein the (meth) atreatoy compound is blended in an amount of 20 to 60% by weight.

[5] The adhesive according to any one of [1] to [4], wherein a photoinitiator is further blended with the adhesive.

[6] The glass transition temperature (Τ g) defined by the peak temperature of tan δ by the viscoelasticity test (measurement frequency: 1 Hz, measurement mode: tensile mode) of the cured adhesive obtained by curing the adhesive is The adhesive according to any one of claims 1 to 5, wherein the adhesive is in the range of 40 to 20 ° C.

[7] A pellicle comprising a pellicle film and a pellicle frame that supports the pellicle film, wherein the pellicle film is obtained by curing the adhesive according to any one of claims 1 to 6. The pellicle is bonded to the pellicle frame via a pellicle.

[8] A method for producing a pellicle, wherein the pellicle film and the pellicle frame are attached using the adhesive according to any one of claims 1 to 6.