JP3101346B2 - Polyvinyl butyral thin film composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to projection printing .
ction printing) relates thin film molded from a specific polyvinyl butyral resin used in, the thin film is deep UV region further in and near U
It is also applicable to the V region . The present invention relates to castable compositions of the thin film for a film for manufacturing. In particular, the present invention relates to polyvinyl <br/> butyral thin film having excellent Ru optical properties and lower absorption properties of polyvinyl butyral thin film existing. The present thin film has excellent nitrogen-introducing molding strength and Young's modulus.

[0002]

BACKGROUND OF THE INVENTION Field of the projection baking, particularly in the manufacture of the semiconductor industry as well as integrated circuits, the use of thin film for protecting a photomask from particles in the air, the more the demand because it has a number of advantages Is growing. Projection printing
The use of thin film in only, e.g., on December 26, 1978 issued to sea (Shea) et al U.S. Pat. No. 4,131,363, as well as 1973 of Electro chromatography Opti local system design Corp Inc. magazine It is described in Chapter 370, pages 362 pages article entitled by published Supibakku (Spivack) et year "evaluation of parylene and other thin film as a beam splitter (beam splitter)." Such use in projection printing reduces mask and printing defects, prolongs mask reticle life, reduces downtime by coordinators, and improves mask quality. And increase the efficiency of production. Prior art are employed have your materials and thin film materials suitable to the available films produced as a film of polyoxyethylene terephthalate, include polymeric films nitrocellulose and parylene.

[0003]

The object of the invention is to be Solved by the movies as a thin membrane film
The polymer film of the prior art other than the polyvinyl butyral useful for shooting printing apparatus has been severely limited in their usefulness. For example, such polymers - the thin film near UV region of the film (wavelength: 340 From 436n
m) and was somewhat effective in the mid- UV range (wavelength: 280 to 340 nm), but none was
Absolutely in the far UV range (wavelength: 200 to 280 nm)
Could not be used . Thin membrane film of the prior art, the near-UV
Although quite effective in frequency and mid UV regions showed no effective optical transparency in the deep UV region <br/>, therefore, your Keru utilized far UV region <br/> was impossible.

[0004] In addition, In addition, the thin membrane film of the prior art,
Have been found to have efficacy in the near UV range and mid UV regions, their performance is not necessarily satisfactory. Among the many factors that result in a diminished effect in these UV regions , their light transmission is not substantially 100% at the projection wavelength, generally 99%.
% Or less. In addition, the argument of the thin membrane film
Tensile strength is typically between 3000 and 5000 psi (210
ranges from kgf · cm-2 350kgf · cm -2), are <br/> film high tensile strength is great hopes to extend the life of the thin membrane film. Further, the rate of adverse light scattering in the prior art thin film films is generally less than 3%.
The range was 0.3% at 65 nm (nanometer). At present, a film having a low light scattering rate is demanded.
Further, the thin membrane film of the prior art, the percent d Taro training, i.e., difference between the maximum and minimum transmission, has only about 18%, in order to increase the average transmittance of the thin film, such as possible It is very advantageous to reduce significant etaloning.

Accordingly, effective in the far UV region, <br/> physician there within is expectation thin membrane film is greatly having similar or better performance and (or) characteristic as that in the near UV region. further. Effective in all UV ranges ,
During or as compared to performance and (or) the characteristics of the materials used in the thin membrane film of the prior art in the near UV range,
Overall, or partially improved thin membrane film is expectation.

[0006] All of the polyvinyl butyral resin film can not than a has optical properties necessary as a thin film for projection baking is well known. The polyvinyl Buchira <br/> Le thin film does not contain impurities which interfere with the transmission of light is desired. A common problem in a polyvinyl butyral thin film, before
Serial in the presence of a carbonyl group that is considered to be obtained from vinyl acetate et al are observed in substance material. Furthermore, in order to form a thin <br/> film, the solvent system used in conjunction with polyvinyl butyral resin previously, it was not become the most effective solvent system to minimize the degree of impurities. Surprisingly, Applicants have found that diethylformamide containing a carbonyl group is an effective solvent.

[0007] The thin film, casting, float calibration
The usual means of sting or spinning
Therefore, it can be manufactured. Typically, the mixture of polymer and solvent will comprise from about 5% to 30% by weight of the polymer. It is also possible to add leveling agents such as shea <br/> Ricoh down fluid.

[0008] pourability <br/> solution of polyvinyl butyral of the present invention, Ru is produced depending on the thin film manufacturing method. Usually fixed
Body matter weight of 15% of the casting from a 10% ratio solution, to produce a film having a thickness of about 1.2 to 2.0 microns, which is molded by a rotary spinning process in 3000rpm 2000.

[0009] Ill E. Wa
U.S. Patent No. 4,482,591, issued to rd) are each less than 13%, less than 2%, is formed from 88%, or more specific hydroxy, particular polyvinyl butyral resin containing acetate and butyral that polybibenzimidazole
Those related to sulfonyl butyral thin film. The patent discloses in particular 2-ethoxyethanol and tetrahydrofurfuryl alcohol or usage of the polyvinyl butyral obtained from a solvent system consisting of methyl ethyl ketone.

An object of the present invention is effective Te far UV region smell <br/>, to provide a thin membrane film having the same or better performance and (or) characteristics as in the middle or near UV region It is in. Furthermore, comparison object of the present invention is effective in all the UV range, the performance of the medium or material used for the thin membrane film of the prior art <br/> Oite in the near UV region and (or) properties to, to provide a thin membrane film Ru whole or partially Yu.

[0011]

Means for Solving the Problems The specific polyvinylidine that were considered not suitable for use as a thin membrane film
Le butyral polymer film, certain Te solvent system odor <br/>, found to exhibit excellent properties than conventional polyvinyl butyral thin film such as the disclosed in U.S. Patent No. 4,482,591 Was . These thin films are near, middle and
May be used for projection baking in the far UV region, comparable to conventional polyvinyl where available heretofore, or over high light transmission, with the performance and (or) physical properties. Furthermore, dimethylformamide or diethylene glycol dimethyl ether: Thin film films molded from pourability solution of a specific polyvinyl butyral resin in (diglyme diglyme) is a film exhibiting a more excellent light transmittance in the far UV region .

Specifically, according to the present invention, the general formula

Embedded image (Where x is 0.18 or more, y is 2.5 or less and z is 0.80 or less) and is molded from a polyvinyl butyral resin represented by the following formula: A thin film for use in projection printing characterized by comprising a film is provided.

The invention according to claim 4, "the polybibenzimidazole
2. The film according to claim 1, wherein the nilbutyral resin has a specific gravity of at least 1.100.
It is. Further, according to the present invention, the general formula

Embedded image (X is 0.18 or more in the formula, y is 2.5 or less, and z is 0.80 or less value) and port <br/> polyvinyl butyral resin represented by dimethyl formamide or <br/> castable solution characterized in that it consists solvent consisting of diglyme is provided.

[0014]

[Action] With this configuration, these thin films may be used for projection baked in the UV range of all forms, hitherto comparable to conventional polyvinyl where available, or over high light transmission, performance and (or) Has characteristics. Furthermore, dimethylformamide or diethylene glycol dimethyl ether: Thin film films molded from pourability solution of a specific polyvinyl butyral resin in (diglyme diglyme) is a film exhibiting a more excellent light transmittance in the far UV region .

[0015]

EXAMPLES The present invention by thin-film is formed to have a better performance characteristics in port <br/> solvent system of polyvinyl butyral resin and dimethyl formamide or Axis rim having the following general formula.

[0016]

Embedded image In the above general formula, x is 0.18 or more, y is 0.0 to 2.5, and z is 0.80 or less. In the polyvinyl Bed <br/> butyral, hydroxyl-containing weight of the polymer expressed as percent polyvinyl alcohol, 18%
Or more, usually in the range from 18% 22%, including the amount of acetate expressed as percent polyvinyl butyral it is at least 80%. That is, x, y, and z are as described above, but preferably, x is equal to or less than 0.
18 to 0.22, y is 0.00 to 2.5, z is 0.
80 or less. It has been discovered that polymers having x of about 0.19, y of about 0.3 to 1.0, and z of about 0.80 are suitable. Suitable polyvinyl <br/> butyral satisfying the criteria, Scientific Polymer Products issued NY Ontario City "Technical Bulletin" 19
87 2011 Edition August catalog is # 381 th polyvinyl butyral <br/> Lumpur resin. Suitable polyvinyl butyral of the present invention has a weight average molecular weight of specific gravity and 50,000 of at least 1.100 150,000.

[0017] Advantageously, the poly-bi, which is used in the present invention
Sulfonyl butyral resin, free of impurities containing substantially carbonyl group. Polyvinyl butyral resin utilized is a free of reliably impurities, they are preferable to wash the resin with a suitable equivalent non solvent.

In the present invention, it is more important to utilize dimethylformamidine DOO or diglyme to shape the casting solution. The dimethylformamide or jig Li
Arm is hydraulic - Product Catalog (Technical Bulletin) State St. Louis Monsanto Co. BUTVAR B-90 and polyvinyl <br/> butyral resin of the 6070D B-
While utilizing 98 provides thin films with excellent spectral properties, uniform thickness and surface uniformity,
Prior to the present invention has been considered to be unable to produce a thin film. A preferred solvent is dimethylamide.

The following examples illustrate embodiments of the present invention. However, these examples are provided only for illustrating the present invention and do not limit the conditions and scope of the present invention. Unless otherwise stated, all figures are given in weight percent.

Example 1 A. Casting solution was prepared by dissolving polyvinyl butyral resin 12.25g purified in dimethylformamidine bets 100 ml. B. According to the method described creation U.S. Patent No. 4,449,231 thin film, 5 inches (13c as an example a casting solution in the A
m) onto a polished flat substrate, such as a clean and dry silicon wafer, and remove the substrate from about 10 to 40
Fill with ml of solution. The substrate is spun at 2000-3000 rpm for 1 minute with a Hetwe-EC101 series spinner to form a uniform film. Release the substrate in a greenhouse overnight to evaporate the solvent.
Place . The y of the polymer was 0.01. Release the cured film.

C. Similar results, even jig rim will be obtained. The treatment was performed 5 times at a spinning speed of 2800 rpm using a spinner. As a result, a film having the following thickness (micron) was obtained. 1. 1.800 2. 1.790 3. 1.806 4. 1.804 5. 1.796

Example 2 According to the procedure of Example 1, (A) cellosolve (cellos) was used.
olve), (B) 60% of cellosolve and 40% dimethylformamide (DMF) and (C) 11.25% of the purified polybibenzimidazole in 100% dimethyl formamide
Film was produced in 10.75% of the purified polyvinyl <br/> butyral resin at nil butyral resin.

The total polyvinyl butyral resins utilized was the product of Scientific Polymer Products catalog number 381. UV / VIS P.I.
E. FIG. The results of the light transmission test of the Lambda 6 spectrometer were as follows. λ (lambda) sample 300 270 250 240 230 210 (A) 100%% / t 99.0 98.1 97.5-96.1 94.0 Cellosolve (1.96 micron) (B) 60/40% / t 99.3 98.5 98.3 97.4 96.4 93.9 (C) 100% DMF% / t (1.36 microns) 99.4 99.0 98.5 98.2 97.3 95 .2

The Bausch and Lomb between Example 3 (A) and thin film in Example 1 (B) thin film produced from BUTVAR B-79 of U.S. Pat. No. 4,482,591 Example 2 (Baus
ch & Lomb) Comparative studies were performed using Spectronic 2000. Cellosolves spectral grade from the solvent as Aldrich (Aldrich) Corporation is used, SiO2 1 cm cuvettes (cuvettes) was used in 5% w / w solution holding of each polymer. Baseline is about 265
nm. The following results were obtained by the experiment. Sample Abs. (Λ = 265) λ-cut-off A 0.18 au None (peak-221) (Abs.-0.58) B up to 0.38 au 236 (Abs. At about 1.0 lambda) Note) au = Absorption unit

[0025]

As described above, in the present invention, the present invention is effective in the far UV range , and has the same or higher light transmittance, good performance and good performance as those in the middle or near UV range. or) characteristics can be provided a thin membrane film having. Moreover, be effective in all the UV range, medium <br/> or compared to the performance and (or) the characteristics of the prior art materials used in thin film film in the near UV range, the whole or partial an excellent effect that it is possible to provide a thin membrane film Ru Yu on.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI // C08L 29:14

Claims (9)

(57) [Claims] (1) a compound represented by the general formula : (Where x is 0.18 or more and y is 2.5 or less)
And z are 0.80 or less).
It consists of a film molded from vinyl butyral resin.
Film used for projection printing
M 2. The method according to claim 1, wherein x is 0.18 to 0.22 and y is 0.
The thin film according to claim 1, wherein 01 to 2.5 and z are 0.80. 3. The method according to claim 1, wherein x is 0.19 and y is 0.3-1.
2. The method of claim 1, wherein 0 and z are 0.80.
The thin film according to the above. 4. The thin film according to claim 1, wherein the polyvinyl butyral resin has a specific gravity of at least 1.100. 5. A compound represented by the following general formula : (Where x is 0.18 or more and y is 2.5 or less)
And z are 0.80 or less).
Livinyl butyral resin and dimethylformamide or
Casting characterized by comprising a solvent consisting of diglyme
Solution . Wherein said solution is according to claim 5, characterized in that it comprises 5 to 30 wt% of polyvinyl butyral
Castability solution . Wherein said solution, pourability solution of claim 5, wherein the consist 10-15 wt% of polyvinyl butyral. 8. The casting solution according to claim 5, wherein the solvent is dimethylformamide. 9. The castable solution according to claim 5, wherein the solvent is diglyme .