JPS63234201A - Thin film body for optical use - Google Patents

Abstract

PURPOSE:To obtain a thin film body for optical use having >=80% transmittance of 300nm light by providing a solvent-soluble dicyclopentadiene ring opening polymer or the partially hydrogenated matter thereof to said body. CONSTITUTION:The ring opening polymer of the dicyclopentadiene or the hydrogenated matter thereof is a polymer having the structural unit body expressed by the formula I. In the formula, between CH and CH is indicated as to be a single bond or double bonds. This ring opening polymer is produced by using the dicyclopentadiene as a monomer and producing the polymer by a known ring opening polymn. method for cyclic olefin. The hydrogenated matter of the ring opening polymer is also produced by utilizing an ordinary hydrogenation reaction method. The thin film body for optical use, the resin material of which has excellent transparency, water resistance, heat resistance, etc., and has >=80% transmittance of 300nm rays, is thereby obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an optical thin film body, and more specifically, to a thin film body for optical use, which has excellent transparency, aqueous properties, and thermal properties, and particularly has excellent light transmittance in the short wavelength region. Between optical thin film bodies.

[Prior art] Glass or polymeric substances are generally used as the surface protective layer of optical recording materials such as compact discs, video discs, computer discs, etc.; Plastic material is preferred. In this case, the properties required of the plastic are: ■ Good optical properties such as being transparent, having high light transmittance, stable refractive index, and low birefringence, and ■ Aluminum as the plastic protective layer. , have properties such as heat deformation resistance to the extent that it can protect recording substrates such as silver-plated aluminum, and no corrosion of the substrate due to moisture absorption; It will be done.

Currently, polycarbonate, polymethyl methacrylate, etc. are used as plastics that can relatively satisfy these characteristics, but polycarbonate has a high glass transition temperature (Tg) and has good heat resistance, but has poor moisture absorption. It is somewhat high, tends to cause birefringence, and has hydrolyzability due to its molecular structure. On the other hand, polymethyl methacrylate is transparent and has excellent optical properties such as a low birefringence, but its high hygroscopicity causes corrosion of the base and warping of the disk surface due to changes in size and shape. . Also,
Since Tg is also around 100°C, deformation at high temperatures cannot be ignored.

Furthermore, although photolithography is currently the mainstream semiconductor microfabrication technology, semiconductor elements are also changing from LSI to VL.
The limit of photolithography is said to be 2 to 3 microns due to high density SI, and the development of ultra-fine processing technology is progressing, and far ultraviolet rays are attracting attention along with electron beams and X-rays. Conventionally, in photolithography for manufacturing LSI, the light source is ultraviolet rays (350 to 450 nm).
), but in recent years, technology has been developed to expose ultraviolet light with a short wavelength of about 300 nm or less for the production of highly integrated wafers and chips. However, conventional optical plastics, such as
Polycarbonate, polymethyl methacrylate, etc.
The light transmittance at 300 nm was as low as 50% or less, and it could not be used for applications such as photoresist protective films in these short wavelength regions.

Problems to be Solved by the Invention The present inventors conducted extensive research in order to obtain an optical thin film body that solved these problems, particularly an optical thin film body with high light transmittance in the short wavelength region. A resin material made of a ring-opened polymer of pentadiene or its partially hydrogenated product has excellent transparency, water resistance -1 heat resistance, etc.
The present invention was completed by discovering that it is possible to provide an optical thin film having a light transmittance of 80% or more.

Means for Solving the Problems The gist of the present invention resides in an optical thin film body comprising a ring-opening polymer of dicyclopentadiene or a partially hydrogenated product thereof.

Hereinafter, the constituent elements of the present invention will be explained in detail.

(Dicyclopentadiene and its hydrogenated product) The ring-opening polymer of dicyclopentadiene or its hydrogenated product used in the present invention is a polymer having a structural unit represented by the following formula [I]. It is a known substance. (For example, Tokuko Sho 57
-17883, JP-A No. 53-111399, JP-B No. 58-43412, etc.) (Left space below) However, where the formula is a single bond or a double bond, this ring-opening polymer can be used as a monomer. It can be produced by a known ring-opening polymerization method for cyclic olefins using dicyclopentadiene. Further, a hydrogenated product of this ring-opened polymer can also be obtained using a conventional hydrogenation reaction method.

(Polymerization catalyst) The ring-opening polymer of dicyclopentadiene is produced by the usual polymerization method of fulbornenes, but as a polymerization catalyst, for example, platinum such as ruthenium, rhodium, palladium, osmium, iridium, platinum, etc. These catalyst systems include metal compounds (for example, Japanese Patent Publication No. 46-14910), or systems of transition metal compounds such as titanium, sodium, molybdenum, and tungsten, and organometallic compounds of groups 1 to 2 of the periodic table. may be combined with a third component (for example, Japanese Patent Publication No. 41-20111).

JP 57-17883, JP 57-61044, JP 54-86600, JP 58-12772
No. 8 etc.).

The polymerization catalyst is not particularly limited as long as it is a metal compound capable of ring-opening polymerization of dicyclopentadiene, but preferably,
A catalyst system containing a transition metal compound and an organic metal, or a catalyst system containing molecular oxygen, alcohol, ether, peroxide, carboxylic acid, acid black hydrate, acid chloride, ester, ketone, nitrogen-containing compound, sulfur-containing compound, etc. It is a catalyst system that combines a third component such as a halogen compound, molecular iodine, and other Lewis acids.

(Solvent) Ring-opening polymerization can be carried out without using a solvent, but it can also be carried out in an inert organic solvent.

Specific examples include aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as n-pentane, hexane, and heptane, alicyclic hydrocarbons such as cyclohexane, methylene dichloride, dichloroethane, dichloroethylene, and tetrachlor. Examples include halogenated hydrocarbons such as ethane, chlorobenzene, dichlorobenzene, and trichlorobenzene, and two or more of these may be used in combination.

(Union Temperature) IJF! There are no particular restrictions on the temperature conditions for ring polymerization, but any temperature from -20''C to 100C is usually selected.

(Polymerization Pressure) The polymerization pressure condition is usually preferably selected from the range of θ to 50 Kg/C.

(Ring-opening polymer) The intrinsic viscosity of the polymer is generally 0. O1~20di/gr
, preferably 0.1 to 5 dll/gr.

In addition, when polymerizing, chain monoolefins, chain non-conjugated diolefins, cycloolefins, etc. are added.
It is also possible to adjust the molecular weight and physical properties. As a specific example,
Butene-1, Pentene-1, Hexene-1, Octene-1
1, butene-2, pentene-2,1,4-hexadiene, cyclopentene, norbornene, and the like.

(Hydrogenation) The partially hydrogenated product used in the present invention is obtained by partially hydrogenating the ring-opened polymer as described above to saturate a portion of its double bonds. From an economic standpoint, the hydrogenation rate is preferably less than 50%.

This hydrogenation reaction of the ring-opening polymer is carried out by a conventional method [see, for example, Japanese Patent Publication No. 58-43412]. As the hydrogenation catalyst, any catalyst commonly used in the hydrogenation of olefin compounds can be used. Examples include, but are not limited to, the following: Examples of heterogeneous catalysts include solid catalysts in which nickel, palladium, platinum, or these metals are supported on a carrier such as carbon, silica, diatomaceous earth, alumina, titanium oxide, etc., such as nickel/silica, nickel/diatomaceous earth, palladium/
Examples include carbon, palladium/silica, palladium/diatomaceous earth, palladium/alumina, and the like. In addition, homogeneous catalysts include catalysts based on metals from group Ⅰ of the periodic table, such as nickel naphthenate/triethylaluminum, cobal(octate)/n-butyllithium, nickel acetylacetonate/triethylaluminum, etc. Examples include those consisting of Ni, Co compounds and organometallic compounds of Group 1-m metals of the periodic table, or Rh compounds.

The hydrogenation reaction is carried out homogeneously or heterogeneously depending on the type of catalyst under a hydrogen pressure of 1-150 atm at a temperature of 0 to 200°C, preferably 20 to 150°C. The hydrogenation rate can be arbitrarily adjusted by changing hydrogen pressure, reaction temperature, reaction time, catalyst concentration, etc.

(Optional Components) In the present invention, a stabilizer such as an ultraviolet absorber may be added to the ring-opening polymer or its partially hydrogenated product as long as the transparency does not deteriorate. It is also possible to mix and use other polymers that are compatible with this.

(Forming method) There are various methods for molding the dicyclopentadiene ring-opening polymer or its partially hydrogenated product used in the present invention into an optical thin film. Because it is soluble in

It can be molded by a molding method such as a casting method or a spin-neat method. In general, dicyclopentadiene resins have poor thermal stability, and tend to be colored during molding in molding methods that require heating, such as melt extrusion molding. However,
If a film is formed without heating by a casting method or a spin cord method, a transparent fi1 film body without coloration or deterioration can be obtained. Furthermore, the obtained thin film has a high light transmittance of 80% or more at a wavelength of 300 nm, which is an advantage that other transparent films do not have.

Examples of solvents that can be used in the cast molding method include aromatic hydrocarbons such as benzene, toluene, and xylene;
- Aliphatic hydrocarbons such as pentane, hexane, heptane, alicyclic hydrocarbons such as cyclohexane, methylene dichloride, dichloroethane, dichloroethylene, tetrachloroethane.

Examples include halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, and trichlorobenzene; two or more of these may be used in combination, and the concentration of the resin solution may be adjusted as appropriate depending on the desired thickness of the thin film body. You can leave the room, but
Usually, a range of 0.1 to 50% by weight is preferred.

Solvents that can be used in the spin code method have a boiling point of 16
An organic solvent having a temperature of 0 to 250°C, preferably 30 to 230°C, such as aromatic hydrocarbons such as benzene, toluene, and xylene, alicyclic hydrocarbons such as cyclohexane,
Examples include halogenated hydrocarbons such as methylene dichloride, dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene, dichlorobenzene, and trichlorobenzene, and two or more of these may be used in combination.

The concentration of the resin solution is 0.01 to 50% by weight, preferably 0.5 to 20% by weight, and the number of revolutions is 1.

10-10. OOOrpm, preferably 100-6, O
OOrpm.

(Applications) - The obtained molded product can be used as a surface protective film for optical recording materials such as compact discs, video discs, and computer discs, as well as a protective film for photoresists, taking advantage of its properties such as transparency, moisture resistance, and heat resistance. It can be used as a carrier film for photoresist, etc. In particular, since the optical thin film body of the present invention has a high light transmittance of 80% or more at 300 nm,
It is useful as a protective film for photoresist in ultrafine processing technology of photolithography.

EXAMPLES The present invention will be explained in more detail with reference to Examples and Reference Examples below.

Reference Example 1 400 ml of dehydrated and purified toluene and 100 mJl of dicyclopentadiene were charged into a 1.0-liter autoclave that had been thoroughly dried and purged with nitrogen.
Hexene 0.37 mmol.

0.370 mmol of tungsten hexachloride and 0.74 mmol of tetraethyltin were added and polymerized at room temperature for 5 hours.
After the reaction was completed, 5 mJ1 of monoethanolamine was added, and 2,6-ditertiarybutylphenol (B
The reaction solution was poured into a sliding door containing HT)Ig and a large amount of methanol to precipitate the polymer, followed by vacuum drying to obtain a toluene-soluble polymer (Polymer A). The yield was 62%. As a result of proton NMR analysis of the obtained polymer, δ
= 5.0 to 5.4 ppm, absorption due to olefin double bond protons was observed, and the absorption intensity almost matched the theoretical value (33.3%) for the absorption intensity derived from all protons. It was confirmed that ring-opening polymerization occurred. The glass transition temperature ('D
SC) was 129°C, and the intrinsic viscosity measured in toluene at 25°C was 0.90 d/g.

Reference Example 2 40.0 g of the cyclohexane solution (concentration 5% by weight) of Polymer A obtained in Reference Example 1 and 2 g of palladium carbon were placed in the autoclave No. 11, and after purging the inside of the reactor with hydrogen, the temperature was raised to 80°C with stirring. When the temperature inside the heated zero reactor became constant, the hydrogen pressure was increased to 70 atm, and the hydrogen was reacted for 3 hours while replenishing the hydrogen consumed by the zero reaction.Then, after the catalyst in the reactant was passed through the mouth, a large amount The reaction product was precipitated in a mixed solvent of 7 setone-isopropyl alcohol (1:1), filtered, and dried.

For the product obtained, proton N M R (7) M
Analysis was carried out, and the hydrogenation rate was calculated from a comparison of the values of absorption (δ=5.0 to 5.4 ppm) due to olefin double bond protons, and was found to be 28%.

Reference Example 3 A polymer (Polymer B) was obtained by carrying out the reaction in the same manner as in Reference Example 1 except that the molecular weight regulator 1-hexene was not used. The yield was 65%. The intrinsic viscosity of the obtained polymer measured in toluene at 25° C. was 1.35 db/g.

Reference Example 4 Polymer B obtained in Reference Example 3 was hydrogenated in the same manner as in Reference Example 2. The hydrogenation rate of the obtained product was 30%.

Example 1 The polymers obtained in Reference Examples 1 to 4 were dissolved in toluene to form a 5% by weight solution. After pouring this solution onto a glass plate,
The solvent was removed to obtain a coating film. Next, the glass plate was immersed in water and the film was peeled off by applying ultrasonic vibrations to obtain a film with a thickness of 15 km. The light transmittance of these films is , 30
It was 83-85% at 0 nm.

The physical property values of the obtained film are shown in Table 1 below.

Table 1 shows the physical properties of films obtained by similar molding of polycarbonate (PC) and polymethyl methacrylate (PMMA).

Example 2 The polymer obtained in Reference Example 1 was made into a 51% by weight toluene solution, and this solution was spin-neat on a glass plate at 800 revolutions (rpm).Then, the solvent was removed and a coating with a thickness of 5 meters was prepared. A membrane was obtained. The light transmittance of this coating film at a wavelength of 300 nm is 83%, the Tg is 129°C, and the water absorption is 0.03%.
, the tensile strength was 520 K g/c rn', and the elongation at break was 7%.

From the above examples, it can be said that the thin film body of the present invention has sufficient performance as an optical thin film body.

Effects of the Invention The present invention provides excellent transparency, water resistance, and thermal properties.
It is possible to obtain an optical thin film having good light transmittance particularly in a short wavelength region, and this thin film can be applied to many optical fields such as photolithography.

Claims (1)

[Claims] Consists of a solvent-soluble dicyclopentadiene ring-opening polymer or its partially hydrogenated product, and has a light transmittance of 80% at 300 nm.
The above optical thin film body.