JPH07257539A - Container and storage method for radiation-sensitive composition - Google Patents

Abstract

PURPOSE:To obtain a container for radiation-sensitive compositions, which is excellent in storage stability of radiation-sensitive compositions and easy to handle after use, by a method wherein at least a layer, other than an innermost layer, is made of resin containing a light shield agent efficient for photosensitivity of the radiation-sensitive compositions and the innermost layer is made of polyolefin resin. CONSTITUTION:Polyolefin resin used for an innermost layer 2 of a container is not added with light-shield agent or metallic compounds that are possibly eluted by solvent. On the other hand, resin used for a light-shield layer can be the same resin as that used for the innermost layer, the same kind of resin different in density, molecular weight, etc., or polycarbonate, polystyrene, polymethyl metacrylate, etc. When used to store a radiation-sensitive composition, the container is excellent in storage stability with less change in photosensitivity of the radiation-sensitive composition after storage, so that the container is very useful to store the radiation-sensitive composition having a high resolving power.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates generally to containers and methods for storing radiation sensitive compositions which are sensitive to radiation. More particularly, it relates to a container and a method for storing a radiation-sensitive composition sensitive to light of 150 to 500 nm.

[0002]

2. Description of the Related Art In recent years, microfabrication technology typified by integrated circuits has been increasingly improved in machining accuracy. Taking dynamic random access memory (DRAM) as an example,
At present, submicron processing technology has been established as mass production level technology. For this sub-micron processing, g-line (436 nm), i-line (365 nm), KrF
A photolithography technique using short-wavelength light such as excimer laser light (248 nm) is used. The radiation-sensitive compositions used in these have also been improved, and various high-performance radiation-sensitive compositions have been proposed (JP-A-59-45439, JP-A-60-238829, JP-A-62-136637, and JP-A-62-1336637, JP-A-62-153950, JP-A-62-269136, JP-A-4-136860, JP-A-4-136941).

Conventionally, a radiation-sensitive composition is capable of preventing deterioration due to irradiation of light in a region in which the radiation-sensitive composition has sensitivity (which includes the above-mentioned light having a short wavelength), and is capable of visually recognizing the inside. Because of their preference, brown glass bottles have typically been used as storage containers. Further, it is said that if a glass bottle is used as a storage container as it is, the storage stability is lowered, and it has been proposed that the bottle needs to be heat-treated in advance with sulfur dioxide in order to maintain the storage stability (Japanese Patent Laid-Open No. Sho 5).
9-35043).

However, the glass bottle is a nonflammable material,
There is a problem that it is heavy and fragile, and the used container cannot be discarded as it is because the radiation-sensitive composition remains, and it takes time and effort to dispose of it after cleaning, and improvement has been demanded. The present inventor has studied the use of a colored synthetic resin bottle molded from a synthetic resin containing a light-shielding agent, but in this case, the light-shielding agent causes some change due to the action of the filled radiation-sensitive composition. Therefore, it was found that the storage stability of the radiation-sensitive composition is adversely affected.

On the other hand, in recent years, finer patterns have been processed by using the high-performance radiation-sensitive composition as described above. Under such circumstances, during the storage period of the radiation-sensitive composition, if a few fine particles are generated in the composition, when a pattern is formed using the radiation-sensitive composition, the radiation-sensitive composition is developed. There is a problem that fine particles remain in the part where the object is removed and the resolution is lowered. Further, during storage of the radiation-sensitive composition, its sensitivity changes (sensitivity increases or decreases), which causes a problem that stable fine processing of line width cannot be performed. There was a strong demand for a solution. As a conventional method for improving the storage stability of a radiation-sensitive composition, a method of incorporating a monooxymonocarboxylic acid ester as a coating solvent in the radiation-sensitive composition (Japanese Patent Laid-Open No. 62-
123434) and a method of incorporating alkyl pyruvate (JP-A-4-36752). However, in any of these methods, since another compound is added to the radiation-sensitive composition, there is a disadvantage caused by the addition, so that a sufficient solution cannot be obtained.

On the other hand, in a semiconductor element, it is known that if Si crystal or the like is mixed with a metal element such as Na or Fe, the electrical characteristics are deteriorated and the operation reliability is deteriorated.
The amount of metal impurities mixed in the radiation-sensitive composition used for photolithography is also required to be low, for example, 16
In the MDRAM, a mixing amount of 50 ppb or less is required, and it is considered that a further lower level of the mixing amount of metal impurities is required with the high integration in the future.

Usually, soda-lime glass is used in the brown glass bottles used for filling and storing the radiation-sensitive composition, and the composition contains a large amount of metal components as shown below. Along with the reduction of the amount of metal impurities mixed in the sensitive composition, the trace amount of metal components eluted from the glass bottle over time has become a level that cannot be ignored.

[0008]

[Table 1]

The above-mentioned technique of sulfur dioxide treatment is a technique of solubilizing the metal component on the surface of the bottle and then washing and removing with water after the treatment to reduce the metal component eluted with time. The components could not be completely removed, and it was not a complete solution. In principle, it was assumed that the resin components would be used instead of glass bottles to eliminate the metal components that would be eluted.However, the light-shielding properties, the visibility of the content liquid, the storage stability of the content liquid, etc. were all at the same time. There is nothing to satisfy, and there has been a demand for a resin bottle that can satisfy these requirements.

[0010]

DISCLOSURE OF THE INVENTION The present inventor has made various studies on the mechanism of impairing storage stability due to fine particles and the like generated during the storage period of the radiation-sensitive composition, and as a result, has been put to practical use. It has been found that there is a significant relationship between the transmission of light of a certain wavelength in a brown glass bottle and the storage stability of the radiation sensitive composition.

FIG. 2 shows the spectral sensitivity of a typical radiation-sensitive composition (naphthoquinone diazidonovolac type resist). On the other hand, FIG. 3 shows the spectral transmittance of a commercially available brown glass bottle that has been conventionally used. As is clear from these figures, the brown glass bottle has good absorption of light having a short wavelength of less than 500 nm, and it seems that it has a light-shielding property which is apparently sufficient for the spectral sensitivity of the radiation-sensitive composition. However, brown glass bottles are highly transparent to light above 500 nm, for example about 30% and about 50% for light with wavelengths of 550 nm and 600 nm.

According to the study by the present inventor, the radiation-sensitive composition has a high sensitivity in that the radiation-sensitive composition does not have a spectral sensitivity but a reduction in transmitted light of 500 to 600 nm, particularly about 550 to 600 nm. It was found to be important for improving the storage stability and maintaining the stability of sensitivity, and filed a patent application first (Japanese Patent Application No. 5-229114).

However, as a result of the subsequent examination, it was found that, particularly in a radiation-sensitive composition containing an organic solvent, particles may be generated by long-term storage depending on the type of resin used in the container. The inventors have found that the use of a polyolefin resin as the resin for the innermost layer can avoid the generation of particles, and have reached the present invention.

An object of the present invention is to provide a container for a radiation-sensitive composition which is light and hard to break. Another object of the present invention is to have a sufficient light-shielding property with respect to the spectral sensitivity region of the radiation-sensitive composition, and without causing a change in the sensitivity of the radiation-sensitive composition, with good storage stability, Moreover, it is to provide a container for a radiation-sensitive composition whose contents can be visually recognized.

Still another object of the present invention is to provide a container for a radiation sensitive composition, which is easy to treat after use. Still another object of the present invention is to provide a container for a radiation-sensitive composition in which the metal component is substantially not eluted from the container during storage. Further, the present invention provides a method of storing a radiation sensitive composition.

[0016]

The present inventor has conducted various studies based on the above-mentioned findings in order to solve the above-mentioned problems, and as a result, a radiation-sensitive composition composed of a resin layer having a specific multilayer structure. The present invention has been completed by finding that the above object can be achieved by a product container. That is, the gist of the present invention is a container composed of multiple resin layers, wherein the innermost layer of the resin layer is composed of a resin containing no light-shielding agent, and at least one layer other than the innermost layer is a radiation-sensitive composition. A container made of a resin containing a light-shielding agent having a light-shielding property with respect to the light sensitivity of an object, wherein the resin of the innermost layer is a polyolefin resin, and a container for a radiation-sensitive composition, There is a storage method for storing the radiation-sensitive composition in the container.

The present invention will be described in detail below. The radiation-sensitive composition contained in the container of the present invention is a uniform solution in which a known radiation-sensitive component and the like are dissolved in a solvent. Depending on the type of the radiation-sensitive component, a photocrosslinking radiation-sensitive composition such as a vinyl cinnamate type or a polyisoprene cyclized rubber type (for example, Journal of Organic Synthetic Chemistry, Vol. 42, Vol. 1).
No. 1, page 979), a radiation-sensitive composition obtained by dissolving a 1,2-quinonediazide compound and an alkali-soluble resin in an organic solvent (for example, Journal of Organic Synthetic Chemistry, 42).
Vol. 11, p. 979, JP-A-62-136637, JP-A-62-153950, etc.) and a radiation-sensitive composition by polymerization or depolymerization by the action of an acid or a base generated by light irradiation. And a so-called chemically amplified radiation-sensitive composition (for example, described in JP-A-59-45439, JP-A-4-136860, JP-A-4-136941) and the like.

The radiation-sensitive composition dissolved in a water solvent is disclosed in JP-A-60-238829 and JP-A-62-2.
Examples of the radiation-sensitive composition include a water-soluble radiation-sensitive compound such as 69136 as a main component. Further, these radiation-sensitive compositions can be classified into two types of negative-type and positive-type radiation-sensitive compositions according to the relationship between the image formed and the exposed portion, but the present invention basically It is commonly applicable to radiation-sensitive compositions.

Examples of the radiation-sensitive composition include polyvinyl cinnamate resin produced from polyvinyl alcohol and cinnamic acid chloride, and cyclized rubber resin mainly containing 1,4-cis-polyisoprene. The thing which melt | dissolved in the organic solvent is mentioned. If necessary, a photocrosslinking agent such as 4,4'-diazidochalcone or 2,6-bis (4'-azidobenzylidene) cyclohexanone may be added.

Used in the above radiation-sensitive composition 1,
Examples of the 2-quinonediazide compound include 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone and 2,2', 3. , 4, 4 '
-Pentahydroxybenzophenone, 2,2 ', 3,
4,5'-pentahydroxybenzophenone, 2,
Such as bisphenol A produced from polyhydroxybenzophenones such as 2 ', 3,4,6'-pentahydroxybenzophenone, polyhydroxybenzoic acid esters such as ethyl gallate, phenols and aldehydes and / or ketones Of polyphenols or novolac resins and other compounds having phenolic hydroxyl groups
2-benzoquinonediazide-4-sulfonic acid ester,
Examples thereof include 1,2-naphthoquinonediazide-4-sulfonic acid ester and 1,2-naphthoquinonediazide-5-sulfonic acid ester.

The alkali-soluble resin used in the above radiation-sensitive composition means phenol, o-, m-,
Or phenols such as p-cresol, o-, m-, or p-ethylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,5-xylenol, resorcinol, catechol, pyrogallol And novolak resins obtained by polycondensing aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and / or ketones such as acetone, or acrylic acid derivatives, cinnamic acid derivatives, styrene derivatives, maleic acid derivatives, etc. as monomers. Examples thereof include polymers obtained by polymerizing these.

Examples of the above radiation-sensitive composition include a resin having an acid labile group such as poly (pt-butoxycarbonyloxystyrene) and a light such as triphenylsulfonium hexafluoroarsenate. Composed of a combination of compounds that generate acid upon irradiation,
A radiation-sensitive composition (Japanese Patent Laid-Open No. 59-45439) in which a light irradiation part is solubilized or insolubilized in a developing solution can be used.

Further, as another example of the above radiation sensitive composition, novolak resins or polyvinylphenols obtained by polycondensing the same phenols and aldehydes as those described above, and alkoxymethylated urea and methyl halide are used. A radiation-sensitive composition comprising a combination of compounds such as triazines, halogenated hydrocarbons, halogenated oxadiazoles, etc., which generate an acid upon irradiation with light, and the light-irradiated portion becomes insoluble in a developing solution (JP-A-4-136860). , JP-A-4
-136941) and the like.

Examples of the organic solvent used in the radiation-sensitive compositions are the aromatic hydrocarbons such as toluene and xylene, acetic acid esters such as ethyl acetate, and mono- or dialkyl glycols such as ethyl cellosolve. Ethers, mono- or dialkyl ethers of mono- or dipropylene glycol such as propylene glycol monomethyl ether, alkyl cellosolve acetates such as ethyl cellosolve acetate, carbonic acid esters such as ethylene carbonate and diethyl carbonate, lactones such as γ-butyrolactone, Ketones such as methyl ethyl ketone, 2-heptanone, cyclopentanone, ethyl lactate, 3
-Hydroxy such as methyl methoxypropionate and ethyl pyruvate, alkoxy, oxyalkyl carboxylic acid alkyls and the like can be mentioned.

These solvents are appropriately selected in consideration of the solubility of the resin and the radiation sensitive agent, the stability of the radiation sensitive composition and the like. On the other hand, examples of the radiation-sensitive composition include a radiation-sensitive compound such as sodium naphthoquinonediazidesulfonate, and a water-soluble polymer compound such as polyvinylpyrrolidone dissolved in water or an aqueous solvent. To be

If necessary, a surfactant for improving coatability, a light absorber for preventing halation, and a sensitizer for improving sensitivity are added to these radiation-sensitive compositions. You can also The present invention relates to a container containing the radiation-sensitive composition as described above and a method for storing the radiation-sensitive composition. The present invention will be described below with reference to FIG. FIG. 1 shows an example of an embodiment of the present invention, in which 1 is a light shielding layer and 2 is an innermost layer. In the present invention, it is essential that the resin layer constituting the container is made up of at least two layers, such as the inner layer side and the outer layer side, and the resin used for the innermost layer must contain no light-shielding agent. It is what For a container in which a light-shielding agent is added to the resin used for the innermost layer, the storage stability is lowered, but it is not preferable in some cases, although the reason is not clear.

Furthermore, it is essential to use a polyolefin resin as the resin used for the innermost layer of the container for the radiation-sensitive composition of the present invention. Here, the polyolefin resin is a homopolymer of olefins or a copolymer of the same with other monomers, and may contain a halogen atom such as a fluorine atom as a substituent. Specifically, ethylene, propylene, butene, pentene, hexene,
A polyolefin resin containing, as a monomer component, at least one kind of monomer selected from methylbutene, methylpentene, ethylene tetrafluoride, propylene hexafluoride, and perfluoroalkyl vinyl ether.

Of these, homopolymers of olefins which may be substituted with a fluorine atom or copolymers of these with other monomers are preferred, and specifically, polyethylene, polypropylene, polymethylbutene, polymethylpentene,
Examples thereof include polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin, tetrafluoroethylene-hexafluoropropylene copolymer resin, and tetrafluoroethylene-ethylene copolymer resin.

The resin has a light transmittance of 600 to 800 n.
A polyolefin resin having a maximum light transmittance of 5% or more at a resin thickness of 0.5 mm in a range of m is particularly preferable from the viewpoint of visually recognizing the content. The maximum light transmittance is preferably 10% or more, more preferably 20% or more. Specific examples include polyethylene, polypropylene, polymethylbutene, polymethylpentene, tetrafluoroethylene-perfluoroalkylvinylether copolymer resin, tetrafluoroethylene-ethylene copolymer resin, tetrafluoroethylene-hexafluoropropylene copolymer. Examples include polymerized resins.

Examples of commercially available products include transparent polyolefin resins such as ZEONEX 280 manufactured by Nippon Zeon Co., Ltd. When a container using a polyethylene terephthalate resin, a polycarbonate resin, or the like as the innermost layer, the organic solvent-containing radiation-sensitive composition is stored, particles may be generated over time, which is not preferable. Therefore, it is particularly effective when the radiation-sensitive composition is a radiation-sensitive composition containing an organic solvent.

As polyethylene, polyethylene which is usually used for blow molding is used, and its density is 0.94.
5 to 0.971 g / cm ³ is preferable, and more specifically, in the case of polyethylene having a melt index of 0.1 to 0.7, 0.948 to 0.958 g / cm ³ is preferable. Number average molecular weight is 3.5 × 10 ^{3 to} 1.6 × 10
⁴ , preferably from 5 × 10 ^{3 to} 1.0 × 10 ⁴ . Further, a Z-average molecular weight / weight-average molecular weight value of 4 to 8, preferably 5 to 7, is suitable.

The method for producing the container composed of the multi-layer resin layer of the present invention is not particularly limited, but from the viewpoint of the translucency of the laminated part, the resistance to the solvent used in the radiation-sensitive composition, the molding strength and the like. It is preferably produced by a resin blow molding method. Particularly, the most simple and preferable embodiment shown in FIG. 1 is preferable because it can be usually produced by a known double blow molding method. The shape of the container of the present invention may be arbitrary, but in general, a bottle type having a screw-shaped or cap-shaped discharge port on the upper portion as shown in FIG. 1 is preferable. On the other hand, the lid for the container is usually
It is desirable to use a resin molded from a synthetic resin containing a light shielding agent. The content of the container is usually about 0.2 to 20 liters.

The case where the container of the present invention is manufactured by the blow molding method will be described in detail below. The polyolefin resin as described above is used as the resin of the innermost layer 2, but it is important not to add a light-shielding agent or a metal compound that may be eluted by a solvent to the resin.

On the other hand, as the resin used for the light-shielding layer, the same resin as the innermost layer 2 may be used, but those having different densities and molecular weights may be used, and polycarbonate, polystyrene, polymethylmethacrylate, etc. may be used. May be. Polyethylene terephthalate resin is a resin having good transparency and is effective. The light-shielding layer is usually one layer, but may be a plurality of layers if necessary. As the light-shielding agent used in the light-shielding layer, any substance can be used as long as it has a light-shielding property with respect to the photosensitivity of the radiation-sensitive composition. In the container of the present invention, having a light-shielding property with respect to the photosensitivity of the radiation-sensitive composition means that the radiation-sensitive composition has absorption in a wavelength region in which the radiation-sensitive composition has absorption and light in the wavelength region is absorbed. Is almost zero. Especially as a light-shielding agent, 6
Those having an excellent light-shielding property with respect to light of 00 nm or less are preferable. As described above, in the conventional radiation-sensitive composition bottle, which blocks light of less than 500 nm, 500
It transmits up to 50% of light of nm or more, and in this case, the radiation-sensitive composition has insufficient storage stability. In addition, as a light-shielding agent selected from the viewpoint of the visibility of the internal liquid, 600
It is recommended to have a property of relatively absorbing light having a wavelength of nm or less with respect to light having a wavelength of more than 600 nm. Light with a wavelength of 600 nm or less is
Relative absorption of light having a wavelength exceeding 00 nm means that the maximum transmittance (T ₁ ) at a wavelength of 150 nm to 600 nm and the maximum transmittance (T ₂ ) at a wavelength of 600 nm to 800 nm. With T ₁ <T ₂ is meant. The light-shielding agent used in the present invention is
In order to obtain the above characteristics, one or more kinds are selected and used from conventionally known inorganic pigments, organic pigments, ultraviolet absorbers and the like.

As the above-mentioned inorganic pigment, any light-shielding pigment that can be mixed in the resin can be used.
Cadmium red (C.I.R-108), molybdenum red, molybdenum orange (C.I.R-104), cadmium yellow (C.I.Y-37), carbon black, titanium white and the like. Further, as the organic pigment, any light-shielding pigment that can be mixed in the resin may be used, for example, anthraquinone pigment, perylene pigment, quinacridone pigment, condensed azo pigment, dialide pigment, Examples include benzimidazolone pigments, azo lake pigments, perinone pigments, quinophthalone pigments, isoindoline pigments, and methyl pigments. As the UV absorber, any UV absorber that can be mixed in the resin may be used. For example, an o-oxybenzophenone derivative, a 2,2′-dioxybenzophenone derivative, a salicylate ester, a benzotriazole derivative, and resorcinol can be used. There are derivatives, etc.

In the present invention, among the above-mentioned light-shielding agents, one having a characteristic of relatively absorbing more light having a wavelength of 600 nm or less with respect to light having a wavelength of more than 600 nm by combining one kind or a plurality of kinds. preferable. As such a combination, for example, a red to orange pigment is indispensable, and an ultraviolet absorber, a yellow pigment, and other pigments may be used in combination with these pigments if necessary. FIG. 4 shows the spectral reflection characteristics of a typical red pigment (anthraquinone red).

Explaining the present invention with reference to FIG. 4, the anthraquinone red shown in FIG. 4 has a characteristic of exhibiting a very low reflectance at a wavelength of 600 nm or less and a very high reflectance at a wavelength of more than 600 nm. is doing. In other words, this red pigment absorbs light with a wavelength of 600 nm or less very well, and does not absorb light with a wavelength of more than 600 nm very well. Therefore, this red pigment alone emits light with a wavelength of 600 nm or less to light with a wavelength of more than 600 nm,
It has a relatively more absorbing property, and the difference is extremely large. Therefore, pigments having this type of property are particularly useful as the light-shielding agent of the present invention.

Specific examples of the red to orange pigments include inorganic pigments such as cadmium red, molybdenum red and molybdenum orange, and anthraquinone pigment anthraquinone red (C.I.R.-177) and perinone. Series pigment perylene red (C.I.R-17)
8), perylene scarlet (C.I.R-149),
Quinacridone pigment PV Fast Pink (C.I.R.
-122), condensed azo pigment Chromophthal Scarlet RN (CIR 166), Chromophthal Red G
(C.I.R-220), Chromophthal Red BRN
(C.I.R-144), Chromophthal Red BG
(C.I.R-248), Chromophthal red 2B
(C.I.R-221), Chromophthal Orange 4R
(C.I.O-31), chromophthal orange (C.I.
I. O-64), dialide pigments pyrazolo red (CIR 38), dialide orange (C.I.
O-13, C.I. I. O-34), benzimidazolone-based pigment Novapalm Red HFT (C.I.R-17)
5), PV Carmine HF3C (C.I.R-176),
PV Carmine HF4C (C.I.R-185), PV Red HF2B (C.I.R-208), Azo Lake type pigment Lake Red C (C.I.R-53), Perinone type pigment Perinone Orange. (C.I.O-43), isoindolinone-based pigment Chromophthal Orange 2G (C.I.
I. Organic pigments such as O-61) are mentioned.

Examples of the yellow pigments include inorganic pigments such as cadmium yellow (C.I.Y-37) and quinophthalone pigments such as pariotor yellow (C.I.
I. Y-138), anthraquinone-based pigment Fillesta Yellow RN (CI.Y-147), isoindolinone-based pigment Irgadine Yellow (CI.Y-109,
C. I. Y-110), condensed azo type pigment chromophthal yellow (C.I.Y-93 to 95), dialide type pigment dialide yellow (C.I.Y-14), and benzimidazolone type pigment PV. Fast Yellow (C.I.
Y-180) and other organic pigments.

When a layer is formed using a resin in which the above-mentioned light-shielding agent is kneaded, an organic pigment is preferable from the viewpoints of light-shielding property with respect to photosensitivity of the radiation-sensitive composition and light-transmitting property with respect to a wavelength of 600 nm or more, The above-mentioned anthraquinone pigments are particularly preferable. Further, it is particularly recommended to use a light-shielding agent in which an organic pigment and an ultraviolet absorber are combined, in view of the effect of the present invention.

In a preferred embodiment of the present invention, the above T ₁
A light-shielding agent having a relationship of <T ₂ is used, or a resin layer containing a light-shielding agent has a relationship of T ₁ <T ₂ , particularly, the type and amount of the light-shielding agent, the type of resin, and the resin layer It is more preferable that T ₂ is twice or more, preferably 5 times or more as large as T ₁ as a light-shielding agent or a resin layer containing the light-shielding agent by appropriately selecting the thickness and the like. The T
_The values measured using a commercially available spectrophotometer are adopted as ₁ and T ₂ .

The amount of the light-shielding agent used is usually 0.
It is from 1 to 1% by weight, preferably from 0.05 to 0.5% by weight. Further, in the container of the present invention, it is preferable that the layer made of a resin containing a light-shielding agent substantially absorbs light having a wavelength of 600 nm or less and partially transmits light having a wavelength of more than 600 nm. More specifically, the layer made of a resin containing a light-shielding agent has a transmittance of 1% or less for light having a wavelength of 500 nm or less, and T ₂ of the layer is twice or more T ₁ of the layer, It is more preferably 5 times or more. Further, for example, as shown in FIG. 5, a layer made of a resin containing a light-shielding agent has a transmittance of 1% or less for light having a wavelength of 570 nm or less, and T ₂ of the layer is T _{1 of the} layer. Of 2
It is preferably at least twice, more preferably at least five times.
T ₂ of the resin layer containing a light shielding agent is preferably not less than 3%,
It is more preferably 5% or more.

Further, in the present invention, the light-shielding agent is 60
It has a characteristic of relatively absorbing light having a wavelength of 0 nm or less with respect to light having a wavelength of more than 600 nm, and a multilayer resin layer almost absorbs light having a wavelength of 600 nm or less and exceeding 600 nm. A container that transmits a part of light having a wavelength is also preferable. The use of such a container is particularly advantageous in visually confirming the presence or absence of the content while maintaining the storage stability of the radiation-sensitive composition.

The storage method of the present invention is to store and store the radiation-sensitive composition in the container for the radiation-sensitive composition of the present invention as described above. The storage condition is not particularly limited, but it is usually a temperature of room temperature or lower. Stored in. When the radiation-sensitive composition is contained in the container for the radiation-sensitive composition of the present invention as described above, there is little change in the sensitivity of the radiation-sensitive composition after storage, and the storage stability is excellent. It is extremely advantageous in providing a high resolution radiation sensitive composition.

[0045]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples unless the gist thereof is exceeded. In the following examples, when the radiation-sensitive composition was handled, it was carried out in a class 100 clean room using a fluorescent lamp that shielded light of 500 nm or less unless otherwise specified (a so-called yellow room). .

Preparation Example 1 Cresol type novolak resin (Mw = 6,500) 3k
g and 1 kg of a photosensitizer synthesized from 2,3,4,4'-tetrahydroxybenzophenone and 1,2-naphthoquinonediazide-5-sulfonic acid chloride were dissolved in 10 kg of ethyl cellosolve acetate. This product has a pore size of 0.
A radiation-sensitive composition was prepared by filtering with a 2 μm membrane filter (radiation-sensitive composition-A).

Preparation Example 2 2 kg of a t-butoxycarbonylated modification of poly (p-hydroxystyrene) (Mw = 10,000) and triphenylsulfonium hexafluoroarsenate 0.1.
4 kg of diethylene glycol dimethyl ether 8 kg
Dissolved in. This was filtered with a membrane filter having a pore size of 0.2 μm to prepare a radiation-sensitive composition (radiation-sensitive composition-B).

Preparation Example 3 Cresol type novolak resin (Mw3500) 14.4
Polycondensate of g and m-cresol and acetaldehyde (Mw 1000) and 1,2-naphthoquinonediazide-
7.34 g of photosensitizer synthesized from 5-sulfonic acid chloride
Was dissolved in 390 g of methyl 3-methoxypropionate. This was filtered with a membrane filter having a pore size of 0.2 μm to prepare a radiation-sensitive composition (radiation-sensitive composition-C).

Preparation Example 4 2.1 g of sodium 1,2-naphthoquinonediazide-5-sulfonate, 1.8 g of pullulan and 1.2 g of polyvinylpyrrolidone were dissolved in 300 ml of water and filtered with a membrane filter having a pore size of 0.2 μm. A radiation-sensitive composition was prepared (Radiation-sensitive composition-D).

Container Production Example 1 As the inner layer resin, the density was 0.963 g / cm ³ , the number average molecular weight was 8.0 × 10 ³ , the Z average molecular weight / weight average molecular weight was 6.0, and the melt index was 0.35 g / 10 min. Density polyethylene (Mitsubishi Kasei Co., Ltd., trade name Novatec (registered trademark)) is used, and polyethylene terephthalate resin (Nihon Unipet Co., Ltd., Unipet) is used as an outer layer resin, and anthraquinone organic pigment (Ciba Geigy Co., Ltd., A parison was extruded from a two-layer extrusion die using a resin in which 0.3% by weight of the product name Cromophthal Red A3B) and 0.4% by weight of an ultraviolet absorber (trade name TINUVIN327, manufactured by Ciba-Geigy Co., Ltd.) were mixed, and the parison was extruded from a two-layer extrusion die, as shown in FIG.
A container having a structure similar to that shown in (1) and having a volume of 0.2 liter was blow-molded (container-A). In addition, FIG. 4 shows the spectral reflection characteristics of the anthraquinone-based organic pigment.

60 high density polyethylene used for the innermost layer
The maximum light transmittance of light in the range of 0 to 800 nm was 10% at the high density polyethylene thickness of 0.5 mm. FIG. 5 shows the spectral transmittance of the resin layer containing the light shielding agent.
The spectral transmittance in the present invention is 100% that of air.
Is a relative value when. As is clear from FIG. 5,
The resin layer containing the light-shielding agent of the present invention exhibits a transmittance of almost zero for wavelengths of 600 nm or less, and has a good transmittance for light of 600 nm or more.

Example 2 of container production In Example 1 of container production, polypropylene (made by Mitsubishi Kasei Co., Ltd.,
Product name Mitsubishi Polypro 4100B, melt index 0.8g / 10min), and anthraquinone-based organic pigment (Ciba Geigy Co., product name Crom) as the outer layer resin
0.9 wt% of optical red A3B and ultraviolet absorber (Ciba Geigy, trade name TINUVIN
327) A container was blow-molded in the same manner except that a resin mixed with 0.5% by weight was used (container-B). FIG. 6 shows the spectral transmittance of the body of the container-B. The maximum light transmittance of the polypropylene used for the innermost layer in the range of 600 to 800 nm is 7 when the polypropylene thickness is 0.5 mm.
It was as good as 0% or more.

Container Production Example 3 In Container Production Example 1, molybdenum red was added in an amount of 0.3 in place of the anthraquinone organic pigment as an additive for the outer layer resin.
Wt% and the same UV absorber as in Production Example 2 TINUVIN
A container was blow-molded in the same manner except that a resin containing 0.4% by weight of 327 was used (container-C).

Container Manufacturing Example 4 In container manufacturing example 3, molybdenum red and UV absorber TINUVIN32, which are the same as the outer layer resin, are used as the inner layer resin.
A container was blow molded using a resin mixed with 7 (container-
D).

Container Production Example 5 In the Container Production Example 1, the same polypropylene as in the Container Production Example 2 was used as the inner layer resin, and as the outer layer resin, Dialesin (registered trademark) Yellow L3G (methine pigment) and Dialesin (registered trademark) were used. ) Orange HS
(Perinone-based pigment) (each manufactured by Mitsubishi Kasei Co., Ltd.) in an amount of 0.06% by weight and an ultraviolet absorber TINUVIN327
A container was blow-molded in the same manner except that a resin containing 0.4% by weight of was used (container-E).

Container Production Example 6 In Container Production Example 5, a container was blow molded using a resin in which the same pigment as the outer layer resin and a UV absorber were mixed in the inner layer resin (Container-F).

Container Production Example 7 In Container Production Example 1, polymethylpentene (trade name: TPX, manufactured by Mitsui Petrochemical Co., Ltd.) was used as the inner layer resin instead of high-density polyethylene, and a light-shielding agent added to the outer layer resin was used. Add anthraquinone organic pigment to 1.2
A container was blow-molded in the same manner except that the weight% and the ultraviolet absorber were increased to 0.7% by weight (container-G). The maximum light transmittance of light in the range of 600 to 800 nm of the polymethylpentene used for the innermost layer was as good as 80% or more when the thickness of the polymethylpentene was 0.5 mm.

Container Production Example 8 In Container Production Example 7, a polyethylene terephthalate resin containing no light-shielding agent was used as the inner layer resin instead of polymethylpentene, and the container was blow-molded (Container-H).

Container Production Example 9 In the container production example 2, the same polypropylene as the inner layer resin was used as the outer layer resin, and the outer layer resin was an anthraquinone-based organic pigment (Ciba-Geigy, trade name Cromoph).
Tal Red A3B) 0.8% by weight, and an ultraviolet absorber (manufactured by Ciba-Geigy, trade name TINUVIN3)
The container was blow-molded in the same manner except that 0.3% by weight of 27) was mixed (container-I).

Example 1 The container-A was washed with pure water and dried, and then about 0.15 liter of the radiation-sensitive composition-A was filled. The filling container was sealed with a cap having a clean polyethylene inner lid, and stored in a dark place in a class 100 clean room at a temperature of 23 ° C. for 3 months. After the storage period, the radiation-sensitive composition is applied to a silicon wafer by a spin coater and prebaked at 95 ° C. for 60 seconds on a hot plate,
A radiation sensitive composition coating film having a thickness of about 1.0 μm was formed.

436n was applied to the coating film of this radiation-sensitive composition.
m of ultraviolet ray was irradiated and the film was developed with an aqueous solution of tetramethylammonium hydroxide, and the minimum exposure dose (Eth) required for completely developing and removing the coating film of the radiation-sensitive composition to the substrate was measured. The result was 67 mJ / cm ² , and the Eth of the radiation-sensitive composition-A before storage was similarly measured to be 67 mJ / cm ² , so that very good storage stability was obtained. When the position of the liquid surface when the radiation-sensitive composition was put in the container-A was visually confirmed, it could be sufficiently confirmed.

Example 2 and Comparative Example 1 As Example 2, the storage condition in Example 1 was changed to a condition of forced deterioration under the illumination of a white fluorescent lamp from a dark place, and storage was carried out under the same conditions as the minimum exposure. The amount (Eth) was measured. Further, as Comparative Example 1, a commercially available 1 liter brown glass bottle was washed with pure water and dried, and then the above radiation-sensitive composition-A was used.
The minimum exposure amount (Eth) was also measured for the sample filled with and stored under the same conditions as in Example 2. These Et
h was 65 mJ / cm ² and 59 mJ / cm ² , respectively. The sensitivity of the radiation-sensitive composition using the container of the present invention changed only slightly, but it changed greatly in the conventional brown glass bottle. The light transmittance of the commercially available 1 liter brown glass bottle used in Comparative Example 1 was as shown in FIG.

Examples 3 and 4 The minimum exposure dose (Eth) was measured in the same manner as in Examples 1 and 2 except that the container-B was used instead of the container-A. As a result, 67 mJ / cm ² ( Example 3) and 65 mJ / cm ² (Example 4). The light transmittance of the body of the container-B is 570 nm as shown in FIG.
The following was 1% or less, 8% at 600 nm and 60% or more at 700 nm or more, and the liquid level visibility of the radiation-sensitive composition in the bottle was better than that in Example 1.

Example 5 and Comparative Example 2 The above-mentioned container-C and container-D were washed with pure water and dried, and then about 0.15 liter of the above radiation-sensitive composition-B was filled. The filling container was sealed with a cap having a clean polyethylene inner lid, and stored in a dark place in a class 100 clean room at a temperature of 23 ° C. for 3 months. After the storage period, the radiation-sensitive composition was applied to a silicon wafer with a spin coater and prebaked at 100 ° C. for 60 seconds on a hot plate to form a radiation-sensitive composition coating film having a thickness of about 0.6 μm.

248n was applied to the coating film of this radiation-sensitive composition.
m of ultraviolet light, further, exposed on a hot plate at 90 ° C. for 30 seconds, baked, and developed with an aqueous solution of tetramethylammonium hydroxide, and the radiation-sensitive composition coating film is completely developed and removed to the substrate. The minimum exposure amount (Eth) required for the measurement was measured. The results are shown in Table-1. The Eth of the radiation-sensitive composition-B before storage was similarly measured and was 15 mJ / cm ² . As is clear from Table 1, the sensitivity of the radiation-sensitive composition contained in the container of the present invention did not change, but the sensitivity changed when the light-shielding agent was contained in the inner layer.

[0066]

[Table 2]

Example 6 and Comparative Example 3 The above-mentioned container-E and container-F were washed with pure water and dried, and then about 0.15 liter of the above radiation-sensitive composition-A was filled. The filling container was sealed with a cap having a clean polyethylene inner lid, and stored in a dark place in a class 100 clean room at a temperature of 23 ° C. for 3 months. After the storage period, the radiation-sensitive composition was applied to a silicon wafer with a spin coater and prebaked at 95 ° C. for 60 seconds on a hot plate to form a radiation-sensitive composition coating film having a thickness of about 1.0 μm.

436n was applied to the coating film of the radiation-sensitive composition.
m was irradiated with ultraviolet rays and developed with an aqueous solution of tetramethylammonium hydroxide, and Eth was measured in the same manner as in Example 2. The results are shown in Table-2. The Eth of the radiation-sensitive composition-A before storage was similarly measured and was 67 mJ / cm 2.
^{Was 2} . Obviously from this table, the sensitivity of the radiation-sensitive composition contained in the container of the present invention did not change at all.

[0069]

[Table 3]

Example 7 and Comparative Example 4 In the same manner as in Example 1, except that the radiation-sensitive composition-C was used,
The radiation-sensitive composition was filled and stored in the same manner as in Example 1 except that Container-G and Container-H were used as the filling container. After the storage, the radiation-sensitive composition was applied to a 5-inch silicon wafer with a spin coater and the temperature was adjusted to 60 at 95 ° C.
Prebaking was performed on a hot plate for 2 seconds to form a radiation sensitive composition coating film having a thickness of about 1 μm.

The number of particles in this coating film was measured by a laser surface inspection device manufactured by Hitachi Electronics Engineering Co., Ltd. In the radiation-sensitive composition stored in the container-G, the number of particles was 5, whereas in the radiation-sensitive composition stored in the container-H, the number of particles was 10.
It was measured as many as 00 or more. At this time, the container H was partially devitrified, and the liquid level position of the radiation-sensitive composition could not be determined.

Example 8 and Reference Example 1 Using the radiation-sensitive composition -D, a container as a filling container-
The radiation-sensitive composition was filled and stored in the same manner as in Example 7 and Comparative Example 4 except that G and Container-H were used, and the number of particles in the coating film after storage was measured. The number of particles stored in each of container-G and container-H is 4 and 6 respectively.
There were only a few.

Example 9 An experiment was conducted in the same manner as in Example 1 except that Container-I was used as the filling container. The sensitivity before storage is 67 mJ / cm ² ,
The storage stability after storage for 3 months was 67 mJ / cm ² , indicating good storage stability.

[0074]

The container for the radiation-sensitive composition of the present invention comprises:
When the radiation-sensitive composition is housed in this, there is little change in sensitivity of the radiation-sensitive composition after storage and excellent storage stability, so that it is extremely useful in providing a high-resolution radiation-sensitive composition. It is useful. Further, the container of the present invention is lightweight and can be incinerated as it is even when it is discarded, which is industrially advantageous.

[Brief description of drawings]

FIG. 1 is a schematic sectional view showing an example of a container of the present invention.

FIG. 2 Radiation-sensitive composition (naphthoquinone diazide-
It is a figure which shows an example of the spectral sensitivity of a novolak resin-type radiation sensitive composition.

FIG. 3 is a diagram showing a spectral transmittance of a brown glass bottle which has been conventionally used.

FIG. 4 is a diagram showing a spectral reflectance of anthraquinone red, which is a typical light shielding agent.

FIG. 5 is a diagram showing an example of spectral transmittance of a resin layer containing a light shielding agent of the container of the present invention.

FIG. 6 is a diagram showing an example of a trunk portion light transmittance of the container of the present invention.

[Explanation of symbols]

 1 Light-shielding layer 2 Innermost layer

Claims (8)

[Claims] 1. A container composed of multiple resin layers, wherein the innermost layer of the resin layer is composed of a resin containing no light-shielding agent, and at least one layer other than the innermost layer is a light-sensitive composition containing light. A container made of a resin containing a light-shielding agent having a light-shielding property with respect to sensitivity, wherein the resin of the innermost layer is a polyolefin resin, the container for a radiation-sensitive composition. 2. The container for a radiation-sensitive composition according to claim 1, wherein the radiation-sensitive composition is an organic solvent-containing radiation-sensitive composition. 3. The radiation-sensitive material according to claim 1, wherein the light-shielding agent has a characteristic of relatively absorbing more light having a wavelength of 600 nm or less with respect to light having a wavelength of more than 600 nm. Container for sexual composition. 4. The radiation-sensitive composition according to claim 3, wherein the multi-layered resin layer substantially absorbs light having a wavelength of 600 nm or less and transmits a part of light having a wavelength of more than 600 nm. container. 5. A layer made of a resin containing a light-shielding agent, 5
The transmittance for light having a wavelength of 00 nm or less is 1% or less, and the maximum transmittance of the layer at a wavelength of more than 600 nm to 800 nm is 2% of the maximum transmittance at a wavelength of 150 nm to 600 nm. The container for a radiation-sensitive composition according to claim 1, wherein the container is twice or more. 6. The resin of the innermost layer is ethylene, propylene,
A polyolefin resin comprising at least one monomer selected from butene, pentene, hexene, methylbutene, methylpentene, ethylene tetrafluoride, propylene hexafluoride and perfluoroalkyl vinyl ether as a monomer component. 6. The container for a radiation-sensitive composition according to claim 5. 7. The resin of the innermost layer is a polyolefin resin having a maximum light transmittance of light in the range of 600 to 800 nm of 5% or more at a resin thickness of 0.5 mm. Item 7. A container for a radiation-sensitive composition according to any one of Item 6. 8. A method for storing a radiation-sensitive composition, which comprises storing the radiation-sensitive composition in the container according to any one of claims 1 to 7.