JPH033238A - Semiconductor carrier - Google Patents

Abstract

PURPOSE:To obtain a semiconductor carrier which has enough strength to bear a large size and has enough solvent resistance to a strong solvent of chlorine, fluorocarbon, etc., by using a polymer, which has fluorine-containing alicyclic structure, as material. CONSTITUTION:A fluorine-containing polymer, which has specific ring structure shown by the next general formula, is adopted suitably for the principal chain. It is possible to add various kinds of additives such as an oxidation inhibitor, an ultraviolet ray stabilizer, etc., to the fluorine-containing polymer to improve practicality. By using the polymer, which has fluorine-containing alicyclic structure, for use in coating, high solvent resistance can be given to a semiconductor carrier made of expensive general purpose resin. Moreover, since the polymer, which has fluorine-containing alicyclic structure, gives a transparent compact, a transparent semiconductor carrier, whose contents can be recognized with eyes even from the side, can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a carrier suitable for cleaning semiconductors and the like, which has at least its surface formed of a polymer having a fluorine-containing aliphatic cyclic structure.

[Prior Art] Conventionally, chlorine-based organic solvents such as Tricene and Tonocrene have been used to clean electronic components such as semiconductors, and the containers (semiconductor carriers) are made of PTFE, P
Fluororesins such as FA were used. However, these fluororesins have poor moldability and low strength, so when a large carrier is made, they cannot withstand the weight.

In addition, if a carrier is made using a general-purpose resin with sufficient strength, its solvent resistance is inferior to that of fluororesin, and there are problems such as the surface being attacked by the solvent used or the resin eluting into the solvent. was there.

[Problems to be Solved by the Invention] The present invention aims to eliminate the drawbacks observed in semiconductor carriers made of conventional materials as described above, and to provide a new semiconductor carrier with excellent solvent resistance and mechanical strength. This is the purpose.

[Means for Solving the Problems] Based on the recognition of the above-mentioned problems, the present inventor has made extensive studies and found that a polymer having a fluorine-containing aliphatic ring structure has high solvent resistance and can be molded. We have newly discovered that this material is extremely advantageous as a material that provides a semiconductor carrier with excellent properties and sufficient strength. Furthermore, since the polymer having a fluorine-containing aliphatic ring structure of the present invention is soluble in special solvents, it is also possible to cover the surface of general-purpose resins by coating. In this case, by selecting a material with sufficient strength as a general-purpose resin, a semiconductor carrier with excellent solvent resistance and strength can be obtained.

Thus, the present invention was completed based on the above findings, and provides a novel semiconductor carrier characterized in that at least the surface thereof is formed from a polymer having a fluorine-containing aliphatic ring structure.

In the present invention, the polymer having a fluorine-containing aliphatic ring structure may be exemplified over a wide range of examples, including those that are conventionally known or well-known. Therefore, in the present invention, a fluorine-containing polymer having the above-mentioned specific ring structure in the main chain is preferably employed.

For example, those having a ring structure as shown in the following formula may be mentioned. Among these, polymers having the following ring structures are representative.

However, the content of the present invention is not limited to these only.

(IJSP 34i8303. GB 1106344
etc.) (2) CF2=CF-CFz-CFCI-C
F2-CF:CF2↓ Radical polymerization There are two methods for producing these polymers as follows. However, it is not limited to these manufacturing methods.

1. By cyclization polymerization (1) CF2=CF-0-CF2CF2-0-CFz
CF2↓ Radical polymerization (USP 3202643 etc.) (3) CF2=CF-0-CF2-CFzCF2↓
Radical polymerization 2, using a cyclic monomer (USP 3978030) In the above, a polymer having a perfluoroaliphatic ring structure was exemplified, but in the present invention, some of the fluorine atoms in the above example are replaced by other hydrogen atoms. Examples include those substituted with atoms or organic groups, or those having a ring structure such as that obtained by metathesis polymerization.

Therefore, the polymer having a specific ring structure in the present invention can be obtained more smoothly and advantageously by the above-mentioned cyclopolymerization, but in particular, the polymer has two polymerizable groups with different polymerizability in the molecule, and By using a monomer in which the linear part of the linking chain that connects these two polymerizable groups has 2 to 7 atoms, it is possible to reduce the side effects of gelation without using ultra-high pressure conditions or large dilution conditions. This allows the cyclization polymerization to proceed smoothly and advantageously while suppressing the occurrence of biochemical reactions.

As a monomer suitable for the above-mentioned cyclization polymerization, first of all, it is desirable that the monomer has two carbon-carbon multiple bonds having different polymerizability. Usually a carbon-carbon double bond is employed. For example, a fluorine-containing monomer with two non-symmetrical multiple bonds, a vinyl group and an allyl group, a vinyl ether group and a vinyl group, a fluorine-containing multiple bond and a hydrocarbon multiple bond, a perfluorinated multiple bond and a partially fluorinated multiple bond. Examples include: Secondly, it is desirable that the number of atoms in the straight portion of the connecting chain connecting these two carbon-carbon multiple bonds is 2 to 7. The number of atoms in the straight part of the connected chain is O~
When the number is 1, cyclization polymerization is difficult to occur, and the same is true when the number is 8 or more. Generally preferred is a case where the number of atoms is 2 to 5.

In addition, the connecting chain is not limited to a straight line, and may have a side chain structure or a ring structure, and the constituent atoms are not limited to carbon atoms, but may also include heteroatoms such as O, S, and H. . Thirdly, it is desirable that the fluorine content be 10% by weight or more. If the fluorine content is too low, the specificity of fluorine atoms will be difficult to exhibit. Naturally, perfluoromonomers are preferably employed.

Specific examples of the above-mentioned specific fluorine-containing monomer include CF2
"CFOCF2CF" CF2. CF2=CFOCF2
CF2CF"CF2CF2"CFOCF2CF"CH2
, CF2"CFOCF2CF2CH"CH2.

(However, X is an integer from 0 to 3)
2CFCOC:H2C:HaCF=CF21 CF3 CH2"cHOc:HzCH2CF20F2CF2 etc. are examples of two-band F2. In the present invention, those having one vinyl ether group CF2CF2- have polymerization reactivity, cyclopolymerizability, gel In particular, perfluoroallyl vinyl ether (CF2=CFOCF2CF=
CF2) and perfluorobutenyl vinyl ether (
CF2:CFOCF2CF20F2CF2) is mentioned as a suitable example.

The above-mentioned monomer components can be used alone or in combination of two or more, and there is no problem even if they are copolymerized in combination with other copolymer components to the extent that the essence of these components is not impaired. If necessary, the polymer may be crosslinked by some method.

Other monomers to be copolymerized are not particularly limited as long as they have radical polymerizability, and include fluorine-containing monomers,
A wide range of hydrocarbons and others may be exemplified. Of course, these other monomers may be used alone in radical copolymerization with the monomer capable of introducing the specific ring structure, or two or more of these other monomers may be used in combination to carry out the above copolymerization reaction. You can let them do it. In the present invention, it is usually desirable to select fluorine-containing monomers such as fluoroolefins and fluorovinylethers as other monomers. For example, preferred examples include tetrafluoroethylene, perfluoromethyl vinyl ether, perfluoropropyl vinyl ether, or perfluorovinyl ether containing a functional group such as a carboxylic acid group or a sulfonic acid group. ,
Examples include chlorotrifluoroethylene.

Regarding the copolymer composition, in order to take advantage of the characteristics of the specific fluorine-containing aliphatic ring structure that is the objective of the present invention, the composition of the cyclic structure is preferably 20% or more, more preferably 40% or more. This is desirable.

In the present invention, as a method for crosslinking the fluoropolymer, commonly used methods can be appropriately used. For example, crosslinking can be achieved by copolymerizing a monomer having a crosslinking site, by adding a crosslinking agent, or by using radiation or the like.

Furthermore, various additives such as antioxidants and ultraviolet stabilizers can be added to the fluorine-containing polymer in the present invention in order to improve practicality.

Since the button having a specific ring structure according to the present invention is soluble in fluorine-based solvents, it is also possible to create a thin protective film by casting from a solution. In addition, as a thermoplastic resin, it has a low melting temperature and a relatively low melt viscosity, so it is easily melted by heat.

The solvent used is not limited as long as it dissolves the above polymer, but examples include perfluorobenzene, "Afluid°" (trade name: fluorine-based solvent manufactured by Asahi Glass Co., Ltd.),
“Florintopa (Product name: Perfluoro manufactured by 3M Company)
Liquids containing 2-butyltetrahydrofuran), trichlorotrifluoroethane, etc. are suitable. Naturally, two or more appropriate types can be used in combination as a solvent. Particularly in the case of mixed solvents, hydrocarbons, alcohols, and other organic solvents can also be used in combination. The solution concentration is o, o
twtχ~50wt! and preferably 0.1wtχ~2
0wt'! It is.

[Examples] Next, Examples of the present invention will be described in more detail, but it goes without saying that this description does not limit the present invention.

Synthesis Example 1 35 g of perfluoroallyl vinyl ether, trichlorotrifluoroethane (hereinafter abbreviated as R113)
5 g of ion exchange water, 150 g of ion-exchanged water, and 35 mg of (C3F7COO)2 as a polymerization initiator, in an internal volume of 200 m
It was placed in a pressure-resistant glass autoclave.

After purging the system with nitrogen three times, suspension polymerization was carried out at 26°C for 23 hours. As a result, 28 g of polymer was obtained.

When we measured the infrared absorption spectrum of this polymer, we found that
1660Cm- due to the double bond present in the monomer
There was no absorption near t, 1840 cm-+. Further, when this polymer was dissolved in perfluorobenzene and a 19F NMR spectrum was measured, a spectrum showing the following repeating structure was obtained.

The intrinsic viscosity [η] of this polymer is “Florinat” FC
-75 (Product name: Liquid whose main component is perfluoro(2-butyltetrahydrofuran) manufactured by 3M Company, hereinafter FC-
75) and 0.530 at 30°C.

The glass transition point of the polymer is 69"C, and it is a tough and transparent glass-like polymer at room temperature. The 10% thermal decomposition temperature is 4629C, the refractive index is as low as 1.34, and the light transmittance is low. was as high as 95%.

Synthesis Example 2 1.20 g of 1,2,4,4,5.5-heptafluoro-3-oxa-1,6-hebutadiene and 40 g of R-113 were placed in a nitrogen-substituted Mitsuro flask, and a polymerization initiator was added. 20 mg of (C3F7C00)2 was added thereto, and the system was further purged with nitrogen, followed by polymerization at 18'C for 10 hours. As a result, 10 g of polymer was obtained. This polymer is R-1
It is a polymer that dissolves in 13, and the intrinsic viscosity [η] at 30"C in meta-xylene hexafluoride was 0.96. It was confirmed by 19F and IH NMR that it was a polymer with a ring structure in the main chain. did,.

Additionally, this polymer is colorless and transparent, and has a refractive index of 1.36.
The light transmittance was as high as 93%.

Synthesis example 3 35 g of perfluorobutenyl rubinyl ether.

5 g of R113, 150 g of ion-exchanged water, and 90 mg of diisopropyl peroxydicarbonate as a polymerization initiator were placed in a pressure-resistant glass autoclave having an internal volume of 200 m1.

After purging the system with nitrogen three times, suspension polymerization was carried out at 40'C for 23 hours. As a result, 28 g of polymer was obtained.

When we measured the infrared absorption spectrum of this polymer, we found that
1660cm- due to the double bond present in the monomer
There was no absorption near t., 1840c+n-r. Moreover, this polymer was soluble in perfluorobenzene, afluid, and fluorinate. Furthermore, N on the 19th floor
When the MR spectrum was measured, as in Synthesis Example 1, a spectrum corresponding to a ring structure was obtained.

The intrinsic viscosity [η] of this polymer is 30°C in FC-75.
It was 0.50. The glass transition point of the polymer is 110
0C, and is a tough, transparent, glass-like polymer at room temperature. Moreover, the 10% thermal decomposition temperature was 465°C.

Example 1 The fluoropolymer obtained in Synthesis Example 1 had a tensile strength of 330 kg/cm 2 at 25°C,
The tensile modulus was 12,000 kg/cm2. These mechanical properties are sufficient to withstand the production of large carriers. Next, this polymer was extruded at 270°C, and the insoluble portion was cut to form a carrier.

Tricene, trichlorethylene, and trichlorofluoroethane were each placed in this carrier and left for 24 hours, but in all cases, no damage was observed on the surface of the carrier, and no dissolution into the liquid was observed. I couldn't stand it. Note that this carrier was transparent.

Example 2 A solution prepared by dissolving the fluorine-containing copolymer obtained in Synthesis Example 1 in FC-75 was used to coat the surface of a polypropylene semiconductor carrier.

The solvent resistance of this carrier was tested in the same manner as in Example 1, but as in Example 1, no damage to the surface or dissolution into the liquid was observed.

Examples 3 to 6 Using the fluorine-containing polymer obtained in Synthesis Example 2.3, semiconductor carriers were prepared and tested in the same manner as in Example 1.2, but similarly good results were obtained. It was done.

[Effects of the Invention] By employing a polymer having a fluorine-containing aliphatic ring structure as a material, the present invention has sufficient strength to withstand large sizes, and is resistant to strong solvents such as chlorine-based and fluorocarbon-based solvents. This has the excellent effect that a semiconductor carrier having sufficient solvent resistance can be obtained. Furthermore, by using a polymer having a fluorine-containing aliphatic ring structure for coating, it is possible to impart high solvent resistance to a semiconductor carrier made of an inexpensive general-purpose resin.

Furthermore, since the polymer having a fluorine-containing aliphatic ring structure used in the present invention provides a transparent molded product, it also has the effect of providing a transparent semiconductor carrier whose contents can be viewed even from the side.

Claims (1)

[Scope of Claims] 1. A semiconductor carrier characterized in that at least the surface thereof is formed from a polymer having a fluorine-containing aliphatic ring structure. 2. The semiconductor carrier according to claim 1, wherein the polymer having a fluorine-containing aliphatic ring structure is a polymer having a ring structure in the main chain obtained by cyclization polymerization. 3. The semiconductor carrier according to claim 1, wherein the entire molded body is made of a polymer having a fluorine-containing aliphatic ring structure. 4. The semiconductor carrier according to claim 1, which is obtained by coating a polymer having a fluorine-containing aliphatic ring structure.