JPH0483360A - Composition for semiconductor device carrying case - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a composition for a semiconductor device transport container.

More specifically, the present invention provides IC) trays, chip trays,
This invention relates to trays used in the manufacturing process of ICs such as wafer carriers.

(Prior art and its section B) During the process of manufacturing ICs, ICs are heated in an open space.
A small amount of water, Br ions, and N contained in &II
There is a baking process to degas volatile impurities such as a ions and CI ions. Baking is a very important part of the manufacturing process because if moisture or gas components remain in the assembled IC, it will cause a fatal defect in the accuracy of the IC.

When baking, each IC is placed in a special tray called a tray, and the trays are stacked in layers and placed in a baking chamber.

Then, by heating, water and impurities are evaporated and degassed. The temperature of the baking chamber must be 110℃ or higher, and in order to improve the reliability of the IC, the temperature must be 110℃ or higher.
30~150''C is required.

The characteristics required of the trays used are that the surface resistance should be at a static level of 10' to 10'' Ω, since ICs will be destroyed if charged with static electricity, and that the trays should be stacked in layers, so they should not warp or deform. Smaller items are required.Also, impact strength is required so that it will not easily break if dropped during work.

Up until now, if the temperature of the baking chamber was 110℃ or lower, conductive agents were added to the base of a non-quality resin such as polystyrene, which does not warp easily, or conductive coating was applied. It has been used in many ways. When the temperature of the baking chamber was raised to about 150''C, non-quality resin could not be used because it would undergo thermal deformation in the baking chamber due to its low heat resistance.

For this reason, it was necessary to use a conductive material based on a thermosetting resin such as phenol resin.

When phenolic resin is used, an increase in costs due to the heavy resin itself and poor productivity during molding is unavoidable.

In addition, the tray had a problem of low impact strength and would break if the tray was dropped during work.

For this reason, there is a need for a composition for trays made of a material that is heat resistant regardless of the temperature of the baking chamber, has surface resistance at an electrostatic level, and has excellent warp deformation and impact strength. is the reality.

(Means for Solving the Problems) In response to these circumstances, the present inventors have conducted intensive research to develop a composition that has heat resistance and electrostatic effect, and has excellent warp deformation and impact strength. We have discovered that these problems can be solved by combining polyethylene terephthalate with mica and special carbon black, and have arrived at the present invention.

That is, the present invention includes: (A) 10 to 94% by weight of polyethylene terephthalate having an intrinsic viscosity of 0.35 dl/g or more; (B) an average particle size of 50 μm;
(C) BET specific surface area of 600rrf/g or more, DBP
Oil absorption amount 25 (117100g or more carbon black 1
~20% by weight, (D) Length in resin is 100. This is a composition for a container for transporting semiconductor devices, which contains 0 to 30% by weight of a fibrous material having a particle size of 0 to 30% by weight, and (E) 0 to 10% by weight of a crystallization improver.

In the present invention, polyethylene terephthalate used as component (A) is at least 60% by mole or more, preferably 80% by mole or more, and more preferably 90% by mole.
Any polyester containing the above repeating unit of ethylene terephthalate may be used. Within this range, acid components such as succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, dodecanedioic acid, isophthalic acid, phthalic acid; 1,2-propylene glycol, trimethylene glycol, Trimethylolpropane, 1.
4-butanediol, 1,3-butylene glycol, 1
, 2-butylene glycol, neopentyl glycol,
1.5-bentanediol, 1.6-hexanediol, 1.9-nonanediol, 1.4-cyclohexane dimetatool, ε-caprolactone, 3-methyl-1,5-
A glycol component such as bentanediol may be copolymerized.

3 in a mixed solution of polyethylene terephthalate used in the present invention in phenol/tetrachloroethane (6/4 weight ratio)
The intrinsic viscosity determined at 5°C is preferably 0°35 a/g or more, more preferably 0.45 dl/g or more.

If the intrinsic viscosity is Q or less than 35 dl/g, the mechanical strength will be low (which is not preferable).

The blending amount of polyethylene terephthalate as component (A) is 10 to 94% by weight. If the polyethylene terephthalate component as a matrix constituting the resin is less than 10% by weight, it becomes extremely brittle (preferably 30% by weight or more, more preferably 40% by weight or more.
If it exceeds 94% by weight, the desired effect of reducing warpage and surface resistance cannot be achieved, preferably 80% by weight or more.
It is not more than 70% by weight, more preferably not more than 70% by weight.

These polyethylene terephthalates can be easily produced by conventional production methods, such as melt polycondensation reaction and solid phase polymerization.

The mica used as component (B) includes muscovite mica, stripite mica (Marietta trademark), fluorine phlogopite (synthetic mica), and the like.

Component (B) is essential for improving warp deformation.

The particle size of the mica used is important; in order to reduce warpage, it is better to use mica with a large particle size, for example 50 μm or more, but the brittleness of the resin is proportional to the particle size. Therefore, it is not preferable to use mica with an unnecessarily large particle size. Weight average particle size: 5
The thickness is preferably 0 to 300 μm, and more preferably 50 to 250 μm.

The type of mica used also depends on resin crosstalk and the temperature during molding (
Mica that releases water of crystallization or contained water at temperatures below 300°C is not preferred, and mica that does not release more than 1% of water (equivalent to normal adhering water) at temperatures below 300°C as measured by a thermal balance analyzer (TGA) is preferred.

The blending amount of component (B) is 5 to 40% by weight, more preferably 10 to 30% by weight based on the total composition weight.

If the amount is less than 5% by weight, it is not sufficient to reduce warping deformation, and if it exceeds 40% by weight, not only will it be difficult to mechanically disperse it into polyethylene terephthalate, but the mechanical properties will decrease. This is not desirable because it causes

The carbon black used as component (C) has a BET specific surface area of 600rd/g or more due to N2 adsorption and a D
It must have a BP oil absorption of 250it/100g or more. Carbon black with a BET specific surface area of 600 m/g or less or a DBP oil absorption of 250 at/100 g or less cannot lower the surface resistance sufficiently.

Among the many carbon blacks on the market, carbon blacks such as acetylene black, furnace black, lamp black, thermal black, channel black, roll black and disc black are B.
There is no material that satisfies both requirements, such as a small ET surface area or a small amount of DBP oil absorption.

It satisfies both BET surface area and DBP oil absorption.
Ketjen Black E C is commercially available and easily available.
C: manufactured by AKZO Co., Ltd.).

The blending amount of component (C) is 1 to 20% by weight, preferably 3 to 10% by weight. If the amount is less than 1% by weight, the surface resistance will not be reduced to the electrostatic level, and even if the amount is more than 20% by weight, the reduction in surface resistance will reach saturation, so there is no point.

The composition of the present invention may contain component (D) in addition to components (A) + (B) + (C). The fibrous material of component (D) has the effect of smoothing the surface of the molded product,
For example, when an IC is placed in an ICray, the bonding area between the IC and the ICray becomes larger. For this reason, the static electricity charged on the IC can be accurately discharged to the outside through the ICl-ray.

Examples of fibrous materials used as component (D) include milled fibers obtained by crushing glass fibers, alumina fibers,
Stainless fiber, asbestos fiber, wollastonite (
Calcium silicate), potassium titanate, aramid fiber, etc., and these fibrous materials have L/D (length/diameter) 1
0 or more is preferable.

Among these, milled fibers made by crushing glass fibers and wollastonite are preferred because of their cost and ease of handling.

The length of the fibrous material used in the resin must be 100 μm or less. If a fibrous material with a length of 11001I or more is blended, the surface smoothness will deteriorate, which is not preferable.

The blending amount of component (D) is 30% by weight or less, preferably 5 to 20% by weight based on the total composition weight.

More preferably, - a Si coupling agent; for example, (HJCHxCHtNHCII*CH Mushroom St (OC
Rs) s) and Ti force y7'! J y agent; for example, ((CHs) tellOTi (OOCCt?
The method is to use 5 to 20 weight of milled fiber or wollastonite, which is obtained by pulverizing glass fiber that has been surface-treated with Bs5)3) or the like. If the amount is too small, the effect of improving surface smoothness will be poor, and if it is more than 30% by weight, the surface smoothness will deteriorate, which is not preferable.

Furthermore, component (E) can be added to the composition of the present invention for the purpose of promoting crystallization. (
Component E) has the effect of facilitating molding processability and improving heat resistance.

The crystallization improver used as component (E) is composed of a crystal nucleating agent and a crystallization promoter. When a crystallization improver is added, crystallization can proceed sufficiently even at a mold temperature of 100° C. or less, and high heat resistance can be exhibited. This is especially important when mass production is required or to eliminate dimensional changes.

Examples of crystal nucleating agents include sodium benzoate, potassium benzoate, sodium acetate, titanium oxide, kaolin, calcium carbonate, talc, clay, and ionomers, as well as general formula (1); % formula % (1) [Formula (1) Inside, M and Mo are metals selected from sodium, potassium, and lithium, respectively.

Ar is a benzene ring, and m and n are integers of 1 or 2.

Since Ketschen Black used as component (C) has the effect as a nucleating agent, when Ketchien Black is blended, it is not necessarily necessary to separately blend a crystal nucleating agent.

As a crystallization accelerator, a compound having a molecular weight of 2, which is obtained by reacting a glycol having a carbon atom number of 02 to C6 with an aliphatic dibasic acid, is used.
Polyester with a molecular weight of 20,000 or more, in which 50% or more of the total end groups are blocked with benzoic acid
-Polycaprolactone, p-toluenesulfone alkylamide (the number of carbon atoms in the alkyl group is 14 to 16), polyvalerolactone, polyethylene glycol with a molecular weight of 500 or more in which 50% or more of all terminal groups are blocked with benzoic acid, etc. .

Preferred examples are polybutylene adipate, polypropylene sebacate, end-capped polycaprolactone, and P-toluenesulfone alkylamide.

More preferably, a benzoic acid-terminated polymer with a molecular weight of 5
It is polybutylene adipate having a molecular weight of 500 to 6,000 and polycaprolactone having a molecular weight of 500 to 10,000 and whose ends are capped with benzoic acid.

The combined amount of the crystal nucleating agent and the crystallization promoter is 10% by weight or less. It is preferable to blend 3 to 10% by weight.

If the blending amount is 3% by weight or less, the mold temperature cannot be lowered to 100°C or less. Even if it were to be molded, the thermal deformation would be low, and even if the amount added exceeds 10% by weight, the effect of promoting crystallization would reach saturation, and adding more than the necessary amount would be wasteful. These crystallization improvers may be used alone or in combination of two or more.

In addition, the composition of the present invention may contain a sufficient amount of a halogen flame retardant and an antimony compound to suppress flammability. Examples of the halogen flame retardant include decabrominated diphenyl ether, brominated polystyrene, brominated crosslinked polystyrene, brominated polycarbonate, brominated epoxy resin, brominated phenoxy resin, brominated (bisphenol A/siameric acid) polymer, and the like. Further, examples of the antimony compound include antimony dioxide, antimony pentoxide, triphenylantimony, and sodium antimonate.

When blending a flame retardant, the ratio of halogenated flame retardant/antimony compound is preferably 93/7 to 6B/32.

The blending amount of the flame retardant is preferably 5 to 45% by weight in total of the halogenated flame retardant and the antimony compound based on the total weight of the composition.

Furthermore, the composition of the present invention may contain UV stabilizing agents, antioxidants, heat stabilizers, mold release agents, and colorants within the range that does not impair its practicality.

EXAMPLES The present invention will be explained below with reference to Examples, but the technical scope of the present invention is not limited by these Examples.

In the examples, "part" and "%" indicate [weight part j and [weight %J].

Reference Example 1 100 parts of dimethyl terephthalate, 7 parts of ethylene glycol
1 part, 0.05 part of manganese acetate tetrachloride, and 0.05 part of antimony trioxide were charged into a reactor, and the mixture was heated at 180~
Transesterification reaction was carried out at 200°C for 3 hours. After most of the methanol was distilled off, 0.03 part of trimethyl phosphate was added, and then the temperature was raised to 260°C and the pressure was reduced to 0.
．． The polymerization reaction was carried out at 280° C. for 3 hours under a vacuum of 5 mmHg.

The obtained polymer was white, had a melting point of 260° C. (DSC method, Perkin Elma type 2C), and an intrinsic viscosity of 0.65.

Reference example 2: Polyethylenyl 100 parts of dimethyl mutilephthalate, 7 parts of ethylene glycol
1 part, 0.5 part of disodium p-phenolsulfonate, 0.05 part of manganese acetate tetrachloride, and 0.05 part of antimony dioxide were charged into a reactor, and the mixture was heated to 180 to 200 g under nitrogen flow.
Transesterification reaction was carried out at 0°C for 3 hours. After distilling off most of the methanol, 0.0
3 parts was added, then the temperature was raised to 260°C, the pressure was reduced, and the temperature was increased to 0.5■H.
The polymerization reaction was carried out at 280° C. for 3 hours under a vacuum of 100 g.

The resulting polymer was white with a melting point of 255°C (DS
C method Perkin Elma type 2C), intrinsic viscosity is 0.60 dl
/g. The content of disodium P-phenolsulfonate in the polymer was 0.5% by weight.

Reference Example 3: 100 parts of dimethyl muadipate, 141 parts of 1,4-butanediol, and 0.05 parts of tetrabrobylisotitane were charged into a reactor and esterified at 160 to 210°C for 3 hours under a nitrogen atmosphere. After an exchange reaction was carried out and most of the methanol was distilled off, the temperature was raised to 260°C, a polycondensation reaction was carried out under a vacuum of 0.3 mmHH, and the mixture was taken out into a Teflon vat.

The obtained polymer has a melting point of 48°C and a molecular weight of Mn=6.
,000 (GPC measurement).

Reference Example 4 100 parts of methyl muadipate, 1 part of 1,4-butanediol
41 parts of tetrapropylisotitanate and 0.05 parts of tetrapropylisotitanate were charged into a reactor, and the transesterification reaction was carried out at 160 to 210°C for 3 hours under a N2 stream. After distilling off most of the methanol, the temperature was raised to 260°C. The polycondensation reaction was carried out under a vacuum of 0.3 mmHH.

Next, 30 parts of methyl benzoate was added and the transesterification reaction was carried out again to remove methanol, and the amount of OH end groups was
After continuing the reaction at 200° C. until the temperature decreased to 50% or less of the level before adding benzoic acid, the system was evacuated again to remove unreacted benzoic acid from the system. After that, it was taken out into a Teflon vat.

The obtained polymer was a viscous solid with a freezing point of 40°C.

Reference Example 5 100 parts of ε-caprolactone with a molecular weight of 1.000, 31 parts of methyl benzoate, and 0.05 parts of isopropylene titanate were charged into a reactor, and heated at 120 to 210°C under a N2 stream for 6 hours.
After distilling off a predetermined amount of methanol, the temperature was raised to 220°C, and unreacted methyl benzoate was removed under a vacuum of 0.5 mmHg to block the terminal OH with 88% benzoic acid. A polyester was synthesized.

Reference Example 6: A of Fu... After mixing 40 parts of silicic anhydride, 30 parts of magnesium oxide, 13 parts of aluminum oxide, and 17 parts of potassium silicofluoride, the mixture was melted at 1,400 to 1,500°C, and further 1, 3
Synthetic fluorine phlogopite CKMg by crystallization at 00 to 1.400
3 (AI Si iso+.) p y) was obtained. The obtained synthetic fluorophlogopite ore lump was crushed to obtain synthetic fluorophlogopite powder. Thereafter, separation was performed using a filter to obtain powder having an average particle size of 150 tIm.

Examples 1 to 6 and Comparative Examples 1 to 5 After weighing so as to have the composition shown in Table 1, the mixture was blended for 10 minutes using a rotary drum blender.
m/m two-wheel co-rotating extruder, cylinder temperature 26
After melting and kneading at 0 to 280°C, the mixture was taken out into water and pelletized using a strand machine. The obtained pellets were dried in an oven-type hot air dryer at 140°C for 14 hours.
100 pp of dry resin was obtained. This resin is l5-150
E (manufactured by Toshiba) injection molding machine, cylinder temperature 275℃,
Injection pressure 600-1,000kg/cj, injection time 1° seconds, cooling time 20 seconds, cycle 40 seconds, mold temperature 90℃
The tray shown in Figure 1 was molded using the following steps.

The surface resistance of this tray was measured using an insulation resistance tester (model 2406/manufactured by Yokogawa Electric).Then, the tray was placed in a baking chamber at 150°C and heated for 2 hours, and then cooled to room temperature. The amount of warp deformation was measured as follows.

Furthermore, the tray was held horizontally and allowed to fall freely onto concrete from a height of 1.5 m to determine whether it would crack. The number of broken pieces out of 10 pieces was counted.

Furthermore, the ASTM No. Tanzak piece was molded using a KC-2 [) injection molding machine (manufactured by Yoro Iron Works) at a resin temperature of 280" C2, a mold temperature of 90° C., and a molding cycle of 40 seconds, and the heat distortion temperature ( HDT) was measured at a load of 18.6 kg/d.

It can be seen that trays made of polystyrene have a low HDT and undergo thermal deformation, and trays made of phenolic resin break when subjected to a drop test.

On the other hand, it can be seen that PET mixed with mica is a material with excellent heat resistance, warp deformation, and impact resistance.

In addition, by blending specific carbon black, 1
It can be seen that an electrostatic level of 04 to IQIIΩ is expressed. The results are shown in Table 1.

Examples 7 to 13 and Comparative Example 6 Molded articles of the compositions shown in Table 2 were similarly obtained and evaluated according to the method of Example 1.

If the amount of mica blended is small, warp deformation will be large, but if the amount of mica blended is increased, cracks will occur due to dropping, so there is an appropriate amount of mica to be blended. The types of mica include striped mica (manufactured by Marietta), muscobicobite mica (Indian mica), and even synthetically produced fluorine phlogopite, which exhibits excellent heat resistance, low warpage, and impact strength.

It can be seen that blending milled fiber made by crushing glass fiber or wollastonite as an appearance improver is also effective. The results are shown in Table 2.

Examples 14 to 18 According to the method of Example 1, molded articles of the compositions shown in Table 3 were similarly obtained and evaluated.

It can be seen that HDT can be further increased by adding a crystallization improver. Therefore, problems caused by thermal deformation due to the temperature during baking are eliminated.

The results are shown in Table 3.

Examples 19-21 According to the method of Example 1, molded articles of the compositions shown in Table 4 were similarly obtained and evaluated.

A flame retardant test piece of 1/32 inch tanzak for UL94 was molded using the same method as in Example 1 using a resin containing the composition shown in Table 4 and a flame retardant, and a combustion test was conducted. Ta.

Even when a flame retardant was added, no deterioration in the properties required for the tray was observed. The results are shown in Table 4.

(Effects of the Invention) The semiconductor device transport container composition of the present invention solves the problems of conventionally used general-purpose plastics such as polystyrene and phenol resins, such as lack of heat resistance, brittleness, and high cost, by using a polyethylene terephthalate-based composition. It is of great significance that we have completed a composition that can be solved for the first time by making improvements and can be applied industrially.

[Brief explanation of drawings]

Figure 1 is a schematic diagram showing the IC) Ray molded product.
FIG. 1 is a top view thereof, and FIGS. 1-2 are side views thereof. FIG. 2 is a schematic diagram for measuring the amount of warp deformation by pressing one side of the IC tray shown in FIG. 1 and lifting the opposite side. (1 other person) Figure 1-2

Claims (1)

[Scope of Claims] (A) 10 to 94% by weight of polyethylene terephthalate having an intrinsic viscosity of 0.35 dl/g or more, (B) Average particle size of 50 μm
5 to 40% by weight of mica or more, (C) BET specific surface area of 600 m^2/g or more, DBP
Carbon black 1 with oil absorption of 250ml/100g or more
~20% by weight, (D) 0 fibrous materials having a length of 100 μm or less in the resin
30% by weight, and (E) 0 to 10% by weight of a crystallization improver.