KR101334249B1 - Composition for EMC mold cleaning comprising cleaning agent grafted inorganic filler - Google Patents

Abstract

Natural rubber (NR), chloroprene rubber (CR), butadiene rubber (BR), nitrile rubber (NBR), ethylene-propylene terpolymer rubber (EPT), ethylene-propylene rubber (EPM), ethylene-propylene diene rubber (EPDM) 10 to 50 parts by weight of an inorganic filler grafted with a cleaner, based on 100 parts by weight of at least one mixture rubber component selected from the group consisting of styrene-butadiene rubber (SBR) and polyisoprene rubber; And it discloses an EMC mold cleaning composition comprising an inorganic filler grafted with a cleaning agent, characterized in that by mixing 1 to 10 parts by weight of the additive. The cleaning material for EMC mold according to the present invention does not generate formalin while hardening, does not generate fume or odor while volatilization, and provides effective release property while providing continuous coating performance inside the mold, thereby providing workability of the EMC mold. It is excellent and can prevent environmental pollution.

Description

Composition for EMC mold cleaning comprising cleaning agent grafted inorganic filler

The present invention relates to a composition for cleaning an EMC mold including an inorganic filler grafted with a cleaner, and more particularly, volatilization does not generate fume or odor, and provides effective mold release property while providing continuous coating performance inside the mold. The present invention relates to an EMC mold cleaning composition comprising an inorganic filler grafted with a cleaner having excellent workability of the EMC mold.

Semiconductor devices such as transistors, integrated circuits (IC), high density integrated circuits (LSI), etc. are typically resin-encapsulated by plastic packaging. Such resin encapsulation is carried out by using a thermosetting resin composition such as an epoxy resin composition or the like, and performing casting, compression molding, injection molding, transfer molding, especially mass transfer productivity with excellent productivity and workability. However, the above-described transfer molding is carried out continuously when the semiconductor element is resin-encapsulated by the transfer molding using the epoxy resin composition, because the molding die or the die is not releasing the mold releasing agent in the epoxy resin composition agent, which causes the molding to fail.

That is, in molding, the mold releasing agent contained in the epoxy resin composition flows out of the resin composition to the inner surface of the cavity formed by the upper mold and the lower mold, resulting in a mold- demolding action, but when the molding is repeated, it flows out to the inner surface of the mold. The deformed mold release agent gradually accumulates and oxidizes on the inner surface to be deteriorated, thereby forming a hard oxidized mold-releasing agent layer (the layer surface is not as smooth as the inner surface of the mold). Further, the molding is carried out on the surface of the oxidized and deteriorated mold-defoliating agent layer, whereby the surface pattern of the oxidized and deteriorated mold-defoliating agent layer is transferred to the surface of the molded article so that the surface of the molded article becomes rough and uneven .

In addition, once such an oxidized and deteriorated mold-releasing agent layer is formed on the inner surface of the mold during molding, the epoxy resin composition, and further, the mold-releasing agent is not oxidized and degraded from the resin composition to the surface of the mold. It flows out to the release agent layer, whereby the mold-release agent cannot sufficiently provide the mold- demolding action.

Generally, when a product is molded using a thermosetting resin, in particular, an EMC molding process for semiconductor manufacturing requires high-quality product reliability. In order to form such a high-quality product, a cleaning operation to remove contaminants remaining in a semiconductor mold must be performed from time to time. In addition, a release agent is coated on the surface of the mold to facilitate detachment of the thermosetting resin by repeated operations.

Such a cleaning and releasing process is indispensable, and its importance becomes more important as semiconductor devices become more highly integrated. In particular, the mold release process directly affects the quality of the semiconductor device. If the mold releasing property is not properly performed on the surface of the mold, it takes much time to repair the product as well as the entire product. Therefore, Are being developed in tandem with the high integration of semiconductor devices.

In the case of melamine resin used as EMC Mold cleaning material, there was a problem that formalin was generated while curing, and in the case of rubber sheet, it was volatilized while curing at high temperature of 150 ~ 180 ℃ of cleaning component to generate fume or odor. There was a problem.

In order to solve the above problems, an object of the present invention is to provide an EMC mold cleaning composition having excellent mold release property without generating fume or odor by mixing an inorganic filler grafted with a cleaning agent.

In order to achieve the above object,

Butadiene rubber (BR), styrene-butadiene rubber (SBR), ethylene-propylene diene monomer rubber (EPDM), nitrile rubber (NR), nitrile-butadiene rubber (NBR), and chloroprene rubber (CR) Based on 100 parts by weight of the above mixture rubber component,

10-50 parts by weight of the inorganic filler grafted detergent; And

Provided is an EMC mold cleaning composition comprising an inorganic filler grafted with a cleaning agent, characterized by mixing 1 to 10 parts by weight of an additive.

The cleaning material for EMC mold according to the present invention does not generate formalin while hardening, does not generate fume or odor while volatilization, and provides effective release property while providing continuous coating performance inside the mold, thereby providing workability of the EMC mold. It is excellent and can prevent environmental pollution.

Hereinafter, the present invention will be described in detail.

The rubber used in the present invention is a natural or artificial rubber, the rubber component is cured by the action of the curing agent contained when the inside of the semiconductor mold is subjected to heat and pressure is formed in the shape of the inside of the mold.

Molding in the mold inside the mold shape to be exactly the same as the inside of the mold to be described later coating components flow out to the rubber is molded to be able to make an accurate coating on the inner surface of the mold. Therefore, the rubber used in the present invention should be able to achieve an accurate shape inside the semiconductor mold.

Rubber components include natural rubber (NR), chloroprene rubber (CR), butadiene rubber (BR), nitrile rubber (NBR), ethylene-propylene terpolymer rubber (EPT), ethylene-propylene rubber (EPM), ethylene-propylene diene One or more mixtures selected from the group consisting of monomer rubber (EPDM), styrene-butadiene rubber (SBR), polyisoprene rubber (IR), butyl rubber (IIR), silicone rubber (Q), fluorinated rubber (FKM) Water.

ETPs are cyclic or acyclic copolymers containing ethylene, α-olefins, and non-cojugated double bonds.

EPDM is a ternary copolymer containing ethylene, α-olefins (particularly propylene) and polyene monomers listed below, examples of the polyene monomers being dicyclopentadiene, 1,5-cyclooctadiene, 1,1 -Cyclooctadiene, 1,6-cyclododecadiene, 1,7-cyclododecadiene, 1,5,9-cyclododecadiene, 1,4-cycloheptadiene, 1,4 Cyclohexadiene, norbornadiene, methylenenorbornene, 2-methylpentadiene-1,4,1,5-hexadiene, 1,6-heptadiene, methyl-tetrahydroindene and 1, 4-hexadiene.

In the present invention, by grafting the cleaning agent to the inorganic filler component, it is characterized by improving the mold release property while enhancing the cleaning performance. Examples of the cleaning agent include glycol ethers, ketones, esters, pyrroles, imidazoles, imidazolines and amino alcohols, and can be used in one or more combinations.

Examples of glycol ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl Ether, diethylene glycol diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether may be used and used in combination of one or more of them.

Examples of ketones include acetone and methyl ethyl ketone.

Ester, ethyl formate, propyl formate, isobutyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, etc. are mentioned.

Examples of imidazoles are 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole and 2,4-diamino-6 [ 2'-methylimidazolyl- (1) '] ethyl-s-triadine, and may be used in one or more combinations.

Examples of imidazolines include 2-methylimidazoline, 2-methyl-4-ethylimidazoline, 2-phenylimidazoline, 1-benzyl-2-methylimidazoline, 2-phenyl-4-methyl- 5-hydroxymethylimidazoline, 2,4-diamino-6 [2'-methylimidazolinyl- (1) '] ethyl-s-triadine, 2,4-diamino-6 [2' -Methyl-4'-imidazolinyl- (1) '] ethyl-s-triadine, 1-cyanoethyl-2-methylimidazoline and 1-cyanoethyl-2-methyl-4-ethyl Midazoline may be included and may be used in one or more combinations.

Representative examples of amino alcohols include monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N, N-dimethylethanolamine, N, N-dibutylethanolamine, N, N-diethylethanolamine , N-methyl-N, N-diethanolamine, 2-amino-2-methylpropanol, 3-aminopropanol and 2-aminopropanol, and may be used in one or more combinations.

The content of the detergent grafted to the inorganic filler may be set in the range of preferably 10 to 30 parts by weight, more preferably 15 to 25 parts by weight with respect to 100 parts by weight of the filler content. If the content of the cleaning agent is less than 10 parts by weight, it is not preferable because it is difficult to achieve a satisfactory cleaning effect on the mold. If the content of the cleaning agent is more than 30 parts by weight, the composition adheres to the mold and the composition of the composition is removed from the mold. It is not preferable because the removal operation efficiency is deteriorated.

Inorganic fillers may include silica, alumina, carbon black, calcium carbonate, calcium silicate, aluminum hydroxide, titanium oxide, titanium dioxide, titanium hydroxide, and the like. The content of the inorganic filler may be preferably set in the range of 10 to 50 parts by weight based on 100 parts by weight of rubber.

Depending on the type of cleaning agent, the method of grafting on the inorganic filler is different. For example, alcohols and ketones are grafted using a hydroxyl group and a carboxyl group, and other cleaning agents are bonded using a coupling agent.

The material composition of the present invention comprises an additive added during general rubber compounding. Such additives correspond to known materials used in general rubber formulation. It can be prepared by adding an additive used in rubber compounding such as a crosslinking agent, an antioxidant and titanium dioxide stearic acid. The content of such additives is preferably 1 to 10 parts by weight based on 100 parts by weight of rubber.

According to the present invention, silicone oil and wax may be further included.

Silicone oil is basically a substance that is used as a coating component by dissolving in a nucleic acid which is an organic solvent in the prior art, in the present invention is a silicone oil and wax is mixed to give a better coating performance.

The basic action of the silicone oil is to improve the mold coating property, and to improve the mold release property of the product after molding the semiconductor product. Since the silicone oil itself is in liquid form, it is difficult to be mixed with rubber alone. Silicone oil alone does not disperse evenly when mixed with rubber, and rubber sheet formation can not be achieved. Therefore, as the silicone oil is added in the presence of the wax, the blendability with the rubber is improved, and the coating oil release property, which is a role of the silicone oil, can be obtained. The silicone oil that can be used is either a reactive silicone oil having reactive groups such as an amino group, an amine group, an epoxy group phenyl group, or a non-reactive silicone oil such as a dimethyl silicone oil. In the case of silicone oil containing reactive group, it can last for a long time when coating on the mold surface, so the durability of mold coating ability is increased, and in the case of non-reactive silicone oil, wax coating ability is increased by increasing wax emulsification. Make it better.

Wax is a material that is conventionally used as a coating component, like natural canon wax. However, in the present invention, as the wax is mixed with the rubber component and the rubber component is cured in the semiconductor mold, the wax component must be eluted. Therefore, for such elution, the wax must be mixed in an appropriate amount. If the wax content is less than 5% by weight, sufficient coating performance may not be exhibited in the mold. If the content of the wax content is more than 15% by weight, the strength of the rubber decreases, thereby causing easy breakage. Rather, it may cause chip out broken in minute parts inside the mold, causing defects in semiconductor manufacturing. In addition, the addition of an excessive amount of wax takes a long time to cure the rubber, and some of the carbonization itself becomes a source of contamination.

Basically, when the rubber is hardened, the temperature is about 120 ℃, so it is necessary to have a wax that is not carbonized even under the above temperature. However, since the wax is vulnerable to heat resistance, it is mixed with a silicone oil having heat resistance to be described later rather than the wax alone. It is desirable to. Therefore, the lack of heat resistance is supplemented with silicon oil is suppressed carbonization, and also the liquid silicone oil can be well blended with the rubber. In addition, waxes that can be used in the present invention allow one or a mixture of two or more of cannober wax, montan opac, ester wax, polyethylene wax, and polypropylene wax to be used.

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to the examples.

Example

Example 1

70 g of monoethanolamine grafted silica, 100 g of rubber component containing 70 g of SBR and 30 g of EPDM, and additives (1 g of stearic acid, 5 g of titanium dioxide, 1 g of antioxidant, 2.5 g of crosslinking agent), followed by kneading and mixing, followed by sheet form The mold was cleaned in a mold for 6 minutes at a pressure of 2000 ~ 2300 PSi at 180 ℃. The results are shown in Table 1 below.

Example 2

70 g of monoethanolamine-grafted silica, 70 g of monoethanolamine, and additives (1 g of stearic acid, 5 g of titanium dioxide, 1 g of antioxidant, 2.5 g of crosslinking agent) were added to 80 g of rubber components containing 70 g of SBR and 30 g of EPDM, and then kneaded and mixed. The mold was cleaned in a mold for 6 minutes at a pressure of 2000 ~ 2300 PSi at 180 ℃. The results are shown in Table 1 below.

Comparative Example 1

80 g of silica, 2 g of amino alcohol detergent, and additives (1 g of stearic acid, 5 g of titanium dioxide, 1 g of antioxidant, 2.5 g of crosslinking agent) were added to 100 g of a rubber component containing 70 g of SBR and 30 g of EPDM, followed by kneading and mixing. The mold was washed in a mold for 6 minutes at a pressure of 2000 to 2300 PSi at 180 ° C. The results are shown in Table 1 below.

Comparative Example 2

After adding 80 g of silica, 2 g of ketone cleaner, and additives (1 g of stearic acid, 5 g of titanium dioxide, 1 g of antioxidant, 2.5 g of crosslinking agent) to 100 g of a rubber component containing 70 g of SBR and 30 g of EPDM, kneading and mixing were carried out to form a sheet. The mold was cleaned for 6 minutes at a pressure of 2000-2300 PSi at 180 ° C in the mold. The results are shown in Table 1 below.

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Cleanliness ◎ ○ ○ △ smog ○ ◎ × △ odor ○ ◎ × △ Formability ○ ○ ○ ○

◎: Very good, ○: Excellent, △: Normal, ×: Poor

Referring to Table 1, Examples 1 and 2 using the inorganic filler grafted cleaning agent can confirm the excellent cleaning properties in the mold compared to the other Comparative Examples 1 and 2 not grafting the cleaning agent. The unique rejection caused by the smell of the cleaner was reduced, and workability was also improved. The moldability in the mold was also shown to remain at the existing level. Changes in the content of grafted inorganic fillers have been shown to affect workability, such as cleanliness and mist / odor.

Claims (5)

Natural rubber (NR), chloroprene rubber (CR), butadiene rubber (BR), nitrile rubber (NBR), ethylene-propylene terpolymer rubber (EPT), ethylene-propylene rubber (EPM), ethylene-propylene diene rubber (EPDM) Based on 100 parts by weight of one or more mixture rubber components selected from the group consisting of styrene-butadiene rubber (SBR) and polyisoprene rubber,
10-50 parts by weight of the inorganic filler grafted detergent; And
EMC mold cleaning composition comprising an inorganic filler grafted with a cleaning agent, characterized in that by mixing the additive 1-10 parts by weight.
The method of claim 1,
The cleaning agent is EMC mold cleaning composition comprising an inorganic filler grafted with a cleaning agent, characterized in that at least one selected from glycol ethers, ketones, esters, pyrroles, imidazoles, imidazolines and amino alcohols.
The method of claim 1,
The inorganic filler is for EMC mold cleaning comprising an inorganic filler grafted with a cleaner, characterized in that at least one selected from silica, alumina, carbon black, calcium carbonate, calcium silicate, aluminum hydroxide, titanium oxide, titanium dioxide and titanium hydroxide. Composition.
The method of claim 1,
EMC mold cleaning composition comprising an inorganic filler grafted with a cleaning agent, characterized in that it further comprises 1 to 5 parts by weight of silicone oil and 5 to 10 parts by weight of the wax as a coating component.
The method of claim 1,
The additive is EMC mold cleaning composition comprising an inorganic filler grafted with a cleaning agent, characterized in that it comprises at least one selected from stearic acid, titanium dioxide, antioxidants, and crosslinking agents.