KR20130104398A - Composition for emc mold cleaning comprising cleaning agent grafted polymer - Google Patents

Abstract

PURPOSE: An EMC mold cleaning composition is provided to give an effective heterogeneity as providing continuous coating performance inside of a mold without having odor or fume during volatilization, and no formation of formalin as the composition is hardened. CONSTITUTION: An EMC mold cleaning composition comprises a polymer with one or more of selected 100 parts by weight of glycolehter, ketones group, aminoalcohols group, pyrroles group, and imidazoles of cleaning agent grafted, 10-50 parts by weight of inorganic filler, and 1-10 parts by weight of additive. The polymer is one or more of selected butadiene rubber, styrene-butadien rubber, ethylene-propylene diene monomer rubber, nitrile rubber, nitrile-butadien rubber, and chloroprene rubber.

Description

Composition for EMC mold cleaning comprising cleaning polymer grafted polymer

The present invention relates to an EMC mold cleaning composition comprising a polymer grafted with a cleaner, and more particularly, it provides volatilization while providing continuous coating performance in a mold without generating fumes or odors while volatilizing. The present invention relates to an EMC mold cleaning composition comprising a polymer grafted with a cleaning agent 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 the above molding, the mold release agent contained in the epoxy resin composition flows out from the resin composition to the inner surface of the cavity formed by the upper mold and the lower mold to cause a mold-demolding action. The spilled mold release agent is gradually deteriorated as it accumulates on the inner surface and oxidizes, forming a hard oxidized mold-depigmenting agent layer (where the surface of the layer 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 .

When such oxidized and deteriorated mold-depigmenting agent layer is once formed on the inner surface of the mold at the time of molding, the epoxy resin composition and further the mold-releasing agent are not oxidized and deteriorated from the resin composition to the surface of the mold, The mold-defoliating agent can not provide sufficient 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.

In order to achieve the above object,

100 parts by weight of a polymer grafted with at least one detergent selected from glycol ethers, ketones, amino alcohols, pyrroles, and imidazoles;

10-50 parts by weight of inorganic filler; And

As an EMC mold cleaning composition comprising a polymer grafted with a detergent, characterized in that the mixture is made by mixing;

The polymer is selected from the group of butadiene rubber (BR), styrene-butadiene rubber (SBR), ethylene-propylene diene monomer rubber (EDPM), nitrile rubber (NR), nitrile-butadiene rubber (NBR), and chloroprene rubber (CR). One or more EMC mold cleaning compositions are provided.

The cleaning composition for the EMC mold according to the present invention does not generate formalin while curing, does not generate fumes or odors while volatilization, and provides effective releasability while providing continuous coating performance inside the mold to operate the EMC mold. It has excellent properties and can prevent environmental pollution.

Hereinafter, the present invention will be described in detail.

In the cleaning composition of the present invention, the base material is a polymer, which is natural or artificial rubber. The rubber component is cured by the action of the curing agent contained when the inside of the semiconductor mold under heat and pressure is formed in the shape of the inside of the mold.

It is required to be formed in the shape of the mold inside the mold so as to exactly coincide with the inside of the mold so that the coating components can flow out to the outside while the rubber is molded so that the coating can be accurately formed on the inner surface of the mold. Therefore, the polymer component used in the present invention should be able to achieve an accurate shape inside the semiconductor mold and should be made to facilitate the outflow of coating components.

Polymer components include butadiene rubber (BR), styrene-butadiene rubber (SBR), ethylene-propylene diene monomer rubber (EDPM), nitrile rubber (NR), nitrile-butadiene rubber (NBR), and chloroprene rubber (CR). At least one mixture selected or a modification thereof. Of these, butadiene rubber and styrene-butadiene rubber having a 1,2-syndiotactic arrangement having a stereoregular arrangement in the butadiene rubber are preferable.

In the present invention, by grafting the cleaning agent to the polymer component, it is characterized by improving the mold release property while enhancing the cleaning performance.

Detergents include glycol ethers, ketones, amino alcohols, pyrrole, imidazoles, and imidazolines, and may be used in one or more combinations.

The 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, and may be used in one or more combinations.

Aminoalcohols include monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N, N-dimethylethanolamine, N, N-dibutylethanolamine, N- Methyl-N, N-diethanolamine, 2-amino-2-methylpropanol, 3-aminopropanol and 2-aminopropanol and may be used in one or more combinations.

The imidazole is selected from the group consisting of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl- -Methylimidazolyl- (1) '] ethyl-s-triadine, which may be used in one or more combinations.

Imidazoline is selected from the group consisting of 2-methylimidazoline, 2-methyl-4-ethylimidazoline, 2-phenylimidazoline, 1-benzyl- 2-methylimidazolinyl- (1) '] ethyl-s-triazine, 2,4-diamino-6 [2'-methyl -4'-imidazolinyl- (1) '] ethyl-s-triazine, 1-cyanoethyl-2-methylimidazoline and 1-cyanoethyl- And may be used in one or more combinations.

The content of the detergent grafted to the polymer may be set in the range of preferably 10 to 30 parts by weight, more preferably 15 to 25 parts by weight based on 100 parts by weight of the polymer rubber. When the content of the cleaning agent is less than 10 parts by weight, it is difficult to exhibit a satisfactory cleaning effect on the mold. When the content exceeds 30 parts by weight, the composition adheres to the mold, The efficiency is deteriorated, which is not preferable.

The inorganic filler 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 set in the range of preferably 10 to 50 parts by weight based on 100 parts by weight of the rubber.

In addition, the cleaning composition of the present invention may include an additive added during general rubber compounding. Such additives are known materials used in general rubber formulation, and include crosslinking agents, antioxidants, separation aids and the like. The content of the additive is preferably 1 to 10 parts by weight based on 100 parts by weight of the rubber content.

The crosslinking agent causes a crosslinking reaction between the rubber molecule chains to form a rubber cured product. Examples include 2,5-dimethyl-2,5-bis- (t-butylperoxy), dt-butylperoxide, 2,5- (t-butylperoxy-i-propyl) -benzene, dicumylperoxide, 4,4-di-t-butylperoxy-n-butylvalerate, t-butylperoxy Benzoate, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, benzoyl peroxide, bis- (2,4-dichlorobenzoyl) -peroxide and the like.

The separation assisting agent may be imidazole or imidazolyl which may be used alone or in combination with an organic solvent such as water, methanol, ethanol, n-propane, etc., or an alcohol such as toluene, Can be increased.

According to one embodiment of the present invention, silicone oil and wax may be additionally included. Silicone oil is basically a substance which is conventionally used as a coating component by dissolving in a nucleic acid which is an organic solvent, and may be mixed with silicone oil to provide excellent coating performance.

The silicone oil improves the mold coatability and improves releasability of the product after molding the semiconductor product. Since the silicone oil itself is in a liquid form, it is difficult to mix it 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 state where the wax is present, it is improved in compatibility with the rubber, and the silicone oil can have coating and releasability. 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.

In the present invention, as the wax is blended 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 too small, sufficient coating performance can not be exhibited inside the mold. If the wax content is too large, the strength of the rubber decreases, causing easy breakage. Chips may be broken into minute portions of the chip, which may cause 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, mixing with silicone oil having heat resistance rather than wax alone desirable. 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 carnauba wax, montan opax, 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 silica filler 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 the rubber component containing 70 g of SBR and 30 g of EPDM grafted with mono ethanolamine, followed by kneading and mixing. The sheet was formed into a sheet, and the mold was washed for 6 minutes at a pressure of 2000 to 2300 PSi at 180 ° C in the mold. The results are shown in Table 1 below.

Example 2

70 g of silica filler 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 component containing 70 g of SBR and 30 g of EPDM grafted with methyl ethyl ketone, and then kneaded and mixed. The sheet was formed into a sheet, and the mold was washed for 6 minutes at a pressure of 2000 to 2300 PSi at 180 ° C in the mold. The results are shown in Table 1 below.

Comparative Example 1

100 g of the rubber component containing 70 g of SBR and 30 g of EPDM, 80 g of silica filler, 2 g of amino alcohol cleaner, and additives (1 g of stearic acid, 5 g of titanium dioxide, 1 g of antioxidant, 2.5 g of crosslinking agent) were kneaded and mixed, and then in the form of a sheet. 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

Prepared in sheet form after kneading and mixing after adding 80g of silica filler, 2g of ketone cleaner, 2g of additives (1g of stearic acid, 5g of titanium dioxide, 1g of antioxidant, 2.5g of crosslinking agent) to 100g of rubber component containing 70g of SBR and 30g of EPDM The mold was cleaned for 6 minutes at a pressure of 2000-2300 PSi at 180 ° C. 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, ○: good, △: normal, ×: bad

Referring to Table 1, Examples 1 and 2 using the grafted polymer rubber can confirm the excellent cleaning properties in the mold compared to other Comparative Examples 1 and 2 without grafting the cleaner. 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 polymeric rubber have been shown to affect workability, such as detergency and mist / odor.

Claims (5)

100 parts by weight of a polymer grafted with at least one detergent selected from glycol ethers, ketones, amino alcohols, pyrroles, and imidazoles;
10-50 parts by weight of inorganic filler; And
As an EMC mold cleaning composition comprising a polymer grafted with a detergent, characterized in that the mixture is made by mixing;
The polymer is selected from the group of butadiene rubber (BR), styrene-butadiene rubber (SBR), ethylene-propylene diene monomer rubber (EDPM), nitrile rubber (NR), nitrile-butadiene rubber (NBR), and chloroprene rubber (CR). At least one EMC mold cleaning composition.
The method of claim 1,
The inorganic filler is EMC mold cleaning composition comprising a polymer 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.
The method of claim 1,
EMC mold cleaning composition comprising a polymer grafted with a detergent, characterized in that it further comprises 1 to 5 parts by weight of silicone oil and 5 to 10 parts by weight of wax as a coating component.
The method of claim 1,
The additive includes a EMC mold cleaning composition comprising a polymer grafted with a detergent, characterized in that it comprises a crosslinking agent, an antioxidant, and a separation aid.
5. The method of claim 4,
The separation aid is EMC mold cleaning composition comprising a polymer grafted with a detergent, characterized in that at least one selected from imidazole and imidazolyl.