TW567213B - Rubber composition for washing mold - Google Patents

Abstract

The present invention relates to a rubber composition for cleaning a mold used for forming a product, particularly a rubber composition used for cleaning contaminants generated in a mold for an EMC forming technique. That is, the composition according to the present invention mainly comprises rubber, mixed with a cleaning compound, a hardener, and inorganic additives. The composition can effectively remove pollutants in a mold, and eliminate the irritating odors and smoke generated in the operation, thereby improving the operation environment and increasing the operation efficiency.

Description

567213 V. Description of the invention (1) [Detailed description of the invention] [Objective of the invention] [Field of the invention and prior art in the field] The finished product is related to the removal of contaminants on the mold. Cleaning rubber compound "Ming" is more specifically about the invention of using β as the main component, and using β compounds, inorganic compound particles, and other additives to obtain β 4 & products. The composition of the invention can be used in molds Moreover, it can be used for the molds used in the manufacture of semiconductors. 8. J 疋 田 & ί The mold used in the stamping or thermoforming process using the solid resin as the raw material is used in the mold as the work process progresses. Fouling will remain in the future / 54 Ϊ. This remaining substance 4 will play a role in contamination in the repeated operation process. This will not only cause the product to be defective, but also in the subsequent molding process: 锸 二 、 九Including the carbonized residue produced by the carbonization of the molded product, it is generally used in the production of complex molded products or molded products. It is remarkable that, for example, the semiconductor manufacturing process is ϋ, and The assembly process surrounded by thermosetting resins (emc molding is also difficult to " " the seeding / dyeing phenomenon has become an important issue, even by hand will be more robust: Carry out the role of 'carbonization residue'. On the mold, so that the mold can no longer function as a normal mold-after a fixed time or number of operations, it must be removed and left in n μ μ In order to effectively perform this cleaning operation, it is now being Cleaning methods that use a variety of thermosetting greases.

567213 V. Description of the invention (2) This cleaning method The inside of the mold is cleaned by the resin mass for cleaning with the application of the normal good process. This cleaning tree has two main ingredients. The month b is low, and it will leave a lot of time for cleaning resin (called, the time required is also short odor, and it will cause the deterioration of the working environment. [The purpose of putting the invention into practice is Elimination has been waiting to solve the irritating odor and smoke on the basis of the existing technology. The second purpose is the secondary pollution of the residue. The third purpose is to improve the cleaning effect. The fourth purpose is to use nuclear solid state. The cleaning resin is injected with heat and pressure to seal the mold, so that the cleaning resin is cured as well as the pollutants such as residues. Therefore, as the cleaning resin is removed, the mold is also coated with honey. Cleaning resins containing amine resin as the main component and rubber containing melamine as the main component have cleaning effect resin residues. This residue requires manual removal and labor. On the contrary, cleaning rubber containing rubber as the main component ") Has excellent cleaning performance, clean, will produce more tar, emit very sub-contamination (that is, re-contamination around the ejector rod) makes the required technical issues ^ The above-mentioned technical problems of the prior art, to solve the past technical problems. Specifically, first, the melamine resin produced in the process of using melamine and rubber must be eliminated. The tar produced in the resin process: By reducing the time compared with the existing honey-faced peppers and daggers, S ... grease or rubber tree is intended to improve the cleaning of molds (especially when cleaning semiconductors)

5162-3542-PF.ptd Page 5 567213 V. Description of the invention (3) When the mold of the body) is produced, the bad working environment caused by odor and smoke. [Composition of the invention] In order to achieve this object, the composition of the present invention is obtained by mixing rubber as a main component 'with a cleaning compound, a hardener, and an inorganic additive and a processing aid. Specifically, the rubber composition for cleaning mentioned above has a rubber content of 30-60%, an inorganic additive of 20-60%, a cleaning compound of 1-20%, and a hardener of 0.5-5%. When the above rubber components are subjected to heat and pressure, they will be hardened in the mold due to the role of the hardener, and contamination will be eliminated accordingly. The rubber used in the present invention can be selected from ethylene-propadiene monopolymer rubber (EpDM), natural rubber (NR), stilbene-butene rubber (SBR), butadiene rubber (BR), air-butadiene rubber ( CR), nitro-butadiene rubber (NRB) fluorinated rubber, polypropylene rubber, silicone rubber and butyl rubber, or a mixture of two or more of them, or a derivative of this material, a mixture of formic EpDM and fluorene Rubber is better. When the above-mentioned rubber component enters the mold and is subjected to heat and pressure, it is hardened under the action of a hardener, and becomes a mixture containing a cleaning compound, an absorbent, and a contaminant. During use, the cleaning compound is added to the inorganic additive, and then it is mixed with rubber and processed into a sheet or the like. This sheet-shaped rubber is hardened after absorbing pollutants in the mold, and the dyed matter is eliminated when the hardened f-piece is removed, so the operation is convenient and effective, and cleaning compounds and inorganic additives are also stained on the hardened rubber. One is eliminated, so the problem of secondary pollution can be improved.唣 The role of the above cleaning compounds is to release the pollutants from the mold, and the rubber is contained in the inorganic absorbent. Representative of this cleaning compound

567213 5. Description of the invention (4) The amino alcohol compounds, hydroxyl groups, and isopyrazole series compounds are the most effective ones. Among them, amino alcohol compounds and isopyrazole series are more effective. Examples of the above-mentioned amino alcohol series compounds include 2-aminoethanol, 2- (2-aminoethoxy) ethanol, monoethanolamine, diethanolamine, 2-amino-2-ethyl-1,3-propanediol, and 2-amino- 2 (Methylmethyl) -1,3-propanediol, 2-amino4-Methyl-6-methylamidine, 2- (2-aminoethylamino) ethanol, 2-amino-3 -hydroxypyridine, Triethanolamine, ethanolamine hydrochloride, 3-amino-1 monopropanol, 2-amino-1-propanol, 1-amino-2-propanol, 3-amino-1, 2-propanediol, 3-amino-1 -Propanol vinyl ether, 2-aminophenol, 2-aminophenyl alcohol, 3-aminophenol, 4-aminophenol, 4-methyl-1,2,4-triazole-3, 5-dione, Dibutylamino) ethanol, 2- (ethylamino) ethanol, and the like. Examples of the above-mentioned compounds of the acyl group and the iso-D ratio are 2-mercaptobenzylamine, 4-basic amine, 2-basic flavor, 1- (2-methylethyl) amidine, (2-hydroxy Ethyl) piperidine, bu (2-hydroxymethyl) -2-pyrrolidine, 2,4-diamidyl-6-methylpyrimidine, 2, 4-diamino-6-hydroxypyridine, 2-hydroxyethyl Hydrazine, 4- (hydroxyamido) imidazole, 2-ethyl-4-amidoimidazole, l- (3-aminopropyl) imidazole, 2-hydroxyethylhydrazine, (2-hydroxyethyl) — 2-imidazolidinone, imidazole, 4-imidazole methanol, 2-imidazole ethanol, 2-imidazolone, and the like. The above-mentioned cleaning compound determines whether the composition of the cleaning rubber composition is appropriate depending on the cleaning ability and whether or not tar is generated. For example, the rubber composition for cleaning semiconductor molds should be selected as a perfect compound which can effectively remove the contaminants in the mold from the mold and can be well mixed with the rubber resin. The above-mentioned cleaning compounds can use one or a mixture of two or more of the normal substances shown above, for example, based on the amino fermentation series as the main component.

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Add a small amount of hydroxyl and isopyrazole to use other than the above compounds. A series of cleaning compounds. According to the situation, other compounds, or mixed with the above-mentioned compounds, can be obtained. 4 The above-mentioned clear: the amount of compounds used in the mesh conveyor is synthetic ... 1-20% of weight, or 3-10%, = fruit. The content of the compound is lower than the lower limit of the above range, and it will cause hardening. It will leave a residue in the mold after hardening. The role of the inorganic additive is to act as a component and absorb and eliminate the cleaning compound. The irritating odor and fumes generated during the operation are used as organic additives, which can be used in inorganic compounds that have a component effect and are beneficial to the formation of irritating odors and fumes. Representative examples of such inorganic additives include silicon dioxide, activated alumina, silicon gel, giant silicon, amorphous aluminum silicate (AmOrphus Aluminosi 1 icate), crystalline aluminum silicate, and the like. Among them, silicone, non-crystalline aluminum silicate and crystalline aluminum silicate are more preferable. These may be used alone or in combination of two or more. Examples of non-crystalline aluminum silicate include diatomite, kaolin, white clay, and the like. There are more than 34 types of zeolites and about 1,000 types of synthetic zeolites. Specific examples of natural zeolites include anal cime, chabaxi te, gmel ini te, epistilbite, heulandite, stilbite, and zeolite (Edingtonite), Mesolite, Boiling

5162-3542-PF.ptd Page 8 567213 V. Description of the invention (6) Brewsterite, Faujasite, Viseite, Offretite, Mordenite 'Specific examples of synthetic zeolites include zeolite A, zeolite L, zeolite T, zeolite K-G, zeolite ZK-5, zeolite X, zeolite Y, zeolite ZSM-5, zeolite D, zeolite S, zeolite R, zeolite P, Zeolite Z-21, zeolite S, etc. The effect of the composition of the present invention varies depending on the number of pores of the coke machine feed, and the more the pores are more excellent. Compared to silicates with smaller pores, zeolites with reasonably large pores (about 3-20 A) are more effective for the composition of the present invention. The pore size is more preferably 6 A or more. If the pores are too small, it will result in the above-mentioned irritating odor and fumes being difficult to be sucked into the pores. However, if an inorganic compound with smaller pores is used, in order to achieve the desired characteristics, the content ratio in the composition can be increased to a higher level than an inorganic compound with an appropriate pore size to supplement this deficiency. The content of the inorganic additive is 20 to the total weight of the composite, more precisely 30-50%. As long as it does not affect the cleaning effect, it can be increased to the above content. In the compound of the present invention, it has a hardener that causes rubber molecules to crosslink when heated to harden the rubber. Typical examples are 2,5_dimethyl_2 5 2T (upper-butylperoxy) _hexyne_3, di-third `` butylperoxy: Dagger, '5-methyl-2,5-bis- (third-butyl peroxy) (Oxygen) monohexyne, tertiary cumyl peroxide, bis- (tertiary alkoxyperoxy-propylpropyl) _benzene 7 dibutyldicyclohexanedi = 4, 4, 4-di-tertiary-butyl Peroxy U-valeric acid, [three: terephthalic acid, i, bis-tertiary-butylperoxy-3,3,5-trimethylbenzidine peroxide, bis (2, 4 — 曱 醯) -over

567213 ------ ------ V. Description of the invention (7) ~ ^ ------ Oxides and sulfur. Among them, bis- (third to 4-bis-third-butylperoxy-n-butylpentanylperoxy-1-propyl) -benzene and 4, cleaning compounds are effective. The ^ of the hardener is 1-4% in the case of the mixed rubber with ⑽ and ⑽. If it is set to 0.5-5% ', it can be added more accurately according to the specific use', and melamine can be used as a cleaning aid. Cellulose and others. Agent or cellulose (cellulose, thereby improving the efficiency of the cleaning process. ♦, can suppress > the flow of cleaning rubber, the amount of addition should be 20% of the total weight of the composition. When each cleaning auxiliary ingredients are included In order to observe the stained 铷 η τ 7 wood objects with or without the mold, the typical substances are titanium oxide, etc., two: Use the color Division A. 1 use of one or two or more kinds of mixing does not affect ^ @ Π _ wr 玍, which is characteristic of the composition of the present invention, can be added, and other compounds or mixtures can be added. &Amp; Others The present invention relates to a method for cleaning a mold, especially a mold for a semiconductor manufacturing process, using the above composition. The process is as follows: First, a certain amount of the rubber composition is added to the mold, and a pressure of 15-100 kgf / cm2 at a temperature of 16-20 ° C is applied for 2-10 minutes to harden the composition into a mold. The internal design shape allows the contaminants in the mold to be absorbed into the hardened rubber resin and then eliminated with the hardened rubber. This cleaning process is repeated in the same way until the contaminants are completely removed. This cleaning It is more appropriate to perform it lightly 2-5 times. Especially after repeated treatments, the stain on the ejector pin (E ject P i η) can be completely eliminated, and the unresolved problems such as cleaning rubber in the past can be completely solved. In addition, the cleaning method of the present invention does not require manual removal of secondary pollution. In order to improve the efficiency of other operations

5162-3542-PF.ptd 567213

Example Test Based on Variation of Oak and Snow Types) (Examples 1 to 5 Example 1 To 100 g of natural rubber (NR) was added 70 g of ethanolamine A and 30 g of u-di-third-butylperoxy-di Isopropylbenzene) 400 g of SILCA and 50 g of titanium oxide were mixed and placed in a test mold (仏 (^? 28 乂 28), 170-175. (: Temperature and 60)) (//: It was hardened for about 400 seconds under 1112 pressure and conditions, and tested for its hardenability, elasticity, heat input during processing, scattering of cleaning compounds caused by heating, odor of oak, and operating characteristics. The results are shown in Table 1. Example 2-5 SBR (Example 2) was used in place of NRBR, and high-viscosity EPDM (Example 3), low-viscosity EPDM (Example 4), and a mixed rubber of EPDM and BR (Example 5) were used. ), Except that the method is the same as that of Example 1, and the test results are not as shown in Table 1 below.

5162-3542-PF.ptd Page 11 567213 V. Description of Invention (9)

[Table 1: Examples of hardening It processing ^ # Clean narratives scattered odor workability relative mixing price 1 D high serious serious no EE 2 D high _ average severe CC 3 B high serious severe-general CC 4 C low Less _ Normal AB 5 A Low Less-Normal AA (Note) A, Very Good B: Good C: Fair D: Not Good E: Very Bad * The above comparison values are for comparative evaluation of the results of Example 丨 -5 The numerical values do not include the comprehensive comparative values of the results of the later examples. (Implementation 6_13: Test based on changes in cleaning compound content) Example 6 Except that ME A was added as a 丨% of the total weight of the cleaning compound, ^ After preparing the clean rubber composition under the same conditions as in Example 5, Test the cleanliness, the degree of irritating odor and smoke generated in the process, the degree of secondary pollution from the Eject Pin, and the scattering of cleaning compounds. The operating environment is harmful. The test results are listed below. (Table 2 ). Example 7-1 3 Test conditions Except changing the content of the cleaning compound to 1% (Example I), 3% (Example 8), 5% (Example 9), 7% (Example 1) ), 9% Example ^), 11% (Example 12), 20% (Example 13), other conditions are the same as in Example 6, and the results are listed below.

567213 V. Description of the invention (10) [Table 2]

Example Cleanliness Stimulation Smell i Smoke generation right ^ Unpolluted Flying hostile operation ring_Colorful ring phase tender error 6 Invalid AAAA-7 CAAAAC 8 BBBABA 9 ACCBCA 10 ADCCDB 11 ADDDDC 12 AEEEEE 13 AEEEEE (Note) A: Very good B: Good C: Fair D: Not good E: Very bad * The above comparison values are the values for comparative evaluation of the results of Examples 6-13, and are not comprehensive comparison values including the results of previous or later examples. (Examples 14-21: Tests based on the content of inorganic additives and pore size) Example 1 4 Except adding 300 g of zeolite A with a pore size of 4 A (20% by weight), it was the same as Example 5 After the composition was prepared under the same conditions, it was added to a test mold (MQFP 28x28) and hardened at a temperature of 1 70-1 75 ° C and a pressure of 60 Kgf / cm2 for about 400 seconds. The degree of irritating odor was measured, The degree of smoke generation and workability are listed below (Table 3). Examples 15-21 In addition to using zeolite A 30% (Example 15), zeolite A 40% (Example 16), zeolite A 50% (Example 17) zeolite X (average pore size 7.4 A 20% (Example 18), Zeolite X 30% (Example 19), Zeolite X 40 ° / 〇

5162-3542-PF.ptd Page 13 567213 V. Description of the invention α) (Example 20) and zeolite X 50% (Example 21), tested under the same conditions as in Example 14, the test results are listed below (table 3 ). 【table 3】

Miscellaneous cases 14 ⑤ ⑤ C 15 ④ ④ B 16 ③ ③ B 17 © ③ C 18 ③ ③ C 19 0 0 B 2D ① ① B 21 ① ① C (Note) A: Very good B: Good C: Fair D : Not good E: Very bad ① · Rare ② · Less ③: Fair ④: Severe ⑤: Very serious * The above comparison values are straightforward for comparison and evaluation of the results of Examples 1 4-21 1 Comprehensive comparison of results from previous examples. Example 2 2 In addition to sulfur, 1,2-di-third-butylperoxy-3, 3,5-trimethylcyclohexane, bis- (third-butylperoxy-butylpropyl) -benzene, 4,4-Di-tert-butylperoxy-n-butylvaleric acid was used as a hardener, and the composition was prepared under the same conditions as in Example 7 and compared. Test results, due to the decomposition of sulfur caused mold corrosion, especially in the need for a period of 5 to 6 months; the use of molds in the production of half of the 77 body is somewhat problematic. Although the initial hardening reaction of oxygen-3, 3, 5-trisylcyclohexane;

5162-3542-PF.ptd Page 14 567213 V. Description of the invention (12) It can be completely hard, and conversely, bis (third-butylperoxy + propylene, ί 2 i 1 1_second- Butylperoxy " " n-Butylvaleric acid accelerates hardening in EPDM and ⑽m, so the least hardening is used

The agent can also achieve complete hardening. & ^ 1C Comparative Example We use one of the NCR (melamine resin: Japan = η γγ = ί) and n-cs__ (clean rubber resin: a comprehensive item of environmental pollution in the industry, etc.) in the current product .... Smoke and testing due to scattering Results When using NCR, the hardened / cleaned body has an irritating effect on the eye essence, and the hardened resin sheet: = dyeing, it takes a long time to completely clean the mold, less than 90-120 minutes), in order to eliminate secondary stains: : N-CS, 00 produces irritation ^ Chapter 1: Fang cleaning ability Xiao, and the present invention cleans the operating soil environment after cleaning. The cleaning effect is weak. 4 Test results of rubber compound compared to Qing [Invention effect] The origin of the clean rubber compound of origin ΓΓ can be contaminated by the irritant i generated during the cleaning process of inorganic additives, which can be converted from ^ ΐΓί: 二 = 清 的The secondary time can also be large :: Cover: Shorten the pollution of cleaning operation. It is generated in the ejector rod when cleaning with rubber.

5162-3542-PF, Ptd Page 15 567213 V. Description of the invention In addition, because the content of the cleaning compound of the composition can be increased, the cleaning effect is improved. The clean rubber composition of the present invention can be used not only in semiconductor molding dies, but also in extrusion molding machines. The field of use has also been greatly expanded. M4 and so on. Also, compared with the melamine resin process, the cleaning process of the present invention has greatly shortened the time of one-time cleaning (melamine resin · 90—20 minutes, the present invention: 35-45 Minutes), which greatly improves the operating efficiency, and "does not require the Lead Frame required by the melamine process, which can bring economic effects."

DC ptd

Claims (1)

Ψ% Case No. 89122957 Amendment m 1C Amendment Scope of Patent Application 1. A rubber compound for mold cleaning, characterized by a 'rubber content of 30-60% and an inorganic additive content of 20 in the total weight of the compound -60%, cleaning compound content is 1-20%, hardener content is 0.5-5%, the rubber in this rubber composition is ethylene-propadiene monopolymer rubber (EpDM), natural rubber (NR) ), Styrenic-butene rubber (sbr), butadiene rubber (ββ), air-butadiene rubber (CR), nitro-butadiene rubber (NRB) fluorinated rubber, polypropylene rubber, stone rubber and One, a mixture of two or more of butyl rubber, or a derivative of these materials; wherein the inorganic additive means silicon dioxide, activated alumina, activated alumina, Giant Fossil, Shi Ximu, Amorphous Lithoic Acid | Lu (A JJJ 〇rph 〇us Aluminosilicate), Crystalline Aluminum Silicate; / Wherein the cleaning compounds refer to amino alcohol compounds, hydroxyl groups and isocyanate compounds One or two or more in the queue Where the hardener refers to 2,5-dimethyl-2,5-bis- (third-butylperoxy) -hexyne-3, di-third-butylperoxide, 2, 5-Difluorenyl-2,1 bis- (third-butylperoxyhexyne, third monobutylcumyl peroxide, bis- (third-butylperoxy-I-propyl) Benzene's dicumyl peroxide, 4 bis-tertiary-butyl ^ oxy-n-butylvaleric acid, tertiary butyl peroxybenzoic acid, mono-di-tertiary-butyl peroxy One or two or more of oxygen 3, 3, 5_trimethylcyclohexane, di-benzyl peroxide, bis- (2, 4-digas benzamidine) -peroxide and sulfur The rubber compound for mold cleaning. 2. The rubber compound as described in item 丨 of the patent application range, characterized in that melamine resin or cellulose auxiliary or fiber is added as a cleaning auxiliary. 5162-3542-PFl.ptc page 17 567213 20% of the total weight of the product, and / or adding a small amount of colorants such as titanium oxide to observe whether the pollutants are separated. 3. The rubber composition according to item 2 of the scope of the patent application, characterized in that the crystalline aluminate is more than 34 kinds of natural zeolites and 1000 kinds of synthetic zeolites and luminescent zeolites. 4. The rubber composition according to item 1 of the scope of the patent application, characterized in that the inorganic additive is a zeolite or other inorganic material having an average pore size of 3-20 A. 5. The rubber composition according to item 丨 of the patent application scope, characterized in that the mold is a mold for semiconductor manufacturing. 6. The rubber composition according to any one of claims 1-5 in the scope of the patent application, characterized in that a certain amount of the rubber composition is added to the mold, and a temperature of 160-21 (TC and 15- A pressure of 100 kgf / cm2 for 2 to 10 minutes to harden the composition into the shape of the mold, and the pollutants in the mold are absorbed into the hardened rubber resin and then removed. 5162-3542-PFl.ptc Page 18