KR100545249B1 - Resin composition for mold cleaning - Google Patents

Abstract

The mold-cleaning resin composition for removing contamination of the mold surface during molding of the curable resin molding material is a melamine resin as the mold-cleaning resin, an average fiber length of 5 to 30 µm, an average fiber diameter of 0.1 to 1.0 µm, and 10 to Fibrous inorganic composites having an aspect ratio of 60.

Curable, Mold, Molding, Resin, Composition, Clean, Melamine, Guanamine, Derivative, Composite

Description

Resin composition for mold cleaning

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for mold cleaning used to clean the surface of an injection or transport molding die for sealing electronic components, and more particularly, to a resin composition for mold cleaning that exhibits satisfactory cleaning properties against various contaminants. .

When the molding of a molded product is continued for a long time to seal an integrated circuit or the like (hereinafter referred to as "IC-LSI") with a thermosetting resin such as an epoxy resin, the inner surface of the forming die is rarely contaminated, This continuation of molding to the contaminated die causes surface contamination of the molded product or the molded product to adhere to the die, making further shots impossible. Therefore, it is necessary to clean the molding die periodically. It is proposed to clean the mold by making several shots with mold cleaning resin every few hundred shots.

For example, JP-B-52-788 proposes a method for removing dirt from the surface of a mold in molding curable resin molding materials (except amino resin molding materials), which mainly uses amino resins. Disclosed is a resin composition for cleaning a mold, comprising molding a material comprising the same, and comprising an amino resin, an organic material and / or an inorganic material, and a release agent. JP-B-64-10162 discloses a resin composition for mold cleaning comprising a polycondensation resin of an amino resin and a phenol resin and a mineral powder having a new Mohs hardness of 6 to 15.

In recent years, many thermosetting resin molding materials useful for IC / LSI sealing have been provided so that the composition of the molding material can be changed depending on the required properties. Therefore, the state and mold components of mold contamination due to repeated molding vary. First of all, the molding materials are repeatedly formed, including biphenyl type epoxy resins, polyfunctional epoxy resins, or dicyclopentadiene type epoxy resins used instead of conventionally used novolak epoxy resins. In this case, mold contamination due to seizure becomes serious. Biphenyl type epoxy resins and multifunctional epoxy resins have been proposed previously, which cause partial contamination and require a significantly increased number of shots to completely remove mold dirt from the mold cleaning resin composition described above. There is a problem that productivity of LSI and the like is greatly reduced.

The difficulty of removing dirt from the mold considered from the form of the cleaning mechanism means that the bonding force between the dirt and the mold is greater than the bonding force between the mold cleaning resin composition and the dirt. On the other hand, the reduction in cleaning performance is caused by an increase in the bonding force between the mold and the dirt or a decrease in the bonding force between the molded resin and the dirt for mold cleaning. With a reduction of at least one, preferably both, these factors will result in improved cleaning performance.

An conceivable approach to eliminate the factors causing a reduction in cleaning performance is to improve the strength of the molded article of the mold cleaning resin, to improve the modulus of the molded article of the mold cleaning resin and to form the mold cleaning resin. To improve the bond between the article and the soil.

It is an object of the present invention to provide a resin composition for mold cleaning which can achieve improved workability of mold cleaning even at large contaminations and can eliminate the diversity of contaminants.

The inventors of the present invention repeatedly mold a molding material mainly containing a biphenyl type epoxy resin, a multifunctional epoxy resin, or a dicyclopentadiene type epoxy resin, which is frequently used as an epoxy resin, to effectively remove contaminants accumulated on the surface of a mold. Extensive research has been conducted for this purpose. As a result, the combination of the specific fibrous inorganic compound with the melamine resin composition for mold cleaning increases the adhesion to contaminants and removes the contaminants without increasing the number of necessary cleaning operations compared with the proposed resin composition for mold cleaning. can do.

Based on the above findings, the present invention provides a melamine resin as a mold cleaning resin, and an average fiber length of 5 to 30 µm, an average fiber diameter of 0.1 to 10 µm, and an fiber having an aspect ratio of 10 to 60. Provided is a resin composition for mold cleaning for removing dirt from the surface of a mold during molding of the curable resin molding material, which is characterized by including an organic compound.

Methods for carrying out the invention will be described in detail below.

Melamine resins that can be used in the present invention are prepared by well-known processes. For example, formaldehyde and melamine crystals are reacted in a molar ratio of 1: 1-3: 1, advantageously 1.5: 1-2: 1 in an aqueous solution to prepare a precondensate aqueous solution. The reaction may be carried out at a melamine crystal concentration of 20 to 60% at a temperature of 70 to 100 ℃ in a weak alkaline state. The reaction is completed in 10-100 minutes.

The melamine resin that can be used in the present invention may be one prepared by the above-mentioned well-known process or commercially possible one.

In the melamine resin used in the present invention, a part of the melamine resin may be substituted with melamine and other compounds which can be multicondensed with formaldehyde such as urea, benzoguanamine and phenol, while being compatible with the effects of the present invention. The amount of such composites used is preferably less than 10 parts by weight relative to 100 parts by weight of melamine.

Some of formaldehyde may be, for example, aliphatic aldehydes such as acetaldehyde; Aromatic aldehydes such as benzaldehyde; Furfural; And paraformaldehyde and non-formaldehyde aldehydes, such as melamine, formaldehyde and other aldehydes that can react with other compounds described above that may be polycondensed. The amount of such composites used is preferably less than 10 parts by weight relative to 100 parts by weight of formaldehyde.

In addition to the melamine resin, the resin composition for metal mold | die cleaning of this invention can contain the auxiliary resin which can be mixed with melamine resin in the addition amount which does not adversely affect the effect of this invention. Such resins include alkyd resins, polyester resins, acrylic resins, epoxy resins and rubbers.

The mold cleaning resin of the present invention, which contains a melamine resin and a fibrous inorganic compound, exhibits improved adhesion to contaminants and the like, thereby producing an excellent cleaning effect.

Examples of fibrous inorganic composites include ALBOREX Y and ALBOREX M20 (both available from Shikoku Chemical Corp.); TISMO-D and TISMO-L (both available from Otuka Chemical Co., Ltd.) and USB-SN-WA and MOS-HIGE (both available from Ube Industries, Ltd.). Among them, ALBOREX Y is suitably used, and any fibrous inorganic composite having an average fiber length of 5 to 30 μm, an average fiber diameter of 0.1 to 1.0 μm and an aspect ratio of 10 to 60 may be used.

It is possible to improve the above-mentioned effect by surface-treating with a fibrous inorganic compound with various resins, such as an epoxysilane compound, an aminosilane compound, and a methacryloxysilane compound. Examples of such surface treated fibrous inorganic composites include ALBOREX YS3A, ALBOREX YS2B and ALBOREX YS4 (all of which are available from Shikoku Chemicals Corp.) and TISMO-D101 and TISMO-D102 (both Otuka Chemical Co., Ltd). Available from.

The content of the fibrous inorganic composite is preferably 1 to 30 parts by weight, more preferably 5 to 20 parts by weight, and particularly preferably 5 to 10 parts by weight with respect to 100 parts by weight of the melamine resin. When the fibrous inorganic compound is less than 1 part by weight, a small cleaning effect is produced. When the fibrous inorganic compound exceeds 30 parts by weight, not only the fluidity of the resin composition for mold cleaning is lowered, but also the fibrous inorganic compound is excessive, which is not economically advantageous.

The resin composition for metal mold | die cleaning of this invention can contain pulp. The pulp includes straw pulp, bamboo pulp and wood pulp (soft wood pulp and hard wood pulp) and may be chemical or mechanical pulp.

Pulps filled with melamine-based resins (melamine-based resin-filled pulp) are also useful.

Herein, the melamine-based resin includes melamine resin, melamine-phenol polymerized condensate and melamine-urea polymerized condensate. Melamine-phenol condensates are for example condensation products prepared from triazines such as melamine, phenol and aldehydes, for example formaldehyde. Melamine-urea condensates are, for example, condensation products prepared from triazines such as melamine, urea and aldehydes.

The melamine-based resin is preferably used in the form of an aqueous solution. For example, the above-described melamine-based resin-filled pulp is prepared by filling the pulp with an aqueous solution of melamine-based resin and drying it.

Some or all of the pulp may be substituted with powder pulp to improve flowability.

Although not limited, the size of the pulp is generally about 5 to 1000 mu m, preferably about 10 to 200 mu m.

The content of pulp is generally 5 to 70 parts by weight, preferably 20 to 60 parts by weight with respect to 100 parts by weight of the melamine resin.

The resin composition for metal mold | die cleaning of this invention can contain mineral powder. Examples of preferred mineral powders include natural products such as corundum, emery, garnets and siliceous stones; Oxides or carbides of silicon, iron, titanium, sodium, calcium, magnesium, aluminum, chromium, boron and the like. Oxides or carbides include silicon oxide, magnesium oxide, aluminum oxide, silicon carbide and boron carbide.

Mineral powders having a new Mohs hardness of 6-15 are preferred.

The particle size of the mineral powder is not limited, but is generally # 100 to # 4000, preferably # 100 to # 2000, more preferably # 100 to # 1000. Mineral powders smaller than # 4000 not only make cleaning poor, but also cause dust to sit down and worsen the working environment during handling. Powders larger than # 100 can destroy the mold and cause inconsistent cleaning.

Although content of a mineral powder is not limited, It is preferable that it is 10-90 weight part with respect to 100 weight part of melamine resin, and it is more preferable that it is 10-30 weight part.

The resin composition for metal mold | die cleaning of this invention can contain a lubrication component. Lubricants include metallic soaps such as zinc stearate, calcium stearate and zinc myristate; Fatty acids such as stearic acid, oleic acid and behenic acid; Fatty acid esters such as butyl stearate and dodecyl stearate; Fatty acid partial esters such as monostearate glycerol, glycerol, monooleate, glycerol monohydroxystearate, stearic acid pentaerythritol, stearic acid polyglycerol and sorbitan trioleate ; Fatty acid amides such as lauric acid amide, myristic acid amide, irisic amide, oleic amide and steaamide; Fatty acid bisamides such as methylenebistearic acid amide, ethylenebistearic acid amide and ethylenebisolaleic acid amide. In order to maintain satisfactory mold cleaning properties, it is recommended to use less than 1.5 parts by weight, preferably less than 1 part by weight of the lubricating component with respect to 100 parts by weight of the melamine resin.

The resin composition for metal mold cleaning of the present invention may further contain other additives such as organic or inorganic fillers, colorants, curing catalysts, lubricating components and antioxidants related thereto, which are not the aforementioned mineral powders. Specific examples of such additives include organic or inorganic fillers such as wood mill, vinylon fiber, glass powder, glass fiber, untreated calcium carbonate, mica, aluminum hydroxide, barium sulfate and zinc sulfate; Inorganic pigments such as titanium oxide, carbon black, zinc white, cadmium yellow and red oxides and organic pigments such as phthalocyanine pigments, azo pigments and diazo pigments, fluorescent pigments such as benzoxazole pigments, naphthotriazole pigments and coumarin pigments And colorants including dyes such as anthraquinone dyes, indigo dyes and azo dyes; Organic acids such as phthalic anhydride, oxalic acid, sulfamic acid and paratoluenesulphonic acid, inorganic acids such as hydrochloric acid and sulfonic acid and triethylamine, triethanolamine, β-dimethylaminoethanol, 2- Curing catalysts comprising salts of these acids with methyl-2-amino-1-propanol and the like; Lubricating components such as zinc stearic acid, steaamide, methylol steaamide, methyleneebissteaamide, paratoluenesulphonic acid amide, cetyl alcohol, paraffin and silicone oil; And antioxidants such as naphthylamine antioxidants, p-phenylenediamine antioxidants and thiobisphenol antioxidants.

It is preferable that the resin composition for metal mold | die cleaning of this invention contains at least 1 selected from melamine type resin-filled pulp, mineral powder which has a particle size of # 100- # 4000, a hardening catalyst, and a lubricating component.

Description of the example of the preferable formula of the resin composition for metal mold | die cleaning which concerns on this invention is shown below.

(A) 100 parts by weight of melamine resin,

(B) 5 to 70 parts by weight of pulp,

(C) 10 to 90 parts by weight of the mineral powder having a particle size of # 100 ~ # 4000 and

(D) 1-30 weight part of fibrous inorganic mixtures which have an average fiber length of 5-30 micrometers, an average fiber diameter of 0.1-1.0 micrometer, and an aspect ratio of 10-60.

In the preparation of the resin composition for metal mold cleaning of the present invention, any means capable of constantly mixing as much as the auxiliary amount of the melamine resin, the fibrous inorganic compound, and other resins, pulp, mineral powder and other additives may be applied as necessary. have. Such means include kneaders, ribbon blenders, Henschel mixers, ball mills, roll mills, grinders and tumbling mixers.

Curable resin mold material to which cleaning with the resin composition for metal mold | die cleaning of this invention can be applied includes an epoxy resin mold material and a phenolic resin molding material. Epoxy resin molding materials are suitable. Epoxy resin molding materials for semiconductor sealing are particularly suitable. The resin composition for metal mold | die cleaning of this invention can be applied to any metal mold | die applied to the automatic metal mold | die of curable resin molding material. In general, it is suitably applied to a mold made of iron, chromium and the like.

The invention will now be described in more detail, but the invention is not to be construed as limited thereto.

Reference Example 1

346 parts by weight of melamine, 522 parts by weight of formalin (37% aqueous solution) and 131 parts by weight of phenol are heated and reacted by a known method for preparing melamine phenol-formaldehyde resin. 248 parts by weight of pulp is added to the resulting liquid resin, and the mixture is kneaded and dried under reduced pressure to make pulp-added melamine phenol-formaldehyde resin powder (melamine-based resin-filled pulp) having a pulp content of 27%.

Reference Example 2

480 parts by weight of melamine and 522 parts by weight of formalin (37% aqueous solution) are heated and reacted by a known method for preparing melamine-formaldehyde resin. 248 parts by weight of pulp is added to the resulting liquid resin. The mixture is kneaded and dried under reduced pressure to make pulp-added melamine-formaldehyde resin powder (melamine-based resin-filled pulp) having a pulp content of 27%.

Example 1                 

30 parts by weight of melamine-based resin-filled pulp obtained in Reference Example 1, 50 parts by weight of commercial melamine resin (Nikeresin S-176 available from Nippon Carbide Industries Co., Inc), 20 parts by weight of siliceous ore with a particle size of # 200 Powder, 5 parts by weight of aluminum borate (ALBOREX YS4 available from Shikoku Chemicals Corp.), 0.2 parts by weight of benzoic acid, 0.5 parts by weight of zinc stearate and 0.3 parts by weight of ethylenebissteaamide were mixed and ball milled to prepare a resin composition A for mold cleaning. From powdered.

Results The characteristic values of the resin composition for mold cleaning and the results of the cleaning test on the composition are shown in Table 1. As can be seen from the test results, the resin composition A for mold cleaning exhibits a satisfactory cleaning effect.

Example 2

1 part by weight of melamine-based resin-filled pulp obtained in Reference Example 1, 29 parts by weight of melamine-based resin-filled pulp obtained in Reference Example 2, and 50 parts by weight of commercially available melamine resin (Niarepon S- obtainable from Nippon Carbide Industries Co., Inc.). 176), 20 parts by weight of siliceous ore powder having a particle size of # 200, 5 parts by weight of aluminum borate (ALBOREX YS4 available from Shikoku Chemicals Corp.), 0.2 parts by weight of benzoic acid, 0.5 parts by weight of zinc stearate and 0.3 parts by weight of ethylene bis Steaamide is mixed to prepare the resin composition B for mold cleaning and powdered in a ball mill.

Results The characteristic values of the resin composition for mold cleaning and the results of the cleaning test on the composition are shown in Table 1. As can be seen from the test results, the resin composition B for metal mold | die cleaning shows satisfactory cleaning effect.

Example 3

30 parts by weight of melamine-based resin-filled pulp obtained in Reference Example 2, 50 parts by weight of commercial melamine resin (Nikeresin S-176 available from Nippon Carbide Industries Co., Inc), 20 parts by weight of siliceous ore with a particle size of # 200 Powder, 5 parts by weight of aluminum borate (ALBOREX YS4 available from Shikoku Chemicals Corp.), 0.2 parts by weight of benzoic acid, 0.5 parts by weight of zinc stearate and 0.3 parts by weight of ethylenebissteaamide were mixed and ball milled to prepare a resin composition C for mold cleaning. From powdered.

Results The characteristic values of the resin composition for mold cleaning and the results of the cleaning test on the composition are shown in Table 1. As can be seen from the test results, the resin composition C for mold cleaning exhibits a satisfactory cleaning effect.

Example 4

The resin composition D for metal mold | die cleaning is prepared by the method similar to Example 1 except the amount of aluminum borate (ALBOREX YS4 available from Shikoku Chemicals Corp.) being changed to 20 weight part.

Results The characteristic values of the resin composition for mold cleaning and the results of the cleaning test on the composition are shown in Table 1. As can be seen from the test results, the resin composition D for cleaning the mold exhibits a satisfactory cleaning effect.

(Comparative Example 1)

The resin composition E for metal mold | die cleaning is prepared by the method similar to Example 1 except the amount of aluminum borate (ALBOREX YS4 available from Shikoku Chemicals Corp.) being changed to 0 weight part.

(Comparative Example 2)

Except that the resin composition F for mold cleaning is changed from ALBOREX YS4 available from Shikoku Chemicals Corp. to ALBORITE PC08, available from Shikoku Chemicals Corp., particulate aluminum borate having a central particle size of 8 μm. It is prepared in the same manner as in Example 1.

(Comparative Example 3)

The resin composition G for mold cleaning was prepared in the same manner as in Example 3 except that the amount of aluminum borate (ALBOREX YS4 available from Shikoku Chemicals Corp.) was changed to 0 parts by weight.

(Comparative Example 4)

The resin composition H for metal mold | die cleaning is prepared by the method similar to Example 1 except the amount of aluminum borate (ALBOREX YS4 available from Shikoku Chemicals Corp.) being changed to 40 weight part.

The mold cleaning test is performed using resin compositions A to H for mold cleaning according to the following test method. The results obtained are shown in Table 1.

(Test Methods)

A commercial biphenyl type epoxy resin mold material (CEL-9200XU, available from Hitachi Chemical Co., Ltd) is molded for 500 shots in molding for TQFP to have mold dirt. Evaluation is made by repeatedly molding the resin composition for mold cleaning using a contaminated mold until the mold surface is cleaned.

(Reference Example 3)

346 parts by weight of melamine and 522 parts by weight of formalin (37% aqueous solution) are heated and reacted by a known method for preparing melamine-formaldehyde resin. 95 parts by weight of pulp is added to the resulting liquid resin. The mixture is kneaded to make pulp-added melamine-formaldehyde resin powder (melamine-based resin-filled pulp) having a pulp content of 15% and dried under reduced pressure.

Reference Example 4

346 parts by weight of melamine, 522 parts by weight of formalin (37% aqueous solution) and 131 parts by weight of phenol are heated and reacted by a known method for preparing melamine formaldehyde-phenol resin. 120 parts by weight of pulp is added to the resulting liquid resin. The mixture is kneaded to make pulp-added melamine formaldehyde-phenolic resin powder (melamine-based resin-filled pulp) having a pulp content of 15% and dried under reduced pressure.                 

Example 5

100 parts by weight of melamine-based resin-filled pulp obtained in Reference Example 3, 100 parts by weight of commercial melamine resin (Nikeresin S-176 available from Nippon Carbide Industries Co., Inc), 8 parts by weight (12.4 to 100 parts by weight of melamine resin) Parts by weight) of powder pulp, 51 parts by weight (27.6 parts by weight of 100 parts by weight of melamine resin) having a particle size of # 200, 10 parts by weight (5.4 parts by weight of 100 parts by weight of melamine resin) Aluminum borate (ALBOREX YS4 available from Shikoku Chemicals Corp.), 0.2 parts by weight of benzoic acid (0.1 parts by weight based on 100 parts by weight of melamine resin), 1.5 parts by weight (0.8 parts by weight of 100 parts by weight of melamine resin) zinc stearate And 0.8 parts by weight (0.4 parts by weight relative to 100 parts by weight of the melamine resin) are mixed to prepare the resin composition I for cleaning the mold, and powdered in a ball mill.

Results The characteristic values of the resin composition for mold cleaning and the results of the cleaning test on the composition are shown in Table 2. As can be seen from the test results, the resin composition I for cleaning the mold exhibits a satisfactory cleaning effect.

Example 6

40 parts by weight of melamine-based resin-filled pulp obtained in Reference Example 3 (including 6 parts by weight of pulp), 110 parts by weight of commercially available melamine resin (Nikeresin S-176 available from Nippon Carbide Industries Co., Inc), 12 parts by weight of melamine 12.5 parts by weight of powdered pulp, 40 parts by weight (27.8 parts by weight of 100 parts by weight of melamine resin) of siliceous ore powder, 100 parts by weight of melamine resin 10.4 parts by weight of aluminum borate (ALBOREX YS4 available from Shikoku Chemicals Corp.), 0.2 parts by weight of benzoic acid, 1.2 parts by weight of zinc stearate and 0.6 parts by weight of ethylenebissteaamide were mixed to prepare a resin composition J for mold cleaning. And powdered in a ball mill.

Results The characteristic values of the resin composition for mold cleaning and the results of the cleaning test on the composition are shown in Table 2. As can be seen from the test results, the resin composition J for mold cleaning exhibits a satisfactory cleaning effect.

Example 7

100 parts by weight of commercial melamine resin (Nikponsin S-176 available from Nippon Carbide Industries Co., Inc), 30 parts by weight of powdered pulp, 28 parts by weight of siliceous ore powder with a particle size of # 200, 5 parts by weight of aluminum borate (Shikoku ALBOREX YS4) available from Chemicals Corp., 0.1 parts by weight of benzoic acid, 0.8 parts by weight of zinc stearate and 0.4 parts by weight of ethylenebissteaamide are mixed and ground in a ball mill to prepare a resin composition K for mold cleaning.

Results The characteristic values of the resin composition for mold cleaning and the results of the cleaning test on the composition are shown in Table 2. As can be seen from the test results, the resin composition K for mold cleaning exhibits a satisfactory cleaning effect.

Example 8

The same method as in Example 5, except that the resin composition L for mold cleaning was changed to the resin-filled pulp powder obtained in Reference Example 4 from the melamine-based resin-filled pulp obtained in Reference Example 3. Are mixed and powdered in a ball mill and prepared.

Results The characteristic values of the resin composition for mold cleaning and the results of the cleaning test on the composition are shown in Table 2. As can be seen from the test results, the resin composition L for mold cleaning exhibits a satisfactory cleaning effect.

The mold cleaning test is performed using the resin compositions I to L for mold cleaning in the same manner as in the resin compositions A to H for mold cleaning. The results obtained are shown in Table 2.

The resin composition for mold cleaning of the present invention shows improved workability in cleaning molds contaminated with severe dirt and can remove the diversity of contaminants.

Claims (8)

A resin composition for mold cleaning for removing dirt on the surface of a mold during molding of the curable resin molding material, comprising a melamine resin as the resin for mold cleaning, an average fiber length of 5 to 30 μm, an average fiber diameter of 0.1 to 1.0 μm, and The resin composition for metal mold | die cleaning characterized by containing 1-30 weight part of fibrous inorganic compounds which have an aspect ratio of 10-60 with respect to 100 weight part of said resin for metal mold | die cleaning. delete The resin composition for cleaning a mold according to claim 1, wherein the fibrous inorganic compound is surface treated. The resin composition of claim 1, further comprising at least one selected from melamine-based resin-filled pulp, mineral powder having a particle size of # 100 to # 4000, a curing catalyst, and a lubricating component. (A) 100 parts by weight of melamine resin, (B) 5 to 70 parts by weight of pulp, (C) 10 to 90 parts by weight of the mineral powder having a particle size of # 100 ~ # 4000 and (D) 1-30 weight part of fibrous inorganic composites which have an average fiber length of 5-30 micrometers, an average fiber diameter of 0.1-1.0 micrometers, and an aspect ratio of 10-60, The curable resin molding material characterized by the above-mentioned. The resin composition for metal mold | die cleaning for removing the dirt of the surface of a metal mold | die at the time of shaping | molding. The resin composition for metal mold | die cleaning of Claim 5 whose one part or all part of the said pulp is powder pulp. The resin composition of claim 5, wherein the pulp comprises melamine-based resin-filled pulp. The resin composition for cleaning a mold according to claim 5, wherein the fibrous inorganic compound is surface treated.