JPH0957762A - Mold cleaning resin composition - Google Patents

Abstract

(57) [Summary] [Object] To provide a mold cleaning resin composition having improved tablet properties while maintaining suitable cleaning properties. A mold cleaning resin composition comprising a metal soap and a non-metallic fatty acid lubricant in the amino resin mold cleaning resin composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a mold cleaning resin composition for cleaning stains on the surface of a mold in the molding of a curable resin molding material, showing a good mold cleaning effect and a good tablet property. The present invention relates to a mold cleaning resin composition.

[0002]

2. Description of the Related Art When molding a molded encapsulation product such as an integrated circuit made of a curable resin such as an epoxy resin, if the molding is continued for a long time, the inner surface of the mold becomes dirty, and if molding is continued continuously,
In many cases, the surface of the molded encapsulant was soiled or the molded encapsulant adhered to the mold and the molding operation could not be continued. Therefore, it is necessary to regularly clean the mold, and there has been proposed a method of cleaning the mold by molding a mold cleaning resin at a rate of several shots every several hundred shots of molding material.

For example, Japanese Examined Patent Publication No. 52-788 discloses that the mold surface stain at the time of molding a curable resin molding material (excluding an amino resin molding material) is molded with a material mainly composed of an amino resin. Therefore, a cleaning method "is proposed, and an amino resin, an organic base material and / or an inorganic base material,
A mold cleaning resin composition comprising a release agent is disclosed. Japanese Patent Publication No. 64-1622 discloses a mold cleaning resin composition containing a co-condensation resin of an amino resin and a phenol resin and a mineral powder having a new Mohs hardness of 6 to 15.

These mold cleaning resin compositions are often used in the form of tablets having the same size as the molding material. By preheating the tablets so that the tablet temperature is 90 ° C to 110 ° C and molding, The mold cleaning resin composition is filled in the whole mold, and the mold surface is cleaned by taking in dirt on the mold surface during curing.

In recent years, a curable resin automatic molding machine has been developed in response to a demand for unmanned molding and cleanliness, and automation of molding has been widely performed. This automatic molding machine
An encapsulation molded article such as an IC / LSI is molded with a small die of several to ten or more pieces, and the encapsulating resin used is supplied as a mini tablet having a diameter of about 5 mm to 40 mm.

On the other hand, high integration and thinness of IC / LSI,
With surface mounting, the diversification of molded products is progressing, and tablets of various sizes are used according to each molded product, and the resin composition for mold cleaning is also a mini resin for sealing. There is a need for mini-tablets of various sizes that are smaller and more compatible with tablets.

[0007]

[Problems to be Solved by the Invention] Therefore, Japanese Patent Publication No. 52-788
It is generally practiced to make a conventionally known mold-cleaning resin composition into a mini-tablet as described in Japanese Patent Publication No. JP-A No. 2004-187, and to use it for cleaning a mold of an automatic molding machine. However, when miniaturizing these mold cleaning resin compositions with a tablet machine, ultra-steel is often used in the mold for tablet molding to avoid mold wear, and the molded minitablet is used. Since it was harder to pull out than the mold, defects such as squeaking noise, cracking, and chipping were likely to occur at the time of extraction, and the defect rate was high.

Therefore, the lubricant content of the mold cleaning resin composition as exemplified in JP-B-52-788 is increased,
Attempts have also been made to improve tablet yield. However, when the lubricant content is increased, the lubricant itself bleeds to contaminate the mold, and the mold cleaning effect is lowered, so that the number of mold cleaning shots is increased.

Particularly for mini tablets, there has been a demand for a mold cleaning resin composition having good tablet properties and good cleanability.

As a result of the research conducted by the present inventors, as a lubricant which does not increase the content of the lubricant and improves the tableting yield, a non-metallic material having excellent lubricity and compatibility with resin and thermal stability is obtained. The present invention has been completed by using a fatty acid-based lubricant of the system, and by using a metal soap as a lubricant involved in fluidity and mold releasability at the time of cleaning molding, the tablet property can be improved while maintaining good cleanability. .

[0011]

The present invention has been made to solve the above-mentioned problems, and in a resin composition for mold cleaning, which removes stains on the surface of a mold at the time of molding a curable resin molding material, The present invention relates to a mold cleaning resin composition containing a metallic soap and a non-metallic fatty acid lubricant.

The present invention will be described in detail below.

The amino resin composition in the present invention means a melamine resin, a melamine-phenol cocondensate or a melamine-urea cocondensate, and the melamine-phenol cocondensate is a triazine such as melamine. ,
The melamine-urea co-condensation resin is a resin that is co-condensed from aldehydes such as phenols and formaldehyde. The melamine-urea co-condensation resin is obtained by co-condensing from triazines such as melamine, ureas and aldehydes.

The melamine resin is obtained by condensing triazines such as melamine with aldehydes, and the urea resin is obtained by condensing ureas with aldehydes. As the triazines, in addition to melamine, 100% by weight of the triazines,
For example, 30% by weight or less of triazines other than melamine such as benzoguanidine and acetoguanamine may be contained.

The above-mentioned phenols include, in addition to phenol, 100% by weight of the phenol,
For example, 30 wt% or less of phenols other than phenol such as cresol, xylenol, ethylphenol and butylphenol may be contained. Further, the above-mentioned aldehydes may contain formaldehydes such as paraform and acetaldehyde in addition to formaldehyde.

Furthermore, the resin composition used in the present invention can be blended with a secondary amount of other resins that can be blended with the resin composition in an amount that does not adversely affect the above-mentioned improving properties of the composition of the present invention. . Examples of such resins include alkyd resins, polyester resins, acrylic resins, epoxy resins, and rubbers.

Examples of the non-metallic fatty acid lubricant used in the present invention include fatty acids such as stearic acid, oleic acid and behenic acid, fatty acid esters such as butyl stearate and dodecyl stearate, stearic acid monoglyceride and olein. Fatty acid partial esters such as acid monoglyceride, hydroxystearic acid monoglyceride, pentaerythritol stearate, polyglycerin stearate, sorbitan trioleate, lauric acid amide, myristic acid amide, erucic acid amide, oleic acid amide, stearic acid amide, etc. Fatty acid amides such as fatty acid amides, methylenebisstearic acid amide, ethylenebisstearic acid amide, and ethylenebisoleic acid amide can be mentioned. Fatty acid, fatty acid amides, preferably fatty acid bisamides, fatty acid amides, more preferably the fatty acid bisamides, also fatty bisamides having excellent thermal stability is particularly preferred. These non-metallic fatty acid lubricants are 0.1 parts by weight per 100 parts by weight of the mold cleaning resin composition.
It is advisable to add them in an amount of 0.1 to 1.5 parts by weight, preferably 0.2 to 0.8 parts by weight, particularly preferably 0.2 to 0.6 parts by weight.

If the lubricant is insufficient, the pressure at the time of withdrawal in tablet molding becomes too high, so that a squeak noise is generated at the time of withdrawing the tablet, and defects such as cracks and chips occur in the tablet, resulting in a high defect rate. In addition, if the amount of the lubricant is too large, the cleaning property is significantly reduced, and in some cases, the lubricant bleeds to contaminate the mold.

The metal soap used in the present invention is involved in improving the fluidity of the molten resin in the mold and the releasability after the resin is cured, and examples thereof include calcium stearate, zinc stearate and zinc myristate. It is illustrated. These metal soaps may be added in an amount of 0.1 parts by weight to 1.5 parts by weight, preferably 0.2 parts by weight to 1 part by weight, particularly preferably 0.3 parts by weight to 0.8 parts by weight, based on 100 parts by weight of the mold cleaning resin composition. .
When the amount of metal soap is insufficient, cleaning failure occurs due to the cleaning resin not reaching the minute parts of the complicated mold, or due to poor release of the cured cleaning resin from the mold.

Although the above-mentioned lubricant is used in combination, the total amount of the lubricant is 1.5 parts by weight or less, preferably 1 part by weight, relative to 100 parts by weight of the resin composition for mold cleaning, in order to maintain good mold cleaning property.
It is better to use less than or equal to parts by weight.

The mold cleaning resin composition of the present invention contains a mineral powder in addition to the resin described above. For example, corundum, emery, garnet, natural materials such as silicate, silicon, iron, titanium, sodium, calcium, magnesium, aluminum, chromium, oxides or carbides such as boron are preferable, and as these compounds, silicon oxide, Examples thereof include magnesium oxide, aluminum oxide, silicon carbide, boron carbide and the like.

The particle size of the above-mentioned mineral powder is not particularly limited, but it is generally # 10 to # 8000, preferably #.
50-4000, more preferably # 100- # 2000
It is good. If the particle size is smaller than # 8000, the cleaning effect will be poor, and defects such as dust will be generated during handling and the working environment will be deteriorated. If the particle size is larger than # 10, the mold will be damaged and cleaning will be uneven. Is likely to occur.

The amount of the mineral powder used is not particularly limited, but the mold cleaning resin composition 1 of the present invention is used.
It is 10 to 90 parts by weight, preferably 10 to 30 parts by weight, relative to 00 parts by weight.

The composition of the present invention contains, in addition to the above-mentioned mineral powder, other inorganic or organic fillers, colorants, curing catalysts,
It may contain other additives such as antioxidants. Examples of such additives include, for example, pulp, wood flour, vinylon fibers, glass powder, glass fibers, untreated calcium carbonate, talc, aluminum hydroxide, barium sulfate, other inorganic or organic fillers such as zinc sulfide. Agents; for example, inorganic pigments such as titanium oxide, carbon black, zinc white, cadmium yellow, red iron oxide, phthalocyanine-based, azo-based, diazo-based organic pigments, benzoxazole-based, naphthotriazole-based, comarine-based fluorescent pigments, Coloring agents such as anthraquinone-based, indico-based, azo-based dyes; for example, organic acids such as phthalic anhydride, oxalic acid, sulfamic acid, paratoluenesulfonic acid, inorganic acids such as hydrochloric acid and sulfuric acid, these acids and triethylamine, Triethanolamine, β-dimethylaminoethanol, 2-methyl-2
Examples thereof include curing catalysts such as salts with -amino-1-propanol and the like; for example, naphthylamine antioxidants, p-phenylenediamine antioxidants, thiobisphenol antioxidants and other antioxidants.

As the pulp, straw pulp, bamboo pulp, wood pulp (softwood pulp, hardwood pulp) and the like are used, and either chemical pulp or mechanical pulp may be used. The size of the cellulose filler such as pulp or wood flour is not particularly limited, but generally 5 μ-100.
0 μ, preferably about 10 μ to 200 μ. The amount of cellulose is generally 15 parts by weight to 70 parts by weight, preferably 20 parts by weight to 60 parts by weight, based on 100 parts by weight of the amino resin.

In preparing the composition of the present invention, any means capable of uniformly mixing the amino resin, the powder of minerals, the resin of other auxiliary amounts, and the additives, if desired, can be adopted. For example, kneader, ribbon blender, Henschel mixer,
Examples thereof include a ball mill, roll kneading machine, raker machine, and tumbler.

The curable resin molding material capable of cleaning the mold using the composition of the present invention is, for example, an epoxy resin molding material, a phenol resin molding material, or the like, preferably an epoxy resin molding material, and particularly a semiconductor encapsulation material. It is an epoxy resin molding material for fixing. As the mold to which the mold cleaning resin composition of the present invention is applied, any mold can be used as long as it is a mold used for automatically molding the cured resin molding material, but in general, iron, A mold made of chrome or the like can be applied.

The mold cleaning resin composition having the composition of the present invention can increase the tablet yield without deteriorating the mold cleaning effect, and in particular, in the molding of mini tablets, the tablet is molded with high yield and high yield. It is possible to

[0029]

EXAMPLES The present invention will be specifically described below with reference to examples. The tablet property and cleaning effect were measured by the following methods.

<Tablet property measuring method> 5 g of raw material powder is weighed in a tablet molding die (20 mmφ × 30 mmH),
Pressurize to 350 Kgf / cm ² with a pressure device and hold the pressure for about 1 minute. Remove the lower part of the mold, read the maximum pressure when pressing out the tablet, and observe if there are defects such as squeaking noise and tablet breakage (cracking, chipping, etc.) during extraction. Similarly, the number of defects when 100 tablets are tabulated is checked, and the defect rate is calculated.

<Cleaning effect test method> A commercially available epoxy resin molding material (Nitron MP manufactured by Nitto Denko Corporation) minitablet was used, and a sealing molding product was molded with a die for an automatic molding machine.
After 0 shot transfer molding and contaminating the mold,
A test mold cleaning resin composition was molded with the mold, and the number of shots and the cleaning effect were evaluated as follows. 5: No cloudiness, etc. 4: Almost no cloudiness, etc. 3: Some cloudiness, 2: Cloudy weather, 1: Many dirt

Example 1 A mixture of 343 parts by weight of melamine, 130 parts by weight of phenol, 517 parts by weight of formalin (37% aqueous solution) and 4 parts by weight of potassium hydroxide was reacted by heating, and a melamine-phenol cocondensation resin was prepared by a known method. 70 parts by weight of liquid prepared and dried under reduced pressure into powder, 20 parts by weight of silica powder having a particle size of # 200, 9.5 parts by weight of powder pulp, 0.1 part by weight of benzoic acid and 0.5 part by weight of zinc stearate. Ethylenebisstearic acid amide 0.3 was crushed with a ball mill.
A resin composition A for cleaning a mold was prepared by adding parts by weight with a Nauta mixer. Table 1 shows the test results of the tablet property and the cleaning effect using the obtained mold cleaning resin composition. As is clear from the test results, a very good cleaning effect was obtained.

Example 2 Melamine-phenol co-condensation resin obtained by kneading 190 parts by weight of the melamine-phenol co-condensation resin liquid obtained in Example 1 and 50 parts by weight of pulp in a kneader, drying and then pulverizing. I got a compound. 30 parts by weight of this compound, 50 parts by weight of a commercially available melamine resin (Nikaresin S-176 manufactured by Nippon Carbide Industry Co., Ltd.),
20 parts by weight of silica powder having a particle size of # 200, 0.1 part by weight of benzoic acid and 0.5 part by weight of zinc myristate were added and ground in a ball mill to obtain 0.3 parts by weight of ethylenebisstearic acid amide. The resin composition B for mold cleaning was added with a mixer. Table 1 shows the test results of the tablet properties and the cleaning effect using the obtained mold cleaning resin composition. As is clear from the test results, a very good cleaning effect was obtained.

Example 3 Using 363 parts by weight of melamine, 87 parts by weight of urea and 550 parts by weight of formalin (37% aqueous solution), a melamine-urea co-condensation resin liquid was prepared by a known method, dried under reduced pressure, and powdered. 60 parts by weight, 19.3 parts by weight of quartz powder having a particle size # 1000, 20 parts by weight of powder pulp, 0.05 parts by weight of phthalic anhydride and 0.5 parts by weight of calcium stearate were pulverized with a ball mill. A resin composition C for mold cleaning was prepared by adding 0.4 part by weight of ethylenebisoleic acid amide with a Nauta mixer. Table 1 shows the test results of the tablet properties and the cleaning effect using the obtained mold cleaning resin composition. As is clear from the test results, a very good cleaning effect was obtained.

Example 4 190 parts by weight of the melamine-phenol co-condensation resin liquid obtained in Example 1 and 50 parts by weight of pulp are kneaded in a kneader, dried, and then ground to obtain a melamine-phenol co-condensation resin. I got a compound. 30 parts by weight of this compound, 50 parts by weight of a commercially available melamine resin (Nikaresin S-176 manufactured by Nippon Carbide Industry Co., Ltd.), 20 parts by weight of silica powder having a particle size of # 200, 0.1 parts by weight of benzoic acid and zinc myristate were added. A resin composition D for mold cleaning was prepared by crushing 5 parts by weight with a ball mill and adding 0.3 parts by weight of erucic acid amide with a Nauta mixer. Table 1 shows the test results of the tablet properties and the cleaning effect using the obtained mold cleaning resin composition. As is clear from the test results, a very good cleaning effect was obtained.

Example 5 A mold cleaning resin composition E was obtained by performing the same operation as in Example 1 except that the ethylenebisstearic acid amide in Example 1 was changed to stearic acid. Table 1 shows the test results of the tablet properties and the cleaning effect using the obtained mold cleaning resin composition. As is clear from the test results, a very good cleaning effect was obtained.

Example 6 A mold cleaning resin composition F was obtained by performing the same operation as in Example 1 except that the ethylenebisstearic acid amide in Example 1 was changed to pentaerythritol stearic acid ester. Table 1 shows the test results of the tablet property and the cleaning effect using the obtained mold cleaning resin composition. As is clear from the test results, a very good cleaning effect was obtained.

Example 7 490 parts by weight of melamine, formalin (37% aqueous solution) 5
17 parts by weight of the mixture was heated and reacted, a melamine resin solution was produced by a known method, and dried under reduced pressure to obtain a powder. This powder 75
Parts by weight, 16 parts by weight of silica powder having a particle size of # 200, 8.2 parts by weight of powder pulp, 0.05 part by weight of benzoic acid and 0.5 part by weight of zinc stearate were crushed with a ball mill,
A resin composition G for cleaning a mold was prepared by adding 0.3 part by weight of ethylenebisstearic acid amide with a Nauta mixer. Table 1 shows the test results of the tablet properties and the cleaning effect using the obtained mold cleaning resin composition. As is clear from the test results, a very good cleaning effect was obtained.

Comparative Example 1 A resin composition for mold cleaning in which the amounts of ethylenebisstearic acid amide and zinc stearate used in Example 1 were both 0 was designated as H. Table 1 shows the test results of the tablet properties and the cleaning effect using the obtained mold cleaning resin composition.

Comparative Example 2 A mold cleaning resin composition in which the amount of ethylenebisstearic acid amide used in Example 1 was 0 was designated as I. Table 1 shows the test results of the tablet properties and the cleaning effect using the obtained mold cleaning resin composition.

Comparative Example 3 A mold cleaning resin composition in which the amount of zinc stearate used in Example 1 was 0 was designated as J. Table 1 shows the test results of the tablet properties and the cleaning effect using the obtained mold cleaning resin composition.

Comparative Example 4 A mold cleaning resin composition in which the amount of ethylenebisstearic acid amide used in Example 1 was 1.2 parts by weight was designated as K. Table 1 shows the test results of the tablet properties and the cleaning effect using the obtained mold cleaning resin composition.

[0043]

[Table 1]

[0044]

EFFECT OF THE INVENTION The mold cleaning resin composition of the present invention contains a metal soap and a non-metal fatty acid-based lubricant, so that it exhibits good tabletability, particularly during mini-tablet formation, and It is characterized by showing a good cleaning effect.

Claims (2)

[Claims] 1. A mold cleaning resin composition for removing stains on a mold surface during molding of a curable resin molding material, characterized in that the resin composition contains a metallic soap and a non-metallic fatty acid lubricant. Amino resin composition for cleaning molds. 2. The non-metallic fatty acid lubricant is a fatty acid,
The mold-cleaning amino resin composition according to claim 1, which is a fatty acid ester, a fatty acid partial ester, a fatty acid amide or a fatty acid bisamide.