KR20040074119A - Resin composition for mold cleaning - Google Patents

Abstract

The present invention relates to a mold cleaning resin composition which removes dirt on the surface of a mold during molding of the curable resin molding material, which contains melamine-based resin as the mold cleaning resin, and at least one guanamine and / or It is a resin composition for metal mold | die cleaning containing at least 1 sort (s) of guanamine resin.

Description

Resin composition for mold cleaning

Conventionally, when the molding of encapsulated products of an integrated circuit or the like (hereinafter abbreviated as IC / LSI) by thermosetting resin such as epoxy resin is continued for a long time, the surface of the mold becomes dirty, and the molding is continued continuously. In many cases, the surface of the molded article is dirty, or the molded article adheres to the mold and the molding operation cannot be continued. Therefore, it is necessary to clean a metal mold | die regularly, and the method of carrying out metal mold | die cleaning by shape | molding resin for metal mold | die cleaning by the ratio of several shots every time several hundred shots of molding material is proposed.

For example, Japanese Patent Application Laid-open No. 52-788 discloses that "the dirt of the surface of a metal mold | die at the time of shaping | molding of a curable resin molding material (except an amino resin molding material) mainly uses amino resin. A method of cleaning by molding from a material is proposed, and a resin composition for metal mold cleaning comprising an amino resin, an organic base and / or an inorganic base, and a release agent is disclosed. In addition, Japanese Patent Publication No. 64-10162 discloses a mold cleaning resin 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. A composition is disclosed.

Japanese Patent Application Laid-open No. Hei 8-57866 also contains a lubricant having a HLB value of 1.5 to 8 in the amino resin composition for mold cleaning to fill every corner of a complex mold or a large mold. The resin composition for metal mold | die cleaning which can be cleaned is disclosed.

In recent years, along with high integration, thinning, and surface mounting of ICs and LSIs, the shape and structure of molded products have been diversified. For example, the gate size is extremely small, such as 0.4 × 0.4 mm, Although the gate dimension is 1.2-1.5 mm, the extremely thin thing of about 0.03-0.04 mm in thickness is increasing, and when the resin composition for metal mold | die cleaning provided previously is used for the ultra-thin and matrix type metal mold | die, it is necessarily cleaning property. This was not enough.

On the other hand, the thermosetting resin molding material which seals IC, LSI, etc. also needs to change a composition by the required characteristic, and many kinds of things are used. Accordingly, the state of mold contamination and the components of the contaminants caused by the repetition of molding of the encapsulated product also vary. Among these, instead of the novolak-type epoxy resin conventionally used, the molding material which uses a biphenyl type epoxy resin, a polyfunctional type epoxy resin, and a dicyclopentadiene type epoxy resin as a main component is used, The contamination of the mold at the time of repeating molding is severe seizure with respect to the mold surface, especially the dirt of the biphenyl-based epoxy resin is severe, and in the resin composition for metal mold cleaning, which is conventionally provided, the mold is dirty The number of moldings necessary to completely remove the sigma has increased significantly, which causes a problem that the productivity of IC, LSI and the like is greatly reduced.

In order to spread the resin composition for metal mold | die cleaning to every corner of an ultra-thin or matrix-type metal mold | die, improvement of fluidity | liquidity is needed, but it is important not to reduce cleaning property and the performance of mold release property.

On the other hand, the phenomenon that the dirt on the mold is difficult to remove means that the dirt and the force of bonding of the mold are stronger than the force of bonding of the dirt with the resin composition for cleaning the mold, when the cleaning mechanism is considered. . That is, deterioration of the cleaning performance is caused by any reason that the bonding force of the interface between the mold and the dirt is increased, or the bonding force of the interface between the resin composition for the mold cleaning and the dirt is weakened. It is possible to improve the cleaning performance by improving at least one of these factors, preferably both.

As a method for improving the factor which lowers the said cleaning performance, the method of improving the intensity | strength of the resin composition for metal mold | die cleaning; A method of improving the modulus of the resin composition for mold cleaning; The method of improving the adhesive force of the resin composition for metal mold | die cleaning with a dirt, etc. are considered.

This invention relates to the resin composition for metal mold | die cleaning which cleans the injection molding metal mold for electronic component sealing, and the metal mold | die for transfer molding. The resin composition for metal mold | die cleaning of this invention shows the favorable fluidity | liquidity and cleaning property with respect to the mold contamination of an ultra-thin or matrix type, and shows the favorable cleaning property also with respect to various various pollutants.

This invention is made | formed in view of the said point, Comprising: It is an object to provide the resin composition for metal mold | die cleaning which can improve the workability of metal mold cleaning even if it is an extremely small and extremely thin shape, and can also clean various various contaminants.

The present applicant cleans contaminants on the surface of a mold formed by repetition of molding using molding materials containing biphenyl epoxy resins, polyfunctional epoxy resins, and dicyclopentadiene epoxy resins, which are frequently used as epoxy resins. As a resin composition for metal mold | die cleaning which can be removed effectively, without increasing the number of shorts of completion, a fibrous inorganic compound of 5-30 micrometers of average fiber lengths, 0.1-1.0 micrometers of average fiber diameters, and an aspect ratio of 10-60 A resin composition containing the same was proposed (see WO 02/30648 A1).

MEANS TO SOLVE THE PROBLEM In order to achieve the said objective, in order to achieve the said objective, in the resin composition for metal mold | die cleaning which mix | blended melamine-type resin, guanamine or guar is not contained, without containing a fibrous inorganic compound as mentioned above. By adding a namin resin, fluidity is improved, the resin composition for mold cleaning can be spread to every corner of the ultra-thin or matrix mold, and the wettability to contaminants is improved, and the cleaning property is excellent. It has been found that the present invention has been reached.

That is, this invention is a resin composition for metal mold | die cleaning which removes the dirt of a mold surface at the time of shaping | molding of curable resin molding material, contains melamine type resin as resin for metal mold | die cleaning, and also at least 1 type of guanamines and / or It is to provide the resin composition for metal mold | die cleaning containing at least 1 sort (s) of guanamine resin.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.

As melamine resin in this invention, 1 or more types chosen from a melamine resin, a melamine phenol cocondensate, a melamine-urea cocondensate, etc. can be used. The melamine-phenol cocondensate is formed by co-condensation with aldehydes such as melamine, phenols and formaldehyde, and the melamine-urea co-condensate is co-condensed with melamine, urea and aldehydes.

The melamine resin in this invention can be manufactured by a well-known method.

For example, an initial condensate aqueous solution is prepared by reacting formaldehyde and melamine crystals in an aqueous solution at a molar ratio of 1: 1 to 4: 1, advantageously 1.5: 1 to 3: 1. It can react at melamine crystal concentration 20-60%, reaction temperature 70-100 degreeC, and weak alkalinity, and reaction is completed in 10-100 minutes.

Part of the formaldehyde is aliphatic aldehydes such as aldehyde components other than paraformaldehyde and formaldehyde, for example acetaldehyde; Aromatic aldehydes such as benzaldehyde; Furfural; And other "aldehyde compounds capable of reacting with melamine and formaldehyde". As for the usage-amount of such a compound, 10 weight part or less is preferable with respect to 100 weight part of formaldehyde.

The resin composition for metal mold | die cleaning of this invention can mix | blend other resin of the secondary quantity which can be blended with the said melamine resin in addition to the said melamine type resin in the quantity which does not adversely affect the effect of this invention. As such resin, an alkyd resin, polyester resin, acrylic resin, an epoxy resin, rubber | gum, etc. can be illustrated.

The resin composition for metal mold | die cleaning of this invention contains at least 1 type of guanamine and / or at least 1 type of guanamine type resin (it may abbreviate as G component hereafter) other than the said melamine type resin.

Examples of the guanamines include formoguanamine (hereinafter sometimes referred to as HG), benzoguanamine (hereinafter sometimes abbreviated as BG), acetoguanamine (hereinafter referred to as AG) May be abbreviated), phenylacetoguanamine (hereinafter sometimes abbreviated as ph-AG), methoxyguanamine (hereinafter abbreviated as MG) and CTU-guanamine (Hereinafter, it may be abbreviated as CTU-G).

As said guanamine type resin, methylolated benzoguanamine resin (it may abbreviate as F-BG hereafter), methylolated acetoguanamine resin (it may abbreviate as F-AG hereafter), methylolation CTU-guar Methylolated guanamine resin (hereinafter may be abbreviated as F-G), such as namin resin (hereinafter sometimes abbreviated as F-CTU-G), melamine-benzoguanamine cocondensation resin (hereinafter M / BG- F may be abbreviated as F), melamine-acetoguanamine cocondensed resin (hereinafter sometimes abbreviated as M / AG-F) and melamine-CTU-guanamine cocondensed resin (hereinafter referred to as M / CTU-G-F And melamine-guanamine cocondensation resins (sometimes abbreviated as M / G-F) may be mentioned.

As said F-G, about 1.5-12 mol of formaldehyde is made to react with a well-known method with respect to 1 mol of guanamines, for example, and a monomethylolation guanamine resin, a dimethylolation guanamine resin, and a trimethylolation guanamine resin And tetramethylolated guanamine resins. These F-G may mix | blend F-G of mono, di, tri, detra, and more molar ratio. In addition, these F-G do not necessarily need to be mononuclear bodies, For example, the binuclear body, trinuclear body, or tetranuclear body formed by condensation of a part of methylol groups by the methylene group may be mixed.

In addition, the M / G-F is not particularly limited in the ratio of melamine and guanamine, but is preferably 30 to 200 parts by weight, more preferably 50 to 100 parts by weight of 100 parts by weight of melamine. Parts by weight are used and are obtained by methylolation with aldehydes such as formaldehyde. The amount of formaldehyde used for methylolation is preferably about 1 mol to about 1.5 mol, more preferably about 2 mol to 4 mol, per 1 mol of the total of melamine and guanamines.

The manufacturing method of said M / G-F is not restrict | limited, For example, after putting melamine and guanamine simultaneously, formaldehyde methylolation, after guanamine and formaldehyde methylolation , By adding melamine and formaldehyde to react, or by adding only melamine, methylolation using guanamines and unreacted formaldehyde, methylolation of melamine, and then methylation by adding guanamines. Any method of production may be used as long as melamine and guanamine are in the preferred weight range.

It is preferable to mix | blend these G components with 3 to 65 weight part of at least 1 sort of guanamine, and / or 5 to 200 weight part of at least 1 sort of guanamine resin with respect to 100 weight part of melamine resin. If the content of the G component is less than or equal to the lower limit, the effect of improving fluidity is small, and the cleaning property is insufficient.

On the other hand, 100 weight part of melamine type resin means the total amount of the melamine type resin powder in the said melamine type resin and the said melamine type resin impregnated pulp when mix | blending the melamine type resin impregnated pulp mentioned later.

The resin composition for metal mold | die cleaning of this invention may contain a pulp.

As the pulp, straw pulp, bamboo pulp, wood pulp (softwood pulp, broadleaf pulp) and the like may be used, and any of chemical pulp and mechanical pulp may be used.

As the pulp, a pulp (melamine resin impregnated pulp) impregnated with melamine resin may be used. The said melamine resin impregnated pulp is impregnated and dried in aqueous solution of melamine resins, such as aqueous solution of melamine-formaldehyde resin and aqueous solution of melamine-phenol-formaldehyde resin.

In addition, a part or all of the pulp may be replaced with powder pulp, whereby the fluidity can be further improved.

The size of the pulp is not particularly limited, but generally 5 to 1000 µm, preferably about 10 to 200 µm.

The content of the 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. If the pulp content is less than 5 parts by weight, the strength is poor, the cleaning effect is insufficient, and if the content of the pulp is more than 70 parts by weight, the fluidity is deteriorated, so that no contaminants remain in the mold and remain in the mold.

In addition, the resin composition for metal mold | die cleaning of this invention may contain mineral powder. As the mineral powder, for example, natural materials such as corundum, emery, garnet and silica and oxides or carbides such as silicon, iron, titanium, sodium, calcium, magnesium, aluminum, chromium and boron These oxides or carbides are preferable, and silicon oxide, magnesium oxide, aluminum oxide, silicon carbide, boron carbide and the like can be given. It is preferable that the said mineral substance powder is new Mohs hardness (6 Mohs hardness) 6-15.

The particle size of the mineral powder is not particularly limited, but is generally # 100 to # 4000, preferably # 100 to 2000, more preferably # 100 to # 1000. When the particle size is smaller than # 4000, the cleaning effect is worsened, and when handling, it is easy to cause defects such as dust and deterioration of the working environment.When the particle size is larger than # 100, mold damage and uneven cleaning are caused. Defects are likely to occur.

Moreover, content of the said mineral substance powder is although it does not specifically limit, Preferably it is 10-90 weight part, More preferably, it is 10-30 weight part with respect to 100 weight part of melamine type resin. If the content of the mineral powder is less than 10 parts by weight, the cleaning effect is insufficient. If the content of the mineral powder exceeds 90 parts by weight, the fluidity is deteriorated.

In addition, the resin composition for metal mold | die cleaning of this invention can be made to contain a lubricating agent. As the lubricant, for example, fatty acids such as zinc stearate, calcium stearate, zinc myristate, metal soaps such as stearic acid, oleic acid, behenic acid, and the like , Fatty acid esters such as butyl stearate and dodecyl stearate, glycerol monostearate, glycerol monooleate, hydroxystearate monoglyceride Fatty acid partial esters such as pentaerythritol stearic acid ester, polyglycerol stearate, sorbitan trioleate, lauric acid amide, myristic acid amide ), Fatty acid amides such as erucic acid amide, oleic acid amide, stearic acid amide, Fatty acid bisamides such as methylenebisstearic acid amide, ethylenebisstearic acid amide, and ethylenebisoleic acid amide. In order to maintain mold cleaning property favorably, content of the said lubricant is 1.5 weight part or less with respect to 100 weight part of melamine resin, Preferably it is good to set it as 1 weight part or less.

Moreover, the hardening catalyst can be contained in the resin composition for metal mold | die cleaning of this invention. Examples of the curing catalyst include organic acids such as benzoic acid, phthalic anhydride, oxalic acid, sulfamic acid, para-toluenesulfonic acid, inorganic acids such as hydrochloric acid and sulfuric acid, and these acids. Salts with triethylamine, triethanolamine, β-dimethylaminoethanol, 2-methyl-2-amino-1-propanol and the like. The curing catalyst promotes curing of the resin composition, increases adhesion and strength of the molded product, and improves mold cleaning. Although content of the said curing catalyst is not specifically limited, It is 10 weight part or less with respect to 100 weight part of melamine resin, Preferably about 0.2-3 weight part is used.

In addition, the resin composition for metal mold | die cleaning of this invention may contain other additives, such as another inorganic or organic filler, a coloring agent, and antioxidant, in addition to the above-mentioned mineral powder, a lubricating agent, etc. Specific examples of such additives include, for example, wood powder, vinylon fiber, glass powder, glass fiber, untreated calcium carbonate, talc, aluminum hydroxide, barium sulfate, Other inorganic or organic fillers such as zinc sulfide; For example, inorganic pigments such as titanium oxide, carbon black, zinc oxide, cadmium yellow, and red oxide, phthalocyanine, azo and diazo Organic pigments, benzoxazole-based, naphthotriazole-based, fluorescent pigments such as coumarin-based, dyes such as anthraquinone-based, indigo-based and azo-based coloring agent; Lubricants such as, for example, paratoluenesulfonic acid amide, cetyl alcohol, paraffin, silicone oils; For example, antioxidants, such as a naphthylamine antioxidant, a p-phenylenediamine antioxidant, a thiobisphenolic antioxidant, etc. are mentioned.

It is preferable that the resin composition for metal mold | die cleaning of this invention contains 1 or more types chosen from said pulp, mineral powder, a curing catalyst, and a lubricating agent.

An example of the preferable compounding example of the resin composition for metal mold | die cleaning of this invention is shown below.

(A) 100 parts by weight of melamine resin

(B) 3 to 65 parts by weight of at least one guanamine and / or 5 to 200 parts by weight of at least one guanamine resin

(C) 5 to 70 parts by weight of pulp

(D) 10 to 90 parts by weight of mineral powder of particle size # 100 to # 4000

At the time of preparation of the resin composition for metal mold | die cleaning of this invention, melamine type resin, guanamine and / or guanamine type resin, and other secondary resins, pulp, mineral powder, and other additives mix | blended as desired. Any means capable of mixing uniformly may be employed. For example, kneaders, ribbon blenders, Henschel mixers, ball mills, roll mills, grinders, tumblers and the like can be exemplified.

As curable resin molding material which can clean a metal mold | die using the resin composition for metal mold | die cleaning of this invention, an epoxy resin molding material, a phenol resin molding material, etc. are mentioned, for example, Preferably it is an epoxy resin molding material, Especially It is an epoxy resin molding material for semiconductor sealing. In addition, the resin composition for metal mold | die cleaning of this invention can be used for any metal mold | die, if it is a metal mold | die used at the time of auto-molding the said curable resin molding material, it is generally applicable to the metal mold | die consisting of iron, chromium, etc. suitably.

Although an Example is given to the following and this invention is demonstrated in detail, this invention is not limited to these Examples.

(Manufacture example 1)

374 parts by weight of benzoguanamine (BG) and 243 parts by weight of formalin (37% aqueous solution) (1.5 moles of formaldehyde per 1 mole of BG) were heated and reacted at 90 to 95 DEG C at pH 7.4 to 7.6, When the reaction system becomes a transparent solution, the reaction is stopped immediately, flowed directly into a bat-shaped container, and allowed to cool and precipitate F-BG crystals at the same time. The reaction system does not separate F-BG and water, but the entire system gels to white. The plate-like gelled product was pulverized, dried at 80 ° C. for 2 hours in a hot air dryer, and water was removed to obtain a white methylolated benzoguanamine resin (a).

(Manufacture example 2)

375 parts by weight of acetoguanamine (AG) and 730 parts by weight of formalin (37% aqueous solution) (3 moles of formaldehyde per 1 mole of AG) were heated and reacted at 65 to 70 ° C. and pH 9 to make the reaction system almost transparent. At that time, the reaction is stopped immediately, and poured into a bat-shaped container as it is, and the crystals of F-AG are precipitated as it cools. The reaction system does not separate F-AG and water, but the entire system gels to white. The plate-like gelled product was pulverized, dried at 80 ° C. for 2 hours in a hot air dryer to remove moisture to obtain a white methylolated acetoguanamine resin (b).

(Manufacture example 3)

126 parts by weight of CTU-guanamine and 651 parts by weight of formalin (3.3 moles of formaldehyde based on 1 mole of melamine and CTU-G in total) were heated and reacted at 90 to 95 ° C. and pH 9, and the reaction system became a clear solution. Methylolation was performed for a minute. Subsequently, 126 parts by weight of melamine was added, and the reaction was heated at 70 to 80 ° C., and if the reaction system became a clear solution, the reaction was stopped immediately, poured into a bat-shaped container, dried at 80 ° C. for 5 hours in a hot air dryer, and moisture was removed. It removed and obtained white M / CTU-G-F resin (c).

(Manufacture example 4)

346 parts by weight of melamine, 522 parts by weight of formalin (37% aqueous solution) and 131 parts by weight of phenol were heated to form a melamine formaldehyde-phenol resin by a known method, and 248 parts by weight of pulp was added to the obtained resin solution, followed by mixing and kneading. It dried under reduced pressure and obtained the pulp mixing melamine formaldehyde-phenol resin powder (melamine type resin impregnated pulp) of 27% of pulp content.

(Manufacture example 5)

480 parts by weight of melamine and 522 parts by weight of formalin (37% aqueous solution) were heated to form a melamine formaldehyde resin by a known method, 257 parts by weight of pulp was added to the obtained resin solution, mixed and kneaded, and dried under reduced pressure to obtain pulp content 27 % Pulp incorporation melamine formaldehyde resin powder (melamine-based resin impregnated pulp) was obtained.

(Example 1)

30 parts by weight of the melamine formaldehyde-phenol resin powder (melamine-based resin impregnated pulp) obtained in Production Example 4, 50 parts by weight of commercially available melamine resin (Nikaresin S-176 from Nippon Kabaido Kogyo Co., Ltd.), aceto 10 parts by weight of guanamine, 20 parts by weight of silica powder having a particle size # 200, 0.5 parts by weight of benzoic acid and 0.5 parts by weight of zinc stearate were added to a ball mill, and 0.3 parts by weight of ethylenebisstearic acid amide was added to a Naughter mixer. The resin composition A for metal mold | die cleaning was obtained.

The characteristic value of the obtained resin composition for metal mold | die cleaning, and the test result of a cleaning effect are recorded in Table-1. As can be seen from the test results, the resin composition A for metal mold | die cleaning showed favorable fluidity | liquidity and the favorable cleaning effect.

(Example 2)

30 parts by weight of melamine formaldehyde-phenol resin powder (melamine-based resin impregnated pulp) obtained in Production Example 4, 30 parts by weight of commercially available melamine resin (Nicar Resin S-176 manufactured by Nippon Kabaido Kogyo Co., Ltd.), in Production Example 2 20 parts by weight of the obtained methylolated acetoguanamine resin (b), 20 parts by weight of the silica powder with a particle size # 200, 0.5 parts by weight of benzoic acid and 0.5 parts by weight of zinc stearate are pulverized in a ball mill, and 0.3 parts by weight of ethylenebisstearic acid amide It added to and obtained resin composition B for metal mold | die cleaning.

The characteristic value of the obtained resin composition for metal mold | die cleaning, and the test result of a cleaning effect are recorded in Table-1. As can be seen from the test results, the resin composition B for metal mold | die cleaning showed favorable fluidity | liquidity and the favorable cleaning effect.

(Example 3)

In Example 2, 20 parts by weight of methylolated benzoguanamine resin (a) obtained in Production Example 1 and 5 parts of acetoguanamine were used in place of 20 parts by weight of the methylolated acetoguanamine resin (b) obtained in Production Example 2. Except having used the part, it carried out similarly to Example 2, and obtained resin composition C for metal mold | die cleaning.

The characteristic value of the obtained resin composition for metal mold | die cleaning, and the test result of a cleaning effect are recorded in Table-1. As can be seen from the test results, the resin composition C for metal mold | die cleaning showed favorable fluidity | liquidity and the favorable cleaning effect.

(Example 4)

Example 3 WHEREIN: Except having used 20 weight part of methylolated benzoguanamine resin (a) obtained by manufacture example 1, except using 30 weight part of methylolated acetoguanamine resin (b) obtained by manufacture example 2 In the same manner as 3, the resin composition D for mold cleaning was obtained.

The characteristic value of the obtained resin composition for metal mold | die cleaning, and the test result of a cleaning effect are recorded in Table-1. As can be seen from the test results, the resin composition D for metal mold | die cleaning showed favorable fluidity | liquidity and the favorable cleaning effect.

(Example 5)

30 parts by weight of the melamine formaldehyde-phenol resin powder (melamine-based resin impregnated pulp) obtained in Production Example 4, 40 parts by weight of a commercially available melamine resin (Nicar Resin S-176 manufactured by Nippon Kabaido Kogyo Co., Ltd.), in Production Example 3 10 parts by weight of the obtained M / CTU-G-F resin (c), 5 parts by weight of acetoguanamine, 5 parts by weight of CTU-guanamine, 20 parts by weight of silica powder of particle size # 200, 0.2 parts by weight of benzoic acid and 0.5 parts by weight of zinc stearate 0.3 part by weight of ethylene bis stearic acid amide was added to the outer mixer by crushing the part in a ball mill to obtain a resin composition E for metal mold cleaning.

The characteristic value of the obtained resin composition for metal mold | die cleaning, and the test result of a cleaning effect are recorded in Table-1. As can be seen from the test results, the resin composition E for metal mold | die cleaning showed favorable fluidity | liquidity and the favorable cleaning effect.

(Comparative Example 1)

In Example 1, the resin composition F for metal mold | die cleaning was obtained like Example 1 except having set the amount of aceto guanamine to 0 weight part, and setting the amount of benzoic acid to 0.2 weight part.

(Comparative Example 2)

In Example 1, the resin composition G for metal mold | die cleaning was carried out similarly to Example 1 except having used CTU- guanamine 50 weight part instead of 10 weight part of aceto guanamine, and changing the amount of benzoic acid to 0.2 weight part. Got.

(Comparative Example 3)

In Example 1, the amount of commercially available melamine resin was 0 parts by weight, and 50 parts by weight of methylolated benzoguanamine resin (a) obtained in Production Example 1 was used in place of 10 parts by weight of acetoguanamine, and the amount of benzoic acid was also used. Except having changed into 0.2 weight part, it carried out similarly to Example 1, and obtained resin composition H for metal mold | die cleaning.

The result of having performed the metal mold | die cleaning test by the following test method using the resin composition for metal mold | die cleaning of AH is recorded in Table-1.

(Test Methods)

Using a commercially available biphenyl epoxy resin molding material (CEL-9200XU manufactured by Hitachi Kasei Co., Ltd.), the mold was stained by 500 shots in a mold of TQFP. Using this soiled mold, evaluation was performed by iteratively molding the resin composition for metal mold | die cleaning until the mold surface was cleaned cleanly.

Mold cleaning resin composition Property value Cleaning completion shorts Curability (seconds) Fluidity (cm) Example One A 429 65 7 2 B 398 60 6 3 C 426 63 7 4 D 419 61 7 5 E 412 60 6 Comparative example One F 323 55 14 2 G 452 Inmeasurement Mold release defect 3 H 619 209 Mold release defect

(Manufacture example 6)

434 parts by weight of CTU-guanamine and 648 parts by weight of formalin (8 moles of formaldehyde per 1 mole of CTU-G) were heated and reacted at 90 ° C to 95 ° C and pH 9, and the reaction system became a clear solution. After performing, it is poured into a vat-shaped container as it is. Since the system did not gel in white, it dried at 80 degreeC for 5 hours by the hot air dryer, and obtained white CTU- guanamine powder (d).

(Manufacture example 7)

126 parts by weight of melamine, 126 parts by weight of benzoguanamine and 271 parts by weight of formalin (37% aqueous solution) (2 moles of formaldehyde relative to 1 mole of the total molar ratio of M and BG) at 85 to 90 ° C and pH 9.5 to 10 When it heat-reacts and when a reaction system turns into a transparent solution, reaction is stopped immediately, it flows into a bat-shaped container as it is, and it cools and precipitates M / BG-F crystal | crystallization simultaneously. The reaction system does not separate into M / BG-F and water, and the entire system gels to white. The gelled product was pulverized, dried at 80 ° C. for 2 hours in a hot air dryer, and water was removed to obtain a white M / BG-F powder (e).

(Manufacture example 8)

126 parts by weight of melamine, 126 parts by weight of acetoguanamine and 651 parts by weight of formalin (4 moles of formaldehyde relative to 1 mole of M and AG total molar ratio) were heated and reacted at a temperature of 80 to 85 ° C. and pH9. When the reaction is complete, the reaction is stopped immediately, and poured into a bat-shaped container as it is, and after cooling, the M / AG-F crystal is precipitated. The reaction system does not separate M / AG-F and water, but the entire system gels to white. The gelled product was pulverized, dried at 80 ° C. for 2 hours in a hot air dryer, and water was removed to obtain white M / AG-F powder (f).

(Manufacture example 9)

346 parts by weight of melamine and 522 parts by weight of formalin (37% aqueous solution) were heated to form a melamine-formaldehyde resin by a known method, and 95 parts by weight of pulp was added to the obtained resin solution, mixed and kneaded, and dried under reduced pressure to obtain pulp content. 15% of pulp mixed melamine-formaldehyde resin powder (melamine-based resin impregnated pulp) was obtained.

(Manufacture example 10)

346 parts by weight of melamine and 522 parts by weight of formalin (37% aqueous solution) are heated to form a melamine-formaldehyde resin by a known method, and 360 parts by weight of pulp is mixed and kneaded with the resulting resin solution, followed by drying under reduced pressure to obtain pulp content. 40% of pulp-blended melamine-formaldehyde resin powder (melamine-based resin impregnated pulp) was obtained.

(Manufacture example 11)

346 parts by weight of melamine, 522 parts by weight of formalin (37% aqueous solution) and 131 parts by weight of phenol were heated to form a melamine formaldehyde-phenol resin by a known method, and 120 parts by weight of pulp was added to the obtained resin solution and mixed and kneaded. It dried under reduced pressure and obtained the pulp mixing melamine formaldehyde-phenol resin powder (melamine type resin impregnated pulp) of 15% of pulp content.

(Example 6)

30 parts by weight of the melamine-formaldehyde resin powder obtained in Production Example 9, 50 parts by weight of a commercially available melamine resin (Nicarazine S-176, manufactured by Nippon Kabaido Kogyo Co., Ltd.), 5 parts by weight of benzoguanamine, and a silicate of particle size # 200 20 parts by weight of powder, 5 parts by weight of powdered pulp, 0.2 parts by weight of benzoic acid and 0.5 parts by weight of zinc stearate were ground in a ball mill, and 0.3 parts by weight of ethylenebisstearic acid amide was added to the outer mixer to obtain a resin composition I for mold cleaning.

The test result of the characteristic value and cleaning effect of the obtained resin composition for metal mold | die cleaning is recorded in Table-2. As can be seen from the test results, the resin composition I for metal mold | die cleaning showed favorable fluidity | liquidity and the favorable cleaning effect.

(Example 7)

30 parts by weight of the melamine phenol-formaldehyde resin powder obtained in Production Example 11, 50 parts by weight of commercially available melamine resin (Nicar Resin S-176 from Nippon Kabaido Kogyo Co., Ltd.), 20 parts by weight of CTU-guanamine, particle size # 200 20 parts by weight of the silica powder, 5 parts by weight of powdered pulp, 0.5 parts by weight of benzoic acid and 0.5 parts by weight of zinc stearate were ground in a ball mill, and 0.3 parts by weight of ethylenebisstearic acid amide was added to the outer mixer to obtain a resin composition J for mold cleaning. .

The test result of the characteristic value and cleaning effect of the obtained resin composition for metal mold | die cleaning is recorded in Table-2. As can be seen from the test results, the resin composition J for metal mold | die cleaning showed favorable fluidity | liquidity and the favorable cleaning effect.

(Example 8)

30 parts by weight of the melamine-formaldehyde resin powder obtained in Production Example 9, 20 parts by weight of the methylolated acetoguanamine resin (b) obtained in Production Example 2, and a commercially available melamine resin (Nippon Kabaido Kogyo Co., Ltd. 176) 30 parts by weight, 20 parts by weight of silica powder with particle size # 200, 5 parts by weight of powdered pulp, 0.5 parts by weight of benzoic acid and 0.5 parts by weight of zinc stearate were pulverized in a ball mill, and 0.3 parts by weight of ethylenebisstearic acid amide was added to the outer mixer. And the resin composition K for metal mold | die cleaning was obtained.

The test result of the characteristic value and cleaning effect of the obtained resin composition for metal mold | die cleaning is recorded in Table-2. As can be seen from the test results, the resin composition K for metal mold | die cleaning showed favorable fluidity | liquidity and the favorable cleaning effect.

(Example 9)

30 parts by weight of the melamine-formaldehyde resin powder obtained in Production Example 9, 25 parts by weight of CTU-guanamine resin powder (d) obtained in Production Example 6, and a commercially available melamine resin (Nicarbine Kogyo Kogyo Co., Ltd. 176) 25 parts by weight, 20 parts by weight of silica powder with particle size # 200, 5 parts by weight of powdered pulp, 0.5 parts by weight of benzoic acid and 0.5 parts by weight of zinc stearate were crushed in a ball mill, and 0.3 parts by weight of ethylenebisstearic acid amide was added to the outer mixer. And the resin composition L for metal mold | die cleaning was obtained.

The test result of the characteristic value and cleaning effect of the obtained resin composition for metal mold | die cleaning is recorded in Table-2. As can be seen from the test results, the resin composition L for metal mold | die cleaning showed favorable fluidity | liquidity and the favorable cleaning effect.

(Example 10)

30 parts by weight of the melamine-formaldehyde resin powder obtained in Production Example 10, 20 parts by weight of the M / AG-F resin powder (f) obtained in Production Example 8, and a commercially available melamine resin (Nippon Kabaido Kogyo Co., Ltd. 176) 30 parts by weight, 20 parts by weight of acetoguanamine, 20 parts by weight of silica powder of particle size # 200, 15 parts by weight of powdered pulp, 0.5 parts by weight of benzoic acid and 0.5 parts by weight of zinc stearate in a ball mill, ethylenebisstearic acid amide 0.3 weight part was added to the outer mixer, and the resin composition M for metal mold | die cleaning was obtained.

The test result of the characteristic value and cleaning effect of the obtained resin composition for metal mold | die cleaning is recorded in Table-2. As can be seen from the test results, the resin composition M for metal mold | die cleaning showed favorable fluidity | liquidity and the favorable cleaning effect.

(Example 11)

30 parts by weight of the melamine-formaldehyde resin powder obtained in Production Example 9, 20 parts by weight of M / BG-F resin powder (e) obtained in Production Example 7, and M / AG-F resin powder (f) 20 obtained in Production Example 8 20 parts by weight, commercially available melamine resin (Nicar Resin S-176 from Nippon Kabaido Kogyo Co., Ltd.), 20 parts by weight of silica powder with a particle size of # 200, 15 parts by weight of powdered pulp, 0.5 parts by weight of benzoic acid and zinc stearate 0.5 0.3 parts by weight of ethylenebisstearic acid amide was added to the outer mixer by crushing the parts by weight in a ball mill to obtain a resin composition N for metal mold cleaning

The test result of the characteristic value and cleaning effect of the obtained resin composition for metal mold | die cleaning is recorded in Table-2. As can be seen from the test results, the resin composition N for metal mold | die cleaning showed favorable fluidity | liquidity and the favorable cleaning effect.

(Example 12)

30 parts by weight of the melamine-formaldehyde resin powder obtained in Production Example 10, 20 parts by weight of the CTU-guanamine resin powder (d) obtained in Production Example 6, and a commercially available melamine resin (Nippon Kabaido Kogyo Co., Ltd. 176) 50 parts by weight, 20 parts by weight of benzoguanamine, 20 parts by weight of silica powder of particle size # 200, 15 parts by weight of powdered pulp, 0.5 parts by weight of benzoic acid and 0.5 parts by weight of zinc stearate in a ball mill, ethylenebisstearic acid amide 0.3 A weight part was added to the outer mixer and the resin composition O for metal mold | die cleaning was obtained.

The test result of the characteristic value and cleaning effect of the obtained resin composition for metal mold | die cleaning is recorded in Table-2. As can be seen from the test results, the resin composition O for mold cleaning exhibited good fluidity and a good cleaning effect.

(Comparative Example 4)

In Example 6, the resin composition P for metal mold | die cleaning was obtained like Example 6 except having made the amount of benzoguanamine into 0 weight part.

(Comparative Example 5)

In Example 11, the amount of the commercially available melamine resin (Nicar Resin S-176 from Nippon Kabaido Kogyo Co., Ltd.) and M / BG-F was 0 parts by weight, and the amount of M / AG-F was 60 parts by weight. Except having made into the negative part, it carried out similarly to Example 11, and obtained resin composition Q for metal mold | die cleaning.

(Comparative Example 6)

In Example 12, the resin composition R for metal mold | die cleaning was obtained like Example 12 except having changed the quantity of CTU-guanamine into 60 weight part.

Using the resin composition for metal mold | die cleaning of I-R, the result of having performed the metal mold | die cleaning test by the same test method as the case of said resin composition for metal mold | die cleaning of A-H is recorded in Table-2.

Mold cleaning resin composition Property value Cleaning completion shorts Curability (seconds) Fluidity (cm) Example 6 I 332 62 7 7 J 384 71 6 8 K 368 67 7 9 L 374 69 7 10 M 388 72 7 11 N 412 75 7 12 O 381 70 7 Comparative example 4 P 340 56 10 5 Q 448 216 Mold release defect 6 R 452 Inmeasurement Mold release defect

The resin composition for metal mold | die cleaning of this invention shows the favorable fluidity | liquidity, it can inject | pour to every corner of metal mold | die, such as an ultra-thin and matrix form, and also has favorable wettability with respect to a contaminant, and has a biphenyl type. The cleaning effect is excellent also with respect to the mold contamination which occurs at the time of molding of the epoxy resin molding material.

Claims (10)

Resin composition for mold cleaning which removes the dirt of a mold surface at the time of shaping | molding of curable resin molding material, Comprising melamine-type resin as resin for metal mold | die cleaning, In addition, at least 1 type of guanamine and / or Resin composition for metal mold | die cleaning containing at least 1 sort (s) of guanamine resin. The resin composition for metal mold | die cleaning of Claim 1 whose content of the said guanamine is 3-65 weight part with respect to 100 weight part of said melamine type resins. The resin composition for metal mold | die cleaning of Claim 1 whose content of the said guanamine resin is 5-200 weight part with respect to 100 weight part of said melamine resin. The resin composition for metal mold | die cleaning of Claim 1 containing 1 or more types chosen from the pulp, the mineral powder of particle size # 100- # 4000, a hardening catalyst, and a lubricating agent. The resin composition for metal mold | die cleaning of Claim 4 whose said pulp is pulp impregnated with melamine type resin. The resin composition for metal mold | die cleaning which contains following (A)-(D) as a resin composition for metal mold | die cleaning which removes the dirt of a metal mold | die surface at the time of shaping | molding of curable resin molding material. (A) 100 parts by weight of melamine resin (B) 3 to 65 parts by weight of at least one guanamine and / or 5 to 200 parts by weight of at least one guanamine resin (C) 5 to 70 parts by weight of pulp (D) 10 to 90 parts by weight of mineral powder of particle size # 100 to # 4000 The resin composition for metal mold | die cleaning of Claim 6 whose said guanamine is benzoguanamine, acetoguanamine, or CTU-guanamine. The resin composition for metal mold | die cleaning of Claim 6 whose said guanamine type resin is methylolation guanamine resin or melamine- guanamine cocondensation resin. The resin composition for metal mold | die cleaning of Claim 6 whose one part or all part of said pulp is powder pulp. The resin composition for mold cleaning according to claim 6, wherein the pulp comprises pulp impregnated with melamine-based resin and / or guanamine-based resin.