KR820001785B1 - Resin composition - Google Patents

Abstract

Fire-resistant compns. having low corrosion to steel molds contain 100 parts blends of 5-80% ABS polymer(I) or MBS with 20-95% cycloolefin-vinyl chloride copolymers and 0.5-15 parts 1:10-15:1 alkyltin maleate-alkyltin mercaptide compds. Thus, a molding contg. I 50, 0.5:100 cyclohexane-vinyl chloride copolymer 50, STAN BM(N)(an alkyltin maleate) 2, T-15MJ(an akiyltin mercaptide)2, and lubricants 3 parts were sandwiched between polished steel, heated lh at 200≰C, and sepd., and the steel was allowed to stand at 25≰C and humidity 65±5% for 10 days with retention of gloss.

Description

Flame Retardant Resin Composition

The present invention relates to a flame retardant resin composition excellent in mold steel corrosion resistance.

Recently, as a building material, synthetic resins used for furniture and vehicle electrical products have been required to be flame retardant, and acrylonitrile butadiene styrene-based copolymer resins (hereinafter referred to as ABS resins) for their use have not undergone flame retardant treatment. There are a lot of cases.

As one of flame retardant methods of ABS resin, a method of blending polyvinyl chloride resin (hereinafter referred to as PVC resin) to ABS resin to form a flame retardant resin is known. This blend resin is a new material that imparts flame retardancy to ABS resin and improves impact resistance of PVC resin and assists each other's shortcomings with each other, and is widely used in injection molding because it is inexpensive compared to other flame retardant resins. .

However, this ABS // PVC blend-based flame retardant resin has caused a problem that the mold is corroded during storage of the mold during injection molding or after molding as the performance of injection molding increases. Molds for injection molding are often complicated and precise and are very expensive. Corrosion from short periods of use is a significant cost problem.

Conventional injection molding resins are mostly polyethylene, polypropylene, polystyrene, ABS resins, and the like, and almost no halogen-containing resin composition does not cause corrosion problems. However, in recent years, as the synthetic resin flame retardant is urgently required, a resin composition containing halogen has been widely used, but the problem of mold corrosion has been greatly increased.

劑)에 의한 처리가 널리 행하여지고 있으나, 금형 세부까지 처리하기가 곤란할 뿐만 아니라 현장의 노력시간도 걸리므로 바람직한 방법이라고 할 수 없다. 또 금형강재에 내부식성 강제를 사용한다는 방법 〔합성수지, 24(8), 5(1978)〕도 있으나 강재가 고가이고 공업적으로 범용화되는데는 아직까지도 시간을 요한다. 따라서 부식성이 극히 적은 난연성 수지가 절실히 요구되고 있는 것이 현상태이다.As a countermeasure against corrosion, rust inhibitors during injection molding and after injection molding

Although the treatment by vi) is widely performed, it is difficult to process the mold details, and it is not a preferable method because it takes time on site. In addition, there are methods for using corrosion-resistant steel in the mold steel (synthetic resin, 24 (8), 5 (1978)), but it still takes time for the steel to be expensive and industrially used. Therefore, there is an urgent need for flame retardant resins having extremely low corrosiveness.

In view of the present situation, the present inventors have intensively studied for the purpose of obtaining a flame-retardant resin composition having excellent corrosion resistance, particularly suitable for injection molding. As a result, (A) ABS resin or methacrylic acid ester-butadiene styrene-based resin Special polyvinyl chloride resin (hereinafter referred to as special PVC resin) obtained by polymerizing a monomer mixture composed mainly of 5 to 80 wt% and (B) vinyl chloride or vinyl chloride in the presence of a cycloolefin compound (hereinafter referred to as MBS resin) Lead-based stabilizer (C) or (d ₁ ) alkyl tin maleate and (d) from (C ₁ ) inorganic acid lead and (C ₂ ) organic acid lead in 100% by weight of the resin composition comprising 95 to 20% by weight, and (d ₂ ) Tin-based stabilizer (D) consisting of alkyl tin melcaptide in a ratio such that the weight ratio of (C ₁ ): (C ₂ ) or (d ₁ ): (d ₂ ) is from 1: 10 to 15: 1 ( 0.5 to 15 parts by weight C) or (D) The resin composition being characterized in that the discovery that achieve the intended purpose, and reached the present invention.

-메틸스티렌을 주체로하는 단량체 혼합물을 그래프트 중합시킨 중합체 또는 이 중합체에 아크릴로니트릴-스틸렌 공중합체를 혼합한 중합체로 대표되지만, 아크릴로니트릴의 일부를 메타 크릴산에스테르 또는 아크릴산 에스테르 등으로 치환한 것도 포함된다. 부타디엔 10내지 40중량% 아크릴로니트릴 10내지 40중량%, 스틸렌 30내지 70중량%를 함유하는 수지가 물 성면에서 바람직하다. 또 스틸렌의 전부 또는 일부를

-에틸스틸렌으로 치환한 수지는 내열성이 우수하다. 또 본 발명에 의한 MBS 수지라는 것은 상기 MBS 수지에 있어서 아크릴로니트릴의 전부를 메타크릴산 에스테르로 치환한 것 및 이 메타크릴산 에스테르의 일부를 아크릴로니트릴 또는 아크릴산 에스테르 등으로 치환한 것을 말한다.As the ABS resin according to the present invention, those generally known as ABS can be used. That is, acrylonitrile and styrene in the base polymer mainly containing butadiene, and

It is represented by the polymer which graft-polymerized the monomer mixture which mainly consists of methyl styrene, or the polymer which mixed the acrylonitrile- styrene copolymer with this polymer, but substituted a part of acrylonitrile with methacrylic acid ester, acrylic acid ester, etc. It also includes. Resin containing 10 to 40% by weight of butadiene 10 to 40% by weight of acrylonitrile and 30 to 70% by weight of styrene is preferable in terms of physical properties. All or part of the styrene

-Resin substituted by ethyl styrene is excellent in heat resistance. The MBS resin according to the present invention refers to the one obtained by replacing all of the acrylonitrile with methacrylic acid ester in the MBS resin and the part of the methacrylic acid ester with acrylonitrile, acrylic acid ester and the like.

Of course, the ABS resin and the MBS resin can be used by mixing. No particular method is necessary for producing these resins, and known methods can be used.

As monomers other than vinyl chloride used as needed in the manufacture of the special PVC resin by this invention, conventional things, such as an olefin, a vinyl ester, an unsaturated acid, an unsaturated acid ester, an unsaturated acid anhydride, a nitrile compound, and a vinylidene compound, are mentioned. have.

The amount of these monomers used is usually 30% by weight or less in the mixture with vinyl chloride. Moreover, as a cycloolefin compound, they are a cycloolefin and the cycloolefin nucleus substituted by halogen or the C1-C8 alkyl group, alkenyl group, or alkoxy group. Here, cycloolefin means cyclic monoolefins, such as cyclobutene, cyclopentene, cyclohexene, and a cyclooctene, cyclopentadiene, cyclohexadiene, cyclooctadiene-1, 3-, etc., for example. In addition, the nuclear substituent of the cycloolefin is C1 to C8 such as halogen, methyl, ethylpropyl, butyl, hexyl, 2-ethylhexyl, aryl, isopropenyl, butanyl group, such as chlorine and fluorine, preferably 1 to 4 It refers to a compound in which the cycloolefin is nuclear-substituted with an alkyl group or an alkenyl group, methoxy, ethoxy, propoxy, butoxy group and the like having 1 to 8 carbon atoms, preferably 1 to 4 alkoxy groups.

Among them, commonly known as telpenes, for example, telpinene, telpinotene and the like. The polymerization is carried out by ordinary radical polymerization, and the cycloolefin compound is added to the polymerization system before the start of the polymerization or after the completion of the reaction after the polymerization of 0.05 to 5 parts by weight per 100 parts by weight of the monomer. A detailed description of the polymerization method is given in publication 47-48904. The special PVC resin may be a graft copolymer of vinyl chloride. Since the special PVC resin gives excellent corrosion resistance despite the degree of polymerization, the degree of polymerization is not particularly limited, but in the case of injection molding use, it is 250 to 2,000, preferably 300 to 1,000.

When (A) ABS resin or MBS resin and (B) use rate of special PVC resin are out of the range defined in the present invention, that is, when (A) is less than 5% by weight, the strength characteristics are poor and flame retardancy is greater than 80% by weight. This lowers and is also disadvantageous in terms of price.

In the present invention, examples of the (C ₁ ) inorganic acid lead used as one component of the lead stabilizer (C) include compounds such as lead tribasic sulfate, basic sulfite, lead basic phosphorous silica gel, lead silicate and lead white.

Examples of the organic lead (C ₂ ) other than the lead stabilizer include metal soaps such as lead tribasic maleate, lead tribasic phthalate, lead basic stearic acid and lead salicylic acid.

On the other hand, as the (d ₁ ) alkyl tin maleate as a component of the tin stabilizer (D), poly (dibutyl tin maleate), poly (dioctyl tin maleate), dibutyl tin bis (alkyl maleate), dioctyl Tin bis (alkylmaleate) and the like.

Further Examples of tin melkap tide compound d ₂ alkyl, such as monobutyltin tris (alkyl melkap Tide), dibutyltin Beast less (alkyl melkap Tide), dimethyl tin bis (alkyl melkap Tide), dioctyltin bis (alkyl melkap Tide) Monoalkyltin tris (alkylmelcaptide) or dialkyltinbis (alkylmelcaptide) dibutyltinbis (alkylmelcaptoacetate), dibutyltinbis (alkylmelcaptopropionate), monobutyltintris (alkyl Monoalkyl tin tris (melcapto acid ester salts) or dialkyl tin bis (melcapto acid ester salts) or dialkyl tin bis (melcap acid ester salts) such as mercapto acetate) and dioctyl tin bis (alkyl melcapto acetate) In addition, thiobis (dialkyl tin melcapto acid ester salt), a monoalkyl tin sulfide, a dialkyl tin sulfide, etc. are mentioned.

The stabilizer according to the present invention is either a lead-based stabilizer (C) consisting of at least one kind of (C ₁ ) and at least one kind of (C ₂ ) or a tin-based stabilizer (D) consisting of at least _one kind of (d ₁ ) and at least one kind of (d ₂ ). When (C) is used, it is preferable to use (d ₁ ) together in order to improve thermal stability again.

(C ₁ ): (C ₂ ) or (d ₁ ): (d ₂ ) have a weight ratio of from 1:10 to 15: 1, preferably from 1: 7 to 10: 1. If this ratio is out of the above range, the difference in corrosion resistance of metals is not recognized as a widely used PVC resin and the special PVC resin according to the present invention. The use amount of (C) or (D) is 0.5 to 15 parts by weight based on 100 parts by weight of the mixture of ABS resin or MBS resin and special PVC resin.

This amount is arbitrarily selected according to the molding conditions, the size of the molded article, etc., but less than 0.5 parts by weight cannot sufficiently suppress thermal decomposition during molding. It is not desirable because it affects.

Moreover, the composition of this invention can contain the additive of the kind and quantity which do not deleteriously affect the effect of this invention.

Examples of this additive include other heat stabilizers, lubricants, plasticizers, chelates, sulfates, ultraviolet absorbers, inorganic fillers, flame retardants, and pigments used in conventional PVC resins such as metal soap stabilizers and epoxy stabilizers. . In addition, when using ABS resin or MBS resin as a main ratio, it is preferable to add antimony trioxide as a flame retardant.

In the mixing of the components of the ABS resin or the MBS resin, the special PVC resin, the lead or the tin stabilizer used in the present invention, these may be added simultaneously or in any addition order and mixed.

The mixer may use a balm mixer, na-double blender, Henschel mixer, ribbon blender, hobar-mixer, extruder, and other suitable mixers.

The flame-retardant resin composition of the present invention can greatly improve the service life against metal corrosion during injection molding, which is extremely short as a conventional product without almost changing the material price, physical properties and moldability of the conventional product. The present invention is also applicable to steel corrosion protection in other processing methods such as extrusion molding, and this processing method is not limited to injection molding.

Hereinafter, the present invention will be described in detail again with reference to Examples, but the present invention is not limited to these Examples. In addition, the use part of resin, an additive, a monomer, and a polymeric chemical agent in an Example is a basis of weight.

Example 1

The number of surface parts of the resin and the additives shown in the first table was simultaneously added to the Henschel mixer, and the resultant composition was heated and mixed up to 120 ° C., pelletized by an extruder, kneaded for 3 minutes by a 170 ° C. hot roller, and the resultant was 5 to 175 ° C. A 40 mm x 30 mm molded tube was created by heat-pressing for minutes.

Separately, a 100 mm x 100 mm x 5 mm steel piece (generally used in a mold for injection molding) of material S-55C having a sufficiently polished surface was prepared.

The molded plate was sandwiched by two polished surfaces of the steel pieces, heated for one hour in a gaya open set at 200 ° C., and then extracted and the molded plate was removed.

On the other hand, the steel pieces were left in a constant temperature chamber prepared with the polished surface thereof at a temperature of 25 ° C and a humidity of 65 ± 5%, and visually determined by visually changing the modified state of the contacted part of the formed plate.

The results are shown in the first table.

TABLE 1

Example 2

250 parts of distilled water, 100 parts of vinyl chloride, 0.5 part of polyvinyl acetate partial saponification, 0.3 part of gelatin, 0.2 part of lauroyl peroxide, and 0.3 part of cycloolefin compound shown in Table 2 were subjected to polymerization reaction at 50 ° C. for 20 hours. As a result, a non-viscosity special PVC resin shown in Table 2 was prepared.

Next, the same corrosion test was carried out using the above-mentioned special PVC resin instead of the special PVC resin used in Example 1 Test No. 1-1. The results are shown in the second table.

In addition, the result of using the similar non-viscosity vinyl chloride resin obtained by providing to a polymerization reaction at 55 degreeC for 20 hours, without adding a cycloolefin compound by the above method composition is shown as a comparative example (2-6).

TABLE 2

Note: 7) is the same as Table 1.

Example 3

The same test as in Example 1 was conducted except that the compounding ingredients shown in Table 3 were used. The results are shown in Table 3.

TABLE 3

Note: 2), 3), 4), 6), and 7) are the same as in the first table, 8) Hybrene B-203 manufactured by Japan Xeon Co., Ltd.

Example 4

The same experiment as in Example 1 was conducted except that the formulations shown in Table 4 were used. The results are shown in Table 4.

TABLE 4

Note: 8) Stainless steel BM (N): manufactured by Sansheng Organic Synthesis Co. 9) T-17MJ: manufactured by Kachida Chemical. 1), 2), 3), 4), 6) and 7) are the same as in the first table.

Example 5

250 parts of distilled water, 100 parts of vinyl chloride, 0.5 part of polyvinyl acetate partial saponified product, 0.3 part of gelatin, 0.2 part of lauroyl peroxide and 0.3 part of cycloolefin compound shown in Table 5 50 degreeC (only the comparative example) 55 The non-viscosity special PVC resin shown in Table 5 was prepared by providing the polymerization reaction at 20 캜 for 20 hours.

Next, the same corrosion test was carried out using the above-mentioned special PVC resin instead of the PVC resin used in Example 4 Test No. 4-1. The results are shown in Table 5.

TABLE 5

Note: 7) is the same as Table 1.

Example 6

The same experiment as in Example 4 was carried out except for using the compounding components shown in Table 6. The results are shown in Table 6.

TABLE 6

Note: 10) Hivren B-203: manufactured by Japan Zeon Co., Ltd.

2), 6) and 7) are the same as the first table, 8) and 9) are the same as the fourth table.

Claims (1)

Acrylonitrile-butadiene-styrene copolymer resin or methacrylic acid ester-butadiene styrene copolymer resin 5 to 80% by weight (A) and a monomer mixture mainly composed of vinyl chloride or vinyl chloride in the presence of a cycloolefin compound Lead-based stabilizer (C) or alkyl tin maleate composed of inorganic lead (C ₁ ) and organic lead (C ₂ ) in 100 parts by weight of a resin composition composed of 95 to 20 wt% (B) of a special polyvinyl chloride resin obtained by polymerization. d ₁ ) and (d ₂ ) tin-based stabilizers (D) comprising (C ₁ ): (C ₂ ) or (d ₁ ): (d ₂ ) in a weight ratio of 1: 10 to 15: 1 The flame-retardant resin composition excellent in the corrosion resistance of the mold steel, characterized in that it is blended 0.5 to 15 parts by weight as (C) or (D) in such a ratio as to be.