JPS62273251A - Production of resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition having excellent mechanical strength and chemical resistance, by melting and mixing a polycarbonate resin with a specific aromatic nylon resin and molding the mixture. CONSTITUTION:(A) A polycarbonate resin is mixed in molten state with (B) an aromatic nylon resin having a water-content of 0.05-2wt%, preferably 0.1-1.5wt% and containing 60-100wt% polyamide-forming component composed of an aliphatic amine and isophthalic acid and/or terephthalic acid. The amount of the aromatic nylon resin is 1-500pts.(wt.), preferably 2-400pts. per 100pts. of the polycarbonate resin.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for producing a resin composition comprising a polycarbonate resin and a specific aromatic nylon resin. The present invention relates to a method for manufacturing a resin composition having excellent mechanical strength and chemical resistance by melting and molding the aromatic nylon resin in which a specific amount of water is present in the resin composition.

[Conventional technology]

Polycarbonate resin has excellent heat resistance and impact resistance, and is widely used in various fields such as cage machine parts such as office equipment and automobile exterior parts such as bumpers, but its poor chemical resistance limits its use. There is.

To improve this, attempts have been made to blend polyester resins such as polyethylene terephthalate and polybutylene terephthalate or polyolefins such as polyethylene into polycarbonate, but the effect of improving chemical resistance and heat resistance is not sufficient. On the other hand, improvements have been attempted by blending aliphatic nylon resins such as nylon 6 with polycarbonate. However, when aliphatic nylon resin is blended with polycarbonate resin, polycarbonate N? At present, the fat decomposes, the molecular weight of the polycarbonate decreases significantly, and the strength decreases, making it impossible to obtain a product that can withstand practical use.

When a certain aromatic nylon is blended, the molecular weight decreases in the same way as aliphatic nylon, but the strength is maintained to some extent because of good compatibility. However, due to the decrease in molecular weight, stable physical properties could not be obtained and this was insufficient for practical use.

[Purpose of the invention]

The present inventors investigated the use of aromatic nylon resin in order to obtain a polycarbonate with less molecular weight reduction and excellent mechanical strength and chemical resistance even when aromatic nylon resin is blended with polycarbonate resin. The present invention was achieved by discovering a method for producing a resin composition that meets the purpose by melt-mixing and molding a resin in the presence of a specific water content.

That is, when producing a composition consisting of a polycarbonate resin and an aromatic nylon resin by melt-mixing, the aromatic nylon resin is characterized in that it contains a water content of 0.0j to -% by weight. The present invention relates to a method for producing a resin composition.

[Structure of the invention]

The present invention will be specifically explained below.

Aromatic polycarbonate resins can be produced using the phosgene method, which involves reacting various dihydroxydiaryl compounds with phosge;
Alternatively, it is a polymer or copolymer obtained by a transesterification method in which a dihydroxydiaryl compound and a carbonate ester such as diphenyl carbonate are reacted.
Examples include polycarbonate resins made from phenyl)propane (bisphenol A).

In addition to bisphenol A, examples of the dihydroxydiaryl compounds include bis(≠-hydroxy7-ale)methane, /17-bis(Hiro-hydroxyphenyl)ethane, λ
, Cocose (≠-hydroxyphenyl)butane, Tip 2
-bis(Hiro-hydroxyphenyl)octane, bis(≠
-hydroxyphenyl)phenylmethane, J, 2-bis(≠-hydroxy-3-methylphenyl)furopane, /
, /-bis(≠-hydroxy-3-tert-butylphenyl)propane, co,corbis(Hiro-hydroxy-3-bromophenyl)propane, co,corbis(4t-hydroxy-3,!dibromophenyl)propane, =, Corbis(Hiro-Hydroxy-31j dichlorophenyl)propane, bis(hydroxyaryl)alka 70, /,
/-bis(Hiro-hydroxyphenyl)cyclopentane,
/, /-bis(hydroxyaryl)fucroalkanes such as bis(ILL-hydroxyphenyl)cyclohexane, Hiro, Hiro'-dihydroxydiphenyl ether,
Hiro, dihydroxydiarylethers such as Hiro'-dihydroxy-3,3r-dimethyldiphenyl ether, Hiro, ≠'-dihydroxy/diphenyl sulfite, μ
, dihydroxydiaryl sulfides such as Hiro'-dihydroxy/-J, J'-dimethyldiphenyl sulfide, ≠, 4L'-dihydroxydiphenyl sulfoxide, and Sapphiro'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide. Examples include dihydroxydiarylsulfoxides, dihydroxydiarylsulfones such as Hiroshi, ≠'-dihydroxydiphenylsulfone, and Hiroshi'-dihydroquine-3,3'-dimethyldiphenylsulfone.

These can be used alone or in combination, but
In addition to these, piperazine, diviveridyl, hydroquinone, resorcinol, ≠, ≠'-dihydroxydiphenyl, etc. may be used in combination.

The nylon resin used in the present invention, which is composed of aliphatic diamine and isophthalic acid and/or terephthalic acid and has a polyamide-forming component of 6θ to 100% by weight, has good compatibility with polycarbonate and has good transparency and dimensional stability. Yes, it is preferable.

Polyamides containing aromatic groups used in the present invention are usually polymerized by the so-called melt polymerization method, in which lactam is added to a nylon salt consisting of diamine and dicarboxylic acid or an aqueous solution thereof as necessary, but isophthalic acid Depending on the composition of terephthalic acid and terephthalic acid, it can also be produced by a solution method or an interfacial polymerization method.

Here, the composition of isophthalic acid and terephthalic acid can be in any ratio, but if the ratio of terephthalic acid is large, the melting point of the polyamide will be 300°C or higher, and terephthalic acid can be
It is preferable that the weight is less than i%. Usually, the weight ratio of isophthalic acid:terephthalic acid e=20:1O-70=20 is used.

Other copolymerizable components include lactams with three or more membered rings, polymerizable ω-amino acids, dibasic acids and diamines, etc.
Specifically, ε-caglolactam, aminocaproic acid,
Polymers such as enantholactam, 7-aminehebutanoic acid, //-aminoundecanoic acid, deaminononanoic acid, α-pyrrolidone, α-piperidone, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, co-corvis, etc. Examples include diamines such as (Hiro-amino-!-methylcyclohexyl)propane and metaxylylene diamine, and dicarboxylic acids such as adipine powder, cepatic acid, dodecanibasic acid, and geltal.

The blending amount of nylon resin is 100% polycarbonate 1.
y00 parts by weight, preferably 1 to ≠ 00 parts by weight. If the amount is small, the effect of improving chemical resistance will be small, and if the amount is too large, the dimensional stability due to moisture absorption will be poor. It won't change.

In the method of the present invention, the proportion of water present in the aromatic nylon resin is 0.0! −u′Mt%, preferably θ,
It is necessary that /~/, j weight f%. The polycarbonate resin may be dried or may be left with its normal saturated water absorption at room temperature. Therefore, as long as the water absorption is within the following range, it is not a particularly important requirement.

The amount of water present in aromatic nylon resin is 0.0! When the amount is less than 2% by weight, the effect of the present invention is insufficient, while when it is more than 2% by weight, foaming occurs and the molecular weight of the polycarbonate resin decreases.

It is preferable that moisture be present in the aromatic nylon resin as uniformly as possible, and it is not so preferable to have moisture adhere only to the surface of the pellets because the concentration will be locally high.

Melt-mix molding of a resin composition consisting of a polycarbonate resin and an aromatic nylon resin containing a specific amount of water can be carried out by various means at any stage immediately before molding the final molded product.

The most convenient method is to tri-blend polycarbonate resin and aromatic nylon resin containing a specific amount of water, and obtain the final molded product by injection molding or extrusion molding.
The above triblend product may be pelletized using an extruder, and the final molded product may be obtained by injection molding/extrusion molding after drying the pellets. It is preferable to use an apparatus that can remove gases such as moisture generated during melt-mixing molding. Therefore, apparatuses commonly referred to as a vent injection molding machine or a vent extruder are preferable because they are simple.

In addition to the above-mentioned formulations, the composition of the present invention may also contain various well-known additives, such as glass fibers, reinforcing agents such as carbon RH1 metal whiskers, silica, alumina, silica-alumina clay iron materials, silica-magnesium It may contain fillers such as clay minerals, calcium silicate, calcium carbonate, asbestos, and carbon black, as well as lubricants, nucleating agents, antioxidants, flame retardants, antistatic agents, weathering agents, and the like.

〔Example〕

EXAMPLES The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited to these Examples.

The measurement items in the examples were carried out using the following methods.

(1) Measurement was performed using an Ostwald viscosity tube according to nylon ηreIJ Engineering 5K-4/10.

(2) Tr (glass transition temperature) determined by differential scanning calorimetry.

(3) Polycarbonate molecular weight device: Toyo Co., Ltd., Ll HtczosvR column: Toyo Page Co., Ltd. Gf000H6, G≠θOOH, □JOO
The solution was measured with tetrahydrofuran using G2θ00H4° (Sanmoto Column) for OH, and the number average molecular weight was measured.

(4) Tensile strength and elongation According to AEITM DtJr.

(5) Izod impact value /// ASTM D-co! using an inch thick test piece. followed.

(6) Gasoline resistance test 0.0 on the tensile test piece. A bending strain of j% was applied, and after immersing in gasoline for 5 minutes, it was air-dried for 211 hours. A tensile test was performed using the test piece to determine the elongation.

(7) Moisture Moisture was determined by the Karl Fischer method according to J.Eng.S.Kdrlo.

[Production example of aromatic nylon]

Hexamethylenediamine aqueous solution (1
0wt%)/3. Add riuna, isophthalic acid, / cod, terephthalic acid, and lily, stir and dissolve evenly, and then add acetic acid! 3?
After adding, put it into an autoclave. -, jky
Water is distilled out while maintaining the internal pressure of /ctti until the concentration of nylon salt reaches 20% by weight, and then /! ky/
After increasing the pressure to -, further water is distilled out, and when the internal temperature reaches 2!0℃, the internal pressure is slowly released, and the final temperature is 100 T.
After polymerization was carried out under reduced pressure of orr for 7 hours, it was extruded into chips. The polymer thus obtained is ηr
ed 2,2.71127°C.

Example/, C, Comparative Example/~7 Water absorption rate 0. The above aromatic nylon resin having a water absorption rate of 0.5- is tri-blended with -j% of bisphenol A type polycarbonate 10θ heavy area having a molecular weight of 23,000 as shown in Table -/, using a Nakatani mechanical split co-axial pent extruder. 2
The mixture was kneaded and made into pellets at rO°C. After drying the pellets with hot air, J, 60Z injection molding machine (Toshiba Machine Works 5-75e)
Samples for physical property tests were made using a molding temperature of 300°C and a mold temperature of RO°C. Using this, normal tensile test,
An Od impact test was conducted. Gasoline resistance was also checked.

In order to determine the degree of molecular weight reduction of the polycarbonate resin, the molded product was pulverized, and then the polycarbonate was reflux-extracted with methylene chloride.

The molecular weight of the extracted polycarbonate was measured.

The results are shown in Table-/.

For comparison, aromatic nylons adjusted to 0.0.2% and 3.2% by vacuum drying or water absorption treatment with hot water were used in the same manner.

In addition, in Comparative Example 7, aliphatic nylon (ηr
The results when using e12J) are also shown.

〔Effect of the invention〕

As shown in Table 1, the composition obtained according to the present invention exhibits extremely excellent chemical resistance and can be used in applications that come into contact with chemicals, so its commercial value is extremely high.

Sender: Mitsubishi Chemical Industries, Ltd. Representative Patent Attorney Hase - Others/Names

Claims (2)

[Claims] (1) When producing a composition consisting of a polycarbonate resin and an aromatic nylon resin containing 60 to 100% by weight of a polyamide-forming component consisting of an aliphatic diamine and isophthalic acid and/or terephthalic acid, the aromatic nylon resin A method for producing a resin composition, characterized in that a resin composition containing 0.05 to 2% by weight of water is used as (2) Aromatic nylon resin is polycarbonate resin 1
The method for producing a resin composition according to claim 1, wherein the amount is 1 to 500 parts by weight based on 00 parts by weight.