JP2018184557A - Coloring prevention agent for polycarbonate resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring prevention agent for polycarbonate resin which suppresses coloring of a polycarbonate resin, is excellent in moldability even when an addition amount is large, and suppresses bleeding of the coloring prevention agent; a polycarbonate resin composition; and a molding formed from the polycarbonate resin composition.SOLUTION: A coloring prevention agent for polycarbonate resin is formed from a polyalkylene glycol derivative represented by formula (I): HO(CHCHCHCHO)/(CHCH(CH)O)/(CHCHO)H. In formula (I), l represents an average addition molar number of an oxytetramethylene group, and represents 2 to 60; m represents an average addition molar number of an oxypropylene group, and represents 1 to 50; and n represents an average addition molar number of an oxyethylene group, and represents 1 to 40; l/(l+m+n) is 0.2 to 0.8; m/(l+m+n) is 0.1-0.7; n/(l+m+n) is 0.1 to 0.4; and an addition condition of the oxyalkyle group is a random form.SELECTED DRAWING: None

Description

  The present invention relates to an anti-coloring agent for polycarbonate resin, a polycarbonate resin composition comprising the anti-coloring agent, and a molded article.

  Polycarbonate resin is excellent in transparency, mechanical properties, thermal properties, electrical properties, weather resistance, etc., and is widely used in OA equipment, electrical / electronic equipment, automotive parts, etc. It is used for optical moldings such as optical fibers. However, since the molding temperature of the polycarbonate resin is high, the molded body is likely to be colored, and the optical performance may be adversely affected in the optical molded body. As a means for solving such a problem, for example, Patent Document 1 proposes a polyalkylene glycol derivative, which shows a polycarbonate resin composition having a good hue and a molded body comprising the same.

  Furthermore, Patent Document 2 proposes polyoxytetramethylene polyoxyethylene glycol as a coloring preventing agent, and when this coloring preventing agent is used, it is highly transparent and has a high light transmittance without yellowing. A polycarbonate resin composition and a molded body comprising the same are obtained. Furthermore, Patent Document 3 proposes polyoxytetramethylene polyoxypropylene glycol as a color preventing agent. When this color preventing agent is used, a polycarbonate resin composition excellent in hue even when molded at a high temperature and A molded body comprising the same is obtained.

In this way, it has been improved to some extent, but in recent years, with the increase in functionality of OA equipment such as copiers and fax machines, and electrical / electronic equipment, the shapes of the parts used for these have become more complex and compared with the conventional one. Therefore, it is required to perform molding at a high temperature. When the molding process is performed at a high temperature, the polycarbonate resin is colored and the yellowness is increased. Therefore, it is considered that the amount of the above-described anti-coloring agent is increased and improved. However, increasing the amount of anti-coloring agent will adversely affect the molded product and cause molding defects such as flow patterns and cracks, resulting in poor molding processability. Could contaminate.
Therefore, there is a need for a color-preventing agent for polycarbonate resin that is excellent in moldability, suppresses coloring of the polycarbonate resin, and has little bleeding of the color-preventing agent even when the amount added is large.

JP 2008-163070 A Japanese Patent No. 5613178 Japanese Patent No. 5801516

  An object of the present invention is to prevent coloration of a polycarbonate resin and to be excellent in molding processability even when the amount of addition is large and to prevent bleeding of the colorant, a polycarbonate resin composition, and the polycarbonate resin It is providing the molded object which consists of a composition.

As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that the above-mentioned color-preventing agent for polycarbonate resin having three types of oxyalkylene groups, oxytetramethylene group, oxypropylene group, and oxyethylene. The present inventors have found the knowledge of solving the problem and have completed the present invention.
That is, the present invention includes the following [1] to [3].
[1] An anti-coloring agent for polycarbonate resin comprising a polyalkylene glycol derivative represented by the following formula (I).
_{HO (CH 2 CH 2 CH 2} CH 2 O) l / (CH 2 CH (CH 3) O) m / (CH 2 CH 2 O) n H
... Formula (I)
(L is the average addition mole number of the oxytetramethylene group and represents 2 to 60. m is the average addition mole number of the oxypropylene group and represents 1 to 50. n is the average addition mole number of the oxyethylene group. 1/40, 1 / (l + m + n) is 0.2 to 0.8, m / (l + m + n) is 0.1 to 0.7, and n / (l + m + n) is 0.1 to 0.7. (The addition state of the oxyalkylene group is random.)
[2] A polycarbonate resin composition obtained by blending 0.01 to 10.0 parts by mass of the anti-coloring agent for polycarbonate resin according to [1] with respect to 100 parts by mass of the polycarbonate resin.
[3] A molded product obtained by molding the polycarbonate resin composition according to [2].

  According to the present invention, it is possible to suppress coloration of a polycarbonate resin and to be excellent in molding processability even when the addition amount is large, and to reduce the bleeding of an anticoloring agent, a polycarbonate resin composition, and the polycarbonate resin composition. Can be provided.

Hereinafter, the present invention will be described in detail.
The anti-coloring agent for polycarbonate resin according to one embodiment of the present invention is composed of a compound represented by the following formula (I) and has three types of oxyalkylene groups: an oxytetramethylene group, an oxypropylene group, and an oxyethylene group. .
_{HO (CH 2 CH 2 CH 2} CH 2 O) l / (CH 2 CH (CH 3) O) m / (CH 2 CH 2 O) n H
... Formula (I)
(L is the average addition mole number of the oxytetramethylene group and represents 2 to 60. m is the average addition mole number of the oxypropylene group and represents 1 to 50. n is the average addition mole number of the oxyethylene group. 1/40, 1 / (l + m + n) is 0.2 to 0.8, m / (l + m + n) is 0.1 to 0.7, and n / (l + m + n) is 0.1 to 0.7. (The addition state of the oxyalkylene group is random.)

  Three kinds of oxyalkylene groups are essential for the coloring preventing agent for polycarbonate resin. By mixing three types of oxyalkylene groups, moderate slipperiness is exhibited, and the moldability and bleedability are improved by being uniformly dispersed in the polycarbonate resin.

  In the formula (I), l represents the average number of added moles of the oxyalkylene group having 4 carbon atoms, which is 2 to 60, preferably 5 to 35. m shows the average addition mole number of a C3 oxyalkylene group, is 1-50, Preferably it is 3-40. n shows the average addition mole number of a C2 oxyalkylene group, is 1-40, Preferably it is 1-30. Moreover, the addition state of three types of oxyalkylene groups is random.

  l / (l + m + n) is 0.2 to 0.8, preferably 0.3 to 0.7, and more preferably 0.4 to 0.7. If l / (l + m + n) is smaller than 0.2, the proportion of oxytetramethylene groups having a large number of carbon atoms decreases, and the compatibility with the polycarbonate resin decreases. When l / (l + m + n) is larger than 0.8, the crystallinity of the polycarbonate resin anti-coloring agent becomes high and does not become liquid, which makes it difficult to handle.

  m / (l + m + n) is 0.1 to 0.7, preferably 0.1 to 0.6, and more preferably 0.1 to 0.5. If m / (l + m + n) is less than 0.1, the proportion of oxypropylene groups becomes small, and molding processability decreases. If m / (l + m + n) is greater than 0.7, the oxypropylene group is sterically bulky, so that it is difficult to continue to be mixed in a highly oriented resin such as a polycarbonate resin, and the bleed property is lowered.

  n / (l + m + n) is 0.1 to 0.4, preferably 0.1 to 0.3, and more preferably 0.1 to 0.2. When n / (l + m + n) is smaller than 0.1, the proportion of oxyethylene groups decreases, and the moldability is lowered. If n / (l + m + n) is greater than 0.4, the proportion of oxyethylene groups is large, so that the bleedability decreases without conforming to the strong hydrophobic structure in the polycarbonate resin.

  The number average molecular weight of the compound represented by the formula (I) is 500 to 10,000, preferably 500 to 5,000. If the number average molecular weight is less than 500, the amount of gas generated increases at the time of molding, and there is a possibility that molding defects due to gas, for example, unfilling, gas burnout, and transfer defects may occur. On the other hand, when the number average molecular weight is greater than 10,000, the compatibility with the polycarbonate resin is deteriorated, and the effect of improving coloring suppression, turbidity suppression, molding processability and bleeding property cannot be obtained sufficiently.

  The compound represented by the formula (I) can be produced by a known method. For example, it can be obtained by random addition polymerization of tetrahydrofuran, propylene oxide, and ethylene oxide to a divalent alcohol in the presence of a Lewis acid catalyst.

  In the polycarbonate resin composition of the present invention, the blending amount of the colorant for polycarbonate resin is 0.001 to 10.0 parts by mass (with respect to 100 parts by mass of the polycarbonate resin), and is compatible with the polycarbonate resin. 0.001 to 5.0 parts by mass, more preferably 0.01 to 1.0 parts by mass. If the blending amount is less than 0.001, the coloring suppression effect is not exhibited, and if it is greater than 20.0, the compatibility with the polycarbonate resin is poor.

  The polycarbonate resin used in the present invention is preferably an aromatic polycarbonate produced by a reaction between a dihydric phenol and a carbonate precursor. The reaction between the dihydric phenol and the carbonate precursor includes a solution method or a melting method. Specific examples include a reaction between the dihydric phenol and phosgene and a transesterification reaction between the dihydric phenol and diphenyl carbonate.

  Divalent phenols include 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis. (4-hydroxy-3,5-dimethylphenyl) propane, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, Bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ketone and the like can be mentioned. In addition, examples of the dihydric phenol include hydroquinone, resorcin, and catechol. These dihydric phenols may be used alone or in admixture of two or more. Particularly preferred dihydric phenols are those based on bis (hydroxyphenyl) alkanes, particularly bisphenol A.

  Examples of the carbonate precursor include carbonyl halide, carbonyl ester, haloformate and the like, and specifically, phosgene, dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate, diethyl carbonate and the like.

  The polycarbonate may have a branched structure, and as the branching agent, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4-hydroxyphenyl)- 1,3,5-triisopropylbenzene, phloroglycine, trimellitic acid, isatin bis (o-cresol) and the like. Moreover, phenol, pt-butylphenol, pt-octylphenol, p-cumylphenol, etc. are used for adjustment of molecular weight.

  The polycarbonate may be not only 100% by mass of polycarbonate but also a so-called polymer alloy in which polycarbonate and other polycarbonate resin are mixed. Examples of such polymer alloys include polycarbonate / ABS resin, polycarbonate / AS resin, polycarbonate / rubber polymer compound, polycarbonate / ABS resin / rubber polymer compound, polycarbonate / polyethylene terephthalate, polycarbonate / polybutylene terephthalate, Examples include polycarbonate / ASA resin and polycarbonate / AES resin. The ratio of polycarbonate resin other than polycarbonate in this case is preferably 40 parts by mass or less in the polymer alloy.

The method for producing the polycarbonate resin composition of the present invention is not particularly limited, and any conventionally known method for producing a resin composition can be employed.
Specifically, for example, after previously mixing the polycarbonate resin and the color-preventing agent for the polycarbonate resin of the formula (I), if necessary, other color-preventing agents using various mixers such as a tumbler or a Henschel mixer, Examples thereof include a melt kneading method using a Banbury mixer, a roll, a Brabender, a single screw kneading extruder, a twin screw kneading extruder, a kneader or the like.
Further, the polycarbonate resin composition may be produced without mixing each component in advance or by mixing only a part of the components in advance and supplying the mixture to an extruder using a feeder, followed by melt kneading. Furthermore, a polycarbonate resin composition obtained by mixing some components in advance, supplying them to an extruder, and melt-kneading is used as a master batch, and again mixed with other components and melt-kneaded to obtain a polycarbonate resin composition. Can also be manufactured.

  In the polycarbonate resin composition of the present invention, a phenolic antioxidant, a phosphorus antioxidant, a thioether antioxidant, a hindered amine light stabilizer, if necessary, as long as the effects of the present invention are not impaired. UV absorber, triazine ring-containing compound, metal hydroxide, phosphate ester flame retardant, condensed phosphate ester flame retardant, phosphate flame retardant, inorganic phosphorus flame retardant, (poly) phosphate flame retardant, Halogen flame retardant, silicon flame retardant, antimony oxide, inorganic flame retardant aid, organic flame retardant aid, antistatic agent, lubricant, nucleating agent, plasticizer, mold release agent, compatibilizer, foaming agent Light absorbing pigments, pigments, dyes, processing aids, metal deactivators, inorganic fine particles, antibacterial agents, antifungal agents, fillers, fillers, and the like can be used.

  By molding the polycarbonate resin composition of the present invention, a molded article excellent in transparency and molding processability can be obtained. The molding method is not particularly limited, and examples thereof include extrusion processing, calendar processing, injection molding, roll, compression molding, blow molding, rotational molding, and the like. Resin plate, sheet, film, bottle, fiber, irregular shape product Various shaped products such as these can be manufactured.

  Molded articles obtained from the polycarbonate resin composition of the present invention include copiers, fax machines, televisions, radios, tape recorders, video decks, personal computers, printers, telephones, information terminals, refrigerators, microwave ovens and other office automation equipment, homes Used in various applications such as electrical appliances, electrical and electronic equipment.

Hereinafter, the present invention will be described in more detail with reference to examples.
[Production Example 1]
In a 5 liter autoclave equipped with a stirrer, thermometer and pressure gauge, 132.3 g (1.47 mol) of 1,4-butanediol, 1632.0 g (22.7 mol) of tetrahydrofuran and diethyl boron trifluoride were added. After 29.4 g of an ether complex was added and the inside of the system was replaced with nitrogen gas, a mixture of 588.0 g (10.1 mol) of propylene oxide and 588.0 g (13.4 mol) of ethylene oxide was obtained at a temperature of 50 ° C. The mixture was injected over 5 hours, and the reaction was continued for another 0.5 hours. Thereafter, the product was taken out from the autoclave, neutralized with sodium hydroxide to pH 6 to 7, heated to 110 ° C. while bubbling nitrogen, and then dehydrated at 4 kPa or less and 110 ° C. for 2 hours. Further, the salt formed after dehydration was separated by filtration to obtain Compound A-1 in Table 1.
[Comparative Production Example 1]
Synthesis was performed in the same manner as in Production Example 1 so that l, m, and n had the ratios shown in Table 1, to obtain Compound A′-1.
[Comparative Production Example 2]
Synthesis was performed in the same manner as in Production Example 1 so that l, m, and n had the ratios shown in Table 1, to obtain Compound A′-2.

[Example 1]
[Preparation of test film]
50 g of polycarbonate resin (manufactured by ACROS ORGANICS) and 0.5 g of compound A synthesized in Production Example 1 (1 part by mass with respect to 100 parts by mass of polycarbonate resin) were put into a 1 L measuring flask, and dichloromethane was added up to the marked line. The obtained solution was allowed to stand at room temperature for about 1 hour to dissolve the polycarbonate resin and Compound A, and then this solution was placed in a petri dish (diameter: 60 mm) with a 4 mL whole pipette and dried at room temperature for 30 minutes. After drying, the polycarbonate resin was peeled off from the petri dish to obtain a film having a thickness of 50 μm.

[Measurement of Yellowness (YI)]
The yellowness (Y.I.) of the obtained film was measured three times with a spectrocolorimeter (LM-2500c, manufactured by KONICA MINOLTA). I. It was.

[Measurement of turbidity (HAZE)]
The turbidity (Haze) of the obtained film was measured three times with a HazeMeter (NDH 4000, manufactured by NUPPON DENSHOKU), and the average value was defined as the Haze of the film.

[Evaluation of moldability]
The obtained film is repeatedly bent 180 degrees along the side surface of a stainless round bar (Φ0.1 mm × 100 mm), and the number of cracks is measured. The average of 3 times was evaluated with 50 times as one unit.

[Bleed evaluation]
The obtained film was observed for 1 day at a temperature of 50 ° C. and then visually observed for the surface condition, and then left for another 10 days to observe the surface condition in the same manner.
○: No oozing, △: Slight oozing, ×: With oozing

[Comparative Examples 1 and 2]
In the same manner as in Example 1, a cast film was prepared using Compound A′-1 and Compound A′-2. I. Measurement, HAZE measurement, molding processability evaluation, and bleeding property evaluation. The results are shown in Table 2.

  As is clear from the table, the polycarbonate resin molded body to which the colorant for polycarbonate resin of Example 1 was added did not reduce the yellowness and turbidity of the polycarbonate resin, and had good moldability and bleeding properties. I found out.

  The polycarbonate resin molded article to which the anti-coloring agent for polycarbonate resin of Comparative Example 1 is added has low molding processability and satisfactory bleeding because the n / (l + m + n) of the anti-coloring agent for polycarbonate resin is out of the range. Was not obtained.

  The polycarbonate resin molded product to which the colorant for polycarbonate resin of Comparative Example 2 was added had molding processability because m / (l + m + n) and n / (l + m + n) of the colorant for polycarbonate resin were outside the scope of the present invention. Both bleedability was low.

Claims (3)

An anti-coloring agent for polycarbonate resin comprising a polyalkylene glycol derivative represented by the following general formula (I).
_{HO (CH 2 CH 2 CH 2} CH 2 O) l / (CH 2 CH (CH 3) O) m / (CH 2 CH 2 O) n H
... Formula (I)
(L is the average addition mole number of the oxytetramethylene group and represents 2 to 60. m is the average addition mole number of the oxypropylene group and represents 1 to 50. n is the average addition mole number of the oxyethylene group. 1/40, 1 / (l + m + n) is 0.2 to 0.8, m / (l + m + n) is 0.1 to 0.7, and n / (l + m + n) is 0.1 to 0.7. (The addition state of the oxyalkylene group is random.)   The polycarbonate resin composition formed by mix | blending 0.01-10.0 mass parts with the coloring inhibitor for polycarbonate resins of Claim 1 with respect to 100 mass parts of polycarbonate resin.   The molded object formed by shape | molding the polycarbonate resin composition of Claim 2.