JPH0356553A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition suitable for light fitments, electrical instruments, etc., having excellent heat resistance and antistatic properties by blending a methacrylimide group-containing polymer with a specific amount of a compound containing a specific polyoxyethylene segment. CONSTITUTION:(A) 100 pst. wt. methacrylimide group-containing polymer containing >=10 wt.% methacrylimide unit shown by formula I (R1 is H, 1-20C aliphatic, aromatic or alicyclic hydrocarbon) is blended with (B) 0.5-20 pts. wt., preferably 5-10 pst. wt. one or more compounds such as adduct of stearic acid with 10 mol ethylene oxide shown by formula II to formula V (R2, R4, R6 and R9 are 8-22C alkyl; R3, R5, R7, R8, R10 and R11 are H or <=22C alkyl; a, b, c, d, e and f are 1-200, c+d=1-200 and e+f=1-200).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a resin composition having excellent heat resistance and antistatic properties.

[Conventional technology]

Methacrylimide group-containing polymers have excellent heat resistance and transparency, have a relatively high heat deformation temperature, have excellent rigidity, surface hardness, etc., and are also excellent in formability. It has the disadvantage of being easily charged.

In order to impart antistatic properties to the resin, a method of internally kneading an antistatic agent is generally used. If an antistatic agent with poor compatibility with the base resin is used in this method, excessive migration of the antistatic agent to the surface may cause surface defects and deterioration of transparency; If you use an antistatic agent with too good compatibility, the antistatic agent will disperse uniformly into the base resin! However, since it does not exhibit antistatic properties, it was necessary to select an antistatic agent that has appropriate compatibility with the base resin.

[Problem to be solved by the invention]

Furthermore, polymers containing methacryimide groups have relatively high glass transition temperatures and high forming temperatures, making it more difficult for antistatic agents to migrate to the surface, and the antistatic agents themselves are required to have thermal stability. , an effective antistatic agent for polymers containing methacriimide groups has not yet been found, and it is currently desired to develop resin materials with good heat resistance and antistatic properties. be.

[Means to solve the problem]

Therefore, the present inventors conducted intensive studies to maintain good heat resistance and improve antistatic properties of methacrinimide group-containing polymers. It was discovered that a resin composition having excellent b1 heat resistance and antistatic properties could be obtained by adding a specific amount of a compound having the following properties, and the present invention was achieved based on this finding.

That is, the present invention provides R1 [in formula (I), R, is a hydrogen atom or a carbon number of 1 to
Represents 20 aliphatic, aromatic or alicyclic hydrocarbons. ] General formula ([I), (ill), (lock, (■0 11 R, -c-o-(an,aH,o)a-R3(II)R
4-0 ((H2011ItO)1)-R4
coarse) 0 ~-a-o-a'H, ! 10-0-((I11.01!,O)8-R,.
(■Snow% O - 0 - (OF12 C 12 0) (
1Rt, (:In), n), beat, N) K > IteR
,,R4,R,,R. represents an alkyl group having 8 to 22 carbon atoms, R,, Hiki, R7, Hiki, R1. , Rll represents a hydrogen atom box or an Akiμ group having 22 or less carbon atoms, and a
1b%c%d, e1f are integers from 1 to 200 and c+d
, e+f is an integer of 1 to 200] is added in an amount of 5 to 20 parts by weight.

The methacrylimide group-containing polymer used in the present invention may be a homopolymer or a copolymer having methacrylimide units represented by the general formula (1) as described above. Usually, R in the general formula (1) is preferably a hydrogen atom, a methyμ group, an ethyl group, a probyl group, a petite p group, or a phenyl group.

The method for producing the methacrylimide group-containing polymer according to the present invention is not particularly limited, but for example, polymethacrylic μ
A methacrylic resin such as a methyl acid, ammonia or a primary amine such as methylamine or ethylamine is dissolved in a suitable solvent (e.g. an aromatic hydrocarbon such as benzene, phosphorus, xylene, etc.) or methanol. , ethanol μ, propanol, etc. alone, or a mixture of two or more of these aromatic hydrocarbons and alcohol μ) in an autoclave at 170°C to 350°C, Preferably 2
A method of forming a methacrylimide ring by carrying out a heating reaction at a temperature of 00°C to 300°C is useful. Kakitata Unexamined Publication 1972
The reaction may be carried out in an extruder such as that described in Japanese Patent No.-63989.

The methacrylic-imide group-containing polymer used in the present invention preferably contains at least 10 by weight, preferably 20 by weight or more of the above-mentioned methacrylimide units. Difficult to obtain sex.

Next, the compound color used in the present invention) is fatty acid ethylene oxide adduct, aliphatic alcohol μ ethylene oxide adduct, fatty acid amide ethylene oxide adduct,
Glycerin monofatty acid ester ethylene oxide adduct, R, , R4, R, , R# in each formula has 8 carbon atoms
~22 are used. Specifically, octanoic acid, lauric acid, cilistic acid, V/I/V tinic acid, stearic acid, montanic acid, oleic acid, behenic acid, octyl alcohol, lauri μ alcohol, stearyl p alcohol μ
, Beheni μA μKo, etc. If the number of carbon atoms is 7 or less, the compatibility with the resin is insufficient, and surging occurs in the extruder during molding, so the housing is not suitable. Among these, cystearic acid and stearic acid are preferred in terms of stability in developing antistatic properties. Further, the amount of ethylene oxide added is 1 to 200 per molecule; if the amount of ethylene oxide added exceeds 200, the antistatic properties of the resulting resin composition deteriorate.

The amount of compound 1'B) added to the methacrylimide group-containing polymer is α5 to 20 parts by weight, preferably 2 to 15 parts by weight, more preferably 1 part by weight, per 100 parts by weight of the methacrylimide group-containing polymer. It is 5 to 10 parts by weight. Compound CB)
If the amount added is as small as (L5 parts by weight), antistatic properties will not be exhibited, while if it exceeds 20 parts by weight, it is not economical.

The heat deformation temperature of the resin composition of the present invention can be arbitrarily set according to the structure of the methacriimide unit of the methacriimide group-containing polymer (A), the content i>, and the amount of compound (B) added. For ordinary uses of methacrylic resin, a heat distortion temperature of around 100°C is sufficient, and for uses requiring high heat resistance, the heat distortion temperature can be set at 100°C to 170°C.

The resin composition of the present invention can be obtained by melt-kneading the methacrylimide group-containing polymer a) and the compound CB) using an extruder or the like, but when producing the methacrylimide group-containing polymer rA) 14-, can also be obtained by adding part or all of the compound (Bl). Generally, the former is preferred from the viewpoint of production stability of the methacrylimide group-containing polymer (4).

The resin composition of the present invention may contain a thermal decomposition inhibitor, an antioxidant, and an ultraviolet absorber in order to improve heat resistance, light resistance, and oxidative deterioration resistance.

Furthermore, plasticizers, dyes, lubricants, etc. can also be blended.

The thermoplastic resin composition of the present invention can be press-shaped, injection molded,
It can be made into various forms of plastic molding products using commonly known plastic molding methods such as extrusion or other methods.

(Example) Hereinafter, the present invention will be specifically explained with reference to examples.

In Examples and Comparative Examples, "part" and "weight" indicate "part by weight" and "weight", respectively.

Na$P! ! In the Examples and Comparative Examples, the physical properties of the polymer were measured by the following method.

(1) The heat distortion temperature was measured based on A8TM D 6as-s6 (load 1a6kll/c-").

(2) The amount of imidization (drink) of the polymer containing methacrylimide groups is measured using the elemental analysis value (measuring device cHN coder (M
T-3) Nitrogen content and proton N at Yanagimoto Seisakusho ml)
MR. yNM-yx-1oo (.ymo!J) x
The measurement was carried out using a vector 100 MHg1.

(3) To measure the surface resistance value, measure the sample at 20℃ and humidity 654℃.
After adjusting the humidity for one day, use a super insulation resistance tester (manufactured by Takeda Riken, TR-8).
601), the surface resistance value (Ω) was measured after 1 minute at an applied voltage of 500 V under conditions of 20° C. and humidity of 65°C.

(4) To measure the charge half-life time, use a static honest meter (
(manufactured by Shishido Shokai), applied voltage 1 (100 mV, sample rotation speed 1300 rpm, application time 30 seconds, 2
The measurement was carried out under conditions of 0° C. and humidity of 65°C, and the sample voltage when voltage was applied was defined as the initial voltage, and the time at which the sample voltage became half of the initial voltage after the voltage was cut off was defined as the charge half-life time (seconds).

A charge half-life time of 2 minutes or more was rated as ■.

(5) Transparency was measured using an integrating sphere haze meter (szp-H-ss, manufactured by Nippon Seimitsu Kogaku Co., Ltd.).

(6) The intrinsic viscosity of the polymer is determined by Bishop Derow (
The flow time (ts) of the chloroform solution of the sample polymer concentration (L5 weight) and the flow time (to) of the chloroform solution were measured using a Deereax-Bishoff viscometer at a temperature of 25°C and 1°C, and the ts/to value was determined. The relative viscosity ηre1 of the polymer was determined from ηre1, and the value was then calculated from the following formula.

(In the formula, C represents the Durham number of the polymer having a molecular weight of 100-100%.) Reference Example A Preparation of methacriimide group-containing polymer: Reference Example A-1 Bud μS Bicycle Stirrer, pressure gauge, sample Intrinsic viscosity (151) of thoroughly dried methacrylic acid methacrylate polymer was placed in a 10 t reactor equipped with an injection container, a kayak and a jacket heater.
After adding 100 parts of aluminum, 90 parts of methanol and 10 parts of methanol/l, the mixture was sufficiently purged with nitrogen, the temperature was raised to 200°C, and the mixture was stirred and dissolved.

Next, 21.7 parts of methyμamine (7 parts) was added from the sample injection container.
After the reaction was completed, a methacrinoleimide group-containing polymer (A-1) was obtained.

After drying, it was powdered and used as a sample.

Reference Example A-2 A methacriimide group-containing polymer (A-2) was obtained in the same manner as in Reference Example A-1, except that 24.8 parts (0.8 mo/It) of methamine was used. Ta.

Reference Example A-3 A methacrylimide group-containing polymer (A-3) was obtained in the same manner as Reference Example A-1, except that 15.5 parts of methipamine ((15 mμ ratio)) was used.

Reference Example A-4 A methacryimide group-containing polymer (A-4) was obtained in the same manner as in Reference Example A-1, except that 12.4 parts (kl mole ratio) of methylamine was used.

Reference Example A-5 A methacrylimide group-containing polymer ( A-5) was obtained.

Table 1 shows the results of evaluating various properties of the methacryimide group-containing polymers A-1 to A-5 obtained in Reference Examples A-1 to A-5.

Table 1 MMA in Table 1: Methyl methacrylate 1. The following compound ('B) was used in this example.

B-1 = stearic acid ethylene oxide 10 μ μ adduct B-2: lauriacic acid μ ethylene oxide 97 μ
Adduct B-3: Peheni μ a μ co〃 Ethylene oxide 20 mo μ Adduct B-4: Stearic acid amide Ethylene oxide 15 mo μ Adduct B-5: Gu! j Serine monostearate ethylene oxide 2 mo μ adduct B-6: Glycerine monostearate ethylene oxide 5 mo μ adduct B-7: Stearic acid ethylene oxide 55 mo μ adduct Examples 1 to 7 Reference example ▲-1 The methacriimide group-containing polymer (A
-1) 100 parts of various compounds CB) are blended,
Pellets were obtained by extrusion shaping.

Using these pellets, injection molding was performed under the injection molding conditions shown below to produce heat resistance evaluation specimens and flat specimens.
Heat distortion temperature, antistatic properties, and transparency were measured. The results are shown in Table-2.

Injection forming conditions> Injection forming machine: Sumitomo Heavy Industries Promatsu} 165/75 Mold temperature: 100°C Cylinder temperature: 330°C Table 2 Examples 8 to 11, Comparative Examples 1 to 5 Reference Examples A-2 to A Compound (B-
Various specimens were molded by injection molding (cylinder temperature: 320°C, mold temperature: 100°C) with a mixture of 10 parts of 1).

The results are shown in Table-2.

In addition, methacrylimide group-containing polymers (A-1) to (A
-5) alone was used to form a sample and evaluate it.

The results are also listed in Table-3.

Table-3 Examples 12 to 17 Methacriimide group-containing polymers (A-1), (A-5)
The experiment was conducted in the same manner as in Example 1, except that 100 parts of the compound (B-6) was blended in the proportions shown in Table 14. The results are shown in Table 4.

Table 4 Comparative Example 6 10 parts of Dasbur 125B (cationic antistatic agent manufactured by Miyoshi Oil Co., Ltd.) was blended with 100 parts of the methacrylimide group-containing polymer (A-1), and a trial was conducted in the same manner as in Example 1 for evaluation. As a result, antistatic properties such as a surface resistance value of Ix10f●Ω or more, a charge half-life time, and a haze value of 614 were not exhibited, and transparency was also inhibited. It was yellowish in color and had no commercial value.

Reference Example 1 Methyμ methacrylic acid polymer 10 used in Reference Example A-1
0 parts and 5 parts of Dameper 125B (cationic antistatic agent manufactured by Miyoshi Oil Co., Ltd.) were blended and extruded to obtain pellets, which were then injection molded (cylinder temperature: 230°C, mold temperature: 70°C).
When various specimens were shaped and evaluated at 100°F (°C), the surface resistance was 9 x 1011Ω, charge half-life time was 2.1 seconds, haze value was 2.04 or less, heat distortion temperature was 85°C, and good antistatic properties. It expressed transparency and transparency.

〔Effect of the invention〕

The resin composition of the present invention has excellent antistatic properties and heat resistance, and can be used for covers and parts for lighting equipment, electric meters, electronic equipment, meter covers, daily necessities sheets, springs, etc. , has excellent industrial effects.

October 20, 1999

Claims (1)

[Scope of Claims] 1) To 100 parts by weight of a methacrylimide group-containing polymer (A) containing at least 10% by weight of methacrylimide units represented by the following general formula (I), ▲ mathematical formula, chemical formula,
There are tables, etc.▼(I) [In formula (I), R_1 represents a hydrogen atom or an aliphatic, aromatic, or alicyclic hydrocarbon having 1 to 20 carbon atoms. ] General formulas (II), (III), (IV), (V) ▲Mathematical formulas, chemical formulas, tables, etc. are available▼(II) R_4-O-(CH_2CH_2O)_b-R_5(I
II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (V) [R_2 in formulas (II), (III), (IV), (V)
, R_4, R_6, R_9 represent an alkyl group having 8 to 22 carbon atoms, R_3, R_5, R_7, R_8, R_1_0, R_1
At least 0.5 to 1 type of compound (B)
A resin composition containing 20 parts by weight.