JPS61275341A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin compsn. having excellent impact resistance, moldability and gloss and improved thermal stability, by adding an ester compd. to a rubber-contg. styrene resin. CONSTITUTION:A thermoplastic resin compsn. is obtd. by adding 0.05-10pts.wt. compd. of the formula to 100pts.wt. rubber-contg. styrene resin. The rubber- contg. styrene resin is composed of a rubber component and a matrix resin and must have such a structure that a graft structure exists at the interface between the rubber component and the matrix resin which is a continuous phase. The rubber-contg. styrene resin having such a structure can be prepd. by a graft polymn. method. Examples of the compds. having the formula are trimethylolpropane monoester, trimethylolpropane diester and pentaerythritol triester.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of application in M industry) The present invention relates to a rubber-containing styrenic resin composition that has excellent impact resistance, moldability, and gloss, and has improved thermal stability.

(Prior art) Rubber-containing styrenic resins are generally recognized as thermoplastic resins with excellent impact resistance, moldability, and gloss.
It has come to be used in a wide variety of industries.

On the other hand, as the uses of rubber-containing styrenic resins become more diverse, the performance that industry expects from these resins is becoming increasingly sophisticated, and in particular, the market demands for moldability and the appearance of molded products, including gloss, are becoming stricter. It is increasing.

Taking ABS resin as an example of rubber-containing styrenic resin, ABSm resin is a composite resin in which rubber particles, typified by polybutadiene rubber, are dispersed in a dispersion medium of thermoplastic resin, typified by AS resin. In order to improve the moldability or gloss of ABS resin, it is effective to reduce the rubber content or reduce the melt viscosity of the dispersion medium (hereinafter referred to as IJ lux resin). is publicly known.

However, a decrease in the rubber content or a decrease in the melt viscosity of the matrix resin both result in a decrease in the impact resistance of the ABS resin, which greatly limits the uses of the resin.

In order to improve the molding processability of rubber-containing styrenic resins or the appearance of molded products without sacrificing impact resistance, for example, a method using a matrix resin having a specified molecular weight (Japanese Patent Publication No. 1983-1999) has been proposed. 37675, JP 53-4862, JP 57-24814, JP 59-2300, JP 59-15145, JP 59-149912, etc.), the particle size of rubber particles and/or gel Method for specifying content (Special Publication No. 57-51404)
No., Special Publication No. 59-28576, Special Publication No. 59-2858
4), a method of copolymerizing specified monomers (JP-A-56-57813, etc.), a method of adding specified additives (JP-A-55-3494, JP-A-55) -17
No. 144, Ger-offen No. 3206136, etc.)
etc. are publicly known. Here, (ma) the method of controlling the molecular weight of IJ lux resin does not include a technique that actively aims to improve impact resistance, and its improvement effect is insufficient for practical use. In addition, the method of controlling rubber particles is
The aim is to improve impact resistance, but to the extent that satisfactory improvement in moldability or appearance of molded products is achieved.
It is not possible to achieve a reduction in the rubber content or in the melt viscosity of the matrix resin. Further, although modification using specified additives is an effective means, the modification effect using polysiloxane, for example, has not yet met market demands. In addition, while some additives significantly improve the impact resistance of rubber-containing styrenic resins, they lack thermal stability and cause the hue of molded products to turn yellow. Esters of higher fatty acids and sorbitan are known.

(Problems to be Solved by the Invention) As described above, attempts to improve the moldability of rubber-containing styrenic resins and the appearance of molded products while maintaining impact resistance have not yet been satisfied. The problem to be solved by the present invention is to simultaneously achieve improvements in the contradictory characteristics of the invention.

(Means for Solving the Problems) That is, the present invention provides a thermoplastic resin composition obtained by adding 0.05 to 10 parts by weight of a compound represented by the general formula [■] to 100 parts by weight of a rubber-containing styrene resin. It is a thing.

General formula [■] CH, OR2 R, CH2-C-CH, OR8 CH2QC(0)R4 In the formula, R1 is H1 alkyl group or -OR.

(R5 is H or 10 (01R6 (Ra is an alkyl group)), R2 is H or 10 (01R? (R? is an alkyl group), R3 is Hl or 10 (OIRa (Ra is an alkyl group) -R4 is an alkyl group.

Monomers constituting the rubber component of the rubber-containing styrenic resin used in the present invention include conjugated diene monomers such as butadiene, imprene, dimethylbutadiene, chloroprene, and cyclopentadiene, 2.5-norbornadiene, 1
, 4-cyclohexadiene, non-conjugated diene monomers such as 4-ethyrytenorbornene, styrene monomers such as styrene, α-methylstyrene, vinyltoluene, nitrile monomers such as acrylonitrile, methacrylonitrile, methyl (Meth)acrylic acid ester monomers such as methacrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, and octyl acrylate, ethylene, propylene, 1-butene, inbutylene, 2-
There are olefin monomers such as butene, and these are used alone or in copolymerization. Further, a polyfunctional vinyl monomer can be copolymerized as a crosslinking monomer, and the polyfunctional vinyl monomers that can be used include divinylbenzene, ethylene glycol dimethacrylate, 1.
3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, propylene glycol dimethacrylate, triallyl cyanurate, triallyl incyanurate, trimethylolpropane trimethacrylate, allyl acrylate, allyl methacrylate, vinyl acrylate, vinyl methacrylate, glycidyl acrylate , glycidyl methacrylate, etc.

The rubber component used in the rubber-containing styrenic resin of the present invention needs to have a graft active site, and specifically preferably has a carbon-carbon double bond in the rubber molecule.

There are no particular restrictions on the method of polymerizing the monomers, including emulsion polymerization,
Known techniques such as solution polymerization can be used.

Furthermore, the rubber component of the rubber-containing styrenic resin does not need to be of one type, and may be a mixture of two or more separately polymerized rubber components.

Monomers constituting the matrix resin of the rubber-containing styrenic resin used in the present invention include styrene monomers such as styrene, α-methylstyrene, vinyltoluene, and t-butylstyrene, and nitriles such as acrylonitrile and methacrylate. Monomers, (meth)acrylic acid ester monomers such as methyl methacrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide,
There are maleimide monomers such as N-cyclohexylmaleimide, N-phenylmaleimide, N-toluylmaleimide, and N-xylylmaleimide, which are used alone or in copolymerization. Required.

The rubber-containing styrenic resin used in the invention consists of a rubber component and a matrix resin as described above, but a graft structure is present at the interface between the rubber component, which has a spherical structure, and the matrix resin, which is a continuous phase. It is necessary.

It is known that such a structure can be achieved by a so-called graft polymerization method in which a part or all of the monomers constituting the IJ lux fat are polymerized in the presence of a rubber component. Rubber-containing styrenic resins can also be produced by known graft polymerization techniques.

In order to adjust the content of the rubber component contained in the rubber-containing styrenic resin, it is possible to mix a separately polymerized matrix resin component with the rubber-containing styrenic resin; does not need to have the same composition as the resin component obtained by graft polymerization.

For example, in the presence of polybutadiene, acrylonitrile-
A matrix resin component obtained by copolymerizing acrylonitrile-styrene-α-methylstyrene can be mixed with a rubber-containing styrenic resin obtained by graft polymerizing styrene-methyl methacrylate.

Specific examples of rubber-containing styrenic resins used in the invention include high-impact polystyrene, ABS (acrylonitrile-butadiene-styrene) resin, and heat-resistant ABS.
(acrylonitrile-phtadiene-styrene-α-methylstyrene) resin, AAS (acrylonitrile-acrylic acid ester, styrene) resin 1, AES (acrylic acid ester, styrene) resin 1,
Examples include nitrile-EPDM-styrene) resin, MBAS (methyl methacrylate-butadiene-acrylonitrile-styrene) resin, and the like.

In the invention, the compound represented by the general formula [I] is added in an amount of 0.05 to 100 parts by weight of the rubber-containing styrenic resin.
It contains 10 parts by weight, preferably 0.2 to 8 parts by weight.

In general formula [I), the alkyl groups of R+, R4, R6, R7 and R6 are methyl group, ethyl group, propyl group, butyl group, pentyl group, heptyl group, nonyl group, undecyl group, tridecyl group, hentadecyl group, respectively. , heptadecyl group, nonadecyl group, etc., but may have an unsaturated bond in the carbon chain.

As a specific compound, for example, CH3CH2-C(
(CH20H)2 (C)I20C(0)C5'Hu
) ] , CHsCH2-C((CH20H)2 (C
HzOC(0)CaH+o)), CH3CH2-C((
CH20H)2 (CH20C(0)C++)h3)
), C) 13CH2-C((CH20H)2 (CH
20C(0)C+1H23) l, CH5CH2-C(
(CH20H)2 (CH20C(0)C17H35 month, CH5CH2-C((-CH20H)2 (-, CH
2QC(0)C,, H39, CH8CH2-C((-
CH20H)2 (CH2QC(0)CI? Hss
) Trimethylolpropane monoester such as
CH8CH2-C((-CH20H) (-CH2QC
(OIC5H,,)2 ), CH3CH2・-C((C
H20H)(-CH20C(0)C7H+s)z),
CH3CH2-C((CH20H)(CH20C(OI
C1lH19)2), CH3CH2-C((CH20
H) (CH20C(OICIIH23)2), CH8
CH2-C((CH20H) ((:H2QC(0)C
+3H27)2 ), CH,C)12-C((-CH2
0H) (-CH2QC(0)C+5H31)2),
CH3CH2-C((CH20H) (CH2QC(O
ICIIH36)2), CH3CH2-C((-CH
20H) (-CH20C(0)C1oH3°)2),
CH8CH, -C((-CH20H) (-CH2QC
(0)C, □Hs3)2), CH3CH2-C(
(-CI(,OH) (-CH2QC(01C0H,,
)(-CH20■)C+5H31) ), CH3CH2
-C((-CH20H) (-CH2QC(0)CI?
Trimethylolpropane diesters such as (-CH2QC(0)CI?H33) (-CH2QC(0)CI?H35)), CH3CH2C
(CH2QC(0)C? Hl5 )s, CH8CH2
-C(-CH20C(0)Cc+H+o)3, CH3C
H2C(1:H2QC(0)C,,H23)3,CH3
CH, -C(-CH2QC(0)C,,H27),,C
H3CH2-C(-CH20C(0)C15H31)a
, CH3CH2-C(-CH2QC(OICII l
L+s )3, CH3C)(2-C(CH20C(0)
C+1H23)s, CH3CH2-C(-CH20C(
0)C17H33)3, CH3CH2C((-CH20
C(0)C9Hu+ )(-CH2QC(0)C, □H
35)2 ), CH3CH2-C((-CH2QC(0
)C+ s H31) (-CH20C(OICI7H
33) Trimethylol propa/triesters such as (CH2QC(0)Cu Hss ) ), (HOCH2
-)3CCH20C(0)C? H15, (HOCH2-
)3CCH2QC(01CGI Hl.,(HOCH2
)a C-CH2QC(0)C,,H3,,(HOCH
2-)3C-CH2QC((j)C, □H36, (HO
CH2-)3C-CH2QC (OIC, pentaerythritol monoester such as 7H33, (HOCH2)2
C(CH2QC(0)C?H15)2, (HOCH2-
)2C(-CH20C(0)C+1H23)2, (HO
CH2)2 C(-CH2QC(0)C+s Hs+
)2, ('HOCH2)2C(, -CH,QC(0)C
, □H35)2 , (HOCH2-)2 C(-CH2
QC(0)C,, T(8,)2, (T(OCH3
-)2 C(-CH2QC(0)C, FuH33)2
, (l(OCH3-), C((-CH2QC(0) C
gHlo ) (-C)(,QC(0)CI7 H35
) ) , (HOCH2)2 C((-CH2QC(0
)C17H33)(-CH2QC(0)C1? Hsa
) pentaerythritol diesters such as ), HOC
H2-C(-CH2QC(0)C?Hl5)3,H
OCH2-C(CH20C(0)CoH19)3,
HOCH2-C(-CH2QC(0)C+3H27)3
, HOCH2-C (-CH20C(0)C+5H31)
3, HOCH2C (CH20C(0)CI?H35)3
, HOCH2-C(-CH20C(0)C+1H23)
3, HOCH2-C(-CH20C(OICl7
H33)3, HOCH2C((-CH20C(01CI
IH23) (-CH20C(0)C+5H31)2),
HOCH2C((CH20C(01C17H33) (
CH20C(0)CI7H35)2L HOCH
2-C((CH20C(0)CoHl,)(CH20C
(0)C+5H31)(CH2OC(0)CI7H
3!1)) pentaerythritol triester, C(-CH2QC(0)C?H15)4,C
(-CH20C(01C,H,.)4,C(CH20C
(0)C+ + H23)4,C(-CH2QC(0)
C+3H27)4 , C(CH20C(0)C15H3
1)4, C(-CH20C(0)C17H3s)4
,C(CH20C(0)C+9H39)4 ,C(-
CH2QC□)C+7H33)4,C((-CH20
C(OICII H13) (CH20C(0)C+5
H31)3 ), C((CH2QC(0)C1? H3
s) (CH20C(0)CI7H35)3),
C((-CH2QC(0)C13H2□) (-CH2
0C(0)C+1H23) (-CH20C(0)C+
1H23)2 ), C((-CH20C(0)CI5
H3t ) (CH2QC(0)C17H33) (C
H2oc(ole,7a3.)2), C((-CH
2QC(0)CQ H1+8 ) (CH2QC(0)
C1l H23) (CH2QC(0)C13H2?
) (-CH2QC(0)C,5Hs□)), C((-
CH2QC(OICl5H2g) (-CH20
C(0)C+ 5 H3t ) (-CH20C(0)
CI? H33) (-〇Hz QC(01C1? H3s
Pentaerythritol tetraesters such as )) can be exemplified, but compounds containing two or more ester bonds in the - molecule are particularly preferred in order to achieve the object of the present invention.

There are no particular restrictions on the method for producing the compound represented by the general formula [■], and for example, the desired product can be obtained by reacting pentaerythritol with higher fatty acids.

When the compound represented by the general formula [■] is produced industrially, R1, R2, R3, R4, R,, Ra % R
It is difficult for 7 and R8 to be produced as pure compounds defined by exactly one structure, and they are usually produced as a mixture of different structures. Even in the case of non-invention, there is no problem in using a mixture of compounds represented by general formula (I).

If the content of the compound represented by the general formula [■] is less than 0.05 parts by weight, the purpose of the present invention, which is to improve moldability and gloss while maintaining impact resistance, will not be achieved;
If it exceeds 0 parts by weight, the effect not only becomes saturated, but also the stiffness of the resulting composition decreases, which is undesirable.

In the present invention, the content of organic acidic substances contained in the rubber-containing styrenic resin is 0.5% or less, more preferably 0.5% or less.
It is preferably 3% or less.

Examples of the organic acidic substances mentioned here include higher fatty acids such as decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, and oleic acid, resin acids such as disproportionated rosin acid, dodecylbensene sulfonic acid, and octadecylpene. Aromatic sulfones such as sensulfonic acid, dodenyl diphenyl ether disulfone modified, and octyl sulfone? IL Examples include alkyl sulfonic acids such as tecylsulfonic acid, dodecylsulfonic acid, and octadecylsulfonic acid, and alkyl sulfates such as octyl sulfate, tecysulfate, dodecyl sulfate, and octadecyl sulfate.

A composition consisting of a rubber-containing styrenic resin containing more than 0.5% of an organic acidic substance and a compound represented by the general formula CI) has poor thermal stability, resulting in melt crosstalk of the composition. Local or general discoloration may be observed during molding or molding.

When rubber-containing styrenic resins are manufactured by emulsion polymerization, it is common to add acids such as hydrochloric acid, sulfuric acid, or acetic acid as a precipitation agent in the precipitation process to recover the resin from the latex obtained by polymerization. This operation converts the emulsifier into the corresponding organic acidic substance. Therefore, ■) to neutralize the generated organic acidic substances, ■) as a precipitating agent,
Using salts such as sodium chloride, potassium chloride, calcium chloride, magnesium sulfate monoaluminum chloride, aluminum sulfate, ■ [) Using an acid and a salt together as a precipitating agent to reduce the amount of acid added, etc. Take action,
It is preferable to reduce the content of organic acidic substances.

Further, although it is common practice to add an organic acidic substance as a lubricant for rubber-containing styrenic resin, in the present invention, it is preferable to limit the amount of the organic acidic substance added.

There is no particular restriction on the method of mixing the rubber-containing styrenic resin and the compound of general formula [I], for example, in an emulsified state, in a solution state,
The purpose can be achieved by mixing each component in either the molten state or the particulate state. More specifically, for example, when the compound of the general formula [■] has a low melting point, the compound of the general formula [■] is added to the rubber-containing styrenic resin latex and mixed by stirring at a temperature above the melting point. Alternatively, after mixing the rubber-containing styrenic resin powder and the compound of general formula CI) in a powder mixing device such as a Henschel mixer or a tumbler, It is possible to obtain a composition by supplying it to a melt-kneading apparatus such as a coneater or the like.

Furthermore, in the present invention, lubricants, plasticizers, weathering agents,
Modifiers such as stabilizers, antistatic agents, fillers, reinforcing agents, colorants, flame retardants, etc. can be added. In particular, tridecyl phosphite, triotadecyl phosphite, monophenyldidecyl phosphite, diphenyl monodecyl phosphite, triphenyl phosphite, tri(nonylphenyl) phosphite, 4.4'-
Butylidene-bis(3-methyl-6-t-butylphenyl-di-hexadecyl)phosphite, 4,4'-
Isopropylidene-bis(monophenyl-di-decyl)
Addition of phosphite such as phosphite, 4,4-isopropylidene-bis(monophenyl-di-tetradecyl)phosphite is effective for improving thermal stability.

(Example) The effect of non-invention will be explained in more detail below by giving an example. Note that all parts and parts used in Examples and Comparative Examples are expressed on a weight basis.

[Reference example - Production of rubber-containing styrenic resin (referred to as component A)]

(Manufacture of A-1, A-2, A-3, A-5, A-6) Manufactured by emulsion polymerization method by continuously adding the corresponding monomers in the presence of the rubber latex shown in Table 1. did.

A-1, A-2, A-3, and A-6 used potassium stearate as an emulsifier, and A-5 used sodium dodecylbensene sulfonate as an emulsifier.

(Production of A-4) A corresponding monomer was added to a toluene solution of EPDM to produce A-4 by a solution polymerization method.

(Production of A-7) Produced by a suspension polymerization method. Relative viscosity of methyl ethyl ketone by weight at a temperature of 30°C 1 rel = 1.
It is 46.

(Manufacture of A-8 and A-9) They were manufactured by an emulsion polymerization method using sodium dodecylbenzenesulfonate as an emulsifier.

The compositions and emulsifier contents of A-1 to A-9 are summarized in Table 1. Note that the emulsifier content refers to the emulsifier content in the polymer.

(Compound of general formula [■] - Name of component B - and its abbreviation) CH20C(01C9H111 B-3; CH3CH2C-(:H20C(OIC
oI(,.

Jiao CH2QC(0)C9Hl.

CHtOC(0)CnHsa ■ B-4: CH3CH2C-CH20C(0)Cr
rH8sCHzOC(OIC+7H35 H20H B 5 : HOCH2-C-CH20C(0)C
t7H3sCH,OH H20H B 6 : HOCH2C-CH20C(0)C1
□H35CH20C(0)Ct ふH3゜CH,OH B 7: HOCH2CCH20C(0)
C1? H33CH20C(0)C17H3゜CH2QC(0)COH,Q B 8 ; HOCH2-CCH20C(O
ICOHIQ0H2QC(0)C0H1゜CH20C(0)C, □H35 B -9: HOCH2-C-CH2QC(0)C
,□H3!1st ward CH20C(0)CI? T(35 CH20C(OICI?H33 B 10: HOCH2CCH20C(0)
C1? H33CHzOC(0)CIyHs.

CH20C(0)CoHl.

B 11 ; CoHtoC(0)OCH2C
-CH20C(0)C9HIQCHz OC(0) C
oH+.

CH20C(OIC17H35 B-12; C1□H35C(010CH2CCH20C
(OICtd(ssCH20C(0)C,,H,.

CH20C(0)C1? H33 B-13; C1? H33C(OIOCH2-C-
CH20C(0)C1□H3CM, QC(0) c1
□H33 In the formula, C(0) represents a -〇- group.

Example 1 and Comparative Example 1 Latex A-1 shown in Table 1 was pressurized into a 2% calcium chloride water bath and precipitated by heating to recover the resin.

The obtained A-1 powder and A-7 powder were mixed into B-1 to B-13.
After mixing with a Henschel mixer, the mixture was fed to VC-40 (single-screw extruder with vent) manufactured by Chuo Kikai Seisakusho Co., Ltd. to obtain pellets.

A molded article was made using the obtained pellets and the physical properties were evaluated, and the results are shown in Table 2.

The stearic acid content Fi in the pellets obtained in Comparative Example 1 Experiment Nα19 was 0.05% or less.

As is clear from comparing Example 1 and Comparative Example 1, the general formula [
By adding compound No. 11, impact strength, flowability and gloss are improved. In addition, the increase in yellowness is not to the extent that it poses a practical problem.

When an attempt was made to improve the impact strength by increasing the rubber content (experiment Nα20), a decrease in stiffness, fluidity and gloss was observed, demonstrating the superiority of the invention.

Example 2 and Comparative Example 2 Table 10 A-2, A-3, A-5 and A-6 latexes were each pressed into a 2% calcium chloride aqueous solution and precipitated by heating to recover the resin.

The obtained component A and A-7 powder were mixed together with B-12 in a Henschel mixer, and then treated in the same manner as in Example 1 to obtain pellets.

Further, after mixing A-4 powder with B-12 in a Henschel mixer, the mixture was treated in the same manner as in Example 1 to obtain pellets.

Using the obtained pellets, molded products were made and their physical properties were evaluated, and the results are shown in Table 3.

Regardless of the type of rubber component, the effect of adding the compound of general formula [I] was observed as in Example 1.

In addition, the organic hostile substance content in the pellets of experiments Nα26 to 30 was all 0.05% or less.

Example 3 and Comparative Example 3 After mixing A-1 latex with A-8 latex or A-9 latex in the proportions shown in Table 4, Example 1
The resin was collected in the same manner as above.

The obtained powder was mixed with B-12 in a Henschel mixer, and then treated in the same manner as in Example 1 to obtain pellets.

Using the obtained pellets, molded products were made and physical properties were evaluated, and the results are shown in Table 4.

In Table 4, the part of component A indicates the number of parts as a polymer.

Note that the content of organic acidic substances in the pellets of Experiments Nos. 33 and 34 was 0.05% or less in both cases.

Example 4 and Comparative Example 4 A-1, A-2, A-3, A-5 and A-6 latexes were pressed into 5% hydrochloric acid and precipitated by heating to recover the resin.

The obtained component A and powder A and -7 were mixed together with B-4, B-6, or B-12 in a Henschel mixer, and then treated in the same manner as in Example 1 to obtain pellets.

A molded article was made using the obtained pellets and the physical properties were evaluated, and the results are shown in Table 5.

The organic acid content of experiments N1142.43, 44.45 and 46 was 0.62%, 0.87%, and 0.71%, respectively.
1.45%, 2.33%.

Example 5 B-1 in 100 parts of A-1 latex (as polymer)
After adding 8.3 parts of 2 powder and stirring at 80° C. for 10 minutes, the resin was recovered according to Example 1.

26 parts of the obtained resin and 76 parts of A-7 powder were mixed in a Henschel mixer to form a pellet.

The physical properties of the obtained pellets were evaluated in the same manner as in Example 1, and the flexural modulus was 26,600 vd.

Izot impact strength 12.8 Ksm/cm % Spiral flow 51 crn, gloss Go 96%, optical iG 7.
92%, yellowness 5.1, stearic acid content 0.
It was less than 0.05%.

In addition, all the physical property measurement values of Examples and Comparative Examples were obtained by the following method.

1) Flexural modulus... ASTM D-7902) Izotsu) [Impact strength... ASTM D-2563
) Spiral flow (flow length) As an index of moldability, the flow length of the resin when injection molded under certain conditions was measured according to the method below.

Molding machine: Kawaguchi Churchill mold, manufactured by Kawaguchi Tekko Co., Ltd. Mold: Long flfl 5-OWan-, short @ 4.6 An Archimedean circle having a cross section obtained by dividing an ellipse of ran into three equal parts along the long axis.

Molding conditions: Injection pressure 50 K, y/crl G cylinder temperature: 260°C Mold temperature: 40°C Measurement method: Evaluation from the gate of the molded product to the free flow end
The distance was measured. It is said that the shorter the flow length, the better the moldability.

4) Gloss and Yellowness The pellets were injection molded using a TS-80CN-■ injection molding machine manufactured by Toshiba Machine Co., Ltd. to create a flat molded product measuring 60 x 100 x 3.0 mm. The molding conditions are as follows.

Molding conditions: Injection speed: 90 Nn/see Cylinder temperature: 280°C' Mold temperature = 50°C Residence time: 0 minutes, 10 minutes Here, the residence time is the time for the molten resin to stay inside the cylinder. , is intended to reflect the thermal history that the resin undergoes during injection molding.

The gloss value of the obtained molded product was measured at an incident angle of 60 degrees using a digital variable angle gloss meter model UC, V-4D manufactured by Suga Test Instruments Co., Ltd. G is the gloss value when the residence time is 0 minutes. , the gloss value after a residence time of 10 minutes was defined as CIO. Even if Go is small, for resins with small GIG, there is a general or local decrease in the gloss value of the molded product depending on the properties of the injection molding machine and/or the injection molding conditions. This is not desirable in practice.

In addition, the yellowness of the molded product after a residence time of 0 minutes was measured using GOLORAND C0LORDIF, manufactured by Denshoku Kogyo Co., Ltd., on the 2nd floor of the day.
FERENCE METER, MODEL ND-10
Measured using 1DC. Resins with dog yellowness are rated as having poor thermal stability. If a resin with poor thermal stability is subjected to injection molding, the hue may vary greatly due to variations in molding conditions, or the hue of the molded product may vary partially, which is extremely undesirable from a practical standpoint.

5) Organic acidic substance content [determination of stearic acid] N component 51 and methyl ethyl ketone sor were placed in a '1100 Erlenmeyer flask with a stopper and shaken at room temperature for 8 hours.

The contents were dropped into 5002 methanol.

Filter out the precipitate and save the filtrate! # Condensation to remove methanol.

Tetrahydrofuran 507 was added to the residue and dissolved by heating, and an appropriate amount of an ether solution of diazomethane was added to esterify stearic acid.

After distilling off excess diazomethane, tetrahydrofuran was added dropwise to adjust the volume to 50 rrLl to obtain sample bath liquid X.

Separately, a solution was prepared in which a known amount of methyl stearate was mixed with tetrahydrofuran to a constant volume of 50 rnl. This was poured into gas chromatography, and the relationship between the chromatographic peak area and methyl stearate concentration was graphed (creation of a calibration curve).

Pour the previous sample bath liquid X into the gas chromatography,
The chromatographic peak area was determined, and the methyl stearate concentration was determined using a calibration curve.

The weight of methyl stearate contained in the sample bath liquid X was converted to the weight of stearic acid S2, and the stearic acid content in component A was determined by (S151×100C%). Detection limit 0
．． 05%.

[Quantitative determination of dodecylbenzene sulfonic acid] A acid component t and methyl ethyl ketone 501 were placed in a 100° Erlenmeyer flask with a stopper and shaken at room temperature for 8 hours.

The contents were dropped into 5002 methanol.

The precipitate was filtered off, and a methanol solution of phenolphthalein was added dropwise to the filtrate for several hours to prepare a sample solution.

A water/methanol solution of potassium hydroxide with a concentration of 1i0.01N was added dropwise to the sample solution Y, and neutralization titration was performed.

Separately, a blank test was conducted to determine the true titration value.

From the titration value, calculate the weight Dt of dodecylbensene sulfonic acid contained in the sample solution Y, and calculate (D15) x 100 (%)
This is the content of dodecylbenzenesulfonic acid in the processed A component. Detection limit: 0.05%.

(Effects of the Invention) The present invention provides a rubber-containing styrenic resin that has excellent impact resistance, moldability, gloss, and thermal stability.

These effects are achieved by adding specific compounds to the rubber-containing styrenic resin.

Patent Applicant Denki Kagaku Kogyo Co., Ltd. Procedural Amendment July 1, 1985 Director of the Patent Office Michibe Uga 1985 Patent Application No. 116514 2 Name of the invention Thermoplastic resin composition 3 Person making the amendment Relationship to the case Patent applicant address 1-4-1 Yurakucho, Chiyoda-ku, Tokyo Contents of the amendment to Detailed Description of the Invention column 5° of the specification (1) [(( -CH20H)2(-CH20C(0)CaHl
g) ) J as [((-CH20H)2(-CH20C
(0) C9HIG) ) Correct as J (2) Specification No. 1
1'-CH3CH2-C(-CI(20C'(0)C1
9H Engineering,)3'' to ``C'E(3CH2-C'(-CH2
Correct it as QC'(0)C'ENG9H39)3J.

Claims (1)

[Claims] 100 parts by weight of a rubber-containing styrenic resin is added with the general formula [I
A thermoplastic resin composition containing 0.05 to 10 parts by weight of a compound represented by the following. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, R_1 is H, an alkyl group, or -OR_5 (
R_5 is H or -C(O)R_6 (R_6 is an alkyl group)) R_2 is H or -C(O)R_7 (R_7
is an alkyl group), R_3 is H or -C(O)R_5
(R_8 is an alkyl group), R_4 is an alkyl group.