JP3359454B2 - Graft copolymer and resin composition using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a graft copolymer using a non-spherical and particulate rubber polymer satisfying specific requirements, and a resin composition containing the graft copolymer.

[0002]

2. Description of the Related Art Rubber polymers represented by polybutadiene are widely used as impact strength improvers for various thermoplastic resins. Above all, a rubber-modified styrene resin using a rubber polymer as an impact strength modifier is HIPS.
It is widely used as a resin exhibiting excellent impact resistance and moldability such as (high impact polystyrene) resin and ABS (acrylonitrile-butadiene-styrene) resin.

Further, a graft copolymer represented by a MBS resin having a rubber polymer as a core and a hard component as a shell is also used for improving the impact resistance and molding processability of a vinyl chloride resin. I have.

[0004] As a rubber polymer for improving the impact resistance of the styrene resin as described above, a monomer having low reactivity such as butadiene is used, and thus it is mainly polymerized by an emulsion polymerization method. For this reason, the surface rubber must be spherical in terms of surface energy, and all conventional rubber polymers are spherical.

[0005]

The main characteristics of the styrene resin, such as impact resistance, fluidity and heat resistance, are the composition, molecular weight of the styrene resin, the composition, amount, particle size, and gel content of the rubber used. Various grades have been produced in which each characteristic is emphasized by balancing these factors, because they are influenced by the rate and the like.

[0006] Therefore, if one of the characteristics is to be enhanced, the other characteristics are reduced, and it is extremely difficult to increase the total balance by merely moving on the characteristic balance line.

For example, in order to improve impact resistance,
If the molecular weight of the styrene resin is increased or the amount of rubber is increased, the fluidity is reduced.

[0008]

Means for Solving the Problems In order to improve mechanical properties such as impact resistance, which is a drawback of styrenic resins, the present inventors have conducted intensive studies focusing on the shape of a rubber polymer. As a result, they have found that the use of a non-spherical rubber polymer having a specific shape can improve impact resistance while maintaining fluidity and heat resistance, and have completed the present invention.

That is, according to the present invention, when a rubber polymer in a molded article is analyzed by a transmission electron microscope analysis-image analysis method (TEM method), the form factor is expressed by the following formula (I): X = (k / b) ) × 100 (I) (where k represents the maximum length of the rubber polymer particle image, and b represents the width of the rubber polymer particle image).

[0010]

[Outside 10]

Is at least 115, and the formula (II): Y = (a / k ² ) × (4 / π) × 100 (II) (where a is the area of the rubber polymer particle image, and k is the same as above) Average value of the form factor Y represented by) in all rubber polymers

[0012]

[Outside 11]

Is less than or equal to 80 and the formula (III): Z = (a / p ² ) × 4π × 100 (III) (where a is the same as above, and p represents the perimeter of the rubber polymer particle image) Of the form factor Z expressed by

[0014]

[Outside 12]

Is a non-spherical particulate rubber polymer (A) having a Tg of 0 ° C. or lower satisfying at least one of 85 or lower, and a graft portion formed from at least one vinyl monomer unit. graft copolymer der consisting (g)
The rubber polymer is acrylic acid, methacrylic acid,
At least one of taconic acid and crotonic acid
5 to 25% by weight of a saturated acid (c) (hereinafter referred to as%),
Alkyl acrylate having 1 to 12 carbon atoms in the kill group
(D) 5-30%, alkyl groups having 1 to 12 carbon atoms
Lukyl methacrylate (e) 80-20% and
Copolymerizable with component (c), component (d) and component (e)
Aromatic vinyl, two or more polymerizable functional groups in the molecule
Having at least one of the monomers and vinyl cyanide
An acid group-containing compound prepared by polymerizing 0 to 40% of one kind
Manufactured by the coagulation enlargement method using latex (S)
Graft polymer (claim 1), characterized in that it is a shaped rubber polymer, and the form factor X of the particulate rubber polymer (A)
Of all rubber polymers

[0016]

[Outside 13]

Is 120 or more, and the average value of the form factor Y in all rubber polymers

[0018]

[Outside 14]

Is not more than 75 and the average value of the form factor Z in all rubber polymers

[0020]

[Outside 15]

Has at least one of 80 or less
The graft copolymer according to claim 1 which satisfies
2), transmission electron microscope analysis-image analysis method (TEM method)
The volume average particle diameter of the particulate rubber polymer (A) is 10
The graft copolymer according to claim 1, which has a thickness of 0 to 2000 nm.
Body (claim 3), transmission electron microscope analysis-image analysis method
(TEM method) for particulate rubber polymer (A)
The volume ratio of the graft portion (g) is 0.10 to 0.90.
The graft copolymer according to claim 1 (claim 4), a graph
(G) is 15 to 60 mol% of a vinyl cyanide unit,
85 to 40 mol% of aromatic vinyl units and copolymers thereof
Formed from 0 to 30 mol% of compatible monomer units
The graft copolymer according to claim 1 (claim 5), rubber weight
The coalesced diene rubber, olefin rubber and acrylic
2. The graph according to claim 1, wherein the graph is at least one of rubber-based rubbers.
G copolymer (claim 6), Transmission electron microscope analysis-image
Analyze rubber polymer in molded product by analysis method (TEM method)
In this case, the form factor is expressed by the following formula (I): X = (k / b) × 100 (I) (where k is the maximum length of the rubber polymer particle image, and b is the rubber weight.
Represents the width of the coalesced particle image)
Average value for all rubber polymers

[0022]

[Outside 16]

Is not less than 115 and the formula (II): Y = (a / k ² ) × (4 / π) × 100 (II) (where a is the area of the rubber polymer particle image, and k is the same as above) Average value of the form factor Y represented by) in all rubber polymers

[0024]

[Outside 17]

Is less than or equal to 80 and the formula (III): Z = (a / p ² ) × 4π × 100 (III) (where a is the same as above and p represents the perimeter of the rubber polymer particle image) Of the form factor Z expressed by

[0026]

[Outside 18]

A non-spherical particulate rubber polymer (A) having a Tg of 0 ° C. or less satisfying at least one of 85 or less and a graft portion formed from at least one vinyl monomer unit graft copolymer der consisting (g)
The rubber polymer is acrylic acid, methacrylic acid,
At least one of taconic acid and crotonic acid
Saturated acid (c) 5 to 25%, alkyl group having 1 to 1 carbon atoms
Alkyl acrylate (d) 5 to 30%, Al
Alkyl methacrylate having 1 to 12 carbon atoms in a kill group
(E) 80 to 20% and components (c) and (d)
And aromatic vinyl copolymerizable with component (e), in the molecule
Monomer having two or more polymerizable functional groups and cyanide
At least one kind of vinyl chloride is polymerized from 0 to 40%
Using acid group-containing latex (S) prepared by
Is a graph showing a rubber polymer produced by the coagulation enlargement method
A resin composition comprising a copolymer and a thermoplastic resin (claim 7 ), wherein the thermoplastic resin has a reduced viscosity of methyl ethyl ketone-soluble component (30 ° C., N, N-dimethylformamide solution) of 0.3 to 1; 2 dl / g of a styrene-based resin, and the rubber polymer content is 5 to 40% based on the total amount of the graft copolymer and the thermoplastic resin.
7, wherein the resin composition (claim 8), and styrene resin, vinyl cyanide units 10 to 70 mol%, the aromatic vinyl unit 30 to 90 mol%, the maleimide compound unit 5
0 mol% or less and a monomer unit 0 copolymerizable therewith
30 mole% consists of (a total of 100 mol%) according to claim 8 resin composition described for (claim 9).

[0028]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Particulate rubber polymer (A) in the present invention
Is the shape factor when the rubber polymer in the molded article is analyzed by transmission electron microscope analysis-image analysis method (TEM method), and the equation (I): X = (k / b) × 100 (I) ( In the formula, k represents the maximum length of the rubber polymer particle image, and b represents the width of the rubber polymer particle image).

[0029]

[Outside 19]

Is 115 or more, preferably 120 or more and 30
0 or less, Formula (II): Y = (a / k ² ) × (4 / π) × 100 (II) (where a is the area of the rubber polymer particle image, and k is the same as described above) Average value of form factor Y in all rubber polymers

[0031]

[Outside 20]

Is not more than 80, preferably not more than 75 and not less than 20 and the formula (III): Z = (a / p ² ) × 4π × 100 (III) (where a is the same as above and p is a rubber polymer particle) (Representing the perimeter of the image)

[0033]

[Outside 21]

Is a non-spherical particulate rubber polymer having a Tg of 0 ° C. or less that satisfies at least one of 85 or less, preferably 80 or less and 15 or more, particularly preferably 75 or less and 20 or more.

The shape factor when the rubber polymer was analyzed by the TEM method was specifically cut out from a molded article of a resin composition containing a graft copolymer produced using a particulate rubber polymer. An image obtained by photographing the test piece with a TEM (transmission electron microscope) was automatically measured by an image analyzer LUZEX IID manufactured by Nireco Co., Ltd., ie, a two-dimensional projected image of each particle was digitally imaged and quantified. Length k: value obtained by calculating the maximum length between any two points on the circumference of each particle, width b: when an image is sandwiched by two straight lines parallel to the maximum length of each particle The value obtained by calculating the shortest distance between the two straight lines, the area a: the value obtained by calculating the actual area of each particle, the perimeter p: the value obtained by calculating the perimeter of each particle, are calculated according to the formula (I). According to the formula (II), the shape factor X representing the degree of needle-like Is the shape factor Y representing the degree of roundness obtained in the above manner, and the shape factor Z representing the degree of unevenness obtained in accordance with the formula (III). The average value of the shape factors is a value obtained by volume-averaging the shape factors X, Y, and Z of all the rubber polymers.

When the ratio of the maximum length k to the width b in the form factor X is 1: 1, X is 100 in a circle. The shape factor Y indicates how close the shape is to a circle by the ratio of the area a to the square of the maximum length k. The shape factor Y becomes larger as the shape becomes closer to a circle. Further, the shape factor Z represents the unevenness of the peripheral shape of the particle by the ratio of the area a to the square of the peripheral length p. The shape factor Z becomes larger as the shape becomes closer to a circle, and becomes a maximum value 100 in the case of a circle.

[0037]

[Outside 22]

Is less than 115,

[0039]

[Outside 23]

Exceeds 80,

[0041]

[Outside 24]

If the value exceeds 85, impact resistance is not sufficiently exhibited. Also,

[0043]

[Outside 25]

Becomes too large,

[0045]

[Outside 26]

If the value is too small, the production tends to be difficult. FIG. 1 is a specific example. FIG. 1 shows AB of Example 12 of the present invention having good impact resistance.
The S resin (composition containing the graft copolymer) was heated at 240 to 270 ° C. using a 75B injection molding machine manufactured by FANUC CORPORATION.
Particulate rubber in a transmission electron micrograph (magnification: 20,000) of a cross-section obtained by cutting the center in the thickness direction of the center of the molded product obtained at a cylinder temperature in parallel with the flow direction of the resin. It is a figure for demonstrating the shape of a polymer, and is the figure which traced the outer edge of the thing clearly shown among the particulate rubber polymers in a transmission electron micrograph. The form factor of the rubber polymer in FIG. 1 by the TEM method is X = 129, Y = 6
0 and Z = 47.

The rubber polymer used for the styrene resin is usually

[0048]

[Outside 27]

In the range of FIG. 2 is given as an example.
FIG. 2 is a diagram for explaining the shape of a particulate rubber polymer in a transmission electron micrograph (magnification: 20,000) of a general ABS resin obtained in the same manner as described above. It is the figure which traced the outer edge of the thing clearly shown among the particulate rubber polymers in a micrograph. The form factor of the rubber polymer in FIG. 2 by the TEM method is X = 106,
Y = 91 and Z = 93.

The particulate rubber polymer used in the present invention has a volume average particle size of preferably 100 to 2,000 nm, more preferably 150 to 1500 nm, as determined by transmission electron microscopy-image analysis (TEM). If the volume average particle size exceeds 2,000 nm, the gloss tends to decrease and the impact resistance does not sufficiently develop (even if the particle size increases, the impact resistance tends to decrease). It tends to stop.

The rubber polymer preferably has a Tg of 0 ° C. or less, more preferably -20 ° C. or less, from the viewpoint of impact resistance.

Specific examples of the rubber polymer include diene rubbers such as polybutadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, butadiene-acrylate rubber, hydrogenated styrene-butadiene rubber, ethylene-propylene rubber, and the like. Olefin rubber such as ethylene-propylene-diene rubber, acrylic rubber such as polyacrylate rubber and ethylene-acrylate rubber, and the like can be mentioned.

The particulate rubber polymer (A) can be produced by, for example, mixing a latex of a usual rubber polymer with an acid group-containing latex (S) to cause coagulation and enlargement.

As the acid group-containing latex (S), at least one of acrylic acid, methacrylic acid, itaconic acid and crotonic acid is used as an unsaturated acid (c) in an amount of 5 to 25%, more preferably 8 to 23%, Alkyl acrylate (d) having 1 to 12 carbon atoms in the group, 5 to 30%;
%, An alkyl methacrylate having an alkyl group having 1 to 12 carbon atoms (e) 80 to 20%, further 75 to 25%, and an aromatic copolymerizable with the components (c), (d) and (e) Vinyl, monomer having two or more polymerizable functional groups in the molecule, and at least one of vinyl cyanide containing 0 to 40%, and more preferably 0 to 35%, containing an acid group. Latex (Sa)
It is particularly preferable from the viewpoint of impact resistance and stability at the time of producing an acid group-containing latex.

When the proportion of the unsaturated acid (c) in the acid group-containing copolymer in the acid group-containing latex (Sa) is less than 5%, there is substantially no hypertrophic ability, %, The polymerization of the acid group-containing latex (Sa) is not impossible, but the formation of a coagulum and the thickening of the latex during the polymerization are liable to occur, which makes it unsuitable for industrial production.

On the other hand, if the proportion of the alkyl acrylate (d) is less than 5%, the enlarging ability is reduced, and if it exceeds 30%, a large amount of coagulum is produced during the production of the acid group-containing latex (Sa), and the alkyl methacrylate ( When the ratio of e) is out of the above range, the hypertrophic ability decreases.

Further, an aromatic vinyl copolymerizable with the unsaturated acid (c), the alkyl acrylate (d) and the alkyl methacrylate (e), a monomer having two or more polymerizable functional groups in the molecule, and If the proportion of at least one kind of vinyl cyanide (hereinafter also referred to as copolymerizable monomer (f)) exceeds 40%, the enlargement ability is undesirably reduced.

In the case where the copolymerizable monomer (f) is a monomer having two or more, preferably 2 to 4 polymerizable functional groups in the molecule, a range of 0 to 3% is used. It is preferable to use it, and if it is exceeded, the hypertrophic capacity is greatly reduced.

Among the unsaturated acids (c) used in the production of the acid group-containing latex (Sa), acrylic acid and methacrylic acid, in particular, have hypertrophic properties, copolymerizability with alkyl acrylates and alkyl methacrylates, and are economical. It is preferable in terms of properties and the like. These may be used alone or in combination of two or more.

The component (d) is, as described above, an ester of acrylic acid and an alcohol having a linear or side chain having 1 to 12 carbon atoms. Specific examples include methyl acrylate and acrylic acid. Ethyl, propyl acrylate,
Examples thereof include butyl acrylate and 2-ethylhexyl acrylate, and particularly those having an alkyl group having 1 to 8 carbon atoms are preferable in view of hypertrophic properties, alkyl methacrylate, copolymerizability with unsaturated acid, economic efficiency, and the like. . These may be used alone or in combination of two or more.

As described above, the component (e) is an ester of methacrylic acid and an alcohol having a linear or side chain having 1 to 12 carbon atoms. Specific examples thereof include methyl methacrylate and methacrylic acid. Ethyl, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and the like, in particular, those having an alkyl group having 1 to 8 carbon atoms have hypertrophic properties, copolymerizability with alkyl acrylates and unsaturated acids, and economy. It is preferable from the point of view. These may be used alone or in combination of two or more.

The aromatic vinyl copolymerizable with the component (c), the component (d) and the component (e) in the acid group-containing latex (Sa) includes styrene, α-methylstyrene, p-methylstyrene and the like. As vinyl cyanide, such as styrene, acrylonitrile, methacrylonitrile, and the like, and as a monomer having two or more polymerizable functional groups in the molecule, allyl methacrylate, polyethylene glycol dimethacrylate, triallyl cyanurate, Triallyl isocyanurate, triallyl trimellitate and the like can be mentioned. These may be used alone or in combination of two or more.

In producing the acid group-containing latex (S), first, an amount corresponding to 5 to 40%, preferably 8 to 35% of the acid group-containing latex (S), and -95 ° C ≦ T
g ≦ 40 ° C., preferably −80 ° C. ≦ Tg ≦ 30 ° C. After polymerizing a monomer portion to be a copolymer having a low Tg, the remaining 95 to 60% of the acid group-containing latex (S), preferably An amount corresponding to 92 to 65% and Tg of -2
0 ° C. ≦ Tg ≦ 80 ° C., preferably −10 ° C. ≦ Tg ≦ 70
A method of polymerizing a monomer portion which becomes a copolymer having a high Tg of as high as ° C. is preferred from the viewpoint of reducing the amount of coagulum at the time of producing the acid group-containing latex (S) and improving the enlargement ability.

The high Tg-low Tg is 0-17.
0 ° C. is preferable from the viewpoint of the hypertrophic ability, and 20 to 15 ° C.
More preferably, it is 0 ° C.

As a method of mixing a general latex of a rubber polymer with an acid group-containing latex (S) to cause coagulation and enlargement, an average particle diameter of about 30 to 300 nm and a concentration of 10 to 50%
About 100 parts of ordinary rubber polymer latex (parts by weight,
The same applies hereinafter) (solid content) at room temperature or higher, preferably 30 to 8
While stirring at a temperature of 0 ° C., the average particle size is 30 to 600 nm.
About 0.1 to 10 parts (solid content) of an acid group-containing latex (S) having a concentration of about 10 to 50%,
There is a method of stirring for about 5 hours. At this time, the particle size and concentration of the rubber polymer, the particle size of the acid group-containing latex (S),
The above range is preferable because the particle size and stability of the enlarged latex vary depending on the concentration, the number of added parts, and the like.

The graft copolymer of the present invention is produced by using the rubber polymer (A) thus produced.

The graft copolymer of the present invention has a volume ratio of the graft portion (g) to the rubber polymer of 0.10 to 0.9.
It has a graft portion (g) of 0, preferably 0.15 to 0.80.

The ratio between the rubber polymer and the graft portion (g) is
It is important from the viewpoint of impact resistance. If the volume ratio or the weight ratio is less than 0.10 or exceeds 0.90, the impact resistance decreases.

The volume ratio of the graft portion (g) can be determined by a TEM method.

The graft portion (g) is formed from one or more vinyl monomer units.

Specific examples of the vinyl monomer forming one or more vinyl monomer units include vinyl cyanide such as acrylonitrile and methacrylonitrile, styrene, α-methylstyrene and p-methylstyrene. , Aromatic vinyl such as chlorostyrene, bromostyrene, vinylnaphthalene, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, ( 2-hydroxyethyl (meth) acrylate, 2- (meth) acrylate
(Meth) acrylate monomers such as ethylhexyl, glycidyl (meth) acrylate, maleimide, N
Maleimide monomers such as -phenylmaleimide; These may be used alone or in combination of two or more.

When the graft portion (g) is a vinyl cyanide 15
-60 mol%, preferably 20-55 mol%, aromatic vinyl 85-40 mol%, preferably 80-45 mol%, and 0-30 mol% of monomers copolymerizable therewith, preferably 0-20 mol% It is preferable that the composition of the present invention is composed of a polymer chain obtained by graft-polymerizing a monomer mixture of mol%, since the impact resistance of the composition of the present invention is effectively improved and the fluidity can be improved.

Specific examples of the vinyl cyanide and aromatic vinyl in the preferred graft portion (g) include the same as those described in the above specific examples. These may be used alone or in combination of two or more. Of these, it is preferable to use acrylonitrile as vinyl cyanide and styrene as aromatic vinyl from the industrial viewpoint. Further, specific examples of the copolymerizable monomer in the preferable graft portion (g) include the above-mentioned specific examples of the vinyl monomer forming one or more kinds of vinyl monomer residues. And those excluding aromatic vinyl.

The production of the graft copolymer is carried out by using any polymerization method, initiator, chain transfer agent and surfactant, as long as the graft copolymer having the composition and properties according to the present invention can be obtained. You may.

For example, the graft copolymer of the present invention comprises
It may be produced by known polymerization methods such as bulk polymerization, solution polymerization, bulk-suspension polymerization, suspension polymerization, emulsion polymerization, emulsion-suspension polymerization, and emulsion-bulk polymerization. The emulsion polymerization method is preferred because the volume ratio between the graft portion and the rubber polymer portion is easily controlled.

The initiator may be a known initiator such as a thermal decomposition initiator such as potassium persulfate or a redox initiator such as Fe-reducing agent-organic peroxide. Known chain transfer agents such as t-dodecyl mercaptan, n-dodecyl mercaptan, α-methylstyrene dimer, and terpinolene may be used in a range where the volume ratio between the graft portion and the rubber polymer portion of the present invention can be controlled.

When the graft copolymer of the present invention is produced, for example, by an emulsion polymerization method, the method for recovering the polymer powder from the graft copolymer latex after polymerization is a conventional method, for example, calcium chloride, Latex is formed by adding alkaline earth metal salts such as magnesium chloride and magnesium sulfate, alkali metal salts such as sodium chloride and sodium sulfate, inorganic acids and organic acids such as hydrochloric acid, sulfuric acid, phosphoric acid and acetic acid. After coagulation, a method of dehydrating and drying can be exemplified.
Spray drying can also be used.

The resin composition of the present invention is prepared by blending the graft copolymer of the present invention with a thermoplastic resin as described above.

Specific examples of the thermoplastic resin include styrene resins, vinyl chloride resins, polycarbonate resins, polyamide resins, polyester resins, methacrylate resins, and polymer alloys thereof.
Preferred specific examples from the viewpoint of the effect of improving impact resistance include:
Polystyrene, styrene-methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-α-methylstyrene-acrylonitrile copolymer, styrene-
Styrene-based resins such as a maleimide copolymer, a styrene-maleimide-acrylonitrile copolymer, a styrene-maleimide, an acrylonitrile-α-methylstyrene copolymer, a styrene-maleic anhydride copolymer, and a blend thereof are exemplified.

Among the styrene resins, an acrylonitrile-styrene resin containing a vinyl cyanide unit, for example, an acrylonitrile unit is preferable, and further, 10 to 70 mol%, preferably 10 to 6 mol% of a vinyl cyanide unit.
0 mol%, maleimide monomer unit 50 mol% or less, preferably 40 mol% or less, aromatic vinyl unit 30 to 90
Mol%, preferably 40 to 90 mol% and 0 to 30 mol%, preferably 0 to 30 mol% of monomer units copolymerizable therewith.
A copolymer having a composition of 20 mol% is particularly preferred.
When the content of the vinyl cyanide unit is less than 10 mol%, the impact resistance is
If the amount exceeds 60 mol%, the processability is increased, and the amount of the aromatic vinyl unit becomes 3%.
If it is less than 0 mol%, the workability is reduced, and if it exceeds 90 mol%, the impact resistance is reduced.

The vinyl cyanide unit includes units derived from acrylonitrile, methacrylonitrile and the like, and the aromatic vinyl unit includes styrene, α-methylstyrene, p-methylstyrene, p-isopropylstyrene, chlorostyrene. , Bromostyrene, vinyl naphthalene and the like. These may be used alone or in combination of two or more. The maleimide-based monomer unit includes maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-phenylmaleimide, N- (p-methylphenyl) maleimide, and the like. Units are given. Further, the copolymerizable monomer units include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylate. Examples include units derived from (meth) acrylate monomers such as 2-hydroxyethyl acrylate, 2-ethylhexyl (meth) acrylate, and glycidyl (meth) acrylate.

The thermoplastic resin has a reduced viscosity of methyl ethyl ketone-soluble component (30 ° C., N, N-dimethylformamide solution) of 0.3 to 1.2 dl / g, preferably 0.1 to 1.2 dl / g.
35 to 1.0 dl / g, particularly preferably 0.4 to 0.1 dl / g.
9 dl / g. The reduced viscosity which is an index of the molecular weight is 0.
If it is less than 3 dl / g, the impact resistance tends to decrease,
If it exceeds 1.2 dl / g, the fluidity tends to decrease.

The thermoplastic resin is prepared by a known bulk polymerization method,
Solution polymerization method, bulk-suspension polymerization method, suspension polymerization method, emulsion polymerization method, emulsion-suspension polymerization method, emulsion-bulk polymerization method or a combination of these polymerization methods and post-imidization method Can be manufactured.

The resin composition of the present invention comprises a graft copolymer and a thermoplastic resin, and has a rubber polymer content of 5 to 5 relative to the total amount of the graft copolymer and the thermoplastic resin.
The graft copolymer is blended so as to be 40%, preferably 8 to 30%. If the rubber polymer content is out of the above range, impact resistance or fluidity tends to decrease.

The method for producing the resin composition of the present invention varies depending on the method for producing the graft copolymer and the thermoplastic resin.
For example, they can be produced by mixing them in the form of latex, suspension, slurry, solution, powder, beads, pellets, or the like, or by combining those in a state of these. If necessary, kneading may be performed by a known melt kneader such as a Banbury mixer, a roll mill, a single screw extruder, or a twin screw extruder.

The resin composition of the present invention may contain, as necessary, a well-known additive, for example, an antioxidant, a heat stabilizer, a UV absorber, a pigment, an antistatic agent, a lubricant and the like. Is also good. In particular, when the resin composition of the present invention is a styrene-based resin composition, hindered phenol-based, sulfur-based antioxidants, phosphorus-based (phosphite-based), hindered amine-based stabilizers used in styrene-based resins, Benzophenone-based, benzotriazole-based ultraviolet absorbers, organopolysiloxanes, aliphatic hydrocarbons, esters of higher fatty acids and higher alcohols, amides or bisamides of higher fatty acids, modified forms thereof, oligoamides, metal salts of higher fatty acids, etc. Inner / outer lubricants can be used to make the resin composition of the present invention more sophisticated as a molding resin composition.

Specific examples of the hindered phenol-based antioxidant include 1,1,3-tris (2-methyl-4
-Hydroxy-5-tert-butylphenyl) butane, n-octadecyl-3- (3 ', 5'-di-ter
t-butyl-4-hydroxyphenyl) propionate, tetrakis [methylene-3 (3,5-di-tert)
-Butyl-4-hydroxyphenyl) propionate]
Methane, triethylene glycol-bis- [3- (3-
tert-butyl-5-methyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-te
rt-butyl-4-methylphenol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-te
rt-butylphenol), tris- (3,5-di-t)
tert-butyl-4-hydroxybenzyl) -isocyanurate) and the like.

Specific examples of the sulfur-based antioxidants include 3,3′-thiodipropionic acid, dialkyl-3,
3'-thiodipropionate, pentaerythritol-
Tetrakis (3-alkylthiopropionate), tetrakis [methylene-3- (alkylthio) propionate] methane, bis [2-methyl4 (3-alkyl-thiopropynyloxy) -5-tert-butylphenyl]
Sulfide and the like.

Examples of the phosphorus-based stabilizer include stearylphenyl phosphite, tris (mono, di, nonylphenyl) phosphite, distearylpentaerythritol diphosphite, and tris (2,4-di-tert-butylphenyl). Phosphite, di (2,4-di-ter
t-butylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4-diphenylene phosphite, bis (2
6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.

These antioxidants and stabilizers may be used alone or in combination of two or more.

Specific examples of the organopolysiloxane include polydimethylsiloxane, polydiethylsiloxane and polymethylphenylsiloxane.

Specific examples of the aliphatic hydrocarbon include synthetic paraffin, polyethylene wax, polypropylene wax and the like.

Specific examples of the esters of the higher fatty acids and higher alcohols include esters of montanic acid, stearyl stearate, and behenerbehenate.

Specific examples of the above-mentioned amides and bisamides of higher fatty acids and modified products thereof include higher fatty acids such as stearamide, ethylenebisstearic acid amide, stearic acid, dicarboxylic acids such as succinic acid, and ethylenediamine such as ethylenediamine. Compounds having a higher melting point than bisamide synthesized by a dehydration reaction from diamine are exemplified.

Specific examples of the metal salts of the higher fatty acids include calcium salts and magnesium salts of higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid and oleic acid, as well as aluminum salts and cadmium salts. can give.

These lubricants may be used alone or in combination of two or more.

When the resin composition of the present invention is required to be flame-retardant, a halogen-based or phosphite-based flame retardant, an antimony compound such as antimony trioxide, a silicon compound such as polydimethylsiloxane, or the like can be used. An aluminum compound such as alumina may be blended and used.

Further, in order to improve mechanical properties such as elastic modulus and heat resistance, reinforcing fibers such as glass fiber and carbon fiber, and fillers such as mica, talc, clay and glass beads may be added. .

Hereinafter, the present invention will be described with reference to specific examples, but these examples do not limit the present invention.

Examples 1 to 7 and Comparative Examples 1 and 2 (1) Production of Rubber Polymer (A) As a first step, a rubber polymer (A) latex for preparing a rubber polymer (A) latex was used. Manufactured. 10
The following were charged into a 0 L polymerization machine.

Pure water 280 parts Potassium persulfate 0.2 parts t-Dodecyl mercaptan 0.2 parts After the air in the polymerization machine was removed with a vacuum pump, the following was charged.

Sodium oleate 1 part Sodium rosinate 2 parts Butadiene 100 parts The temperature of the system was raised to 60 ° C. to initiate polymerization. The polymerization was completed in 20 hours. The polymerization conversion (calculated from the solid content concentration, the same applies hereinafter) was 96%.

The average particle size of the obtained rubber polymer (a) latex was 80 nm. The average particle size was measured by a Nicomp particle size analyzer manufactured by Pacific Science (hereinafter the same).

As a second step, an acid group-containing latex (S) used for preparing the rubber polymer (A) latex from the rubber polymer (a) latex was produced as follows.

The following were charged into a reactor having a stirrer, a reflux condenser, a nitrogen inlet, a monomer inlet, and a thermometer.

Pure water 250 parts Dioctyl sodium sulfosuccinate 0.4 part (use amount of S1) or 0.2 parts (use amount of S2 and S3) Sodium formaldehyde sulfoxylate 0.5 part Under a nitrogen stream while stirring To 70 ° C. 7
After reaching 0 ° C., the monomers shown in Table 1 were continuously and uniformly dropped over 6 hours. 1.5 hours after the start of the monomer dropping, 0.8 parts of sodium dioctylsulfosuccinate was added. After completion of the dropwise addition, stirring was continued at 70 ° C. for 1 hour to terminate the polymerization and obtain acid group-containing latexes (S1) to (S3). Table 1 shows the polymerization conversion.

The average particle diameter of the obtained latex is 100 nm for the acid group-containing latex (S1), 150 nm for the acid group-containing latex (S2), and the acid group-containing latex (S3).
Was 170 nm.

In Table 1, BMA is butyl methacrylate, BA is butyl acrylate, St is styrene, M
AA represents methacrylic acid, tDM represents t-dodecyl mercaptan, and CHP represents cumene hydroperoxide.

[0109]

[Table 1]

Next, 100 parts (solid content) of the rubber polymer (a) latex produced in the first stage were mixed with acid group-containing latexes (S1) to (S3) at 60 ° C. in an amount shown in Table 2 (solid content). ) After the batch addition, stirring was continued for 1 hour to complete the enlargement, and a latex of the rubber polymer (A1) to (A4) was obtained.

The Tg of the obtained rubber polymers (A1) to (A4) was determined by the following method. Table 2 shows the results.

(Tg of rubber polymer (A)) 100 parts (solid content) of rubber polymer (A) latex was added with 3 parts of calcium chloride, coagulated, dehydrated and dried to obtain rubber polymer (A). I got it.

DSC using the obtained rubber polymer (A)
The temperature was measured at a heating rate of 10 ° C./min using a DSC-7 manufactured by PerkinElmer.

[0114]

[Table 2]

(2) Production of graft copolymer (I) Stirrer, reflux condenser, nitrogen inlet, monomer inlet,
The following was charged into a reactor having a thermometer.

Pure water 280 parts Rubber polymer latex shown in Table 3 Amount (solid content) shown in Table 3 Sodium formaldehyde sulfoxylate 0.3 part EDTA 0.01 part Ferrous sulfate 0.0025 part Chip with stirring The temperature was raised to 60 ° C. under a stream of air. 6
After reaching 0 ° C., the monomer mixture shown in Table 3 was continuously added for 6 hours.
Dropped in time. After completion of the dropping, stirring was continued at 60 ° C. for 1 hour to terminate the polymerization, and the graft copolymers (I-1) to (I-1)
-9) Latex was obtained.

Using the obtained graft copolymer latex, the form factors X, Y, Z of the rubber polymer were obtained by the following method.
The average of

[0118]

[Outside 28]

The volume average particle diameter and the volume ratio of the graft portion (g) to the rubber polymer were determined. Table 3 shows the results.

(Average of Shape Factors X, Y, Z of Rubber Polymer)

[0121]

[Outside 29]

After mixing 25 parts (solid content) of the graft copolymer latex and 75 parts (solid content) of the latex of the thermoplastic resin (II-1) described below, a phenolic stabilizer (BHT) ) 0.5 part was added, 3 parts of calcium chloride was added, coagulated and dehydrated and dried to obtain a graft copolymer-containing thermoplastic resin composition powder.

100 parts of the obtained powder was mixed with 1 part of ethylenebisstearylamide, uniformly blended with a 20-liter blender manufactured by Tabata Co., Ltd., and then 240 ° C. with a 40 m / m single screw extruder manufactured by Tabata Co., Ltd. To produce pellets.

The obtained pellet was prepared by FANUC CORPORATION 1
ASTM standard No. 1 dumbbell molded product was molded at a cylinder temperature of 240 ° C. using a 00B injection molding machine.

A test piece was cut out from the obtained molded article using a microtome, stained with osmium tetroxide, and the stained test piece was observed with a transmission electron microscope at a magnification of 20,000 times (the rubber polymer portion was blackened. , The graft portion and the thermoplastic resin portion appear white) and photographed.

With respect to the transmission electron microscope observation photograph,
Image analysis of the rubber polymer portion was performed using LUZEX IID manufactured by Nireco Co., Ltd., and the shape factors X, Y, and Z were determined for all rubber polymers, and the volume average

[0127]

[Outside 30]

Was obtained. The shape factors X, Y, and Z were analyzed for a 20 cm × 15 cm field of view in a 20,000 × image. The volume average particle size was also determined.

Note that the test piece was cut out from the center of the anti-gate portion, where the outer layer portion and the vicinity of the gate of the molded article were less likely to be deformed because the particulate rubber polymer was easily deformed by molding.

(Volume ratio of graft portion (g) to rubber polymer) Average value of shape factors X, Y and Z of rubber polymer

[0131]

[Outside 31]

Then, 1 g of a pellet of the thermoplastic resin composition produced for the measurement of the volume average particle diameter is placed in 1 dl of methyl ethyl ketone, dissolved by shaking at room temperature, and then subjected to centrifugation to separate soluble components other than the graft copolymer. Was removed to obtain a graft copolymer portion. The graft copolymer portion was redispersed in methyl ethyl ketone, a small amount of this dispersion was added to the epoxy resin, and the mixture was thoroughly mixed and dispersed. Thereafter, the epoxy resin in which the graft copolymer portion was dispersed was cured by heating.

Using a microtome from the obtained cured product, a test piece was cut out, dyed, photographed in the same manner as in the case where the shape factor of the rubber polymer was determined, and the rubber polymer portion and the graft were obtained by image analysis. The volume average particle diameter of the entire copolymer was determined, and the volume ratio of the graft portion (g) to the rubber polymer was determined from this.

In Table 3, the rubber polymer (b) is Nipol LX111NF manufactured by Zeon Corporation, AN is acrylonitrile, St is styrene, MMA is methyl methacrylate, tDM is t-dodecyl mercaptan, CH is CH.
P represents cumene hydroperoxoid.

[0135]

[Table 3]

Examples 8 to 18 and Comparative Examples 3 to 6 (3) Production of thermoplastic resin (II) Stirrer, reflux condenser, nitrogen inlet, monomer inlet,
The following was charged into a reactor having a thermometer.

Pure water 250 parts Dioctyl sodium sulfosuccinate 1.0 part Sodium formaldehyde sulfoxylate 0.5 parts EDTA 0.01 parts Ferrous sulfate 0.0025 parts The temperature is raised to 65 ° C. under a nitrogen stream while stirring. I let it. 6
After reaching 5 ° C., the monomers shown in Table 4 were converted into II-1, II-
In the case of No. 3, the solution was continuously dropped for 6 hours, and in the case of II-2, the first stage was added at once and then the second stage was dropped in 6 hours. Also, 0.5 part of sodium dioctyl sulfosuccinate was added at the first hour of polymerization time and 0.5 part at the third hour.
After completion of the dropwise addition, stirring was continued at 65 ° C. for 1 hour to terminate the polymerization and obtain a latex of the thermoplastic resins (II-1) to (II-3).

A part of the obtained latex was coagulated with calcium chloride, dehydrated and dried to obtain a powder,
Analysis and NMR analysis, and the obtained thermoplastic resin (I
It was confirmed that the analyzed compositions of I-1) to (II-3) were the same as the charged compositions.

The obtained thermoplastic resins (II-1) to (I-1)
I-3) Reduced viscosity of methyl ethyl ketone soluble component (30
C, N, N-dimethylformamide solution) was determined by the following method. Table 4 shows the results.

(Reduced viscosity) thermoplastic resin (II) 0.3
g was dissolved in 1 dl of methyl ethyl ketone with shaking at room temperature and centrifuged to obtain a methyl ethyl ketone soluble portion of a thermoplastic resin. This soluble matter was taken out, and the reduced viscosity was measured at 30 ° C. as a 0.3 g / dl N, N-dimethylformamide solution.

In Table 4, St is styrene, αSt is α-methylstyrene, PMI is N-phenylmaleimide, AN is acrylonitrile, tDM is t-dodecylmercaptan, and CHP is cumene hydroperoxide.

[0142]

[Table 4]

(4) Production of a Graft Copolymer-Containing Thermoplastic Resin Composition The latex of the graft copolymer (I) produced in (2) and the thermoplastic resin (II) produced in (3) are mixed together. After mixing at the ratio (solid content) shown in Table 5, 0.5 part of a phenolic stabilizer (BHT) was added, and 3 parts of calcium chloride was added to coagulate. The solidified slurry was dehydrated and dried to obtain a powder of a graft copolymer-containing thermoplastic resin composition.

One hundred parts of ethylenebisstearylamide was blended with 100 parts of the obtained thermoplastic resin composition powder containing the graft copolymer, and uniformly blended with a 20-liter blender manufactured by Tabata Co., Ltd. 40m / m 1 made by Tabata Co., Ltd.
In a screw extruder, melt-knead at a temperature of 240 to 270 ° C,
Pellets were produced.

The obtained pellets were used to evaluate impact resistance, heat resistance and workability by the following methods. Table 5 shows the results.

(Impact resistance) 100B manufactured by FANUC CORPORATION
Using an injection molding machine, cylinder temperature 240-270 ° C
A flat plate of 100 mm × 150 mm and a thickness of 3 mm was prepared under the conditions described above, and the drop weight strength at 23 ° C. was determined using this as a test piece. The evaluation value was represented by half-fracture height × drop weight load = half-fracture energy (unit: kgfm).

(Heat resistance (HDT)) ASTM D-64
8 was evaluated at the heat deformation temperature of 18.6 kg / cm ² load (unit: ° C.).

(Processability) Using a 100B injection molding machine manufactured by FANUC CORPORATION, resin flow in a spiral mold having a thickness of 3 mm and a width of 10 mm at a cylinder temperature of 250 ° C. and an injection pressure of 1350 kg / cm ^2. Length (unit: m
m).

[0149]

[Table 5]

From the results shown in Table 5, it is understood that the resin compositions of the present invention described in Examples 1 to 11 are particularly excellent in impact resistance, heat resistance and workability.

[0151]

By using the graft copolymer of the present invention, the impact resistance can be improved while maintaining the fluidity and heat resistance of the thermoplastic resin.

[Brief description of the drawings]

FIG. 1 is a view for explaining the shape of rubber polymer particles in a transmission electron micrograph (magnification: 20,000 times) of a molded article of an ABS resin of Example 12, wherein the rubber polymer particles in the photograph are shown. It is the figure which traced the outer edge of the thing clearly shown among them.

FIG. 2 is a view for explaining the shape of rubber polymer particles in a transmission electron micrograph (magnification: 20,000 times) of a normal ABS resin molded product. It is the figure which traced the outer edge of what is clearly shown.

Continuation of the front page (56) References JP-A-54-64583 (JP, A) JP-A-57-14612 (JP, A) JP-A-57-34111 (JP, A) JP-A-60-118734 (JP , A) JP-A-60-250057 (JP, A) JP-A-61-123648 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 279/02 C08F 255/02 C08F 265/04 C08C 1/07

Claims (9)

(57) [Claims] 1. Transmission electron microscope analysis-image analysis method (T
When the rubber polymer in the molded article is analyzed by the EM method, the shape factor is expressed by the following formula (I): X = (k / b) × 100 (I) (where k is the maximum size of the rubber polymer particle image) Length, b represents the width of the image of the rubber polymer particles), and the average value of the shape factor X in all the rubber polymers is 115 or more, and the formula (II): Y = (a / k ² ) × (4 / π) × 100 (II) (where a is the area of the rubber polymer particle image, and k is the same as above), and the average value of the shape factor Y in all the rubber polymers is 80 The following and the formula (III): Z = (a / p ² ) × 4π × 100 (III) (where a is the same as above and p represents the peripheral length of the rubber polymer particle image) Tg satisfying at least one of the following average values of Z in all rubber polymers: ℃ graft copolymer der consisting of non-spherical particulate rubber polymer (A) and the graft portion formed from one or more vinyl-based monomer unit (g)
The rubber polymer is acrylic acid, methacrylic acid,
At least one of taconic acid and crotonic acid
5 to 25% by weight of a saturated acid (c), wherein the alkyl group has 1 carbon atom
5 to 30% by weight of alkyl acrylate (d)
Alkyl methacrylates Leh carbon atoms in the alkyl group 1 to 12
(E) 80 to 20% by weight and (c) component, (d)
Aromatic vinyl copolymerizable with component (e) and component (e)
A monomer having two or more polymerizable functional groups in the
0 to 40% by weight of at least one of vinyl cyanide
-Containing latex prepared by polymerizing
Rubber polymer produced by coagulation enlargement method using (S)
A graft copolymer, characterized in that: 2. The form factor X of the particulate rubber polymer (A)
Is 120 or more in all rubber polymers, the average value of the form factor Y is 75 or less in all rubber polymers, and the average value of the form factor Z is 75 or less in all rubber polymers. Satisfies at least one of 80 or less. 3. Transmission electron microscope analysis-image analysis method (T
2. The graft copolymer according to claim 1, wherein the volume average particle diameter of the particulate rubber polymer (A) by EM method is 100 to 2000 nm. 4. Transmission electron microscope analysis-image analysis method (T
The graft copolymer according to claim 1, wherein the volume ratio of the graft portion (g) to the particulate rubber polymer (A) is from 0.10 to 0.90 by EM method). 5. The graft portion (g) is formed from 15 to 60 mol% of a vinyl cyanide unit, 85 to 40 mol% of an aromatic vinyl unit and 0 to 30 mol% of a monomer unit copolymerizable therewith. The graft copolymer according to claim 1, wherein 6. The graft copolymer according to claim 1, wherein the rubber polymer is at least one of a diene rubber, an olefin rubber and an acrylic rubber. 7. Transmission electron microscope analysis-image analysis method (T
When the rubber polymer in the molded article is analyzed by the EM method, the shape factor is expressed by the following formula (I): X = (k / b) × 100 (I) (where k is the maximum size of the rubber polymer particle image) Length, b represents the width of the image of the rubber polymer particles), and the average value of the shape factor X in all the rubber polymers is 115 or more, and the formula (II): Y = (a / k ² ) × (4 / π) × 100 (II) (where a is the area of the rubber polymer particle image, and k is the same as above), and the average value of the shape factor Y in all the rubber polymers is 80 The following and the formula (III): Z = (a / p ² ) × 4π × 100 (III) (where a is the same as above and p represents the peripheral length of the rubber polymer particle image) The Tg satisfying at least one of the following average values of Z in all rubber polymers: ℃ graft copolymer der consisting of non-spherical particulate rubber polymer (A) and the graft portion formed from one or more vinyl-based monomer unit (g)
The rubber polymer is acrylic acid, methacrylic acid,
At least one of taconic acid and crotonic acid
5 to 25% by weight of a saturated acid (c), wherein the alkyl group has 1 carbon atom
12 alkyl acrylate les over preparative (d) 5 to 30 wt%,
Alkyl methacrylate having 1 to 12 carbon atoms in the alkyl group
(E) 80 to 20% by weight and (c) component, (d)
Aromatic vinyl copolymerizable with component (e) and component (e)
A monomer having two or more polymerizable functional groups in the
0 to 40% by weight of at least one of vinyl cyanide
-Containing latex prepared by polymerizing
Rubber polymer produced by coagulation enlargement method using (S)
A resin composition comprising a graft copolymer and a thermoplastic resin. 8. The thermoplastic resin is a styrene resin having a reduced viscosity of methyl ethyl ketone soluble component (30 ° C., N, N-dimethylformamide solution) of 0.3 to 1.2 dl / g, and a rubber polymer. The resin composition according to claim 7, wherein the content is 5 to 40% by weight based on the total amount of the graft copolymer and the thermoplastic resin. 9. A styrene resin comprising 10 to 70 mol% of a vinyl cyanide unit, 30 to 90 mol% of an aromatic vinyl unit, 50 mol% or less of a maleimide compound unit and a monomer unit 0 copolymerizable therewith. ~ 30 mol% (total 10
The resin composition according to claim 8, which comprises 0 mol%).