JP3408275B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a thermoplastic resin composition.
Related. More specifically, the present invention relates to specific graft copolymers.
Rigid copolymer with two kinds of polymers or two kinds of specific graft copolymers
Impact resistance, chemical resistance and good molding
Workable, itself used as impact resistant material
Not only that, it is blended with other
Graft copolymer resin composition useful for making compositions
About. [0002] 2. Description of the Related Art One of the methods for obtaining an impact-resistant resin is as follows.
Raft copolymerization is well known,
(Eg, conjugated diene polymer latex)
In addition, the monomer to give the resinous polymer (for example,
(Lens + acrylonitrile)
The graft copolymer resin composition to be produced has an impact-resistant resin and
Widely used. Of these, polybutadi
Grafts consisting of ene / styrene / acrylonitrile
The polymer is famous as an ABS resin. However, for example, in ABS resin,
Contact with certain chemicals under force loading will cause cracks
In severe cases, a break phenomenon is observed.
Properties such as chemical properties were also inferior. Due to these properties
Acrylonitrile in ABS resin to obtain excellent resin
A method of increasing the content of the tolyl component (for example,
No. 47-5594), ABS resin and acrylic rubber
/ Styrene / Acrylonitrile (ASA resin)
(Japanese Patent Publication No. 54-40258, Japanese Patent Publication No.
No. 28460, JP-B-63-22222),
For those who mix acrylate polymer with ABS resin
Law (Japanese Patent Publication No. 63-22222), two distinctive
A method of mixing a graft copolymer (Japanese Patent Publication No. 57-220)
No. 64, JP-A-2-175745), etc.
Have been. [0004] However, these technologies exist in existing departments.
A meaningful solution to the subject
But to the best of our knowledge,
Not satisfactory. That is, of the proposed method
Among them, JP-A-47-5594, JP-B-54-40
No. 258, Japanese Patent Publication No. 63-22222, Japanese Patent Publication No.
In JP-A-63-28460, etc., the surface condition of an injection molded product is described.
Defective phenomenon, for example, surface appearance called flow mark
Poor or surface peeling phenomenon may be observed.
Surface appearance called die band in the surface condition of extrusion molding
Defects may be observed, causing a major problem in use.
I was Also, Japanese Patent Publication No. 57-2264 and
Japanese Patent Application Laid-Open No. 2-175745
Is insufficient in chemical resistance and needs more chemical resistance
In the field where it is used, it is still a problem in use. [0006] SUMMARY OF THE INVENTION The present invention addresses the above problems.
Have a specific average particle size, with the aim of solving the point
Diene rubbery polymer with a specific proportion of aromatic vinyl
Monomer, vinyl cyanide monomer and copolymerizable with them
Emulsion polymerization of monomer mixture consisting of other vinyl monomers
Specific average particle system obtained by graft polymerization reaction
(A) having a specific average particle diameter
Acrylic rubbery polymer with
Group vinyl monomer, vinyl cyanide monomer,
Other vinyl monomers that can be combined, and polyfunctional vinyl monomers
The monomer mixture consisting of
A graft copolymer having a specific average particle system
Polymer (B) and hard copolymer having affinity for them
This purpose is achieved by mixing (C) uniformly.
What you want to do. [0007] The gist of the present invention is as follows.
The following shows the graft copolymer A shown below,
The copolymer B and the hard polymer C are represented by the following formulas (1) and (2).
Thermoplastic resin, characterized in that it is contained in a composition ratio
In the composition. [0008]Graft copolymer A: Graft copolymer A
Is defined as follows: Weight average particle
Diameter0.15 to 0.45 μmDiene rubbery polymerization
In the presence of 100 parts by weight of the body latex (based on solid content),
40 to 80% by weight of aromatic vinyl monomer, vinyl cyanide
20 to 60% by weight of monomer and other copolymerizable with them
Monomer mixture 4 comprising 0 to 20% by weight of a vinyl monomer
Graft copolymerization obtained by emulsion polymerization of 5-450 parts by weight
Being a body,Graft copolymer B : The graft copolymer B is as follows:
It is defined as follows. (1) The weight average particle diameter is 0.05 to 0.50 μm.
100 parts by weight of acrylic rubbery polymer latex (solid
In the presence of an aromatic vinyl monomer60-80 weights
amount%, Vinyl cyanide monomer20-40% by weight, And this
0-20% by weight of other vinyl monomers copolymerizable therewith
Emulsion polymerization of at least 200 parts by weight of a monomer mixture consisting of
Being the obtained graft copolymer, (2) The acrylic rubbery polymer is composed of 2 to 12 elementary elements
Ester compound 7 of a certain monohydric alcohol and acrylic acid
0 to 100% by weight of another vinyl monomer copolymerizable therewith
0 to 30% by weight of a monomer and 0 to 3 of a polyfunctional vinyl monomer
Polymerization obtained by emulsion polymerization of a monomer mixture consisting of
Being a body,Hard polymer C : Hard polymer C is defined as follows:
Things. (1) Aromatic vinyl monomer 40 to 80% by weight, cyanide
20 to 60% by weight of vinyl monomer and copolymerizable with them
Monomer mixture consisting of 0 to 20% by weight of other functional vinyl monomer
A hard polymer obtained by polymerizing a compound. (Equation 3) (Equation 4) [0009]Graft copolymer B: Graft copolymer
B is defined as follows. (1) The weight average particle diameter is 0.05 to 0.50 μm.
100 parts by weight of acrylic rubbery polymer latex (solid
Of the aromatic vinyl monomer in the presence of 40 to 80
%, 20 to 60% by weight of a vinyl cyanide monomer, and
0-20% by weight of other vinyl monomers copolymerizable therewith
Emulsion polymerization of at least 200 parts by weight of a monomer mixture consisting of
Being obtained graft copolymer (2) Acrylic rubbery polymer having 2 to 12 carbon atoms
Ester compound 7 of a certain monohydric alcohol and acrylic acid
0 to 100% by weight of another vinyl monomer copolymerizable therewith
0 to 30% by weight of a monomer and 0 to 3 of a polyfunctional vinyl monomer
Polymerization obtained by emulsion polymerization of a monomer mixture consisting of
Being a body [0010]Hard copolymer C: The hard copolymer C is
It is defined as described. (1) 40 to 80% by weight of an aromatic vinyl monomer, cyan
20-60% by weight of vinyl chloride monomer and copolymerizable with them
Monomer mixture consisting of 0 to 20% by weight of other functional vinyl monomer
Rigid copolymer obtained by polymerizing compound [0011] (Equation 3) [0012] (Equation 4) [Specific description of the invention] The thermoplastic resin composition according to the present invention
Is identified in the presence of a diene rubbery polymer latex
Polymerization obtained by subjecting a monomer mixture to emulsion polymerization
In the presence of body A and an acrylic rubbery polymer latex
First, a group obtained by subjecting a specific monomer mixture to emulsion polymerization
Raft copolymer B and a substantially group consisting of a specific monomer
It is a mixture of a uniform hard copolymer C. [I] Graft copolymer 1) General explanation As usual for graft copolymers, monomers that should become "branches"
Are combined with the rubbery polymer that is
Although it is not necessarily the case, the term “graft
`` Polymers '' are also
Of polymers derived from monomers for “branches” that are not “branches”
It allows coexistence. (1) Rubbery polymer The graft copolymers A and B in the present invention are rubbery heavy
In the presence of coalesced latex, a monomer mixture to become a "branch"
The compound was graft-polymerized by an emulsion polymerization method.
You. The rubbery polymer that is the "backbone" of the graft copolymer is
Those whose glass transition temperature is lower than room temperature are targeted.
Such a rubbery polymer is prepared by a conventionally known emulsion polymerization method.
And can be manufactured. (2) Graft polymerization The graft copolymers A and B in the present invention will be described later.
In the presence of rubbery polymer latex, aromatic vinyl monomer
Body, vinyl cyanide monomer, other copolymerizable with these
In the case of vinyl monomer and graft copolymer B, more
Emulsion polymerization of monomer mixture consisting of functional vinyl monomer
It is obtained by a graft polymerization reaction according to the method. The conditions for the graft polymerization reaction are as defined in the present invention.
As long as the requirements are met, it is commonly used in the production of ABS resin
It is not essentially different. Also, the graft copolymer
The conditions for the graft polymerization reaction of A and B need not be the same.
No, it is possible to select the optimal conditions for each particle size
You. <Monomer> The aromatic vinyl monomer used in the present invention
Is styrene, and side-chain or (and) core-substituted styrene
(The substituent is a lower alkyl group, a lower alkoxy group,
Fluoromethyl group, halogen atom, etc.), for example, α
-Methylstyrene, p-methylstyrene, o-methyls
Tylene, m-methylstyrene, nuclear halogenated styrene,
α- or β-vinylnaphthalene and others.
These may be used together within a group or between groups. Graft
Used for copolymers A and B (and hard copolymer C)
The types of monomers to be used may be the same or different. Graph
In copolymer B, polyfunctional vinyl monomer is present
Let it. The vinyl cyanide monomer used in the present invention
Include acrylonitrile, methacrylonitrile, α-c
Loloacrylonitrile and the like. These are one or two
A mixture of the above may be used. Monomers are the purpose of the present invention.
Unless the other monomer is copolymerizable with the above monomer,
A small amount of body may be used in combination. Such monomers include:
Acrylic acid, methacrylic acid and carbon number in the range of 1 to 10
Esters with monohydric alcohols, especially methyl methacrylate
There are rates and others. <Graft polymerization reaction> Graft copolymerization reaction
Is carried out in the presence of a polymerization initiator. Initiators that can be used
Or catalysts) such as persulfuric acid, peracetic acid, and perphthalic acid.
Any peracid catalyst, persalt catalyst such as potassium persulfate, peroxidation
Hydrogen, benzoyl peroxide, chlorobenzoyl peroxide, peroxide
Naphthyl oxide, acetyl peroxide, benzoyl acetate
Peroxide catalysts such as tyl and lauroyl peroxide, hydroperacids
Alkyl peroxides such as t-butyl chloride, azobisiso
There are azo catalysts such as butyronitrile, which can be used alone.
Alternatively, two or more kinds can be used as a mixture. These are reducing agents
Can be used as a redox catalyst in combination with
You. The graft copolymerization reaction is carried out in the presence of a chain transfer agent.
Can be done below. Chain transfer agent used in the present invention
Is not particularly limited, for example, n-octylmerca
Butane, n-dodecyl mercaptan, t-dodecyl mer
Captan, etc. or terpinolene, α-methylstyrene
Non-linear dimers and the like are used. Graft copolymerization reaction
The polymerization temperature at the time of the reaction is 50 to 85 ° C, preferably 5 to 85 ° C.
A range of 5 to 75C is suitable. Heavy if less than 50 ° C
The reaction rate is low and impractical, and exceeds 85 ° C
When the reaction occurs, the reaction occurs at once, and solidifies in the reaction product.
A large amount of matter is generated or adhered to the reaction vessel (can) (scale)
Causes a decrease in polymerization rate and quality of the final product.
It is not preferable. The other conditions for the graft polymerization reaction are ABS
If it is essentially different from what is commonly used in resin production
Absent. All of the monomers for graft copolymerization are polymerized
Or may be introduced in stages. Also, heavy
All initiators and chain transfer agents are introduced into the polymerization system at one time.
Or may be introduced in stages. In addition, during polymerization
The temperature of the polymerization system can be changed over time. In producing the graft copolymer resin composition,
First, the graft copolymer specified in the above range
Manufacture latex, aromatic vinyl monomer, cyanide vinyl
Nyl monomers and other vinyl monomers copolymerizable with them
Polymerization obtained by copolymerizing a monomer mixture consisting of
Latex or hard polymer latex
Graft copolymer resin composition directly without mixing
May be manufactured. In the former case, graft weight to be mixed
The weight ratio of the monomer for the “branch” monomer of the combined latex and
Even if the weight ratio of the monomers of the hard polymer latex is the same,
Good or different. 2) Graft copolymer A (1) Rubbery polymer The rubbery polymer of the “backbone” of the graft copolymer A is a diene
It is a rubbery polymer. Specifically, it has 4 to 5 carbon atoms.
Dienes such as 1,3 butadiene, isoprene or chloro
A homopolymer of prene and 50 such conjugated dienes
Typical are copolymers containing more than 1% by weight. Copolymer
Is either a random copolymer or a block copolymer.
You may. Conjugated dienes, especially butadiene, in the case of copolymers
Monomers that can be used to copolymerize with
Aroma such as Tylene, α-methylstyrene, vinyltoluene
Group vinyl monomers, acrylic acid, methacrylic acid and
Acrylic such as methyl, ethyl, propyl, n-butyl
Monomer, acrylonitrile, methacrylonitrile, etc.
And vinyl cyanide monomers. Diene
Rubber polymer may be used alone or in combination of two or more.
it can. Rubbery polymerization of the "backbone" of the graft copolymer A
The body has a weight average particle size0.15 to 0.45 μmRange
AndBelow the lower limit,Of the finally obtained resin composition
Poor impact resistance, poor moldability,When exceeding the upper limit
IsLatex instability and scale during emulsion graft polymerization
Not only inconveniences such as an increase in
Poor appearance of molded product obtained from fat compositionSo yes
Displacement is also undesirable. The relatively large average particle size
For ene-based rubbery polymer latex, select production conditions and
A large particle size can be obtained, and a small particle size
To produce a polymer latex and increase the particle size.
You can also get it through the work. Operation to enlarge particle size
Cropping is performed by a known method, for example, by freezing latex once.
And re-thaw, add mineral acid to latex
A method for temporarily lowering the pH of latex,
Method of applying a shearing force to the box (Japanese Patent Application Laid-Open No. 54-1335)
No. 88, Japanese Unexamined Patent Publication No. 59-20221).
Therefore, it can be performed. In particular, phosphoric acid or latex
Is easy to adjust the particle size by adding acetic anhydride.
Therefore, it is preferable. Weight average of diene rubbery polymer latex
The average particle size does not need to be unimodal (single-peak distribution),
Peaks (two peaks, three peaks), that is, different average particle diameters
Or a mixture of various latexes. Jie
Weight average particle size of rubber-based rubber polymer latex
Measured by Coulter "Nanosizer"
It is. The diene rubbery weight in the graft copolymer
The weight average particle diameter of the coalesced was molded by an injection molding machine.
The ultra-thin layer section cut from the test piece was examined under an electron microscope.
Therefore, it can be measured. (2) Graft polymerization The graft copolymer A is composed of 100 diene rubbery polymers.
Parts by weight of aromatic vinyl monomer and vinyl cyanide
Monomer and other vinyl monomers copolymerizable therewith.
45 to 550 parts by weight of the total amount of the monomer mixture
Or 55 to 400 parts by weight to react.
Things. If the amount of the monomer mixture is higher than the upper range,
Sufficient impact resistance is not developed and the amount of monomer mixture is
If it is less than the range, sufficient rigidity will not be exhibited, and
Not preferred. The “branch” monomer in the graft copolymer A
The weight ratio is 40 to 80% by weight of the aromatic vinyl monomer,
20 to 60% by weight of vinyl anhydride monomer, and
0-20% by weight of other polymerizable vinyl monomers, preferably
Are 45 to 80% by weight, 20 to 55% by weight, 0
-20% by weight. From these weight ratio ranges,
Processability and color tone decrease when vinyl halide increases
However, when the amount is reduced, the chemical resistance is lowered, which is not preferable. 3) Graft copolymer B (1) Rubbery polymer The rubbery polymer of the “backbone” of the graft copolymer B is an acrylic polymer.
It is a rubber-based polymer. Specifically, carbon number 2-12
Of monohydric alcohol and acrylic acid
70 to 100% by weight of the polymer and other vinyl copolymerizable therewith
0 to 30% by weight of a monomer and 0 of a polyfunctional vinyl monomer
Obtained by emulsion polymerization of a monomer mixture consisting of ３3% by weight
It is a polymer. If the carbon number is outside the above range, sufficient
This is not preferable because the rubber elasticity cannot be obtained. More specifically
Is ethyl acrylate, propyl acrylate, n-
Butyl acrylate, butyl acrylate, amyl acrylate
Relate, hexyl acrylate, octyl acrylate
G, 2-ethylhexyl acrylate, cyclohexyl
Alkyl compounds such as acrylate and dodecyl acrylate
Related. Particularly preferred are those having 4 to 4 carbon atoms.
Esterification of 8 monohydric alcohols with acrylic acid
It is a compound. These ester compounds may be one kind,
A mixture of two or more types may be used. Other binders copolymerizable with the above ester compound
As the vinyl monomer, the aromatic vinyl monomer,
Vinyl monomer, acrylic amide, matacryloama
Id, vinylidene chloride, alkyl (1-6 carbon atoms)
Vinyl ether and the like, and these may be one kind,
A mixture of two or more types may be used. Acrylic rubbery polymerization
When manufacturing the body, you can use polyfunctional vinyl monomers.
You. This polyfunctional vinyl monomer is made of acrylic rubber
It performs the function of cross-linking the union
A monomer having two or more vinyl groups therein. Polyfunctional
Specific examples of the functional vinyl monomer include divinylbenzene,
Aromatic polyfunctional vinyl monomers such as divinyltoluene,
Ethylene glycol dimethacrylate, trimethylol
Methac of polyhydric alcohol such as propane triacrylate
Acrylates, acrylates, diallyl malates, dialys
Rufumarate, triallyl isofumanulate, allylmeth
Tacrylate, allyl acrylate and the like.
May be one kind or a mixture of two or more kinds. In producing the acrylic rubbery polymer,
The amount of polyfunctional vinyl monomer that can be used depends on the acrylic resin.
Composition of monomer for polymer production, polyfunctional vinyl monomer
Can be changed depending on the type, etc., but within the range of 3% by weight or less.
Shall choose. If it exceeds 3% by weight, acrylic rubber
The elasticity of the porous polymer decreases, the graft ratio becomes poor,
Not good. Acrylic-based “backbone” of graft copolymer B
The rubbery polymer has a weight average particle diameter of 0.05 to 0.50.
μm range. If the thickness is less than 0.05 μm,
Impact resistance of molded resin composition is poor and molding processability is also insufficient
And is not preferred. If it exceeds 0.50 μm, use resin
The appearance of the molded article obtained from the composition is not excellent, etc.
Not good. Particularly preferred in the above range is 0.10 to
The range is 0.40 μm. The relatively large average particle size
For cryl rubbery polymer latex, select manufacturing conditions
Large particle size can be obtained directly, and small particle size
Manufacture rubbery polymer latex and increase particle size
It is also possible to obtain via the operation
The same applies to the case of rubbery polymers. Acrylic rubbery polymerization
The latex weight average particle size is unimodal (one-peak distribution)
Need not be multimodal (two mountain distribution, three mountain distribution)
A mixture of various latexes having different average particle diameters
It may be. Acrylic rubbery polymer latex
The weight average particle diameter was measured by an electron microscope as described above.
Can be specified. (2) Graft polymerization The graft copolymer B used in the present invention is limited.
Graft copolymer resin. That is,
With respect to 100 parts by weight (solid content) of the ril-based rubbery polymer content
And at least 200 parts by weight of the monomer mixture, preferably 2 parts by weight.
It is in the range of 00 to 550 parts by weight. The monomer mixture
If the amount is less than the range, a good appearance is formed from the resin composition.
If it is higher than this range, sufficient chemical resistance will not be obtained.
I can't get it. Of the "branch" monomer in the graft copolymer B
Weight ratio is aromatic vinyl monomer60-80% by weight,
Vinyl anhydride monomer20-40% by weightAnd with them
0-20% by weight of other polymerizable vinyl monomersIt is.This
More vinyl cyanide monomer than these weight ratio ranges
Processability and color tone are reduced,
The properties deteriorate, which is not preferable. [II] Hard copolymer C The hard copolymer constituting the resin composition according to the present invention has excellent properties.
40 to 80% by weight of aromatic vinyl monomer, vinyl cyanide
20-60% by weight, and other copolymerizable with them.
0-20% by weight of vinyl monomer, preferably 4% each
0-80% by weight, 20-60% by weight, and 0-20% by weight
% Of a monomer mixture. these
If the amount of vinyl cyanide monomer exceeds the weight range,
When the workability and color tone decrease, the chemical resistance decreases as the amount decreases.
But not preferred. Aromatic vinyl that is a component of the above copolymer
Monomer, vinyl cyanide monomer, and copolymerization with them
Specific examples of other possible vinyl monomers are described in
Found in those exemplified as constituents of coalescence A and B
Can be Polymerization method and polymerization strip of the above copolymer
Cases include solution polymerization, bulk polymerization, and suspension polymerization.
Can be appropriately selected from batch or continuous methods (manufactured by
For details of the fabrication method, see, for example, JP-A-62-1720.
See). The graft copolymer A according to the present invention and
B, and a set of monomer components constituting the hard copolymer C
The composition may be within the range defined above.
Does not necessarily mean that the composition of
There is no. However, both are selected within the aforementioned range and
However, if the compositions of the two are significantly different,
The raft copolymer is inferior in compatibility and deteriorates in physical properties.
Not good. [III] Thermoplastic resin composition The thermoplastic resin composition according to the present invention is as described above.
Graft copolymers A and B and hard copolymer C
And the composition ratio is (1) to
It is within the range shown by the equation (2). Distribution of each copolymer
If the combined amount is out of the range defined by the equations (1) and (2),
Thermoplastic with good physical properties and good moldability
It cannot be a resin composition. [0036] (Equation 5) [0037] (Equation 6) As shown in the above formula (1), the thermoplastic resin according to the present invention
The rubbery polymer contained in the fat composition is graft copolymerized.
The rubbery polymer derived from the union A is a graft copolymer A
20 to 90% by weight of the total of the rubbery polymers of
I have to. Further, as shown in the above equation (2), the present invention
Rubbery polymerization contained in the thermoplastic resin composition according to the present invention
The copolymer is a mixture of the graft copolymers A and B and the hard copolymer C.
It must be between 5 and 50% by weight per total. Less than 5%
Is difficult to develop the impact resistance of the resulting resin composition,
The effect as an impact improver is also reduced. 5
If it exceeds 0%, the graft copolymer resin composition is molded.
In this case, the processability is reduced, and the gloss of the molded product is
And the impact resistance is also reduced. Graft copolymer A, graft copolymer B
And hard copolymer C are blended and mixed and kneaded.
May be used. At this time, kneading temperature
Is selected as long as the resin composition does not cause resin burning
Is good. Powder, beads, flakes or pellets
A mixture of two or three of these copolymers can be uniaxially pressed.
Output machine, twin screw extruder, or Banbury mixer, pressurized
The resin composition is mixed with a kneader such as a
Can be In some cases, the polymerization has been completed
Two or three of these copolymers are left undried
Mix, precipitate, wash, dry and knead.
You can also. The resin composition according to the present invention comprises
Types and amounts of lubricants, plasticizers, and antistatics that do not impair properties
Stopping agents, flame retardants, UV absorbers, lightfast stabilizers, heat resistant
Various resin additives such as stabilizers and fillers are added in appropriate combinations
can do. The resin composition according to the present invention is prepared by injection molding.
Various methods such as molding method, extrusion molding method, compression molding method, thermoforming method, etc.
It is made into a molded product by the construction method and has excellent chemical resistance, workability and
Applications requiring impact resistance, such as inner box materials for electric refrigerators
As electrical parts and industrial parts
it can. [0041] The following examples and comparative examples further illustrate the present invention.
The purpose of the present invention is to provide a specific description.
However, the present invention is not limited to the following examples as long as the value does not exceed.
In the following examples, “parts” means parts by weight.
You. In each of the following Examples and Comparative Examples, impact-resistant steel
The physical properties of the len-based resin were measured by the following methods. (1) Tensile strength It was measured according to JIS K7113. Unit: Kg / cm^Two (2) Izod impact strength It was measured in accordance with JIS K7110. Unit: Kg-cm /
cm (3) VICAT softening point It was measured according to JIS K7206. Unit: ° C (4) Melt flow rate Based on JIS K7210, temperature 220 ° C, load 10
The measurement was carried out under the condition of kg, and the result was indicated by the number of g of the outflow for 10 minutes.
Unit: g / 10 minutes (5) Latex weight average particle size Measured by Coulter's "Nanosizer"
Was. Unit: μm (6) Appearance Specimen molded by injection molding (2.5mm thick,
(75mm width, 160mm length)
Was. Judgment results were displayed as follows. [0042] [Table 1] ：: No decrease in gloss or flow mark was observed. Δ: A decrease in gloss or a slight flow mark was observed.
You. ×: Decrease in gloss or considerable flow mark
You. (7) Chemical resistance Compression molded test piece (2 mm thick, 35 mm wide, 230 long
mm) at 23 ° C by the bending form method.
The critical strain value for crack initiation for Ron 123 was measured. Size
The results are shown as follows. [0043] [Table 2] ：: Extremely good chemical resistance with a critical strain value of 0.8% or more
It is. ：: Critical strain value of 0.8 to 0.6%, good chemical resistance
is there. X: Critical strain value is 0.6% or less and chemical resistance is poor.
You. [Production example] 1: Production of graft copolymer (A) [0044]A-1 (1) Production of conjugated diene rubbery polymer Stirrer, heating / cooling device, thermometer, each raw material, auxiliary additive
5 liter stainless steel auto equipped with a heating device
In a clave, 150 parts of deionized water, higher fatty acid soap (charcoal)
Sodium salt of a fatty acid having a prime number of 18 as a main component) 4.0
Parts, sodium hydroxide 0.075 parts, nitrogen gas
And the internal temperature was raised to 68 ° C. Same haute
90 parts of 1,3-butadiene monomer (BD)
10 parts of styrene monomer (ST) and t-dodecyl merca
20% of the monomer mixture consisting of 0.3 parts of butane
After charging, 0.135 parts of potassium persulfate was added.
An exotherm occurred a few minutes later, confirming the start of polymerization. Persulfur
One hour after the addition of potassium acid,
Start adding 80% of the monomer mixture and start at 6:00
Continuous addition over time. Finish adding the above monomer mixture
Thereafter, the internal temperature is raised to 80 ° C., and the temperature is further increased for 1 hour at this temperature.
The combined reaction was continued. After that, the internal temperature is immediately cooled to room temperature,
A tadiene-styrene rubber copolymer was obtained. The obtained rubber
Polymer latex has a solid content of 39.5% by weight,
The average particle size was 0.08 μm, and the gel content was 95%. (2) Particle size enlargement Divide the rubbery polymer latex obtained above into anhydrous vinegar
Fertilize particles with a solution of acid diluted with deionized water.
The weight average particle diameter is 0.25 μm;
0.65 μm was obtained. (3) Graft copolymerization Same rubber used for the production of rubbery polymer latex
In the autoclave, the above-mentioned particle diameter enlargement and weight average particle diameter
0.25μm and 0.65μm rubbery polymer latex
Are mixed at a ratio of 80 parts and 20 parts as solids
(Double distribution: weight average particle diameter of mixed latex is 0.3
3 μm) and 347 parts of deionized water (moisture in latex)
Including). The internal temperature of the autoclave is raised to reach 60 ° C.
When done, 1.0 part of sodium pyrophosphate, dextro
0.5 part of ferrous sulfate and 0.01 part of ferrous sulfate in deionized water 2
An aqueous solution dissolved in 0 parts was added. The internal temperature reaches 70 ° C
2 hours and 30 minutes while maintaining this temperature
In short, 70 parts of styrene monomer (ST), acrylonitrile
Ryl monomer (AN) 30 parts, t-dodecyl mercaptan
1.1 parts of a monomer mixture, and cumene hydro
0.5 part peroxide, disproportionated potassium soap
1.8 parts and 0.37 parts of potassium hydroxide were added to 35 parts of deionized water.
The aqueous solution dissolved in the autoclave
Added. After completion of the addition, maintain the temperature at 70 ° C.
The reaction was continued for 30 minutes, and then the internal temperature of the autoclave was cooled.
The reaction was terminated. The obtained graft polymer latex was used
Magnesium sulfate heated to 95 ° C after addition of 5 parts of antioxidant
The solution was added to an aqueous solution of water while stirring to solidify the solution. Coagulate
Was washed with water and dried to obtain a powder of graft copolymer A-1.
Was. [0048]A-2 (1) Production of conjugated diene rubbery polymer The same procedure as in A-1 (1) was followed. (2) Particle size enlargement The above-mentioned butadiene-styrene rubber copolymer latex
, The particle size is enlarged using acetic anhydride,
The diameter was 0.30 μm. (3) Graft copolymerization By the same procedure as in A-1 (3), the graft
A powder of the polymer A-2 was obtained. [0049]A-3 (1) Production of conjugated diene rubbery polymer The same procedure as in A-1 (1) was followed. (2) Particle size enlargement The same procedure as in A-1 (1) was followed. (3) Graft copolymerization In the example described in A-1 (3), when the internal temperature reaches 70 ° C.
From the time when the monomer mixture was added to the autoclave
Styrene monomer 60 parts, acrylonitrile monomer 4
0 parts, 0.8 parts of t-dodecyl mercaptan
The procedure was the same as in the previous example, except that
A powder of the fuft copolymer A-3 was obtained. [0050]A-4 (1) Production of conjugated diene rubbery polymer The same procedure as in A-1 (1) was followed. (2) Particle size enlargement The above-mentioned butadiene-styrene rubber copolymer latex
The particle size is enlarged using phosphoric acid,
The diameter was 0.25 μm. The same procedure as in A-1 (1) is used.
Was. (3) Graft copolymerization Same rubber used for the production of rubbery polymer latex
In the autoclave, add the rubbery polymer
100 parts as solids and 361 deionized water
(Including water in latex). The internal temperature of the autoclave was raised to 74 ° C.
Was. When the temperature reaches 74 ° C, 44.6 parts of deionized water is persulfurized.
An aqueous solution in which 0.59 part of potassium acid was dissolved was added. same
Sometimes 130 parts of styrene monomer, acrylonitrile unit
55.7 parts of body, 0.55 parts of terpene mixture
Autoclave the body mixture in 4 hours 30 minutes
Was added. On the way, 30 minutes after the start of addition of the monomer mixture
And 0.37 parts of potassium hydroxide after 1 hour and 2 hours
After 30 minutes, add 27.6 parts of deionized water to a higher fatty acid soap.
(Sodium salt of fatty acid having 18 carbon atoms as a main component)
2.0 dissolved in water, respectively.
Was. After the addition is completed, maintain the temperature at 74 ° C. for a further 3
After continuing the reaction for 0 minutes, cool the autoclave
The reaction was terminated. The obtained graft polymer latex is aged
Magnesium sulfate heated to 95 ° C after addition of 5 parts of antioxidant
The solution was added to an aqueous solution of water while stirring to solidify the solution. Coagulate
Was washed with water and dried to obtain a powder of graft copolymer A-4.
Was. [0054]A-5 (1) Production of conjugated diene rubbery polymer The same procedure as in A-1 (1) was followed. (2) Particle size enlargement The above-mentioned butadiene-styrene rubber copolymer latex
, The particle size is enlarged using acetic anhydride,
The diameter was 0.18 μm. (3) Graft copolymerization Same rubber used for the production of rubbery polymer latex
In the autoclave, add the rubbery polymer
100 parts as solids and deionized water 347
(Including water in latex). The internal temperature of the autoclave is raised to reach 60 ° C.
When done, 1.0 part of sodium pyrophosphate, dextro
1.0 part of ferrous sulfate and 0.01 part of ferrous sulfate in deionized water 2
An aqueous solution dissolved in 0 parts was added. The internal temperature reaches 65 ° C
3 hours and 30 minutes while maintaining this temperature
In short, 50 parts of styrene monomer, 50 parts of acrylonitrile
Parts, 1.5 parts of t-dodecyl mercaptan
A mixture, and cumene hydroperoxide 0.5
Parts, disproportionated potassium rosinate 1.8 parts, potassium hydroxide
Aqueous solution obtained by dissolving 0.37 parts of aluminum in 35 parts of deionized water.
Were each added continuously. After the addition is complete, raise the temperature to 6
After continuing the reaction for another 30 minutes while maintaining at 5 ° C,
The reaction was completed by cooling the internal temperature of the autoclave. The obtained graft polymer latex was washed with aged
Magnesium sulfate heated to 95 ° C after addition of 5 parts of antioxidant
The solution was added to an aqueous solution of water while stirring to solidify the solution. Coagulate
Was washed with water and dried to obtain a powder of graft copolymer A-5.
Was. [0057]A-6 (1) Production of conjugated diene rubbery polymer The same procedure as in A-1 (1) was followed. (2) Particle size enlargement The same procedure as in A-1 (2) was followed. (3) Graft copolymerization In the example described in A-1 (3), when the internal temperature reaches 70 ° C.
From the time when the monomer mixture was added to the autoclave
With styrene monomer 90 parts, acrylonitrile monomer 1
0 parts, 0.2 parts of t-dodecyl mercaptan
The procedure was the same as in the previous example, except that
Thus, a powder of ft copolymer A-6 was obtained. [0058]A-7 (1) Production of conjugated diene rubbery polymer The same procedure as in A-1 (1) was followed. (2) Particle size enlargement The same procedure as in A-1 (2) was followed. (3) Graft copolymerization In the example described in A-1 (3), when the internal temperature reaches 70 ° C.
From the time when the monomer mixture was added to the autoclave
Styrene monomer 20 parts, acrylonitrile monomer 8
0 parts, 1.5 parts of t-dodecyl mercaptan
The procedure was the same as in the previous example, except that
A powder of the fuft copolymer A-7 was obtained. [0059]A-8 (1) Production of conjugated diene rubbery polymer The same procedure as in A-1 (1) was followed. (2) Particle size enlargement The above-mentioned butadiene-styrene rubber copolymer latex
, The particle size is enlarged using acetic anhydride,
The diameter was 0.80 μm. (3) Graft copolymerization By the same procedure as in A-1 (3), the graft
A powder of polymer A-8 was obtained. [0060]A-9 (1) Production of conjugated diene rubbery polymer The same procedure as in A-1 (1) was followed. (2) Particle size enlargement The particle size was not enlarged. (3) Graft copolymerization By the same procedure as in A-1 (3), the graft
A powder of polymer A-9 was obtained. Graft copolymer A-1
A-9 Graft copolymer amount, particle size, grafting
Table 1 shows the composition ratio of the monomer mixture.
You. 2: Production of graft copolymer (B) 2-1: Production of rubbery polymer (B1) [0061]B1-1 (Rubber polymer) stirrer, heating / cooling device, thermometer,
And a 5-liter capacity stage equipped with
Stainless steel autoclave, 151 parts of deionized water, high
Grade Fatty Acid Soap (Nato of fatty acid with 18 carbon atoms as main component)
2 parts of lithium salt) and 1 part of sodium hydrogen carbonate.
The gas was replaced by elemental gas, and the internal temperature was raised to 75 ° C. The same
0.135 parts of potassium persulfate added to the autoclave
And immediately, 95 parts of butyl acrylate monomer (BA),
Acrylonitrile (AN) 5 parts, allyl methacrylate
0.5 parts of stell (AMA) and t-dodecyl mercap
4 of the monomer mixture consisting of 1.2 parts of tan (TDM)
The department was charged. A few minutes later, an exotherm occurred, confirming that polymerization had started.
It has been certified. Twenty times after charging the monomer mixture, the remaining
Of the monomer mixture was started over 3 hours and 20 minutes.
Was added continuously. 2 hours after continuous addition, higher fatty acid stone
Add 1 part of soap and add potassium persulfate at 2 hours 30 minutes
0.015 parts were added. After adding the monomer mixture,
The temperature was raised to 80 ° C and the reaction was continued at this temperature for another 30 minutes.
After continuing, cool the temperature inside the autoclave to complete the reaction.
The acrylic rubbery polymer latex B1-1 was obtained.
Was. The obtained latex has a solid content of 39.5% by weight.
%, The weight average particle diameter was 0.10 μm. [0063]B1-2 In the example described in B1-1, the monomer is butyl acrylate.
Except that the monomer was replaced with 100 parts, the same
A reaction is performed to obtain an acrylic rubbery polymer latex B1.
-2 was obtained. The resulting latex has a solids content of 3
9.2% by weight and a weight average particle size of 0.095 μm.
Was. [0064]B1-3 In the example described in B1-1, the monomer is butyl acrylate.
100 parts of monomer, allyl methacrylate (AM
A) 0.3 parts, t-dodecyl mercaptan (TDM)
Except for replacing the monomer mixture consisting of 0.9 parts,
Polymerization reaction in the same manner as
Latex B1-3 was obtained. The latex obtained is solid
Form concentration 38.6% by weight, weight average particle size 0.096
μm. [0065]B1-4 In the example described in B1-1, the monomer is butyl acrylate.
90 parts of monomer, 10 parts of styrene monomer (ST), t-do
Monomer consisting of 0.6 parts of decyl mercaptan (TDM)
Other than replacing the mixture, the polymerization reaction was performed in the same manner as in the same example.
Then, an acrylic rubbery polymer latex B1-4 was obtained.
Was. The obtained latex has a solid content of 39.0% by weight.
%, The weight average particle diameter was 0.090 μm. [0066]B1-5 In the example described in B1-1, the monomer is butyl acrylate.
70 parts of monomer, 30 parts of methyl methacrylate (MMA)
Except that the monomer mixture was replaced with
Acrylic rubbery polymer latex
B1-5 was obtained. The resulting latex has a solids concentration
39.0% by weight and a weight average particle size of 0.078 μm.
Was. [0067]B1-6 In the example described in B1-1, the monomer is butyl acrylate.
Consists of 50 parts of monomer and 50 parts of styrene monomer (ST)
Polymerized in the same manner as in the same example except that the monomer mixture was replaced.
After the reaction, an acrylic rubbery polymer latex B1-
6 was obtained. The resulting latex had a solids concentration of 39.
The weight-average particle size was 9% by weight, and the particle size was 0.102 μm. Go
Ratio, physical properties, etc. of the rubbery polymers B1-1 to B1-6
Is shown in Table-2. 2-2: Production of graft copolymer (B) [0068]B-1 Stirrer, heating / cooling device, thermometer, each raw material, auxiliary additive
5 liter stainless steel auto equipped with a heating device
In a clave, an acrylic rubbery polymer B1-1
100 parts, 1 part of sodium hydrogen carbonate, deionized water
Charge 402 parts (including moisture in latex) and add nitrogen
After the gas replacement, the internal temperature was raised to 80 ° C. Oat crepe
After the internal temperature of the heater reaches 80 ° C, maintain the internal temperature at this temperature
It takes 3 hours and 30 minutes while the styrene monomer 15
4 parts, acrylonitrile 66 parts, t-dodecyl mercap
A monomer mixture consisting of 0.44 parts of tan
1.1 parts of lithium, 3.96 of disproportionated potassium rosinate soap
And an aqueous solution consisting of 88.2 parts of deionized water, respectively.
Added continuously. After the addition is completed, maintain the temperature at 80 ° C.
The reaction was continued for another 30 minutes while
The internal temperature was cooled to complete the reaction. Graft obtained
After adding 5 parts of an antioxidant, the polymer latex was added at 95 ° C.
Into the aqueous magnesium sulfate solution
And solidified. The coagulated material is washed with water, dried, and
A white powder of polymer B-1 was obtained. [0069]B-2 In the example described in B-1, the acrylic rubbery polymer
Grouping was performed in the same procedure as described in the same example except that B1-2 was used.
Raft polymerization reaction is performed, and the white color of the graft copolymer B-2 is obtained.
A powder was obtained. [0070]B-3 In the example described in B-1, the acrylic rubbery polymer
The procedure was the same as that described in the same example except that B1-3 was replaced.
Raft polymerization reaction is performed, and the graft copolymer B-3 becomes white.
A powder was obtained. [0071]B-4 In the example described in B-1, the acrylic rubbery polymer
Grouping was performed in the same procedure as described in the same example except that B1-4 was used.
Raft polymerization reaction was performed, and the graft copolymer B-4 was white.
A powder was obtained. [0072]B-5 In the example described in B-1, the acrylic rubbery polymer
The procedure was the same as that described in the same example except that B1-5 was replaced.
Raft polymerization reaction is performed, and the graft copolymer B-5 becomes white.
A powder was obtained. [0073]B-6 In the same autoclave used in B-1, acrylic-based
100 parts of rubbery polymer B1-1 as solid content, carbonated water
1 part of sodium hydrogen chloride, 440 parts of deionized water (in latex
Of water), replace with nitrogen gas, and cool the internal temperature.
The temperature was raised to 80 ° C. Autoclave internal temperature reaches 80 ℃
3 hours 30 minutes while maintaining the internal temperature at this temperature
175 parts of styrene monomer, acrylonitrile
75 parts, t-dodecyl mercaptan 0.5 part
Monomer mixture and potassium persulfate 1.25 parts, disproportionation
4.5 parts of potassium rosin acid soap, 93.8 parts of deionized water
In each case were added continuously. End of addition
After completion, react for another 30 minutes while maintaining the temperature at 80 ° C.
After cooling, the temperature inside the autoclave is cooled to
finished. The obtained graft polymer latex was aged
Magnesium sulfate heated to 95 ° C after addition of 5 parts of antioxidant
The solution was added to an aqueous solution of water while stirring to solidify the solution. Coagulate
Is washed with water and dried to give a white powder of graft copolymer B-6.
I got [0075]B-7 In the same autoclave used in B-1, acrylic-based
100 parts of rubbery polymer B1-1 as solid content, carbonated water
1 part of sodium hydrogen chloride, 505 parts of deionized water (in latex
Of water), replace with nitrogen gas, and cool the internal temperature.
The temperature was raised to 80 ° C. Autoclave internal temperature reaches 80 ℃
3 hours 30 minutes while maintaining the internal temperature at this temperature
Required, styrene monomer 210 parts, acrylonitrile
90 parts, 0.6 parts of t-dodecyl mercaptan
1.43 parts of a dimer mixture and potassium persulfate, disproportionation
5.4 parts of potassium rosinate soap, 105 parts of deionized water
The resulting aqueous solutions were each added continuously. End of addition
Thereafter, the reaction was continued for another 30 minutes while maintaining the temperature at 80 ° C.
After continuing, cool the temperature inside the autoclave to complete the reaction.
Done. The obtained graft polymer latex was aged
Magnesium sulfate heated to 95 ° C after addition of 5 parts of antioxidant
The solution was added to an aqueous solution of water while stirring to solidify the solution. Coagulate
Is washed with water and dried to give a white powder of the graft copolymer B-7.
I got [0077]B-8 In the example described in B-1, the acrylic rubbery polymer
The styrene monomer 143
Parts, acrylonitrile 77 parts, t-dodecyl mercapta
Except that the monomer mixture consisted of 0.44 parts
Perform a graft polymerization reaction in the same procedure as described
A white powder of ft copolymer B-8 was obtained. [0078]B-9 In the example described in B-1, the acrylic rubbery polymer
The monomer mixture to be grafted is
Parts, acrylonitrile 88 parts, t-dodecyl mercapta
Except that the monomer mixture consisted of 0.44 parts
Perform a graft polymerization reaction in the same procedure as described
A white powder of ft copolymer B-9 was obtained. [0079]B-10 In the example described in B-1, the acrylic rubbery polymer
The monomer mixture to be grafted is a styrene monomer 110
Part, acrylonitrile 66 parts, methyl methacrylate 44
Parts, 0.44 parts of t-dodecyl mercaptan
The procedure was the same as described in the same example except that the mixture was replaced with a body mixture.
A raft polymerization reaction is performed, and the graft copolymer B-10 becomes white.
A colored powder was obtained. [0080]B-11 In the same autoclave used in B-1, acrylic-based
100 parts of rubbery polymer B1-1 as solid content, carbonated water
1 part sodium bicarbonate, 204 parts deionized water (in latex
Of water), replace with nitrogen gas, and cool the internal temperature.
The temperature was raised to 80 ° C. Autoclave internal temperature reaches 80 ℃
3 hours 30 minutes while maintaining the internal temperature at this temperature
Styrene monomer 35 parts, acrylonitrile 1
5 parts, 0.1 part of t-dodecyl mercaptan
Body mixture and 0.25 parts of potassium persulfate, disproportionation
0.9 parts of potassium formate soap, 22.2 parts of deionized water
The resulting aqueous solutions were each added continuously. End of addition
Thereafter, the reaction was continued for another 30 minutes while maintaining the temperature at 80 ° C.
After continuing, cool the temperature inside the autoclave to complete the reaction.
Done. The obtained graft polymer latex was aged
Magnesium sulfate heated to 95 ° C after addition of 5 parts of antioxidant
The solution was added to an aqueous solution of water while stirring to solidify the solution. Coagulate
Was washed with water and dried to obtain a white powder of the graft copolymer B-11.
I got the end. The same autoclave used in B-1
The acrylic rubbery polymer B1-1 was converted to a solid content of 1%.
00 parts, 1 part of sodium hydrogen carbonate, 258 parts of deionized water
(Including the moisture in the latex) and replace with nitrogen gas
After that, the internal temperature was raised to 80 ° C. Autoclave internal temperature
After the temperature reaches 80 ° C, keep the internal temperature at this temperature
3 hours and 30 minutes, 70 parts of styrene monomer
30 parts of acrylonitrile, t-dodecyl mercaptan 0.
A monomer mixture consisting of 2 parts and potassium persulfate
5 parts, disproportionated potassium rosinate soap 1.8 parts, deionized
An aqueous solution consisting of 47.7 parts of water was continuously added.
did. After completion of the addition, maintain the temperature at 80 ° C.
After continuing the reaction for 30 minutes, cool down the internal temperature of the autoclave.
Then, the reaction was completed. The obtained graft polymer latex was aged
Magnesium sulfate heated to 95 ° C after addition of 5 parts of antioxidant
The solution was added to an aqueous solution of water while stirring to solidify the solution. Coagulate
Was washed with water and dried to obtain a white powder of the graft copolymer B-12.
I got the end. The same autoclave used in B-1
The acrylic rubbery polymer B1-1 was converted to a solid content of 1%.
00 parts, 1 part of sodium hydrogen carbonate, 307 parts of deionized water
(Including the moisture in the latex) and replace with nitrogen gas
After that, the internal temperature was raised to 80 ° C. Autoclave internal temperature
After the temperature reaches 80 ° C, keep the internal temperature at this temperature
3 hours and 30 minutes, 105 parts of styrene monomer,
Acrylonitrile 45 parts, t-dodecyl mercaptan
0.31 parts of a monomer mixture and potassium persulfate
0.75 parts, 2.7 parts of disproportionated potassium rosin acid soap,
An aqueous solution consisting of 72.7 parts of deionized water was continuously applied
Was added. After the addition, keep the temperature at 80 ° C.
After continuing the reaction for another 30 minutes,
The temperature was cooled to complete the reaction. The obtained graft polymer latex was aged
Magnesium sulfate heated to 95 ° C after addition of 5 parts of antioxidant
The solution was added to an aqueous solution of water while stirring to solidify the solution. Coagulate
Was washed with water and dried to give a white powder of graft copolymer B-13.
I got the end. In the example described in B-1, an acrylic resin
Monomer mixture to be grafted to
44 parts of monomer, 176 parts of acrylonitrile, t-dodecy
Replaced with a monomer mixture consisting of 1.5 parts of rumercaptan
Otherwise, the graft polymerization reaction is performed in the same procedure as described in the same example.
As a result, a white powder of the graft copolymer B-14 was obtained. In the example described in B-1, the acrylic resin
Monomer mixture to be grafted to
198 parts of monomer, 22 parts of acrylonitrile, t-dodecy
Replaced with a monomer mixture consisting of 0.2 parts of rumercaptan
Otherwise, the graft polymerization reaction is performed in the same procedure as described in the same example.
Was carried out to obtain a white powder of a graft copolymer B-15. In the example described in B-1, the acrylic resin
The polymer B1-1 is enlarged in particle size using acetic anhydride.
And the weight average particle diameter was changed to 0.50 μm.
Otherwise, the graft polymerization reaction was performed in the same procedure as described in the same example.
To obtain a white powder of the graft copolymer B-16.
Was. In the example described in B-1, the acrylic resin
Except that the polymer was replaced with B1-6.
The graft copolymerization reaction is performed according to the same procedure, and the graft copolymer
A white powder of B-17 was obtained. Graft copolymer B-1
Table 3 shows the details of the production of B-17. 3: Production of hard copolymer (C)C-1 Curved turbine type stirring device, heating and cooling device, thermometer, and
Stainless steel autocrate equipped with each raw material and auxiliary additive equipment
Autoclave
The inside gas phase was replaced with nitrogen gas. [0091] [Table 3]     70 parts of deionized water (parts by weight)     Acrylonitrile monomer 45〃     Styrene monomer (# 1) 10〃     Terpene mixture 0.44４     Di-t-butyl-p-cresol 0.02%     Acrylic acid / 2-ethylhexyl acrylate copolymer (suspension stabilizer)                                                 0.03 〃     Sodium bromide 0.4 〃 While stirring, the internal temperature of the autoclave was adjusted to 106
° C and dissolved in a small amount of styrene monomer.
Add 0.15 parts of azo-cyanocyclohexane and add
The polymerization reaction was started at the temperature. Immediately after starting polymerization
And 36 parts of styrene monomer (# 2) for 4 hours and 30 minutes
It is necessary to continuously add to the polymerization system at a constant rate,
Sometimes, it took 4 hours and 30 minutes to raise the internal temperature to 128 ° C. End of continuous addition of styrene monomer to polymerization system
Thereafter, it took 45 minutes to raise the internal temperature to 145 ° C. Polymerization
5 hours and 15 minutes after the start, the internal temperature of the autoclave was raised to 1
Perform stripping for 1 hour while maintaining at 45 ° C.
Unreacted monomer was recovered. After this stripping,
The internal temperature of the autoclave is cooled down, filtered, washed with water, and dried.
After drying, a bead-shaped hard copolymer C-1 was obtained. Hard joint
The acrylonitrile content (AN%) of the polymer C-1 is:
39.9%. [0094]C-2 SAN-L manufactured by Monsanto Kasei Co., Ltd. (AN% = 30)
%) Was used as is. [0095]C-3 In the example described in C-1, the acrylonitrile monomer is
70 parts, 3 parts of styrene monomer (# 1) and styrene
Same as in the example except that the monomer (# 2) was replaced with 27 parts
The reaction was carried out in the same manner as above, and the hard copolymer C-3
I got Acrylonitrile content of hard copolymer C-3
(AN%) was 69.9%. [0096]II. Production of the composition Examples 1 to 19 Graft copolymer obtained by the method described in the above Production Example
A, graft copolymer B and hard copolymer C were prepared as shown in Table 4
According to the mixing ratio (parts) described in
To form pellets of the copolymer resin composition
did. From the pellets of the copolymer resin composition,
Injection molding and compression molding methods for measuring physical properties and chemical resistance
A test piece for a property test was formed. Mel about pellets
Flow rate for Izod injection molded specimens
Impact resistance and chemical resistance of compression molded test pieces
Measured. The results are as shown in Table-4. [0098]Comparative Examples 1 to 15 Graft copolymer obtained by the method described in the above Production Example
A, each of the graft copolymer B and the hard copolymer C
In Example 1 according to the blending ratio (parts) described in Table-5.
As well as kneading using a Banbury mixer.
Thus, pellets of the copolymer resin composition were prepared. The melt flow rate for the pellets is
Izod impact strength, compression molding for injection molded test pieces
The test pieces were measured for chemical resistance. result
Is as shown in Table-4. In the following Table-1 to Table-5
Abbreviations have the following meanings. [0100] [Table 4][0101] [Table 5] [0102] [Table 6] [0103] [Table 7][0104] [Table 8][0105] [Table 9][0106] [Table 10][0107] [Table 11][0108] [Table 12] ST = styrene monomer AN = acrylonitrile monomer MMA = methyl methacrylate monomer BA = butyl acrylate monomer AMA = allyl methacrylate monomer TDM = t-dodecyl mercaptan [0109]Table-1 to Table-5It is clear that
Become. (1) The thermoplastic resin composition according to the present invention has an impact strength and
And workability,In various physical propertiesBalance
(Examples 1 toSee Example 17). (2) The thermoplastic resin composition according to the present inventionFromIn appearance
A molded article having excellent chemical resistance is obtained (Examples 1 to 5).
See Example 17).(3) In contrast, the requirements defined in the claims of the present invention
Unsatisfactory thermoplastic resin composition has impact strength and processability
Both are unbalanced and inferior to those of the examples
(See Comparative Examples 1 to 15). (4) Do not satisfy the requirements specified in the claims of the present invention.
From thermoplastic resin composition, both appearance and chemical resistance
Excellent molded products cannot be obtained. In addition, obtained from Comparative Example 11
Molded products are excellent in both appearance and chemical resistance.
Poor impact strength and impractical (see Comparative Examples 1 to 15)
See). [0110] The thermoplastic resin composition according to the present invention is characterized in that:
Constant graftCopolymer A,as well asGraft copolymer BIf
And hard copolymer CIs eachBe a certain ratio
So it could not be obtained with the conventional thermoplastic resin composition
Excellent workability, impact resistance and chemical resistance.
Has a very large industrial utility value.

Continuing on the front page (72) Inventor Takeshi Watanabe 1 Toho-cho, Yokkaichi-shi, Mie Pref. Monsanto Kasei Co., Ltd. (72) Inventor Yuichi Kanayama 1-Tohocho, Yokkaichi-shi, Mie pref. References JP-A-4-170460 (JP, A) JP-A-60-118733 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 55/02 C08L 25/12 C08L 51 / 00

Claims (1)

(57) [Claim 1] A graft copolymer A, a graft copolymer B and a hard polymer C shown below are mixed with a composition ratio of the following formulas (1) and (2). A thermoplastic resin composition, characterized in that: Graft copolymer A : Graft copolymer A is defined as follows. Weight average particle size is 0.15
In the presence of 100 parts by weight (based on solid content) of a diene-based rubbery polymer latex of about 0.45 μm , 40 to 80% by weight of an aromatic vinyl monomer and 20 to
60 wt%, and it is a graft copolymer obtained by emulsion polymerization of a monomer mixture from 45 to 450 parts by weight of a copolymerizable therewith other vinyl monomer 0 to 20 wt% as possible, the graft Polymer B : The graft copolymer B is as defined below. (1) In the presence of 100 parts by weight (based on solid content) of an acrylic rubbery polymer latex having a weight average particle diameter of 0.05 to 0.50 μm, an aromatic vinyl monomer of 60 to 80 weight
% , 20 to 40% by weight of vinyl cyanide monomer, and 200 parts by weight or more of a monomer mixture composed of 0 to 20% by weight of another vinyl monomer copolymerizable therewith. (2) an ester compound 7 of a monohydric alcohol having 2 to 12 monovalent alcohols and acrylic acid, wherein the acrylic rubbery polymer is a graft copolymer;
0 to 100% by weight, 0 to 30% by weight of another vinyl monomer copolymerizable therewith, and 0 to 3 of a polyfunctional vinyl monomer.
A polymer obtained by emulsion polymerization of a monomer mixture consisting of 100% by weight. Hard polymer C: Hard polymer C is defined as follows. (1) A monomer composed of 40 to 80% by weight of an aromatic vinyl monomer, 20 to 60% by weight of a vinyl cyanide monomer, and 0 to 20% by weight of another vinyl monomer copolymerizable therewith. A hard polymer obtained by polymerizing a mixture. (Equation 1) (Equation 2)