JPH03174421A - Multilayered structure polymer and resin composition - Google Patents

Abstract

PURPOSE:To obtain a multilayered structure polymer of excellent weathering resistance by forming a multilayered structure polymer having specified properties and comprising alkyl (meth)acrylate units, unsaturated nitrile units and aromatic vinyl units. CONSTITUTION:A multilayered polymer comprising 2-30wt.% alkyl methacrylate units, 50-80wt.% alkyl acrylate units, 5-20wt.% unsaturated nitrile units and 5-40wt.% aromatic vinyl units, wherein said polymer is constituted so that it may consist of annular inner and outer layers, the mean diameter of the inner part of the inside ring may be 2000-6500Angstrom , the average thickness of the outer layer circulating the inner part may be 200-500Angstrom , a plurality of very small particles may be dispersed in the entire inner part, the degree of swelling of the acetone-insoluble part in methyl ethyl ketone may be 1.5-10, and the tensile modulus may be 1000-10000kg/cm<2>.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention provides a novel multilayer structure polymer with excellent weather resistance, etc.
The present invention also provides a thermoplastic resin composition containing the multilayer structure polymer and having excellent weather resistance, impact resistance, and appearance.

(Conventional technology) Among plastics, polycarbonate and methacrylic resin have relatively good weather resistance, but these resins have poor mechanical strength, processability, price, etc.
The scope of application is narrowed because the balance is not necessarily well-balanced.

On the other hand, ABS resin is widely used in fields such as automobiles and electrical parts due to its excellent impact resistance, excellent balance of mechanical properties, ease of molding, and relatively low price. . However, on the other hand, ABS resin has a drawback in weather resistance because it uses polybutadiene as one of the groove bottom components, making it unsuitable for outdoor use. It has been a long-awaited demand for the appearance of plastics that can be used for a variety of purposes.

From this background, it has been considered to use rubbers other than diene-based rubbers, and various proposals have been made to use saturated rubbers. Acrylic ester polymers are one example of this, and although this method improves weather resistance, it also causes a decline in impact resistance and appearance of molded products, leaving practical problems. there were.

For example, Japanese Patent Publication No. 55-27576 discloses a method for producing a multistage, sequential structure polymer consisting of a hard polymer in the first stage, a rubber-like elastic polymer in the intermediate stage, and a hard polymer in the third stage. However, in this method, a grafting agent and a crosslinking agent are used in the first step to provide a low haze impact resistant resin composition.

However, this resin composition has low impact strength, which limits its practical use.

Further, Japanese Patent Publication No. 59-36645 discloses a method for producing a multi-stage polymer consisting of meccrylic acid ester and acrylic acid ester, but it is insufficient in impact strength.

(Intelligence to be Solved by the Invention 8) In view of the current situation, the present invention provides a novel multilayer structure polymer that does not have the above-mentioned problems, that is, has excellent weather resistance, and The object of the present invention is to provide a thermoplastic resin composition having both impact resistance and excellent appearance.

(Means for Solving the Problems) That is, the present invention provides: (1) (a) methacrylic acid alkyl ester unit, (D
) acrylic acid alkyl ester units, (c) unsaturated nitrile units, and (d) aromatic vinyl units. It consists of two layers, an inner layer and an outer layer, in a ring shape, and the average diameter of the inner layer [βN] inside the ring is 2,000 to 6,500 people, (bl The outer layer (α layer) surrounding the inner layer in a ring shape A multilayer structure polymer characterized in that the average thickness of the portion is 200 to 500 Å, and (C) a plurality of small particles (7 layers) are further microdispersed throughout the inner layer portion, ( d) Moreover, its composition is (a) 2 to 30% by weight of methacrylic acid alkyl ester units, (b) 50 to 80% by weight of acrylic acid alkyl ester units, (c) 5 to 20% by weight of unsaturated nitrile units, (ni) ) Aromatic vinyl units 5-4
0% by weight, (e) the degree of swelling of the acetone-insoluble portion with respect to (i) methyl ethyl ketone is 1.5 to 10, and (b+) the tensile modulus is 1. 000-10.
000 kg/c, and (2) the multilayer structure polymer according to claim (1) (
A) and one or more thermoplastic resins (8) having a Tg of 60°C or more (C), comprising (e
) ° The acetone-insoluble part of the resin composite sole (C) has (a) a degree of swelling in methyl ethyl ketone of 1°5 to 10, and (b+) a tensile modulus of 1,000 to 10,000.
kg/ci, and is excellent in weather resistance, impact resistance, etc., and (3) the thermoplastic resin having a Tg of 60°C or higher is: ■ polycarbonate resin, ■ methacrylic resin, ■ non-containing resin. Saturated nitrile-aromatic vinyl copolymer, unsaturated dil
-IJ-aromatic vinyl-N-substituted maleimide terpolymer; (1) one or more selected from the group consisting of unsaturated nitrile-aromatic vinyl-acrylic acid alkyl ester terpolymer; The resin composition, which is a resin consisting of a combination of the following, also has characteristics.

The present invention will be explained in more detail.

A. Multilayer structure polymer; (2) Composition of the multilayer structure polymer; The multilayer structure polymer in the present invention includes (a) methacrylic acid alkyl ester units, (0) acrylic acid alkyl ester units, ( It is a multilayer structure polymer consisting of (c) unsaturated nitrile units and (c) aromatic vinyl units, and (v) also containing a polyfunctional crosslinking agent.

Examples of the (a) methacrylic acid alkyl ester unit constituting the multilayer structure polymer include methyl methacrylate, ethyl methacrylate, and propyl methacrylate, with methyl methacrylate being particularly preferably used.

(Example) Examples of the acrylic acid alkyl ester unit include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and butyl acrylate is preferably used.

(c) Examples of the unsaturated nitrile unit include acrylonidrile and methacrylonitrile, with acrylonitrile being preferably used.

Examples of the (=) aromatic vinyl unit include styrene, α-methylstyrene, and halogenated styrene, with styrene being preferably used.

Furthermore, (ne) polyfunctional crosslinking agents include crosslinking monomers having at least two C-C double bonds, such as triallyl isocyanurates such as triallyl cyanurate and triallyl isocyanurate, and unsaturated alcohols. Esters with: Divinyl compounds such as divinylbenzene; commonly known crosslinking agents such as diallyl compounds and dimethacrylic compounds such as ethylene glycol dimecrylate can be used, but triallylisocyanurate is preferably used.

■, composition ratio of the multilayer structure polymer, etc.; On the other hand, the m acid ratio of the multilayer structure polymer is basically (a)
2 to 30% by weight of methacrylic acid alkyl ester units, preferably 5 to 15% by weight, (D) 50 to 80% of acrylic acid alkyl ester units, preferably 55 to 70% by weight, (c) unsaturated nitrile units 5 ~20% by weight, preferably 6-10% by weight, (=) 5-4 aromatic vinyl units
0% by weight, preferably 8-35% by weight.

If it deviates from this range, it is unfavorable in terms of impact resistance.

In addition, the degree of swelling of the acetone-insoluble portion with respect to methyl ethyl ketone is 1.5 to 10, and the tensile modulus is 1.0.
00-10. 000kg/c+J.

If it deviates from this range, a product with poor impact resistance will be obtained, which is not preferable.

(2) Fine structure of the multilayer polymer; The multilayer polymer of the present invention has a structure in which a plurality of seven layers are microscopically dispersed in the β layer, and the average diameter of the β layer is 2. It has a very special structure: 000 to 6,500 people, and the average thickness of the alpha layer surrounding it is 200 to 500 people.

It is thought that this special structure greatly improves surface gloss while maintaining impact resistance and weather resistance.

This was difficult to expect from the multilayer structures that have been proposed in the past.

On the other hand, in the method disclosed in Japanese Patent Publication No. 47-109811, when a grafting agent or crosslinking (crosslinking) agent such as allyl methacrylate is used during the first stage of polymerization of the hard polymer, β In the layer portion, the first stage (crossed) hard polymer, which is not dyed with osmic acid, exists in a spherical shape. More specifically, there is a part where small particles of the γ layer are microdispersed in the β layer, and a part where the 7th layer does not exist at all (independent).
This results in a multilayered polymer containing two regions of spherical parts.

In this case, a significant decrease in impact strength is a problem.

Therefore, in the multilayer structure polymer of the present invention, if the β layer is not covered with the α layer, a polymer with poor impact resistance and weather resistance will be obtained, and a plurality of seven layers will be formed in the β layer portion. If the particles are not dispersed into individual particles, it will not be possible to obtain a product that satisfies both surface gloss and impact resistance.

Furthermore, the average diameter (particle size) of the β layer is 2. 000～
Must have 6,500 people, preferably 2,50
It is 0 to 4,000 Å. The average diameter of the β layer is 2,000
Impact resistance is not sufficient for less than 6.50OA
Even if it exceeds 20%, a product with poor impact resistance can be obtained.

In addition, the average thickness of the α layer surrounding the β layer is 200
~500 people are required, preferably 300-400 people. If the average thickness of the α layer is less than 200 Å, the impact resistance will be poor, and if it exceeds 500 λ, the gloss will be significantly reduced.

In the multilayer structure polymer of the present invention, in order to microdisperse a plurality of γ layers in the β layer, the composition, molecular weight, crosslink density, and distance between crosslinking points of the β layer should be appropriate. is necessary.

In the multilayer structure polymer of the present invention, a plurality of γ layers are microscopically dispersed throughout the β layer means that a plurality of 7-layer small particles are dispersed relatively evenly throughout the β layer. Therefore, as in the conventional multilayer structure mentioned above, γ is present in the β layer.
If the layer contains two regions: a part where the small particles of the layer are dispersed in the fruit black, and a spherical part where no seven layers are present (independent), it cannot be said that the entire layer is microdispersed.

In case B, where a plurality of seven layers are microdispersed throughout the β layer, it is preferable that a plurality of seven layers are uniformly microdispersed throughout the β layer, but the present invention is not limited to this. Further, the number of small particles in the seven layers is not particularly limited and may be any number, but it is more preferable that a relatively large number of small particles be uniformly microdispersed.

Furthermore, it is preferable that the small particles of this γ layer have a relatively uniform size, but it is acceptable if there is some variation.

(2) Method for producing a multilayer structure polymer: The method for producing a multilayer structure polymer of the present invention can use a known emulsion polymerization method carried out in the presence of a seven-mer emulsifier, a polymerization initiator, a chain transfer agent, etc. It's advantageous.

Furthermore, in order to form such a multilayer structure polymer, it is advantageous to use a seed polymerization method in which a multilayer structure polymer can be formed by sequentially adding and reacting each monomer or monomer mixture. be.

The method for producing the multilayer structure polymer of the present invention is specifically shown below.

1st stage polymerization> A monomer mixture of 2 to 301% by weight of alkyl methacrylate and 1 to 6% by weight of alkyl acrylate is added with an emulsifier and a polymerization initiator at a monomer/water ratio of 0.3.
Polymerize at ~i, o.

Note that if a crosslinking agent or a grafting agent is used at this stage, the impact resistance will be lowered.

<Second Stage Polymerization> A part of the seed latex obtained in the first stage is polymerized with the same monomer mixture as in the first stage, and the particle size can be controlled. This second stage polymerization can also be omitted.

Third Stage Polymerization> A monomer solution containing 45 to 70% by weight of an acrylic acid alkyl ester and 0.05 to 5% by weight of a crosslinking agent is emulsion polymerized together with an emulsifier and a polymerization initiator.

4th stage polymerization〉 Acrylic acid alkyl ester 4-8% by weight unsaturated 2)
IJ Lu 4-8% by weight aromatic vinyl
2-5% by weight crosslinking agent o,
A monomer solution containing oos to 0.5% by weight is subjected to emulsion polymerization together with an emulsifier and a polymerization initiator.

<5th stage polymerization> Acrylic acid alkyl ester 0-2% by weight aromatic vinyl 1-16% by weight unsaturated nitrile
A 3 to 38% by weight monomer solution is emulsion polymerized together with an emulsifier and a polymerization initiator.

At this time, when conducting the third and subsequent stages of polymerization, it is necessary to select conditions that suppress the generation of new particles as much as possible, but for this, the amount of emulsifier used must be adjusted to the critical straw cell concentration. This can be achieved by making it less than Moreover, the presence or absence of new particle generation can be confirmed by observation using an electron microscope.

In addition, in order to control the particle size (diameter) of each layer of the multilayer structure polymer within a specific range, a part of the seed latex of the innermost layer hard polymer (obtained in the first stage polymerization) is removed. This can be done by adjusting the amount of seed latex taken out and controlling the number of particles of the seed latex when continuing seed polymerization by adding ion-exchanged water, an emulsifier, and a sulfuric acid.

The appropriate polymerization temperature for forming the polymer and/or copolymer in each polymerization step is 30-120°C for each polymerization step.
"C1 is preferably selected in the range of 50 to 100°C.

There are no particular restrictions on the emulsifier used in the polymerization, and any emulsifier can be selected from conventionally used emulsifiers.For example, C! ~Ctz carboxylic acids, C
Examples include anionic emulsifiers of 1 to C0 alcohols or sulfonates of alkylphenols, nonionic emulsifiers with alkylene oxide added to aliphatic amines or amides, and cationic emulsifiers such as quaternary ammonium-containing compounds. Preferably, carboxylic acid salts, alkylbenzene sulfonate salts, and the like are used.

In addition, there are no particular restrictions on the polymerization initiator used at this time; for example, water-soluble peroxides such as alkali metal salts of persulfuric acid and ammonium salts; inorganic initiators such as perborates; and hydrogen peroxide. , azo-based compounds such as abbisbutyronitrile can be used alone or in combination with sulfites, thiosulfates, etc. as redox initiators. Additionally, redox initiators such as oil-soluble organic peroxides/ferrous salts, organic peroxides/sodium sulfoxylates can also be used.

Furthermore, examples of the chain transfer agent used include alkyl mercaptans such as t-dodecyl mercaptan, toluene, xylene, chloroform, halogenated hydrocarbons, and the like.

Regarding the method of adding monomers, it is possible to add monomers in batches, but it is better to add the monomers in several portions or to add them continuously.In that case, the polymerization reaction can be controlled, and superheating and coagulation can be avoided. can be prevented.

When producing the multilayer structure polymer of the present invention advantageously, each layer may be prepared by a method adjusted as follows.

The rubber-like elastic body may be formed by completing the polymerization reaction of the acrylic ester cross-linked product and then adding a rubber-like elastic body monomer and polymerizing sequentially, or by completing the polymerization of the acrylic ester cross-linked product. unsaturated nitrile (c), aromatic vinyl (=), with unreacted monomer remaining.
A rubber-like elastic body may be formed by adding the like.

(V) Others: The multilayer structure polymer with a special structure obtained by such a polymerization method can be transformed into particles by performing treatments such as salting out, washing, drying, etc. from the polymer latex state by a known method. Obtained as a solid.

Such multilayer polymers are usually obtained as a mixture of the pure multilayer polymer itself, which is insoluble in solvents such as acetone, and non-grafted polymers, which are soluble in solvents such as acetone. The multilayer structure polymer mentioned above includes the multilayer structure polymer itself and a mixture of the multilayer structure polymer and the above-mentioned non-grafted polymer.

The multilayer structure polymer having a special structure of the present invention is basically obtained by the polymerization method as explained in (rV) above, but the characteristics of the polymer obtained at each polymerization step are: The polymer obtained in the second stage polymerization serves to increase the elastic modulus of the multilayer structure polymer, and is also important in seed polymerization in terms of determining the final particle size of the multilayer structure polymer.

In particular, if a grafting agent or crosslinking agent is present during the first stage polymerization, only a multilayer structure polymer with low impact resistance can be obtained.

■ The acrylic acid ester crosslinked product mainly obtained in the third stage polymerization plays the role of imparting impact strength.

■ The rubber-like elastic body obtained mainly in the fourth stage polymerization is a combination of the hard polymer in the first and second stage polymerization, the acrylic ester crosslinked product in the third stage polymerization, and the final polymer. It serves to improve the adhesion between.

■ The final polymer obtained in the final stage of polymerization serves to improve the compatibility with the thermoplastic resin to be further blended.

B. Structure of thermoplastic resin composition containing multilayer structure polymer: Multilayer structure polymer (A) of the present invention thus obtained
is blended with a thermoplastic resin, preferably a thermoplastic resin (B) having a Tg of 60° C. or higher, to provide a thermoplastic resin composition (C) that is excellent in weather resistance, impact resistance, and appearance. can.

The blending ratio of both is not particularly limited and varies depending on the type and purpose of the thermoplastic resin (C) used, but generally a range of 5 to 95% by weight of each can be effectively used.

If the multilayer structure polymer (A) is less than 5% by weight, it will not be effective in improving impact resistance, and if it exceeds 95% by weight, rigidity and
Heat resistance etc. decrease.

In the present invention, thermoplastic resins having a Tg of 60°C or higher include: (1) polycarbonate resin, (2) methacrylic resin, (2) unsaturated nitrile-aromatic vinyl copolymer,
■ One or two selected from the group consisting of unsaturated nitrile-aromatic vinyl-N-phenylmaleimide terpolymer, and unsaturated nitrile-aromatic vinyl-acrylic acid alkyl ester terpolymer. Resins consisting of a combination of more than one species can be preferably used.

Furthermore, these thermoplastic resins will be specifically explained.

■ As polycarbonate resin, 22'-(4,
4°-dihydroxy-diphenyl)-propane polycarbonate and 4,4″-dioxydiallylalkane-based polycarbonate can be preferably used.

■ Methacrylic resins refer to homopolymers of methacrylic esters or copolymers of methacrylic esters and acrylic esters.Methacrylic esters include methyl methacrylate, ethyl methacrylate,
Examples include methacrylic acid alkyl esters such as propyl methacrylate, or methacrylic acid aromatic esters such as phenyl methacrylate and hensyl methacrylate, and the use of methyl methacrylate is particularly preferred.

Examples of acrylic esters include acrylic alkyl esters such as methyl acrylate, ethyl acrylate, and butyl acrylate, and aromatic acrylic esters such as phenyl acrylate and benzyl acrylate. , ethyl acrylate and butyl acrylate are preferably used.

The copolymer of methacrylic ester and acrylic ester preferably contains 80 to 99% by weight of methacrylic ester units and 1 to 20% by weight of acrylic ester units.

■ Unsaturated nitrile-aromatic vinyl copolymers include unsaturated nitriles such as acrylonitrile and methacrylonitrile, especially acrylonitrile, and aromatic vinyls such as styrene, α-methylstyrene, vinyltoluene, and halogenated styrene, especially Examples include copolymers with styrene.

This unsaturated nitrile-aromatic vinyl copolymer is produced by conventional solution polymerization, suspension polymerization, or emulsion polymerization of unsaturated nitrile and aromatic vinyl.

The unsaturated nitrile-aromatic vinyl copolymer preferably contains 20 to 50% by weight of unsaturated nitrile units.

■ The unsaturated nitrile-aromatic vinyl-N-substituted maleimide terpolymer has 5 to 4 unsaturated nitrile units.
0% by weight, preferably 10-30% by weight, 30-70% by weight, preferably 35-60% by weight of aromatic vinyl units and 26-50% by weight, preferably 26-40% by weight of N-substituted maleimide units. Preferably.

Examples of the unsaturated nitrile and aromatic vinyl constituting the terpolymer are the same as in the case (2) above.

Examples of N-1 substituted maleic compounds include those having a structure represented by the general formula: (wherein R is an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group), for example, N- Examples include methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-chlorophenylmaleimide, and the like. Among these, N-phenylmaleimide is particularly preferred from the viewpoint of improving heat resistance, easy availability, economical efficiency, and the like.

The terpolymer is produced by polymerizing unsaturated nitrile, aromatic vinyl, and N-7-substituted maleic acid by conventional solution polymerization, suspension polymerization, or emulsion polymerization.

If the aromatic vinyl unit content is less than 30% by weight, the mechanical strength will be low, and if it exceeds 70% by weight, the heat resistance will decrease. Furthermore, if the content of unsaturated nitrile units is less than 5% by weight, mechanical strength will be low, and if it exceeds 40% by weight, heat resistance will decrease. Furthermore, if the content of N-substituted maleigodo units is less than 26% by weight, the effect of improving heat resistance will not be sufficiently exhibited, and if it exceeds 50% by weight, mechanical strength will decrease.

■ The unsaturated nitrile-aromatic vinyl-acrylic acid alkyl ester terpolymer contains 20-50% by weight of unsaturated nitrile units, 5-15% by weight of acrylic acid alkyl ester units, and 35-75% by weight of aromatic vinyl. % is preferred.

Examples of the unsaturated nitrile and aromatic vinyl constituting the terpolymer are the same as in the case (2) above.

Further, the alkyl acrylate is the same as in the case (2) above, but it is particularly preferable to use butyl acrylate.

The multilayer structure polymer (A) and the thermoplastic resin (B) having a Tg of 60″C or more are melt-kneaded in a commercially available single-screw extruder or single-screw extruder to obtain the resin composition of the present invention. be able to.

Such a resin &111'Ii of the present invention can be easily separated into the above-mentioned multilayer structure polymer (A) which is insoluble in a solvent such as acetone and the above-mentioned thermoplastic resin (B) which is soluble in the acetone. Note that the thermoplastic polymer produced as a mixture with the multilayer structure polymer (A) without being grafted during the polymerization of the multilayer structure polymer (A) is an acetone-soluble component].

Therefore, the acetone-insoluble part [multilayer structure polymer (A)]
The degree of swelling with respect to methyl ethyl ketone is 1.5 to 10, and the tensile modulus is 1,000 to 10. 000
kg/ci.

If it deviates from this range, a product with poor impact resistance will be obtained, which is not preferable.

When kneading to obtain the resin composition of the present invention, ultraviolet absorbers, stabilizers, lubricants, fillers, reinforcing agents, dyes, pigments, etc. can be added as necessary.

By injection molding or extrusion molding the composition of the present invention thus obtained, a molded article with excellent surface gloss and impact resistance can be obtained.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited in any way by this.

Note that measurements in Examples and Comparative Examples were performed using the following methods or measuring instruments.

(i) Izot impact strength, based on ASTM D256; (i) Preparation of specimen for electron microscopy; The average diameter of the β layer and the average thickness of the α layer of the multilayer structure polymer of the present invention are measured as follows.

That is, the multilayer structure polymer is PMMA (Delpet 8ON
AS-30, 30m manufactured by Nakagama Kikai Seisakusho
Knead using a 1φ twin-screw extruder. Next, an ultra-thin section of 0.5 an square or less is prepared, and the surface is cut and finished using a diamond knife. This sample was exposed to the vapor of a 1% ruthenic acid aqueous solution for several hours in a closed container in a light-shielded state for staining.

When this composition is observed with an electron microscope, it has a seabird structure, and the island part consists of a part that is stained with ruthenium and a part that is not.The part that is not stained with ruthenic acid is the β layer, and the part outside the β layer is the β layer. The part surrounding the layer in a ring shape and dyed with ruthenic acid is called the α layer, and the small particles in the β layer, which are dyed with ruthenic acid and dispersed in plurality, are called the γ layer.

■ Average diameter (particle size), average thickness: As mentioned above, prepare transmission electron micrographs (100,000x magnification) of ultrathin sections of samples cut from the molded product and stained with ruthenic acid, and randomly The diameters of 100 particles selected in 1 were measured, and the arithmetic mean of the measurements was taken as the average diameter (particle diameter).

At this time, if the particle cannot be considered spherical, determine its major axis and minor axis, and calculate the arithmetic average value as the average diameter (particle diameter).
And so.

The thickness was similarly measured for 100 randomly selected particles, and the results were arithmetic averaged to obtain the average thickness. At this time, if the thickness is uneven, the maximum thickness and minimum thickness were measured, and the arithmetic average value was taken as the thickness.

■ Swelling degree: Add 30% of methyl ethyl ketone to about 0.5 g of pellets, soak at 25°C for 24 hours, shake for 5 hours, and incubate at 5°C for 1 hour.
Centrifuge at 8,000 rpm for 1 hour. After removing the supernatant liquid by decantation, add 30 m of methyl ethyl ketone, shake at 25°C for 1 hour, and incubate at 5°C at 18°C.
, OO rpm for 1 hour. Remove the supernatant and weigh the weight (W,). Thereafter, vacuum drying was performed at 100° C. for 2 hours, and the weight of the residue was weighed (W4).

The degree of swelling is calculated using the following formula.

W, -W.

(2) M1rj2 analysis: The acetone-soluble portion was obtained by pouring the supernatants (A) and (I+) obtained from the acetone separation into a large amount of methanol, and drying the precipitate under vacuum.

For the acetone-insoluble portion, a sample obtained by acetone fractionation was used. Compositional analysis of each sample was performed by pyrolysis gas chromatography.

■ Tensile modulus: The insoluble part obtained by acetone fractionation was compression molded at 150°C to make a film, which had a width of I5±0.5+ni,
A test piece with a thickness of 0.50±0.05a* and a length of 70 ribs was prepared.

Tensile! Measurement was carried out using a V machine at a distance between chucks of 50 strokes and a tensile speed of 50 ron/min.

(2) Surface gloss: Specular gloss was determined based on ASTM-D523-62T at an incident angle of 60 degrees.

■ Weather resistance: Irradiated at 6°C using a Dupanel light control weather meter (UPWL-5 type) manufactured by Suga Test Instruments ■,
A weather resistance acceleration test was conducted using a cycle of swelling and condensation at 0°C.

■ Melt viscosity; After treating the acetone-soluble part with alcohol and drying the precipitate, dissolve it in methyl ethyl ketone to create a 10% by weight polymer solution, put this solution 10a1 into a viscometer, and
The number of seconds of falling was measured in a constant temperature bath at ℃. On the other hand, a viscometer whose viscosity is already known is used with a calibration standard solution (JIS Z8809
- 1978) using the same procedure as above to find the number of falling seconds 1, calculate the pre-viscosity coefficient K using the following formula, and multiply the number of seconds the polymer solution falls by the viscosity coefficient. The viscosity was obtained. The unit is centipoise (Cps)
* M・d.

η. : Viscosity (cps) of standard solution at 25°C t6
: Falling time (sec) of standard solution at 25°C d : 1
Density (g/d) of 00 parts polymer solution: Density (g/cd) of standard solution at 25°C Example 1 (1) Polymerization of the innermost layer of hard polymer (1st stage of seeds)
, 248.3 parts by weight of ion-exchanged water and 0.05 parts by weight of sodium dihexyl sulfosuccinate were charged into the reactor, and after sufficiently purging with nitrogen while stirring, the temperature was raised to 75°C.
Make it. After adding 0.02 parts by weight of ammonium persulfate to this reactor, 8 parts by weight of methyl methacrylate and 2 parts by weight of butyl acrylate.

The mixture was added continuously over 50 minutes. After addition, 0.01 part by weight of ammonium persulfate was further added, and then 75
The reaction continued for 45 minutes at °C. The polymerization rate was 99%.

(2) Polymerization of the hard polymer in the innermost layer (second stage of seeds), 1/4 of the latex obtained in (1) (2°5 in terms of solid content)
186.2 parts by weight of ion-exchanged water and 0.03 parts by weight of sodium dihexylsulfosuccinate were added to the reactor, and after sufficiently purging with nitrogen while stirring, the temperature was raised to bring the internal temperature. Bring to 75℃. After adding 0.02 parts by weight of ammonium persulfate to this reactor, a mixture of 6.0 parts by weight of methyl methacrylate and 1.5 parts by weight of butyl acrylate was continuously added over 50 minutes. After the addition was completed, the reaction was continued at 75° C. for 45 minutes to complete the reaction. The polymerization rate was 98%.

(3) Polymerization of the acrylic acid ester crosslinked product (third stage polymerization), in the presence of the latex of (2), 0 ammonium persulfate,
11 parts O, 0 parts sodium dihexyl sulfosuccinate
．． After adding 05 parts by weight, 63 parts by weight of butyl acrylate,
A mixture of 1.2 parts by weight of triallylisocyanurate as a crosslinking agent was continuously added at 70° C. over 80 minutes.

After the addition was completed, the reaction was further continued at 70°C for 20 minutes. The polymerization rate through the first layer and the second layer was 85%.

(4) Polymerization of rubber-like elastic body (4th stage polymerization), (3)
In the presence of 11 parts by weight of unreacted butyl acrylate and 0.18 parts by weight of triallyl isocyanurate, 0.045 parts by weight of ammonium persulfate and 0.45 parts by weight of sodium dihexylsulfosuccinate were added, and 3 parts by weight of acrylonitrile was added. A mixture of .8 parts by weight, 11.4 parts by weight of styrene, and 0.025 parts by weight of t-dodecylmercaptan was heated at 75°C.
It was added continuously over a period of 90 minutes. The polymerization rate was 93%.

Further, the amount of residual monomer in the latex was measured by gas chromatography, and the copolymerization composition ratio of layer (1) was calculated, and the acrylonitrile/styrene/butyl acrylate ratio was 10/43/47, respectively.

(5) Polymerization of the final polymer (5th stage polymerization): In the presence of the latex of (4), 2.05 parts by weight of acrylonitrile, 8.86 parts by weight of styrene, and 0.02 parts by weight of dodecyl mercaptan. portions of the mixture were added continuously over 70 minutes at 75°C. 85 to further complete the polymerization.
The zero polymerization rate after continuing the reaction at ℃ for 1 hour was 97%.

Further, the amount of residual monomer in the latex was measured by gas chromatography, and the copolymerization composition ratio of the layer (1) was calculated. As a result, the acrylonitrile/styrene/butyl acrylate ratio was 24/65/11, respectively.

The latex thus obtained was poured into a 3% by weight warm aqueous sodium sulfate solution for salting out and coagulation, followed by repeated dehydration and washing, followed by drying to obtain a multilayered polymer.

(6) Resin composition made by tJR; 35 parts by weight of this multilayer structure polymer and ST/AN copolymer (ST/AN=70/30 weight ratio, η3p/C=0
．． 75a/g (0,307a')oo; hrum solution,
25°C)) and 65 parts by weight in a Henschel mixer.
After mixing for a minute, pelletization was carried out at 240'C using a 30+NO+ vented twin-screw extruder (manufactured by Nakayo Kikai, Model A).

The resulting pellets were processed into an in-line screw injection molding machine (
Molding temperature 2 using Toshiba Machine ■ Model IS-75S)
Predetermined test pieces were prepared under the conditions of 50'C1 injection pressure of 900 kgf/c4 and mold temperature of 50°C, and physical properties were measured.

The obtained resin composition also had good surface gloss and impact resistance.

(7) Analysis of multilayered polymers, etc.; (i) Staining with ruthenic acid and observation with an electron microscope: In addition, a test piece was prepared using the method described above, and an ultrathin section stained with ruthenic acid was prepared from the test piece. When observed using a transmission electron microscope, it was found that island phases 2 made of a multilayer polymer were scattered in a groove phase 1 made of a thermoplastic resin, as shown in the schematic diagram in Figure 1. be observed.

The average particle size of Layer 4, which is not dyed with ruthenic acid, is 5,000λ, and the average particle size of the whole island 2 (multilayer structure polymer) is 5.700 Å, which is dyed with ruthenic acid. The average thickness of the α layer 3 is 350 pieces.

In the β layer portion 4 not stained with ruthenic acid, a plurality of portions (7 layers) 5 stained with ruthenic acid were microscopically dispersed throughout.

In addition, considering the characteristics of the monomers for each hard 'jt polymer, monomer for rubber elastic body, and monomer for acrylic acid ester crosslinked body used to polymerize this multilayer structure polymer, (a) β layer portion 4 is butyl acrylate, methyl methacrylate unit for the hard polymer obtained in the 1st and second stage polymerization, and butyl acrylate, crosslinking agent or grafting for the acrylic ester crosslinked product in the third stage polymerization. The agent unit is considered to be the main component, and (+1>
The α layer portion 3 consists of butyl acrylate, styrene, and acrylonitrile units for the rubber elastic body produced in the fourth stage of polymerization, and styrene, acrylonitrile, and remaining butyl acrylate units for the final polymer produced in the fifth stage of polymerization. is considered to be the main component. Furthermore, (c) the 7 layers 5 microscopically dispersed in the 8 layers 4 are formed when a part of the hard components, mainly styrene, charged in the α layer portion 3 flows into the 0 layer 4 and polymerizes. It is thought that the

This mechanism is only a guess, and the reason for this is not clearly clear.

(11) Swelling degree, tensile modulus: The swelling degree of the multilayer polymer with respect to methyl ethyl ketone was 3.5. The tensile modulus of the film is 2,50
It was 0 kg/C-.

(ni) Composition analysis: The results of composition analysis by pyrolysis gas chromatography were as follows: MMA 7.0% by weight, BA 65.9% by weight, 5L20
．． 0% by weight, AN 7.1% by weight.

Comparative Example 1 (1) Polymerization of innermost layer hard polymer (1st stage of seeds)
and (2) polymerization of the innermost layer of hard polymer (seed second stage)
was carried out in the same manner as in Example 1, except that 0.19 part of allyl methacrylate was added.

(Polymerization of acrylic acid ester crosslinked product (third stage polymerization), in the presence of the latex of (2), ammonium persulfate 0.
13 parts by weight, sodium dihexyl sulfuccinate 0.0
After adding 5 parts by weight, a mixture of 63 parts by weight of butyl acrylate and 1.2 parts by weight of triallylisocyanurate as a crosslinking agent was continuously added at 80° C. over 80 minutes. After the addition was completed, the reaction was further continued at 80°C for 90 minutes. Said (1
The polymerization rate was 99.5% throughout the polymerizations 1 to (3).

(4) Polymerization of the final polymer (4th stage polymerization): After adding 0.045 parts by weight of ammonium persulfate and 0.045 parts by weight of sodium dihexyl sulfate in the presence of the latex of (3), acrylonitrile 6 .75 parts by weight, 20.25 parts by weight of styrene, 0.75 parts by weight of L-dodecyl mercaptan.
045 parts by weight of the mixture were added continuously over 160 minutes at 75°C. Further, the reaction was continued at 85° C. for 1 hour to complete the polymerization. The polymerization rate was 98%.

In addition, as a result of measuring the amount of residual monomer in the latex by gas chromatography and calculating the copolymerization composition ratio of layer (1), the acrylonitrile/styrene/butyl acrylate ratio was 25/7510 (5) Analysis etc.: The latex obtained was subjected to the same treatment as in Example 1 and evaluated.

As a result of electron microscopic observation, as shown in the schematic diagram of FIG. 2, island phases 2 made of a multilayer polymer are scattered in a groove phase 1 made of a thermoplastic resin, and the island phases 2 are formed into rings. 2 in shape
The inner layer (β layer) portion 4 inside the ring had an average diameter of 4,900 Å, and the outer layer (α layer) portion 3 surrounding the ring had an average thickness of 340 Å. Example 1 in 8 layers 4
It was not present, and it was not stained by mucoid acid.

An independent spherical N6 with a diameter of 1.200 Å was observed. There was no microdispersed rN5 in this spherical layer 6.

Example 2.3 and Comparative Example 2.3 In Example 1, the seed polymerization was continued by reducing the amount of latex obtained by the first stage seed polymerization of the innermost layer hard polymer. Further, the amount of sodium dihexyl sulfosuccinate in the first seed stage was increased and seed polymerization was continued.

The latex thus obtained was subjected to the same treatment as in Example 1 and evaluated. The results are listed in Table 1.

According to Table 1, the average diameter of the β layer and the average thickness of the α layer are:
2,000 people each, if it is smaller than 200 people, the gloss is excellent but the impact resistance is low;
It can be seen that when the thickness exceeds 6,500 Å, the impact strength is excellent, but the gloss is low.

Comparative Example 4 Using ABS resin (Stylac ABS manufactured by Asahi Kasei Kogyo ■), the results are shown in Table 2 along with the results of a weather resistance acceleration test using a dual-panel light control weather meter.

According to Table 2, it can be seen that the weather resistance of the resin composition of the present invention is superior to that of ABS resin.

Table 2 Comparative Example 5 In the polymerization of the acrylic ester crosslinked product of Example 1,
The same experiment as in Example 1 was conducted except that the crosslinking agent triallyl isocyanurate was not used.

It can be seen that the copolymer without triallylisocyanurate has an Izot impact strength of 2.1 kg-cm/C11 at 23°C, which is significantly inferior to that of Example 1.

When observed by electron microscopy, there was no α layer or β layer.

Example 5 Styrene 65 heavy 161S, N-phenyl male 41118
parts by weight, 17 parts by weight of acrylonitrile, 0.2 parts by weight of t-butyl 2-ethylhexanoate, and 0.1 parts by weight of octyl mercaptan as a monomer layer, 0.05 parts by weight of polyvinyl alcohol, and 200 parts by weight of pure water. A tragic polymerization occurred in the water layer. The zero polymerization rate after polymerizing at 80″C for 5 hours was 98
%Met.

This is called copolymer B-1.

The copolymer composition ratio was determined by nitrogen analysis and H-NMR measurement, and the styrene/acrylonitrile/N-phenylmaleimide content was 65/16/19% by weight, respectively.

Furthermore, after mechanically mixing the multilayer structure polymer obtained in Example 1 and copolymer B-1 so that the butyl acrylate content in the multilayer structure polymer was 22% by weight of the entire resin, , (Multilayer structure polymer A/B-1=35/65% by weight)
The mixture was kneaded in a melt extruder at 250"C and pelletized.

Using this pellet, various test pieces were produced using an injection molding machine, and various physical properties were evaluated. The results are shown in Table 3 below.

From Table 3, it can be seen that the resin composition of the present invention has excellent high impact strength and appearance.

After mechanically mixing the multilayer structure polymer obtained in Example 1 with Depet 8ON (methacrylic resin manufactured by Asahi Kakai Kogyo ■) such that the butyl acrylate content was 22% by weight of the entire resin. , 250'C in a twin-screw extruder and pelletized. Using this pellet, various test pieces were prepared using an injection molding machine, and various physical properties were evaluated.

The physical properties of the blend with methacrylic resin are shown in Table 4 below.

Table 4 (Evaluation of scratch resistance and weather resistance) It can be seen that the resin m-acid of the present invention has excellent high impact strength and excellent appearance.

Example 7 The multilayer structure polymer obtained in Example 1, a polycarbonate resin (manufactured by Mitsubishi Kasei, trade name: Tubarex 7025A), and an acrylonitrile-styrene copolymer (manufactured by Asahi Kakai Kogyo, trade name: Tubarex 7025A).
Product name Nistylac AS-7833, 20 each
After mechanical mixing in a ratio of 150/30% by weight, 280
The mixture was kneaded in a twin-screw extruder at ℃ and pelletized.

Using this pellet, various test pieces were made using an injection molding machine and various physical properties were evaluated. The results are shown in Table 5 below.

Example 8 Multilayer structure polymer obtained in Example 1 and acrylonitrile/styrene/butyl acrylate copolymer (weight ratio 3715
2/11, solution viscosity 10.1 cps) and mechanically mixed so that the butyl acrylate content in the multilayer structure polymer was 22% by weight of the entire resin, and then kneaded with a melt extruder at 250 ° C. Pelleted. Using this pellet, various test pieces were produced using an injection molding machine, and various physical properties were evaluated.

The gel percentage and particle size of the multilayer polymer are listed in Table 1. Further, the physical properties of the blend with acrylonitrile/styrene/butyl acrylate copolymer are listed in Table 6.

Table 6 (Effects of the invention) Thermoplastic resin m using the novel multilayer structure polymer of the present invention
The s product has improved weather resistance compared to conventional ABS resins, etc., and provides an unprecedented new weather and impact resistant resin that has both impact resistance and excellent appearance. .

This resin can be used unpainted for many years in a wide range of applications including automobile parts and electronic parts, especially for outdoor applications where conventionally painted products such as metal materials or ABS resin were used, and it will play a role in these industries. It has a big role to play.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of a transmission electron micrograph of a ruthenic acid-stained ultrathin section of a multilayer structure polymer according to the present invention and a thermoplastic resin composition containing the same, and FIG. 2 is a multilayer structure polymer according to a comparative example. This is a schematic diagram of a transmission electron micrograph of a ruthenic acid-stained ultrathin section of a structural polymer and a thermoplastic resin composition containing the same. 1: groove phase, 2: island phase, 3: α layer, 4: 0 layer. , 5: 7 layers・ , 6: Independent layer, Figure 1

Claims (3)

[Claims] (1) A multilayer structure polymer (A) consisting of (a) methacrylic acid alkyl ester units, (b) acrylic acid alkyl ester units, (c) unsaturated nitrile units, and (d) aromatic vinyl units, The multilayer structure polymer (A) consists of (a) essentially two layers, an inner layer and an outer layer in a ring shape, and an inner layer (
(b) The average diameter of the outer layer (α layer) surrounding the inner layer in a ring shape is 200 to 500 Å, (c) There are also small particles in the inner layer. It is a multilayer structure polymer characterized by having a plurality of (γ layers) microdispersed throughout; (b) 50-80% by weight of acrylic acid alkyl ester units, (c) 5-20% by weight of unsaturated nitrile units, (d) 5-4 aromatic vinyl units.
0% by weight, (e) the acetone-insoluble portion has (a) a swelling degree of 1.5 to 10 in methyl ethyl ketone, and (b) a tensile modulus of 1,000 to 10,000 kg/cm^2. A multilayer structure polymer characterized by the following. (2) The multilayer structure polymer (A) according to claim (1), and T
A resin composition (C) containing one or more thermoplastic resins (B) with g of 60° C. or higher, and (e)' (i) of the acetone-insoluble part of the resin composition (C). ) The degree of swelling with respect to methyl ethyl ketone is 1.5 to 10, and (b) the tensile modulus is 1,000 to 10,000 kg/
A resin composition with excellent weather resistance, impact resistance, etc., characterized by having a thickness of cm^2. (3) The thermoplastic resin having a Tg of 60°C or higher is [1]
Polycarbonate resin, [2] Methacrylic resin, [
3] Unsaturated nitrile-aromatic vinyl copolymer, [4]
Unsaturated nitrile-aromatic vinyl-N-substituted maleimide terpolymer, [5] Unsaturated nitrile-aromatic vinyl-
3. The resin composition according to claim 2, which is a resin comprising one type or a combination of two or more types selected from the group consisting of acrylic acid alkyl ester-based terpolymers.