JPS592463B2 - Manufacturing method of thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a thermoplastic resin composition, particularly a resin composition that has excellent mechanical strength and moldability, and also provides molded articles with low surface gloss.

Acrylonitrile-butadiene-styrene copolymer resin (hereinafter referred to as ABS resin) has traditionally been used for various purposes because it has excellent properties such as mechanical strength, moldability, and chemical resistance, and its molded products have a rich surface gloss. However, for example, for cameras, suitcases, etc., there is a demand for a so-called matte surface with less gloss. Generally, methods for detanning thermoplastic resins include mixing inorganic fillers, such as oxides of titanium, magnesium, and calcium, or their carbonates, with thermoplastic resins, or adding diene-based rubber-like materials to thermoplastic polymer latex. A method of mixing polymer latex has been proposed, but the former does not produce the desired matte state, and what's more? The molded products were inferior in impact strength, and the latter had the disadvantage that the impact strength decreased less than the base thermoplastic resin, but the rigidity decreased significantly.

The present invention aims to solve these drawbacks and
A thermoplastic resin obtained by mixing S resin latex and a specific unsaturated carboxylic acid ester latex in a latex state and then precipitating it as a homogeneous mixture, without reducing the various properties that ABS resin has. , provides a method for producing a thermoplastic resin composition with reduced surface gloss.

That is, the method for producing the thermoplastic resin composition of the present invention includes (A
component), a graft copolymer latex obtained by copolymerizing an aromatic vinyl monomer and an ataryl monomer in the presence of a diene-based rubbery polymer latex; and component (B), one or more types of An unsaturated carboxylic acid ester monomer and a polyfunctional vinyl monomer, or one or more unsaturated carboxylic acid ester monomers, a vinyl monomer copolymerizable therewith, and a polyfunctional vinyl monomer A latex obtained by emulsion polymerization of a mixture consisting of do.

According to the method of the present invention, it is possible to obtain a thermoplastic resin composition that has various properties of conventional ABS resins and has reduced surface gloss of molded products thereof.

This composition is useful in applications requiring the formation of a matte surface, such as cameras, suitcase housings, automobile interior parts, household appliance parts, and other miscellaneous goods.
Component (4) used in the present invention consists of one or more aromatic vinyl monomers and one
It consists of a graft copolymer latex obtained by emulsion polymerization of more than one type of acrylic monomer, and diene rubber-like polymer latex is a graft copolymer latex obtained by emulsion polymerization of acrylic monomers such as butadiene, isoprene, dimethylbutadiene, chloroprene, etc. or emulsion copolymerization of one or more monomers selected from monomers copolymerizable with the diene monomers, such as styrene, α-methylstyrene, acrylonitrile, acrylic esters, methacrylic esters, etc. It is made of latex.

In addition, the aromatic vinyl monomers to be emulsion graft polymerized in the presence of the diene-based rubbery polymer latex include styrene,
α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene,
Monochlorostyrene, dichlorostyrene, etc.

Similarly, the acrylic monomers to be subjected to emulsion graft polymerization include acrylonitrile, methacrylonitrile, acrylic esters, methacrylic esters, and the like. These monomers may be used alone or as a mixture thereof.

Various known methods can be used to emulsion graft copolymerize these monomers, and there are no particular restrictions.

Next, component (B) will be explained.

03) The components are an unsaturated carboxylic acid ester monomer and a polyfunctional vinyl monomer, or an unsaturated carboxylic acid ester monomer, a vinyl monomer copolymerizable therewith, and a polyfunctional vinyl monomer. The unsaturated carboxylic acid ester monomers include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, and diacrylic acid. -Ethylhexyl, 2-hydroxyethyl acrylate 2-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 2-hydroxyethyl acrylate
-Ethoxyethyl, 2-butoxyethyl acrylate, 2-dimethylaminoethyl acrylate, 2-diethylaminoethyl acrylate, glycidyl acrylate, and monomers of these monomers substituted with a cyano group, methyl group, halogen, etc. at the α-position It is one or more types selected from these monomers.

In addition, vinyl monomers copolymerizable with these unsaturated carboxylic acid ester monomers include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, Aromatic vinyl monomers such as monochlorostyrene and dichlorostyrene, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, olefin monomers such as ethylene, propylene, 1-butene, isobutylene, and 2-butene, vinyl acetate, These monomers include aliphatic vinyl ester monomers such as vinyl propylate, halogenated olefin monomers such as vinyl chloride and vinylidene chloride, and vinyl ether monomers such as methyl vinyl ether, ethyl vinyl ether, and phenyl vinyl ether. One or more of the selected types. Particularly preferred combinations include (meth) acrylic ester-vinyl acetate-ethylene, (meth) acrylic ester-vinyl acetate-vinyl ether, (meth) acrylic ester-vinyl acetate, (meth) acrylic ester-styrene etc. can be given.

Addition of a polyfunctional vinyl monomer promotes gelation of the polymer, and an increase in gel-like substances in the component lowers the surface gloss of the molded product of the resulting composition.

Examples of polyfunctional vinyl monomers include ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, propylene glycol dimethacrylate, triallyl cyanurate, triallyl isocyanurate, and trimethylolpropane trimethacrylate. , divinylbenzene, etc. Henceforth. What is particularly important in the present invention is that component (8) has a glass transition temperature of -40 to 5°C, preferably -40 to 5°C. It is to use a polymer in the 0°C range. The reason is that the glass transition temperature is -60℃
This is because a resin precipitated by mixing a latex with a lower temperature than that of component (1) will have a significant decrease in rigidity, and a resin with a temperature higher than 5°C will have a significant decrease in impact strength, which is not preferable. Further, as the component (B), particles whose volume average particle diameter is 0.2 μm or more, preferably 0.5 μm or more are used.

The reason for this is that if the resin is less than 0.2μ, even if the resin is precipitated by mixing latex with component (4), not only will the surface gloss of the molded product not be sufficiently reduced, but the impact strength will also be significantly reduced. It is. In addition, component (8) is present in the dry polymer recovered from the polymer solids, that is, the latex.
It contains 0% by weight of gel, preferably 70% by weight or more.

The gel content referred to herein is determined by the following method. That is, Polymer 17 was added to 100y of methyl ethyl ketone and stirred vigorously for 6 hours at room temperature. This material is centrifuged at 15,000 rpm for 1 hour, and the dry weight of the precipitate is determined. The obtained dry weight is multiplied by 100 to obtain the gel content (% by weight). (B) As a method for gelling the component polymer solid, the purpose can be achieved by adding a small amount of a polyfunctional vinyl monomer during polymerization. Next, component (4) and component I3) are mixed in a latex state to precipitate resin solids.

Examples of precipitating agents include hydrochloric acid and sulfuric acid. Acetic acid, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, aluminum chloride, sodium sulfate, potassium sulfate,
Magnesium sulfate, aluminum sulfate, etc. can be used alone or in combination as an aqueous solution.

The latex to which the precipitating agent has been added is heated and stirred to precipitate it, and is then subjected to dehydration, water washing, and drying steps to form a resin composition. The reason why components (A) and (B) are mixed in the latex in this way in the present invention is that when the latex is precipitated separately and then mixed by a known mechanical mixing means as in the past, it has a lower mechanical strength. As the surface gloss of the molded product decreases, the surface gloss of the molded product becomes non-uniform, and a practically preferable reproducibility cannot be obtained, making it impossible to obtain the desired molded product.

Another method of the present invention is to combine the above (4) component and (
The thermoplastic resin composition comprising component B) is further blended with a copolymer comprising an acrylic monomer and an aromatic vinyl monomer.

That is, another invention comprises (4) component, a graft copolymer latex obtained by copolymerizing an aromatic vinyl monomer and an acrylic monomer in the presence of a diene rubber latex; 8) Component, one or more unsaturated carboxylic acid ester monomers and a polyfunctional vinyl monomer, or one or more unsaturated carboxylic acid ester monomers and a vinyl monomer copolymerizable therewith. and a latex with a glass transition temperature of 5 to -60°C and an average particle size of 0.2μ or more obtained by emulsion polymerization of a mixture consisting of a polyfunctional vinyl monomer; This is a method for producing a thermoplastic resin composition, which is characterized in that a copolymer consisting of an acrylic monomer and an aromatic vinyl monomer is blended into a thermoplastic resin composition obtained by precipitating.

The acrylic monomers constituting the copolymer blended here include acrylonitrile, methacrylonitrile, acrylic esters, methacrylic esters, etc., and the aromatic vinyl monomers include styrene, α-methylstyrene, These include o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, monotalolostyrene, dichlorostyrene, and the like.

When ABS resin is used as component (A), an acrylonitrile-styrene copolymer is preferably used as the copolymer to be blended. When the above copolymer is blended into a thermoplastic resin composition consisting of components (A) and (8), the resin solid content in component (B) is 2 to 30% of the total resin solid content.
The percentage by weight should preferably be between 2 and 20% by weight. When a copolymer consisting of an acrylic monomer and an aromatic vinyl monomer is not blended, the (B) component is mixed with the (4) component and the (self) component in a latex state. The mixing ratio is the resin solid content, i.e.
The dry weight percentage is 2 to 30% by weight, preferably 2 to 20% by weight of the total resin solid content. If the component (B) is less than 2% by weight of the total resin solids in the resin composition, the surface gloss of the molded product will not be reduced sufficiently, and if it exceeds 30% by weight, the rigidity of the molded product will decrease, which is undesirable. . Furthermore, known additives such as a plasticizer L stabilizer, a lubricant, an antistatic agent, and a coloring agent can be added.

The present invention will be further explained with reference to Examples below, and all parts and percentages mentioned in the specification are expressed on a weight basis.

Example 1 (4) Preparation of component Polybutadiene latex (solid content 3) was placed in an autoclave.
0%, volume average particle size 0.3μ), then 120 parts of pure water, 1 part of sodium dodecylbenzenesulfonate, 0.002 part of ferrous sulfate, 0.004 part of tetrasodium ethylenediaminetetraacetate, and sodium 0.12 part of aldehyde sulfoxylate was added and stirred under nitrogen atmosphere.

While keeping the contents at 60°C, a monomer mixture consisting of 45 parts of styrene, 15 parts of acrylonitrile, 0.6 parts of t-dodecylmercaptan, and 0.2 parts of benzoyl peroxide was continuously added to the above latex over 6 hours. did. After the addition of the monomer mixture was completed, the mixture was further stirred at 70° C. for 2 hours to complete polymerization, thereby obtaining an ABS resin latex. (B)
Production of ingredients 2.7 parts of partially saponified polyvinyl alcohol, 0.1 part of sodium acetate, 0.0 ferrous sulfate in a pressure autoclave.
03 parts, tetrasodium ethylenediaminetetraacetic acid 0.00
6 parts, sodium aldehyde sulfoxylate 0.18
An aqueous solution prepared by dissolving 1 part in 80 parts of pure water was added thereto, and then 25 parts of vinyl acetate was added and emulsified while stirring.

After creating a nitrogen atmosphere inside the autoclave, ethylene 15
The part was press-fitted. After heating the contents to 50°C, which is the polymerization temperature, a mixed monomer prepared by dissolving 10 parts of ethylene glycol dimethacrylate in 60 parts of butyl acrylate, and 20 parts of a 0.1% ammonium persulfate aqueous solution were separately added to 8 parts of each. Continuous addition was made over time. After addition, add 7 more
The polymerization was completed by stirring at 0'C for 5 hours. The volume average particle diameter of the obtained latex particles was 0.8μ, and the glass transition temperature of the acrylic polymer recovered from the latex was -
It was 32°C. Manufacture of composite ABS resin After mixing and stirring the latexes of component (A) and component (3) in the ratio (weight) shown in Table 1 as solid content in the latex state, 30 parts of a 10% calcium chloride aqueous solution was added, and the temperature was increased. The mixture was stirred at 100° C. for 5 minutes to obtain a polymer mixture in a slurry state, which was further dehydrated, washed with water, and dried to obtain a polymer mixture.

Next, 100 parts of this polymer mixture was mixed with a commercially available acrylonitrile-styrene suspension polymer (AS resin acrylonitrile content 25%, methyl ethyl ketone 1% solution, relative viscosity ηRell at a temperature of 30°C) in the proportions shown in Table 1.
．． 52).
The two parts were mixed and melted into pellets using an extractor.

A test piece was prepared from this pellet and its physical properties were measured. The results are shown in Table 1. The measured values of the Examples and Comparative Examples described below were all obtained by the following method. ι(1) Tensile strength (yield point) ASTM
2) Izot impact strength ASTM Volume 256 (3) Melt flow index ASTM l}-1238 (
4) Gloss ASTM [}-523(5) Flexural modulus ASTM 790 The molding was performed at a molding temperature of 230°C and a mold temperature of 40°C, and the measurement was performed at an angle of incidence of 60°.

Example 2 Q was carried out in the same manner as in Example 1 except that 60 parts of 2-methoxyethyl acrylate was used in place of 60 parts of butyl acrylate.
3) Component latex was obtained.

The volume average particle diameter of the obtained latex particles was 1 micron, and the glass transition temperature of the acrylic polymer recovered from this latex was -40'C. This component 03) was treated in the same manner as in Example 1 to obtain a test piece, which was then subjected to physical property tests.
The results are shown in Table 2. Example 3 Polybutadiene latex (solid content 3) was placed in an autoclave.
0%, volume average particle diameter 0.45μ), 186 parts of pure water, 3 parts of sodium dodecylbenzenesulfonate, 0.002 parts of ferrous sulfate, 0.004 parts of tetrasodium ethylenediaminetetraacetate, and sodium Aldehyde sulfoxylate 0.12 parts Acrylonitrile 4.8 parts, Styrene 11.2 parts, Benzoyl peroxide 0.
096 parts were added and stirred under nitrogen atmosphere.

After heating the contents to 50°C and holding for 2 hours, 19.2 parts of acrylonitrile, 44.8 parts of styrene, 0.384 parts of t-dodecylmercaptan, and 0.1 part of benzoyl peroxide were added.
The 2 parts monomer mixture was added continuously over a period of 7 hours. After the addition was completed, the mixture was further stirred at 70° C. for 2 hours to complete polymerization, thereby obtaining an ABS resin latex. The ABS resin latex obtained here and the component (8) latex described in Example 1 were mixed in a latte state at the ratios shown in Table 4, and after thorough stirring, a calcium chloride 10 (fl) aqueous solution was prepared. A slurry-like polymer mixture was obtained by stirring at 100° C. for 5 minutes, which was further dehydrated, washed with water, and dried to obtain a polymer mixture. Next, 2,6-
0.3 part of di-t-butyl-4-methylphenol and 0.2 part of triphenyl phosphite were mixed, and the mixture was melted using an extruder to form pellets. A test piece was prepared from this pellet in the same manner as in Example 1, and its physical properties were measured. The results are shown in Table 3. Comparative Example 1 2.7 parts of partially saponified polyvinyl alcohol, 0.1 part of sodium acetate, 0.003 part of ferrous sulfate, 0.006 part of tetrasodium ethylenediaminetetraacetate, and 0.18 part of sodium aldehyde sulfoxylate in a pressure autoclave. An aqueous solution prepared by dissolving 80 parts of pure water was added thereto, and then 40 parts of vinyl acetate and 10 parts of ethyl acrylate were added and emulsified while stirring.

After creating a nitrogen atmosphere inside the autoclave, ethylene 10
The part was press-fitted. After heating the contents to 50°C, which is the polymerization temperature, 40 parts of vinyl acetate and 0.0 parts of ammonium persulfate were added.
20 parts of a 1% aqueous solution were added separately and continuously over a period of 10 hours. After the addition was completed, the mixture was further stirred at 70° C. for 5 hours to complete the polymerization. The volume average particle diameter of the obtained latex particles was 1 μm, and the glass transition temperature of the acrylic polymer recovered from the latex was 17°C. 20 parts as resin solid content of the acrylic polymer latex obtained here and ABS obtained as component (A) in Example 1
80 parts of the resin solid content of the resin latex was mixed in the latex state and stirred thoroughly, followed by precipitation treatment in the same manner as in Example 1 and the resin was recovered. 10 AS resin beads were added to 100 parts of the obtained polymer mixture in the same manner as in Example 1.
A test piece was prepared by mixing 0 parts, and a physical property test was conducted. The results are shown in Table 4. Comparative Example 2 In a pressure autoclave, 1 part of partially saponified polyvinyl alcohol, 2.5 parts of sodium dodecylbenzenesulfonate, 0.003 parts of ferrous sulfate, 0.006 parts of tetrasodium ethylenediaminetetraacetate, and 0.18 parts of sodium aldehyde sulfoxylate. An aqueous solution prepared by dissolving 1 part in 80 parts of pure water was added thereto, and the mixture was stirred under a nitrogen atmosphere.

After keeping the contents at the polymerization temperature of 50°C, a monomer mixture consisting of 83 parts of butyl acrylate, 17 parts of styrene, 5 parts of ethylene glycol dimethacrylate, and 0.2 parts of benzoyl peroxide was continuously added over 12 hours. Added. After the addition was completed, a solution of 0.1 part of benzoyl peroxide dissolved in 4 parts of styrene was added, and the mixture was further stirred at a temperature of 70° C. for 2 hours to complete the polymerization. The volume average particle diameter of the obtained latex particles was 0.1 .mu., and the glass transition temperature of the acrylic polymer recovered from the latex was -5.degree. 20 parts of the resin solid content of the component (3) latex obtained here was mixed with 80 parts of the resin solid content of the component (4) ABS resin latex obtained in Example 1 in a latex state, and the resin was mixed as shown in Example 1. The material was treated using the same method as described above, and physical property tests were conducted. The results are shown in Table 4. Comparative Example 3 30 parts of a 10% calcium chloride aqueous solution was added to 100 parts (as resin solid content) of component (A) obtained in Example 1,
Stir for 5 minutes at 10°C, dehydrate the resulting slurry,
The ABS resin was recovered by washing with water and drying.

In addition, the component (B) obtained in Example 2 was freeze-precipitated at -30°C, which was then dehydrated, washed with water, and dried to recover an acrylic polymer. ABS resin 8 obtained in this way
0 parts and 20 parts of the acrylic polymer were mixed with 100 parts of AS resin beads and treated in the same manner as in Example 1, and a physical property test was conducted. The results are shown in Table 4. The composite ABS resin obtained in this comparative example not only has poor impact strength, but also
The surface condition of the molded product was non-uniform. Comparative example 4 Polybutadiene latex (volume average particle diameter 0.3μ)
20 parts (as resin solid content) and (A
) component latex (80 parts as resin solid content) were mixed in a latex state, treated in the same manner as in Example 1, and tested for physical properties.

The results are shown in Table 4. Top b Ichiko Example 5 ABS resin 100 recovered from latex in Comparative Example 3
120 parts of AS resin beads, 2,6 di-t-butyl-
A mixture of 0.3 parts of 4-methylphenol and 0.2 parts of triphenyl phosphite was melt-kneaded in an extruder,
A pellet-shaped resin was obtained.

This was molded into a predetermined test piece, and a physical property test was conducted. The results are shown in Table 4. 2.7 parts of partially saponified polyvinyl alcohol and 0.1 part of sodium acetate in a pressure autoclave.
An aqueous solution prepared by dissolving 0.003 parts of Onmin ferrous sulfate, 0.006 parts of tetrasodium ethylenediaminetetraacetate, and 0.18 parts of sodium aldehyde sulfoxylate in 80 parts of pure water was added, and then acetic acid was added while stirring. 25 parts of vinyl was added and emulsified.

After creating a nitrogen atmosphere inside the autotaleve, 15 parts of ethylene was injected under pressure. After the contents were heated to the polymerization temperature of 50° C., 60 parts of butyl acrylate and 20 parts of a 0.1% ammonium persulfate aqueous solution were separately added continuously over 8 hours. After the addition was completed, the mixture was further stirred at 7°C for 5 hours to complete the polymerization. The volume average particle diameter of the obtained latex particles was 0.8 .mu., and the glass transition temperature of the acrylic polymer recovered from the latex was -32.degree.
This component (8) was treated in the same manner as in Example 1 to obtain test pieces, which were then subjected to physical property tests.

Claims (1)

[Scope of Claims] 1. Component (A), a graft copolymer latex obtained by copolymerizing an aromatic vinyl monomer and an acrylic monomer in the presence of a diene rubber-like polymer latex; (B) Component, one or more unsaturated carboxylic acid ester monomers and a polyfunctional vinyl monomer, or one or more unsaturated carboxylic acid ester monomers and a vinyl monomer copolymerizable therewith. A latex with a glass transition temperature of 5 to -60°C and an average particle size of 0.2μ or more obtained by emulsion polymerization of a mixture consisting of a polyfunctional vinyl monomer and a polyfunctional vinyl monomer is mixed in a latex state, and then a resin solid A method for producing a thermoplastic resin composition characterized by precipitating a component. 2. Claim 1, wherein the resin solid content in component (B) is 2 to 30% by weight of the sum of the resin solid content in component A and the resin solid content in component (B). A method for producing the described thermoplastic resin composition. 3 Component (A), a graft copolymer latex obtained by copolymerizing an aromatic vinyl monomer and an acrylic monomer in the presence of a diene-based rubbery polymer latex; and Component (B), 1 One or more unsaturated carboxylic acid ester monomers and a polyfunctional vinyl monomer, or one or more unsaturated carboxylic acid ester monomers, a vinyl monomer copolymerizable therewith, and a polyfunctional vinyl A latex with a glass transition temperature of 5 to -60°C and an average particle size of 0.2μ or more obtained by emulsion polymerization of a mixture consisting of monomers; mixed in a latex state, and then precipitating the resin solid content. A method for producing a thermoplastic resin composition, which comprises blending a copolymer comprising an acrylic monomer and an aromatic vinyl monomer into the thermoplastic resin composition obtained. 4 The resin solid content in component (B) is 2 to 3 of the total resin solid content.
The method for producing a thermoplastic resin composition according to claim 3, wherein the thermoplastic resin composition is blended so that the content is 0% by weight.