KR100384380B1 - Weatherproof resin composition with excellent transparency and its manufacturing method - Google Patents

Abstract

The present invention relates to a method for producing a weather resistant resin having excellent transparency. In the present invention, an acrylic acrylate polymer is prepared by administering an emulsifier selected from the group consisting of a vinyl compound, an alkyl sulfosuccinate metal salt derivative, an alkyl sulfuric acid ester, and a sulfonic acid metal salt derivative to an alkyl acrylate. ) A thermoplastic resin is prepared by graft copolymerization by administering an acrylic acid alkyl ester compound, an aromatic vinyl compound, a vinyl cyan compound, and an fatty acid metal salt or a rosin acid metal salt, and the prepared thermoplastic resin is made of polyacrylic rubber latex having excellent weather resistance. By optimizing the refractive index by controlling the mixing ratio of the monomer to graft copolymerization, it has excellent impact resistance, chemical resistance, processability, etc., excellent weatherability and transparency, improves the impact strength, and effectively reduces the moisture in the resin particles dry Productivity can be improved.

Description

Weather resistant resin composition excellent in transparency and manufacturing method thereof

[Industrial use]

The present invention relates to a method for producing a weather-resistant resin excellent in transparency, and more particularly to graft copolymerization of methacrylic acid alkyl esters, aromatic vinyl compounds, and vinyl cyan compounds in polyacrylic rubber latex having excellent weather resistance. By optimizing the refractive index by the impact resistance, chemical resistance, processability and the like and particularly relates to a method for producing a weather resistant resin composition extremely excellent in transparency.

[Prior art]

Recently, as the industry is advanced and differentiation of product models is actively promoted, a lot of researches are being conducted to give high functionality such as transparency to materials used in products. Examples of providing transparency to the material include a PCS transparent window, a washing machine cover for viewing laundry contents, a monitor housing for viewing internal components of a computer monitor, a game console housing, and the like. However, the acrylonitrile-butadiene-styrene (hereinafter referred to as ABS) copolymer resin used for these components is excellent in impact resistance, processability and surface gloss, but is opaque material due to the characteristics of the resin and weather resistance and light resistance. It is not good for use in outdoor use, poor thermal stability, there is a problem that the physical properties are large and chemical resistance is weak as time passes.

On the other hand, ASA (acrylate-styrene-acrylonitrile) resin is excellent in weatherability, chemical resistance and thermal stability, but a large amount of foam (foam) occurs during the polymerization and aggregation, and the moisture content in the ASA particles, the cake (caking) when dehydration after aggregation A phenomenon occurs and a decrease in drying efficiency has been a production problem. In addition, in terms of physical properties, the impact strength is weak, fluidity is low, there is a constraint on the molding, and problems such as pearl color when color matching (color matching) has emerged. Therefore, in actual commercial production, foaming occurs during agglomeration, it is very difficult to dry due to high moisture content in the particles after agglomeration, and low impact strength has been recognized as the biggest technical difficulty to overcome in the production of ASA resin. .

In Japanese Patent Laid-Open No. 5-202264, a method of manufacturing a bimodal type ASA and improving its physical properties includes ASA having a small particle size of 50-200 nm and a large particle size of 200-1000 nm. After preparing ASA, these latexes are blended, and then, a method of blending them with a styrene-acrylonitrile (SAN) copolymer prepared separately is proposed. However, this method not only complicates the production process because the two ASA resins need to be prepared separately, but also does not effectively reduce the water content in the ASA particles and does not exhibit sufficient impact strength. The manufacturing method associated with this patent is described in detail in German Patent No. 1,260,135.

In addition, Japanese Patent Application Laid-Open No. 4-180949 discloses a method for preparing ASA by making multi-layer graft copolymer particles, wherein a hard core is prepared using a monomer having a high glass transition temperature, and a butyl acrylate and a crosslinking agent are formed thereon. After preparing a crosslinked core using a crosslinking agent, a crosslinked shell is prepared using a styrene monomer, an acrylonitrile monomer, and a crosslinking agent having a high glass transition temperature, and then crosslinking. A method for producing a soft shell from unstyrene styrene monomer and acrylonitrile monomer is proposed. However, this method also does not effectively reduce the water content in the ASA particles and does not exhibit sufficient impact strength.

On the other hand, as a technology to give transparency to the material so far

1) a method of using a transparent polycarbonate resin,

2) a method of imparting impact resistance to transparent PMMA (polymethylmethacrylate) resin (US Pat. No. 3,787,522, Japanese Patent No. 63-42940),

3) Method of imparting transparency to HIPS (high impact polystyrene) resin (European Patent 0,703,252)

Etc. are known.

However, the method of using a polycarbonate resin has an advantage of excellent transparency and impact resistance at room temperature, but has a problem of weak chemical resistance and poor impact resistance at low temperature, and lacks workability and has limitations in application to large parts. In addition, the method using PMMA is excellent in transparency and processability, but the impact resistance is extremely weak and has a limitation in application, the method using HIPS has a problem that the chemical resistance and scratch resistance is lowered.

In US Patent No. 4,767,833, graft copolymerization of monomers such as methyl methacrylate, styrene, and acrylonitrile to styrene-butadiene rubber (SBR) rubber latex to solve such problems is excellent in impact resistance, chemical resistance, and workability. Although a method of preparing a transparent resin has been proposed, this method has a poor low temperature impact resistance and has a limitation in obtaining an extremely transparent resin.

The present invention is to solve the problems of the prior art as described above, the present invention is excellent in impact resistance, chemical resistance, processability, extremely excellent weatherability and transparency, impact strength is improved, and the moisture in the resin particles It is an object of the present invention to provide a method for producing a weather resistant resin which is an ASA thermoplastic resin which can be reduced.

[Means for solving the problem]

In order to achieve the above object, the present invention provides a) 5-15 parts by weight of an alkyl acrylate, 0.1-15 parts by weight of a vinyl compound, an alkyl sulfosuccinate metal salt derivative of C ₁₂ -C _{18, and} an alkyl of C ₁₂ -C ₂₀ . Preparing an acrylic rubber polymer latex by continuously or dividedly administering 0.2-1.0 parts by weight of an emulsifier selected from the group consisting of sulfuric acid esters and sulfonic acid metal salt derivatives, and b) alkyl (meth) acrylates to the acrylic rubber polymer latex obtained in step a). Emulsifier 0.5 which is 65-90 parts by weight of an ester compound, 0.5-5 parts by weight of an aromatic vinyl compound, 0.5-5 parts by weight of a vinyl cyan compound, 1-15 parts by weight of an alkyl acrylate and a fatty acid metal salt or rosin acid metal salt of C ₁₂ -C ₂₀ . It provides a method for producing a weather-resistant resin excellent in transparency comprising graft copolymerization by continuous or divided doses of -3.0 parts by weight.

Moreover, this invention provides the weatherproof resin composition excellent in transparency manufactured by the said method.

Hereinafter, the present invention will be described in detail.

MEANS TO SOLVE THE PROBLEM The present inventors researched in order to solve the problem in the ASA resin manufacturing process and the problem in the transparent resin manufacturing process, The acrylonitrile component which gives the outstanding chemical-resistance, the acrylic rubber component which gives the outstanding impact resistance, and the outstanding processability In preparing a transparent ASA resin composed of styrene components to be imparted, a methyl methacrylate component is introduced, and the content of each component to be introduced is adjusted so that the refractive index of the polyacrylic rubber and the methyl methacrylate, styrene, and acryl grafted thereon are adjusted. By optimizing the refractive index of the ronitrile mixture, a thermoplastic resin having excellent impact resistance, chemical resistance, and processability and extremely excellent weatherability and transparency has been completed.

In the present invention, a method for producing an ASA resin having excellent weather resistance and transparency, improved impact strength and efficient water content reduction in resin particles is largely 1) manufacturing a crosslinked acrylic resin and 2) graft copolymer. It consists of a manufacturing process. The method for producing the resin of the present invention is as follows.

1) Manufacturing process of crosslinked acrylic resin

In the manufacturing process of the crosslinked alkyl acrylate rubber polymer of the present invention, the effective surface area of the rubber (rubber) is copolymerized by simultaneously copolymerizing 5-25 parts by weight of the alkyl acrylate monomer and 0.1-8 parts by weight of the vinyl compound based on 100 parts by weight of the total monomers. It is characterized by maximizing the efficiency of the alkyl acrylate rubber polymer as wide as possible and optimizing the monomer to graft the refractive index of the monomer.

In preparing the crosslinked alkyl acrylate rubber polymer, the main monomer is 5-25 parts by weight of alkyl acrylate based on 100 parts by weight of the total monomer, wherein the alkyl acrylate is butyl acrylate, ethyl acrylate or methyl acrylate. In addition, to improve the efficiency of the rubber particles, to improve the pearl color and to optimize the refractive index with the grafted monomer, an auxiliary monomer is used, and the functional monomer can be copolymerized as necessary. 0.1-15 parts by weight of a vinyl compound is used as the auxiliary monomer, and styrene, α -methylstyrene, p-methylstyrene, acrylonitrile or vinyl derivative may be used as the vinyl compound, and acrylonitrile is particularly preferable. Functional monomers that can be copolymerized include methacrylic acid, acrylic acid, maleic acid, itaconic acid, fumaric acid, and the like.

As the emulsifier, 0.2-1.0 parts by weight of a C ₁₂ -C ₁₈ alkyl sulfosuccinate metal salt derivative, a C ₁₂ -C ₂₀ alkylsulfuric acid ester or a sulfonic acid metal salt derivative having a pH of 3-9 is used. Examples of alkyl sulfosuccinate metal salt derivatives of C ₁₂ -C ₁₈ are dicyclohexyl sulfosuccinate, dihexyl sulfosuccinate, di-2-ethylhexyl sulfosuccinate or sodium of dioctyl sulfosuccinate Or potassium salts, and the alkyl sulfate ester or sulfonic acid metal salts of C ₁₂ -C ₂₀ include sodium lauryl sulfate, sodium dodecyl sulfate, sodium dodecyl benzene sulfate, sodium octadecyl sulfate, sodium oleate sulfate, Alkyl sulfate metal salts, such as potassium dodecyl sulfate and potassium octadecyl sulfate, can be used. Of these, sodium or potassium salts of dioctyl sulfosuccinate are particularly preferred in view of the foaming, drying characteristics and graft reaction of the grafting phase to the crosslinked alkyl acrylate rubber polymer.

If an emulsifier is used, derivatives of carboxylic acid metal salts such as C ₁₂ -C ₂₀ fatty acid metal salts or rosin acid metal salts having a high pH of aqueous solution of 9-13 have a lower water content in the ASA resin, which is advantageous for drying. The methacrylic acid methyl ester is difficult to be grafted to the rubber polymer, which causes peeling due to phase separation, which is not preferable because the impact strength is significantly decreased.

The polymerization initiator uses an inorganic or organic peroxide compound, and both water-soluble initiators and oil-soluble initiators can be used. Potassium persulfate, sodium persulfate, ammonium persulfate, etc. may be used as the water-soluble initiator, and cumin hydroperoxide, benzoyl peroxide, etc. may be used as the oil-soluble initiator, and the amount of the polymerization initiator is 100 parts by weight of the total monomers. 0.05-0.2 weight part is preferable.

As the grafting agent, aryl methacrylate, triaryl isocyanurate, triarylamine, diarylamine and the like are used, and the amount of use thereof is preferably 0.01-0.07 parts by weight.

As crosslinking agent, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol Dimethacrylate, trimethylolpropane trimethacrylate, trimethylolmethane triacrylate and the like are used in an amount of 0.05 to 0.3 parts by weight based on 100 parts of the total monomers.

The electrolyte material uses NaHCO ₃ , Na ₂ S ₂ O ₇ , K ₂ CO ₃ , and the like, with NaHCO ₃ being particularly preferred, and 0.05-0.4 parts by weight based on 100 parts by weight of the total monomers.

The reaction may be a method in which the emulsion polymerization alone or the emulsion-free polymerization and the emulsion polymerization are appropriately mixed, and the method of adding the monomer may also be performed by using the continuous addition method alone or by mixing the continuous addition method and the batch addition method.

The pH of the crosslinked alkyl acrylate rubber polymer latex after polymerization is preferably in the range of 5-9, more preferably in the range of 6-8. Further, the particle diameter of the polymerized rubber polymer is preferably in the range of 2500-5000 mm 3, more preferably in the range of 3000-4500 mm 3.

2) Manufacturing Process of Graft Copolymer

As a monomer of the reaction for grafting to the crosslinked alkyl acrylate rubber polymer prepared according to the above method, 65-90 parts by weight of the (meth) acrylic acid alkyl ester compound is used as the main monomer, and 0.5-5 parts by weight of the aromatic vinyl compound and vinyl 0.5-5 parts by weight of the cyan compound and 1-15 parts by weight of the alkyl acrylate are used as auxiliary monomers, and functional monomers may be copolymerized as necessary. This grafting reaction can effectively reduce the moisture inside the ASA particles to improve dry productivity, significantly improve the impact strength of the ASA resin, and maintain transparency.

As a (meth) acrylic-acid alkylester compound, (meth) acrylic-acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid decyl ester, (meth) Acrylic acid lauryl ester etc. are mentioned, Especially, methyl methacrylate which is (meth) acrylic-acid methyl ester is the most preferable.

The aromatic vinyl compound includes styrene, α -methylstyrene, p-methylstyrene, and the like as the styrene monomer derivative. In particular, styrene is preferable, and the vinyl cyan compound is preferably acrylonitrile or methacrylonitrile. Further functional copolymerizable monomers include methacrylic acid, acrylic acid, maleic acid, itaconic acid, fumaric acid, and the like.

As the emulsifier, 0.5-3.0 parts by weight of derivatives of carboxylic acid metal salts such as C ₁₂ -C ₂₀ fatty acid metal salts and rosin acid metal salts having an aqueous pH of 9-13 are used. Examples of the fatty acid metal salts are waste thiic acid and lauryl. Sodium or potassium acid or oleic acid, and the sodium rosin or potassium salt is used as the rosin metal salt.

When derivatives of alkyl carboxylic acid metal salts such as C ₁₂ -C ₂₀ fatty acid metal salts or rosin acid metal salts having a high pH of 9-13 in an aqueous solution of an emulsifier are used, the pH of the entire system is gradually increased to lower the glass transition temperature. While the carboxyl groups of the rubber polymer are about to come out, as the polymerization proceeds, the grafting phase with a high glass transition temperature enters the interior of the alkyl acrylate rubber polymer particles, thereby lowering the surface glass transition temperature. As a result, atmospheric pressure aggregation becomes possible, and the moisture content in the ASA particles is significantly reduced to facilitate dehydration, thereby facilitating drying.

An inorganic or organic peroxide compound is used as a polymerization initiator, and both a water-soluble initiator and an oil-soluble initiator can be used. Potassium persulfate, sodium persulfate, ammonium persulfate, and the like can be used as the water-soluble initiator, and cumene hydroperoxide, benzoyl peroxide, etc. can be used as the oil-soluble initiator, and the amount of the initiator is 0.05-200 parts by weight of the total monomers. 0.3 parts by weight is preferred.

As a molecular weight regulator for controlling the molecular weight of the graft polymer, tertiary dodecyl mercaptan is used, and the amount of use is preferably 0 to 0.2 parts by weight. If the amount of the molecular weight regulator exceeds 0.2 parts by weight, the rate of decrease in impact strength is large, which is not preferable.

In the graft reaction, a method of adding a mixed monomer including an emulsifier is preferably a continuous addition method.As a batch addition method, the pH of the polymerization system is temporarily increased to make grafting difficult, and the stability of the particles is poor and the internal structure of the particles is not uniform. It is not desirable because it is not.

The pH of the polymerized latex is preferably in the range of 8-11, more preferably in the range of 9-10.5, and the particle diameter of the polymerized rubber polymer latex is preferably in the range of 3000-6000 mm 3, further in the range of 3500-4500 mm 3 desirable. Latex particle size can be measured by dynamic laser light scattering method using Nicomp 370HPL.

EXAMPLE

The following presents preferred examples and comparative examples to aid in understanding the invention. However, the following examples are merely provided to more easily understand the present invention, and the present invention is not limited to the following examples.

Example 1

1 stage polymerization

The composition was placed in a nitrogen-substituted polymerization reactor and heated to 70 ° C., and reacted for 1 hour.

Two stage polymerization

After mixing all the components except for the potassium persulfate catalyst as a component of the above components, the mixture and the catalyst was added to the first stage polymerization reaction in succession at 70 ℃ for 2 hours, respectively, the polymerization was carried out. The particle size of the latex thus obtained was 4000 mm 3, the pH was 8 and the polymerization conversion was 98%.

3-step polymerization

A mixture was prepared by mixing all components except for potassium persulfate, which is a catalyst. The mixture and the catalyst were added to a two-stage polymerization product continuously at 70 ° C. for 5 hours, followed by polymerization conversion. In order to increase the temperature, the reaction was further performed at 80 ° C. for 1 hour and then cooled to 60 ° C. The particle size of the polymerized latex was 4800 mm 3, the pH was 9.5, the polymerization conversion was 99%, the graft rate was 45%.

The latex obtained was subjected to atmospheric condensation at 85 ° C. using an aqueous calcium chloride solution, aged at 95 ° C., dehydrated and washed, and then sampled to measure the moisture content of wet powder. The remaining wet particles were dried with hot air at 90 ° C. for 30 minutes to obtain ASA powder particles.

The moisture content of the wet particles is obtained by the following equation.

Stabilizers and lubricants were added to the obtained ASA powder particles, mixed in a mixer, pelletized using a 40 pie extruder, and then obtained by using an injection molding machine. The measurement conditions of each physical property are as follows.

Izod impact strength: ASTM D 256 (1/4 "notch, 25 ℃, unit: kg.cm/cm)

-Fluidity: ASTM D 1258 (220 ℃, 10kg / ㎠, Unit: g / 10 min)

Haze value: ASTM D 1003

Example 2

3.0 parts by weight of the styrene monomer in the two-step polymerization of Example 1 was prepared in the same manner as in Example 1 except that the refractive index of the acrylic rubber was adjusted to 1.4866.

Example 3

Except for using triaryl isocyanurate instead of ethylene glycol dimethacrylate in Example 1 was prepared in the same manner as in Example 1.

Example 4

Except for using ammonium persulfate instead of potassium persulfate as a catalyst in Example 1 was prepared in the same manner as in Example 1.

Comparative Example 1

In the two-step polymerization of Example 1, sodium lauryl sulfate was used instead of dioctyl sulfosuccinate, and 0.5 parts by weight of sodium lauryl sulfate was used instead of potassium rosinate in the third step.

Comparative Example 2

The same procedure as in Example 1 was conducted except that potassium rosin was used instead of dioctyl sulfosuccinate in the two-step polymerization of Example 1.

Comparative Example 3

In the two-step polymerization of Example 1, it was prepared in the same manner as in Example 1 except that 5 parts by weight of acrylonitrile was added.

The physical properties of the specimens prepared in Examples 1-5 and Comparative Examples 1-3 were measured, and the results are shown in Table 1 below.

TABLE 1

The weather resistance resin having excellent transparency prepared according to the method of the present invention is excellent in impact resistance, chemical resistance, processability, etc. by optimizing the refractive index by controlling the mixing ratio of the monomer to be graft copolymerized using polyacrylic rubber latex having excellent weather resistance, The weather resistance and transparency are extremely excellent, the impact strength is improved, and the moisture in the resin particles can be efficiently reduced to improve drying productivity.

Claims (10)

a) a group consisting of 0.1-8 parts by weight of a vinyl compound, alkyl sulfosuccinate metal salt derivative of C ₁₂ -C ₁₈ , alkyl sulfate ester of C ₁₂ -C ₂₀ and sulfonic acid metal salt derivative of 5-25 parts by weight of alkyl acrylate; Preparing an acrylic rubber polymer latex by continuously or dividedly administering 0.2-1.0 parts by weight of an emulsifier selected from; And b) 65-90 parts by weight of (meth) acrylic acid alkyl ester compound, 0.5-5 parts by weight of aromatic vinyl compound, 0.5-5 parts by weight of vinyl cyan compound, alkyl acrylate 1-15 to the acrylic rubber polymer latex obtained in step a) Graft copolymerization by continuous or divided administration of 0.5 to 3.0 parts by weight of the emulsifier, which is by weight and C1 ₁₂ -C ₂₀ fatty acid metal salt or metal rosin acid salt. Method for producing a weather resistant resin comprising a. The method of claim 1, The particle size of the acrylic rubber polymer latex obtained in step a) is 2500-5000 mm 3, the pH is 5-9, the particle size of the thermoplastic resin obtained in step b) is 3000-6000 mm 3, and the pH is 8-11. Method for producing a resin. The method of claim 1, PH of the emulsifier used in step a) is 3-9, pH of the emulsifier used in step b) is 9-13. The method of claim 1, And said alkyl acrylate is selected from the group consisting of butyl acrylate, ethyl acrylate and methyl acrylate. The method of claim 1, And said vinyl compound is selected from the group consisting of styrene, α -methylstyrene, p-methylstyrene, acrylonitrile and vinyl derivatives. The method of claim 1, The said (meth) acrylic-acid alkylester compound is a (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid decyl ester, and (meth) A method for producing a weather resistant resin selected from the group consisting of acrylic acid lauryl ester. The method of claim 1, The aromatic vinyl compound is a method for producing a weather resistant resin selected from the group consisting of styrene, α -methylstyrene and p-methylstyrene. The method of claim 1, The said vinyl cyan compound is an acrylonitrile or methacrylonitrile manufacturing method of the weather resistant resin. The method of claim 1, In the process for producing the acrylic rubber polymer latex of step a) of the weather resistance resin carried out by further using a grafting agent selected from the group consisting of aryl methacrylate, triaryl isocyanurate, triarylamine and diarylamine Manufacturing method. The method of claim 1, Ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanedi dimethacrylate, 1,6 in the process for producing the acrylic rubber polymer latex of step a) A process for producing a weather resistant resin, which is further carried out by further using a crosslinking agent selected from the group consisting of hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, and trimethylolmethane triacrylate.