KR0154911B1 - Polymeric gloss modifier and its preparation method - Google Patents

Abstract

The present invention provides a surface gloss of a thermoplastic resin through the production of an ABS-based latex having a core / shell structure composed of a core crosslinked through emulsion polymerization and a shell grafted thereon. The present invention relates to a method for preparing a resin for controlling glossiness, comprising: a rubber core manufacturing step including PBL, PBA, SBR, and NBR; and a cyanide compound, an aromatic vinyl monomer, an acrylic monomer, and an acrylamide-based interparticle crosslinking agent and a molecular weight regulator. Secondary emulsion polymerization of the shell with a monomer to prepare a latex of the core / shell structure, and also by polymerizing a second latex having a partial crosslinking or crosslinking structure containing an interparticle cross-linking agent and blending the two latexes in a proportion to agglomeration The crosslinking between the two latex particles in the step is also characterized in that the addition of an acid to activate the crosslinking reaction.

Description

Manufacturing method of resin for gloss control

The present invention relates to a method for producing a gloss control resin for reducing the surface gloss of a thermoplastic resin such as ABS (Acrylonitrile-Butadiene-Styrene copolymer) resin.

There may be various methods for reducing the surface gloss of the thermoplastic resin, such as by a processing method and the addition of inorganic additives such as silica gel.However, organic additives such as polymer resins may be affected due to the cost of the product and the effects on the mechanical properties of the product. Has been developed and used. This is because when synthetic polymer resins with smaller heat shrinkage than thermoplastic resins to reduce gloss are mixed and processed with thermoplastic resins, polymer particles with low heat shrinkage are distributed on the surface of the molded part due to the difference in mutual shrinkage rate when cooling the molded part. When the size is large enough to scatter light, the gloss of the product is reduced. Therefore, the size of the polymer particles in which the surface of the molded product exists is very important, and manufacturing a particle having a size that can exhibit a matt effect is a key technology for reducing the surface gloss of the resin.

Currently, thermoplastic resins produced by emulsion polymerization, in particular, ABS-based gloss control resins, have carboxylic acid introduced during emulsion polymerization to induce condensation reactions between carboxylic acids during compounding, so that they have particles having a matte effect. However, the yield of condensation reaction is low, so the matt effect is not good and the reproducibility is poor.

ABS-based resin for gloss adjustment produced in the manner of suspension polymerization or bulk polymerization and suspension polymerization meets the above requirements, but shrinkage occurs greatly in molding and hardness is lowered, and its use is limited.

Therefore, the present inventors earnestly researched to develop a resin for adjusting gloss without the above problems, firstly, a thermoplastic resin capable of controlling the gloss of ABS and related products was prepared by adopting a completely different emulsion polymerization method. In the present invention, a crosslinked structure was introduced in order to lower shrinkage rate than a matrix resin. First, a latex having a core / shell structure was agglomerated through a two-step polymerization such as preparing a crosslinked core and grafting it. By crosslinking again between the particles to make a high molecular weight gel to prepare a resin for controlling gloss for thermoplastic resin. However, the production method of the present invention has a problem in that the yield is low because the crosslinking reaction between the particles does not proceed well when the ratio of the grafting step of the gloss control resin is large or when the molecular weight of the grafted chain is large. Therefore, the present inventors prepared another latex of the cross-linked or cross-linked structure containing the cross-linking agent between the particles in order to solve the above problems by mixing a certain amount in the flocculation process of the latex for controlling the gloss prepared by the above method to agglomerate It was found that the crosslinking reaction between the particles can be smoothly completed the present invention.

That is, the present invention in preparing a resin for controlling gloss by core-shell structure ABS-based latex consisting of a core having a crosslinked structure and a shell grafted thereto by emulsion polymerization, the partial cross-linking or crosslinking comprising a crosslinking agent between particles during aggregation It relates to a method for producing a gloss control resin, characterized in that 5 to 30% by weight of mixing the latex of the structure.

Hereinafter, the present invention will be described in detail.

Partially crosslinked or crosslinked structured latex comprising an interparticle crosslinking agent is a latex consisting of 30 to 100% of the ratio of the crosslinking polymerization step in one latex particle. It consists of only the steps to create. That is, a linear structure is prepared by emulsion polymerization with only a monomer mixture including an aromatic vinyl monomer, an acrylic monomer, a cyanide compound, and a molecular weight regulator or an acrylic monomer, a cyanide compound, and a molecular weight regulator, and an aromatic vinyl monomer, an acrylic monomer, a cyanide compound, a crosslinking agent, and an acrylamide. Emulsion polymerization of cross-linking agents between particles is used to prepare latex having a partially crosslinked structure or to prepare only latex having a crosslinked structure.

First, the present invention describes a core having a cross-linked structure by emulsion polymerization and a method of manufacturing a resin-based resin latex for controlling gloss of a core / shell structure subjected to a two-step polymerization process by grafting thereon. The polymer is polymerized by polybutadiene latex (PBL), polybutylacrylate (PBA), acrylonitrile-butadiene rubber (NBR), or styrene-butadiene rubber (SBR), respectively. At this time, the particle size of the latex (latex) is about 90-400mm.

One step latex selected at least one of the above prepared is introduced into the reactor before the two-stage polymerization. The amount of latex introduced at this time is such that the ratio of cores in the core / shell structure is 90% or less. As the monomer used in the grafting step, an aromatic vinyl monomer, a cyanide compound, an acrylic monomer and an acrylamide-based interparticle crosslinking agent and a molecular weight regulator are introduced.

Aromatic vinyl monomers include styrene, monochloro styrene, methyl styrene, dimethyl styrene, α-methyl styrene, vinyltoluene, and the like. One of these monomers may be used, or two or more thereof may be mixed.

Acrylonitrile, methacrylonitrile, etc. can be used for a cyanide compound. As the acrylic monomer, methacrylate monomers such as methyl methacrylate, ethyl methacrylate and butyl methacrylate or acrylate monomers such as butyl acrylate, ethyl acrylate and ethyl hexyl acrylate can be used.

As the acrylamide-based interparticle crosslinking agent, various derivatives of N-hydroxy alkyl acrylamide such as N-methylol acrylamide or N-alkyl ether acrylamide such as N-methyl ether acrylamide may be used. It can also mix and use. At this time, their content is suitably 0.1 to 15 parts by weight per 100 parts by weight of all monomers used in the grafting step.

In the grafting step, the aromatic vinyl monomer is 90 parts by weight or less per 100 parts by weight of all monomers used in the grafting step, 40 parts by weight or less for the cyanide compound, 20 parts by weight or less for the acrylic monomer, and the content of the emulsifier is in the grafting step. 0.01 to 3 parts by weight per 100 parts by weight of all monomers used in the formulation are suitable.

As the initiators, persulfate-based water-soluble initiators such as potassium persulfate and ammonium persulfate are mainly used, but an initiator system generally used for emulsion polymerization such as oil-soluble initiator and redox system can be used, and the content can be used in all the grafting steps. It is appropriate to make 0.05 to 3 parts by weight per 100 parts by weight of the monomer.

An emulsifier is used as an anionic surfactant, and alkyl sulfones such as alkyl aryl sulfonates such as sodium dodecyl benzene sulfonate, potassium dodecyl benzene sulfonate and sodium alkyl benzene sulfonate, sodium dodecyl sulfonate and potassium dodecyl sulfonate Sulfates such as acid salts, sodium dodecyl sulfate, sodium octyl sulfate, sodium octadecyl sulfate, rosin-based emulsifiers such as potassium rosinate and sodium rosinate or fatty acid-based emulsifiers such as potassium oleate and potassium stearate . The content is preferably 0.01 to 3 parts by weight per 100 parts by weight of all monomers used in the grafting step.

Molecular weight regulators include mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan or terpenes such as dipentene and t-terpene or halogenated hydrocarbons such as chloroform and carbon tetrachloride.The content is used in the grafting step. Up to 6 parts by weight per 100 parts by weight of all monomers incorporated are suitable.

The reaction temperature is suitable 50 ℃ to 90 ℃ and the reaction time is suitable 2 hours to 12 hours.

In the agglomeration process to the latex polymerized in the above manner, 5-30% by weight of the second crosslinked or crosslinked second latex having a crosslinked structure is caused to aggregate and cause crosslinking reaction between different particles. In order to make the acid, the acid is added to aggregate in an acid atmosphere. The hydrogen ion concentration at this time is preferably pH 1 to pH 6.

The resin produced can be mixed with thermoplastics, for example ABS, PC / ABS blends, under conventional conditions to reduce the gloss of the thermoplastics.

Matte effect of the resin produced by the present invention was observed using the following method: ABS (Lucky XR-401) 86 to 95 parts by weight 0.4 parts by weight of EBA (ethylene bis stearamide), IR-1076 (Ciba -Geigy) 0.15 parts by weight, 5 to 14 parts by weight of the resin of the present invention is dispersed in a HellShell mixer, extruded in a single screw extruder to make pellets, and then a plate-shaped injection commercially obtained, using a gloss meter (TOYO SEIKI) 60 Measure gloss at an angle.

Hereinafter, the following examples are described in order to specifically illustrate the present invention, but the present invention is not limited thereto.

[Production Example 1]

[Production Example of ABS Latex Resin Resin]

In a known method, 170 g of PBL (Polybutadiene Latex, Lucky PBL 1000) having a polymerized particle size of 100 mm was used as the core. Using a core latex prepared by the above method to prepare a latex having a core and shell ratio of 4: 6, a monomer composition 100g of styrene 70 wt% and 30 wt% acrylonitrile, N-methylol acryl 2.5 g of amide, 200 g of water, 0.1 g of cumene hydroperoxide, 0.1 g of dextrose, 0.12 g of sodium pyrrolate, 2 mg of ferrous sulfide, 0.5 g of sodium dodecyl sulfate, and 1 g of t-dodecyl mercaptan. The reaction was carried out for 10 hours.

[Production Example 2]

[Production Example of ABS Latex Resin Resin]

200 g of PBL having a particle size of 230 cm polymerized by a known method was used as a core. Using the core latex prepared by the above method to prepare a latex with a core ratio of 5: 5, 75 wt% of styrene as a shell preparation step, 15 wt% of acrylonitrile, and 10 wt% of methyl methacrylate 70 g of monomer and 7 g of N-methylol acrylamide, 130 g of water, 0.2 g of cumene hydroperoxide, dextrose 0.2 g, sodium pyrolate 0.3 g, ferrous sulfide 5 mg, sodium rosinate 2 g, t-dodecyl mercaptan 1.5 g and the like were added and reacted at 70 ° C. for 10 hours.

Example 1

Into a 1 L flask, 200 g of water, 2 g of sodium dodecyl sulfate, 0.4 g of potassium persulfate, 0.5 g of t-dodecyl mercaptan and 50% by weight of styrene as a composition of the non-crosslinking step and a monomer of 50% by weight of butylacrylate 100 g was added and reacted at 70 ° C. for 10 hours. By using the core latex prepared in the above method to prepare a latex having a 1: 1 ratio of core and shell, the monomer composition 98g of butyl acrylate 40% by weight, 60% by weight of styrene acrylate, N-methylol acrylic 1.75 g of amide, 0.25 g of divinyl benzene, 200 g of water, 0.1 g of potassium persulfate, and 0.5 g of sodium dodecyl sulfate were added and reacted at 70 ° C. for 10 hours. The latex thus obtained was mixed with 30 g of 270 g of ABS-based gloss-resin resin latex having a core / shell structure obtained in Preparation Example 1, and 5 g of 5% sulfuric acid solution was added to 550 g of 60 ° C. and 0.5% calcium chloride aqueous solution and aged at 70 ° C. for 30 minutes. .

The aggregated resin was filtered and dried to obtain a powder. The glossiness of the ABS compound was measured by the above-mentioned method using the obtained resin, and the results are shown in Table 1.

Example 2

In a 1 L flask, 200 g of water, 1 g of sodium dodecyl sulfate, 0.4 g of potassium persulfate, 0.5 g of t-dodecyl mercaptan and 30% by weight of methyl methacrylate as a composition of the crosslinking step, 50% by weight of butyl acrylate, 100 g of a monomer made of 20% by weight of acrylonitrile, 1 g of hexanediol diacrylate, and 3 g of N-methylol acrylamide were added and reacted as in Example 1. The latex prepared by the above method was treated in the same manner as in Example 1 like the latex of Preparation Example 2 to measure the glossiness, and the results are shown in Table 1.

Comparative Example 1

Glossiness was measured by aggregating only with the ABS-based gloss adjustment resin latex made in Preparation Example 1, and the results are shown in Table 1.

Comparative Example 2

The same procedure as in Example 2 was carried out without mixing the acid with the aqueous calcium chloride solution during the flocculation process. The test results are shown in Table 1.

Claims (8)

In the manufacturing method of the resin for controlling gloss by manufacturing the ABS-based latex of the core / shell structure consisting of a core crosslinked through emulsion polymerization and a shell grafted thereto, a partial crosslinking comprising an intergranular crosslinking agent in an acidic atmosphere during aggregation. Method for producing a gloss control resin, characterized in that for mixing the cross-linked latex in 5 to 30% by weight. The method of claim 1, wherein the crosslinked or crosslinked structure of the latex containing the intergranular crosslinking agent has a ratio of 30-100% of the crosslinking polymerization step in one latex particle. 3. The partially crosslinked or crosslinked structure of the latex comprising an interparticle crosslinking agent is a monomer mixture or an acrylic monomer, a cyanide compound and a molecular weight comprising an aromatic vinyl monomer, an acrylic monomer, a cyanide compound and a molecular weight modifier. It is a latex or aromatic vinyl monomer, an acrylic monomer, a cyanide compound, or a partially crosslinked structure prepared by emulsifying and polymerizing an aromatic vinyl monomer, an acrylic monomer, a cyanide compound, a crosslinking agent, and an acrylamide particle crosslinking agent. A crosslinking agent, a method for producing a gloss control resin, characterized in that the latex having a crosslinked structure prepared by emulsion polymerization of the crosslinking agent between acrylamide-based particles. The method of claim 3, wherein the acrylamide-based interparticle crosslinking agent is N-hydroxyalkyl acrylamide or N-alkyl ether acrylamide. The method of claim 3, wherein the content of the acrylamide-based crosslinking agent introduced into the crosslinking step is 0.1 to 15% by weight of all monomers of the crosslinking step. According to claim 1, ABS-based gloss control resin latex of the core / shell structure consisting of a core cross-linked through emulsion polymerization and a shell grafted thereto (A) PBL, PBA, Core / shell obtained by secondary emulsion polymerization of (B) an aromatic vinyl monomer, a cyanide compound, an acryl monomer and an acrylamide-based interparticle crosslinking agent and a monomer containing a molecular weight modifier by using at least one rubber as a core in SBR or NBR. Method for producing a gloss control resin, characterized in that consisting of a structure. The method of claim 1, wherein the acrylamide-based interparticle crosslinking agent is N-hydroxyalkyl acrylamide or N-alkyl ether acrylamide. The method of claim 6, wherein the content of the acrylamide-based crosslinking agent introduced into the shell manufacturing step is 0.1 to 15 parts by weight per 100 parts by weight of the monomer of the grafting step.