CN111201253B - Vinyl chloride-based resin composition and preparation method thereof - Google Patents

Abstract

The present disclosure relates to vinyl chloride-based resin compositions and methods of making the same. According to the present disclosure, there is provided a vinyl chloride-based resin composition and a preparation method thereof, the vinyl chloride-based resin composition is excellent in transparency, long-term storage stability and gloss, especially compatibility with ethylene-vinyl acetate It has excellent properties and can be suitably used as a binder for paint inks.

Description

Vinyl chloride-based resin composition and preparation method thereof

technical field

The present disclosure relates to vinyl chloride-based resin compositions and methods of making the same.

Background technique

Binder resins are used in inks, paints, coatings, adhesives, etc. to improve pigment dispersion and adhesion. Polymer materials used as binder resins generally include acrylic resins, vinyl resins, and urethane resins.

Among them, the vinyl chloride-based resin can be obtained in the form of fine particles by drying the polyvinyl chloride resin slurry, wherein the vinyl chloride-based monomer is used alone or by mixing the vinyl chloride-based monomer and copolymerizable therewith. Another comonomer mixture, suspending agent, buffer and polymerization initiator, etc., are prepared by suspension polymerization method to prepare polyvinyl chloride resin slurry.

Specific examples of vinyl chloride-based resins may include vinyl chloride, vinyl acetate, hydroxyl and carboxylic acid monomers, and vinyl chloride-based resins are widely used in gravure due to their excellent adhesion to metals as well as various plastic materials Ink adhesives and adhesives for food packaging.

Meanwhile, in the ink field, polyurethane (PU), ethylene-vinyl acetate (EVA), and the like are blended with vinyl chloride-based resins as binder resins. However, unlike vinyl chloride-based resins prepared by saponification treatment, vinyl chloride-based resins prepared by non-saponification treatment are limited in application fields due to poor compatibility with EVA.

SUMMARY OF THE INVENTION

technical problem

An object of the present disclosure is to provide a method for preparing a vinyl chloride-based resin composition having excellent compatibility with ethylene-vinyl acetate through a non-saponification treatment method.

The present disclosure aims to provide a vinyl chloride-based resin composition prepared by the above-mentioned method.

The present disclosure also aims to provide a coating ink comprising the vinyl chloride-based resin composition.

Technical solutions

According to an embodiment of the present disclosure, there is provided a method for preparing a vinyl chloride-based resin composition comprising, in the presence of an initiator, a vinyl chloride-based monomer, an ethylenically unsaturated monomer, having a C10 Steps to polymerize (meth)acrylate monomers and hydroxyl monomers to C20 linear, branched or cyclic alkyl groups.

wherein the vinyl chloride-based monomer is added for the first time before polymerization, and within 100 minutes after reaching the polymerization temperature, or when the pressure in the reactor is reduced by 0.5kgf/ ^cm2 to 1.0kgf relative to the initial pressure of the polymerization /cm ² when added for the second time.

According to another embodiment of the present disclosure, there is provided a vinyl chloride-based resin composition prepared by the above method, comprising a vinyl chloride-based monomer, an ethylenically unsaturated monomer, a linear chain having C10 to C20 , copolymers of branched or cyclic alkyl (meth)acrylate monomers and hydroxyl monomers.

According to another embodiment of the present disclosure, a coating ink including the vinyl chloride-based resin composition is provided.

Hereinafter, a method for preparing a vinyl chloride-based resin composition, a vinyl chloride-based resin composition prepared by the method, and a coating including the vinyl chloride-based resin composition according to embodiments of the present invention will be described in detail ink.

Unless expressly stated otherwise, the terminology used herein is applicable only to a particular embodiment and is not intended to limit the present disclosure.

Singular expressions in the present disclosure may include plural expressions unless the context expresses differently.

The terms "comprising", "comprising" and the like in this disclosure are used to enumerate certain features, ranges, integers, steps, operations, elements and/or components, and these do not preclude the presence or addition of certain other features, ranges, integers, steps , operations, elements and/or components.

As a result of continuous research by the present inventors, it was confirmed that when reducing the content of hydrophilic monomers such as hydroxyl monomers and introducing A monomer having a bulky and hydrophobic hydrocarbon group can provide a vinyl chloride-based resin composition having excellent compatibility with ethylene-vinyl acetate (EVA) even by a non-saponification treatment method.

The vinyl chloride-based resin composition comprising the copolymer in which a hydrophobic structure is introduced into the molecule has excellent EVA compatibility and excellent wettability to the pigment in the composition, and thus is suitable for use in metal and various Coating ink with excellent coating properties and color on plastic materials.

Furthermore, in the present disclosure, vinyl chloride-based monomers are separately added in the preparation of the copolymer, so that the monomers are irregularly distributed in the resin to be prepared. Therefore, the solubility of the vinyl chloride-based resin composition in the acetate-based solvent can be improved, thereby improving the transparency of the vinyl chloride-based resin composition and the storage stability of the solution.

1. Preparation method of vinyl chloride-based resin composition

According to an embodiment of the present disclosure, there is provided a method for preparing a vinyl chloride-based resin composition comprising, in the presence of an initiator, a vinyl chloride-based monomer, an ethylenically unsaturated monomer, having a C10 Steps to polymerize linear, branched or cyclic alkyl (meth)acrylate monomers to C20 and hydroxyl monomers.

Wherein, the vinyl chloride-based monomer is added for the first time before the polymerization, within 100 minutes after reaching the polymerization temperature, or when the pressure in the reactor is reduced by 0.5kgf/ ^cm2 to 1.0kgf/ ^cm2 relative to the initial pressure of the polymerization the second time to join.

In the method for preparing a vinyl chloride-based resin composition, when a copolymer is prepared using a vinyl chloride-based monomer and an ethylenically unsaturated monomer, a hydroxyl monomer and a monomer having a bulky and hydrophobic hydrocarbon group are introduced as monomer. Therefore, the vinyl chloride-based resin composition prepared by the above-described method may have excellent transparency and gloss, and particularly, exhibit excellent compatibility with EVA.

The method for preparing a vinyl chloride-based resin composition according to an embodiment of the present disclosure includes the steps of: making a vinyl chloride-based monomer, an ethylenically unsaturated monomer, having a direct C10 to C20 monomer in the presence of an initiator Chain, branched or cyclic alkyl (meth)acrylate monomers and hydroxyl monomers are polymerized.

The monomers can be added to the reactor together at the same time, or can be added separately at optimized times.

In particular, the vinyl chloride-based monomer may be added for the first time before polymerization, and within 100 minutes after reaching the polymerization temperature, or when the pressure in the reactor is reduced by 0.5 kgf/cm ² to the initial polymerization pressure At 1.0kgf/ ^cm2 , it was added for the second time.

Therefore, by separately adding the vinyl chloride-based monomers, the monomers are irregularly distributed in the polymer to be prepared, and as a result, excellent solubility in solvents, especially in acetate-based solvents, can be exhibited. In addition, the transparency and gloss of the vinyl chloride-based resin composition can be improved.

More particularly, 10 to 90 wt %, preferably 40 to 60 wt %, more preferably 50 wt % of the total vinyl chloride-based monomer is first added prior to polymerization. The remainder of the vinyl chloride based monomer, ie 10 to 90 wt % of the total vinyl chloride based monomer, preferably 40 to 60 wt %, more preferably 50 wt % may be available 100 minutes after reaching the polymerization temperature A second addition was made when the pressure in the reactor or in the reactor was reduced by 0.5 kgf/cm ² to 1.0 kgf/cm ² relative to the initial pressure of the polymerization.

When the addition timing and the addition amount are simultaneously controlled, the irregularity of the monomer distribution in the polymer is further increased, and as a result, the solubility in the solvent is improved, thereby improving the transparency and gloss of the vinyl chloride-based resin composition and storage stability.

Even more particularly, 10 to 90 wt%, preferably 40 to 60 wt%, more preferably 50 wt% of the total vinyl chloride-based monomer is first added prior to polymerization. And, the remaining vinyl chloride-based monomer, ie, 10 to 90 wt % of the total vinyl chloride-based monomer, preferably 40 to 60 wt %, more preferably 50 wt %, is added a second time. And, when the temperature in the reactor reaches the polymerization temperature, the remaining vinyl chloride-based monomer can be added a third time. In this case, in addition to the above-mentioned effects, excellent storage stability without phase separation can be exhibited.

The ethylenically unsaturated monomer may be at least one compound selected from the group consisting of vinyl ester-based monomers, such as vinyl acetate monomers and vinyl propionate monomers; olefin-based monomers, such as ethylene, Propylene, isobutyl vinyl ether, and halogenated olefins; (meth)acrylate-based monomers, such as alkyl (meth)acrylates; maleic anhydride monomers; acrylonitrile monomers; styrene monomers; and vinylidene halide monomers. Preferably, a compound having excellent solubility in water among the above-mentioned ethylenically unsaturated monomers can be appropriately used.

More preferably, the ethylenically unsaturated monomer may comprise a monomer selected from the group consisting of vinyl acetate monomer, vinyl propionate monomer, ethylene, propylene, isobutyl vinyl ether, maleic anhydride monomer, acrylonitrile monomer, At least one compound of styrene monomer and vinylidene halide monomer.

The ethylenically unsaturated monomer may be added in an amount of 0.1 parts by weight to 50 parts by weight based on 100 parts by weight of the vinyl chloride-based monomer.

In particular, based on 100 parts by weight of the vinyl chloride-based monomer, the addition amount of the ethylenically unsaturated monomer may be 0.1 part by weight or more, 0.5 part by weight or more, or 1.0 part by weight or more; and 50 parts by weight or less, 45 parts by weight or less, 40 parts by weight or less, 35 parts by weight or less, 30 parts by weight or less, 25 parts by weight or less, 20 parts by weight or less, 15 parts by weight or less, or 10 parts by weight or less.

When the ethylenically unsaturated monomer is used within the above range, the amount of unreacted monomer remaining in the resin after polymerization can be reduced, thereby minimizing the change of the resulting vinyl chloride-based resin composition due to the external environment .

The ethylenically unsaturated monomer may be added to the reactor simultaneously with other monomers prior to polymerization, ie, prior to initiating the polymerization reaction.

The method for preparing a vinyl chloride-based resin composition according to an embodiment of the present disclosure uses a (meth)acrylate monomer having a C10 to C20 linear, branched or cyclic alkyl group.

The (meth)acrylate monomer is a compound having a linear, branched or cyclic alkyl group having 10 to 20 carbon atoms.

Since the (meth)acrylate monomer has a bulky hydrophobic hydrocarbon group in the molecule, a vinyl chloride-based resin composition having excellent EVA compatibility can be provided even by a non-saponification treatment method.

In addition, copolymers comprising repeating units derived from (meth)acrylate monomers can exhibit high wettability to pigments through bulky and hydrophobic hydrocarbon groups.

The (meth)acrylate monomer can be selected from isodecyl acrylate, isodecyl methacrylate, isobornyl acrylate, isobornyl methacrylate, dipentyl maleate, dihexyl maleate At least one compound of ester, dioctyl maleate and dinonyl maleate.

And, the (meth)acrylate monomer may be added in an amount of 1 part by weight to 50 parts by weight based on 100 parts by weight of the vinyl chloride-based monomer.

In particular, based on 100 parts by weight of the vinyl chloride-based monomer, the (meth)acrylate monomer may be added in an amount of 1.0 parts by weight or more, 1.5 parts by weight or more, 2.0 parts by weight or more, 2.5 parts by weight or more, or 3.0 parts by weight or more; and 50 parts by weight or less, 45 parts by weight or less, 40 parts by weight or less, 35 parts by weight or less, 30 parts by weight or less, 25 parts by weight or less, 20 parts by weight or less, 15 parts by weight or less, or 10 parts by weight or less.

Preferably, the (meth)acrylate monomer is added in an amount of 1.0 parts by weight or more based on 100 parts by weight of the vinyl chloride-based monomer to achieve the above effects through the bulky and hydrophobic hydrocarbon groups of the copolymer.

However, when the (meth)acrylate monomer is added in excess or the copolymer contains an excess of bulky and hydrophobic hydrocarbon groups, the glass transition temperature (Tg) of the composition decreases due to plasticization, thereby drying in a commercial process The composition becomes difficult. Therefore, preferably, the addition amount of the (meth)acrylate monomer is 50 parts by weight or less based on 100 parts by weight of the vinyl chloride-based monomer.

The hydroxyl monomer can be selected from glycerol monoacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylamide, hydroxypolyethoxyallyl ether, hydroxypropyl acrylate, methyl methacrylate Hydroxypropyl acrylate, pentaerythritol triacrylate, poly(propylene glycol) methacrylate, acryloyloxyethoxyhydroxybenzophenone, allylhydroxyacetophenone, butoxystyrene and (methacrylic acid) At least one compound in acyloxy) hydroxybenzophenone.

The hydroxyl monomer may be added in an amount of 1 part by weight to 30 parts by weight based on 100 parts by weight of the vinyl chloride-based monomer.

In particular, based on 100 parts by weight of the vinyl chloride-based monomer, the addition amount of the hydroxyl monomer may be 1.0 parts by weight or more, 1.5 parts by weight or more, 2.0 parts by weight or more, 2.5 parts by weight or more, 3.0 parts by weight or more, 3.5 parts by weight or more, 4.0 parts by weight or more, 4.5 parts by weight or more, or 5.0 parts by weight or more; and 30 parts by weight or less, 25 parts by weight or less, 20 parts by weight or less, 15 parts by weight or less, or 10 parts by weight or less.

When the hydroxyl monomer is used within the above range, transparency and gloss can be improved by imparting hydrophilicity to the vinyl chloride-based resin to be prepared. It is also possible to reduce the amount of unreacted monomers remaining in the resin after polymerization, thereby minimizing the change of the resulting vinyl chloride-based resin composition due to the external environment.

Hydroxyl monomers can be added simultaneously with other monomers prior to polymerization or prior to initiating the polymerization reaction. In addition, the hydroxyl monomer may be separately added within 100 minutes after reaching the polymerization temperature, or when the pressure in the reactor is lowered by 0.5 kgf/cm ² to 1.0 kgf/cm ² relative to the initial pressure of the polymerization.

When hydroxyl monomers are added with other monomers prior to polymerization, most molecules react in the initial stages of polymerization. However, when added individually at a specific time, the monomers are distributed throughout the vinyl chloride-based resin to be prepared, thereby uniformly improving overall transparency and gloss.

Meanwhile, in the method of preparing the vinyl chloride-based resin composition, a polyethylene glycol-based reactive additive containing a (meth)acrylate group may be further added to the polymerization reaction together with the above-mentioned monomers.

In particular, the polyethylene glycol-based reactive additive containing a (meth)acrylate group may be a compound represented by the following Chemical Formula 1:

[Chemical formula 1]

Among them, in Chemical formula 1,

n is an integer from 2 to 100,

R1 and R2 are each independently hydrogen, a C1 to C10 hydrocarbon group or a (meth)acrylate group, and at least one of R1 and R2 is a (meth)acrylate group.

The compound represented by Chemical Formula 1 is a compound having one or more reactive functional groups in a molecule, and may be polymerized with a vinyl chloride-based monomer. And, the molecular weight of the compound can be adjusted according to the number of ethylene glycol repeating units in Chemical Formula 1, that is, the value of n.

Preferably, n may be 2 to 50, or 2 to 20.

The polyethylene glycol-based reactive additive containing a (meth)acrylate group can improve compatibility with pigments, increase curing speed in polymerization reaction, and impart hydrophilicity to the prepared vinyl chloride-based resin.

The weight average molecular weight (Mw) of the (meth)acrylate group-containing polyethylene glycol-based reactive additive may preferably be 200 g/mol to 5000 g/mol.

In particular, the weight average molecular weight (Mw) of the polyethylene glycol-based reactive additive may be 200 g/mol or more, 250 g/mol or more, 300 g/mol or more, 350 g/mol or more, 400 g/mol or more, 450 g/mol or more , or more than 500 g/mol; and less than 5000 g/mol, less than 4500 g/mol, less than 4000 g/mol, less than 3500 g/mol, less than 3000 g/mol, less than 2500 g/mol, less than 2000 g/mol, less than 1500 g/mol, or 1000 g /mol or less.

The polyethylene glycol-based reactive additive having a weight average molecular weight within the above range is excellent in compatibility with vinyl chloride-based monomers, and can improve the plasticity, dispersibility, and polymerizability of the monomer mixture during polymerization. Therefore, the transparency and gloss of the vinyl chloride-based resin composition to be prepared can be improved.

The polyethylene glycol-based reactive additive containing (meth)acrylate groups may be selected from the group consisting of methoxy polyethylene glycol acrylate, methoxy polyethylene glycol methacrylate, ethoxy polyethylene glycol Alcohol acrylates, ethoxylated polyethylene glycol methacrylates, aryloxy polyethylene glycol acrylates, aryloxy polyethylene glycol methacrylates, polyethylene glycol diacrylates and polyethylene glycols At least one compound in dimethacrylate.

The polyethylene glycol-based reactive additive containing a (meth)acrylate group may be added in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the vinyl chloride-based monomer.

In particular, the addition amount of the (meth)acrylate group-containing polyethylene glycol-based reactive additive may be 0.1 part by weight or more, 0.2 part by weight or more, 0.3 part by weight based on 100 parts by weight of the vinyl chloride-based monomer parts by weight or more, 0.4 parts by weight or more, or more than 0.5 parts by weight; and less than 5.0 parts by weight, less than 4.5 parts by weight, less than 4.0 parts by weight, less than 3.5 parts by weight, less than 3.0 parts by weight, less than 2.5 parts by weight, less than 2.0 parts by weight, or 1.0 parts by weight or less.

In order to obtain the above effects by adding the components, preferably, the polyethylene glycol-based reactive additive is added in an amount of 0.1 part by weight or more based on 100 parts by weight of the vinyl chloride-based monomer.

However, when this component is used in excess, unreacted additives may remain after polymerization, thereby reducing the physical properties of the copolymer. Therefore, preferably, the polyethylene glycol-based reactive additive is added in an amount of 5 parts by weight or less based on 100 parts by weight of the vinyl chloride-based monomer.

The polyethylene glycol-based reactive additive can be added simultaneously with other monomers prior to polymerization or prior to initiating the polymerization reaction. In addition, when the degree of polymerization of other monomers is 30% to 80%, the polyethylene glycol-based reactive additive may be added alone.

According to an embodiment of the present disclosure, when a monomer is added, an organotin compound represented by the following Chemical Formula 2 may be optionally further added:

[Chemical formula 2]

Among them, in Chemical formula 2,

Sn is tin, and

R11 to R14 are each independently hydrogen, mercapto (—SH), a C1 to C15 linear or branched alkyl group, or a C1 to C15 linear or branched alkylthio group.

In particular, the organotin compound may be at least one selected from the group consisting of tetramethyltin, tetrabutyltin, monomethyltin mercaptide, octyltin mercaptide, and dioctyltin mercaptide.

The organotin compound can act as a polymerization retarder in a polymerization reaction, and can improve transparency and gloss, prevent discoloration, and improve storage stability of a solution of a vinyl chloride-based resin to be prepared.

The organotin compound may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the vinyl chloride-based monomer.

In particular, based on 100 parts by weight of the vinyl chloride-based monomer, the content of the organotin compound may be 0.1 parts by weight or more, 0.15 parts by weight or more, or 0.2 parts by weight or more; and 5.0 parts by weight or less, 4.0 parts by weight or less , 3.0 parts by weight or less, 2.0 parts by weight or less, or 1.0 parts by weight or less.

When the organotin compound is used within the above range, it is possible to prevent a delay in the polymerization reaction and a decrease in productivity due to a change in the content of a molecule serving as a polymerization inhibitor.

The organotin compound may be added prior to polymerization, ie before initiation of the polymerization reaction.

Meanwhile, as the initiator, one or more compounds of a water-soluble initiator and an oil-soluble initiator may be used.

For example, the oil-soluble initiator may be selected from the group consisting of tert-butyl peroxyneodecanoate, diisopropyl peroxydicarbonate, methyl ethyl ketone peroxide, di-2-ethylhexyl peroxydicarbonate, di-3 -At least one compound of methoxybutylperoxydicarbonate, tert-butylperoxypivalate, tert-amylperoxypivalate, and tert-hexylperoxypivalate.

Monomers containing vinyl chloride-based monomers, ethylenically unsaturated monomers, (meth)acrylate monomers having C10 to C20 linear, branched or cyclic alkyl groups and hydroxyl monomers based on 100 parts by weight The oil-soluble initiator can be used in an amount of 0.01 to 1.00 parts by weight, preferably 0.02 to 0.50 parts by weight, more preferably 0.02 to 0.25 parts by weight. When the oil-soluble initiator is used within the above range, the polymerization reactivity is excellent and the heat of polymerization can be easily controlled.

For example, the water-soluble initiator may be at least one compound selected from the group consisting of potassium persulfate, ammonium persulfate, sodium persulfate, sodium hydrogen sulfate, and sodium hydrosulfite.

As the initiator, an oil-soluble initiator and a water-soluble initiator may be mixed in a weight ratio of 95:5 to 5:95, preferably 90:10 to 10:90. When the oil-soluble initiator and the water-soluble initiator are used in the above ratio, the productivity can be improved by appropriately adjusting the polymerization time.

According to an embodiment of the present disclosure, the polymerization may be suspension polymerization or emulsion polymerization.

For example, in the case of suspension polymerization, the above components are mixed and polymerized by a suspension polymerization method to prepare a slurry. Then, unreacted monomers are removed from the slurry, and the slurry is dewatered and dried. Here, the components are added in the manner as described above.

In the suspension polymerization, polymerization water at room temperature or high temperature can be used as the reaction medium. Specifically, the monomer and the dispersant are uniformly dispersed in the polymerization water, and the oil-soluble initiator is decomposed at a specific temperature such as 50°C to 70°C, thereby polymerizing by a chain reaction with the vinyl chloride-based monomer. After that, when the reaction conversion of the monomer mixture reaches a certain point, the polymerization can be terminated.

According to embodiments of the present disclosure, one or more additives of suspending agent and emulsifier may be optionally further added during the polymerization process. When the additive is further added, the conversion rate can be increased by initiating the reaction of the ethylenically unsaturated monomer.

In particular, as a suspending agent, polyvinyl alcohol, cellulose, gelatin, acrylic polymer, methyl alcohol, cellulose, gelatin, acrylic polymer, methyl alcohol, etc. based acrylic acid polymer, itaconic acid polymer, fumaric acid polymer, maleic acid polymer, succinic acid polymer or mixtures thereof.

Based on 100 parts by weight of the monomer mixture, the suspending agent may be used in an amount of 0.01 parts by weight to 5 parts by weight, 0.03 parts by weight to 5 parts by weight, or 0.05 parts by weight to 2.5 parts by weight. When the suspending agent is used within the above range, uniform vinyl chloride-based resin particles can be produced.

Anionic emulsifiers, nonionic emulsifiers or mixtures thereof can be used as emulsifiers.

The anionic emulsifier can be an alkali metal or ammonium salt of C6 to C20 fatty acid, an alkali metal or ammonium salt of C6 to C20 alkyl sulfonic acid, an alkali metal or ammonium salt of C6 to C20 alkylbenzene sulfonic acid, Alkali metal or ammonium salts of C6 to C20 alkylsulfuric acid, alkali metal or ammonium salts of C6 to C20 alkyl diphenyl ethers, or mixtures thereof.

The nonionic emulsifier can be C6 to C20 alcohol, polyethylene oxide, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, sorbitan monolaurate, polyvinyl alcohol, polyvinyl ethylene glycol or mixtures thereof.

Based on 100 parts by weight of the monomer mixture, the emulsifier may be added in an amount of 0.005 part by weight to 1.0 part by weight, 0.01 part by weight to 0.5 part by weight, or 0.01 part by weight to 0.1 part by weight. When the emulsifier is used within the above range, the polymerization conversion rate and particle stability of the ethylenically unsaturated monomer and the hydroxy monomer having a higher water solubility than that of the vinyl chloride-based monomer can be improved.

When the anionic emulsifier and the nonionic emulsifier are used in combination, within the above content range, the anions may be mixed in a weight ratio of 1:0.5 to 1:200, 1:2 to 1:100, or 1:2 to 1:50 Emulsifiers and nonionic emulsifiers.

When the anionic emulsifier and the nonionic emulsifier are mixed within this weight ratio range, the stability of the slurry can be ensured, and the reaction conversion rate of the ethylenically unsaturated compound can be improved as much as possible. In addition, heat transfer from the surface of the polymerized vinyl chloride-based resin to the inside of the resin can be suppressed as much as possible.

When an emulsifier is used as an additive and a water-soluble initiator is used as an initiator, it can be used at 1:50 to 50:1, 1:20 to 20:1, 1:1 to 20:1, or 2:1 to Emulsifier and water-soluble initiator were mixed in a weight ratio of 15:1.

Emulsifiers or water-soluble initiators may be located on the surface of the polymerized vinyl chloride-based resin to prevent heat transfer to the interior of the resin and minimize resin modification. In particular, ethylenically unsaturated monomers have higher solubility in water relative to vinyl chloride and are therefore more likely to be distributed on the outside of vinyl chloride droplets or in water in suspension polymerization using oil-soluble initiators phase, not the interior of the vinyl chloride droplet. At this time, the ethylenically unsaturated monomers distributed outside the vinyl chloride droplets or in the aqueous phase due to hydrophilicity are collected and induced to participate in the polymerization, thereby improving the reaction conversion rate of the compound. Water-soluble initiators can also increase the reaction conversion of ethylenically unsaturated monomers. Additionally, emulsifiers and water-soluble initiators can induce the formation of particle morphologies distributed on the surface of the polymerized vinyl chloride-based resin to minimize thermally induced changes in molecular structure. Therefore, when the emulsifier and the water-soluble initiator are mixed and used within the above ratio range, a resin having excellent gloss can be obtained while minimizing the decrease in adhesion due to the use of the emulsifier.

Meanwhile, the polymerization reaction may be performed while stirring.

The stirring process can be performed according to a conventional method.

According to an embodiment of the present disclosure, stirring may be performed by increasing the stirring speed within 100 minutes after reaching the polymerization temperature, or when the pressure in the reactor decreases by 0.5 kgf/cm ² to 1.0 kgf/cm ² relative to the initial pressure of the polymerization .

In particular, stirring may be performed at 100 to 500 rpm in the initial stage of the polymerization, and within 100 minutes after reaching the polymerization temperature, or when the pressure in the reactor decreases by ^0.5 kgf/cm to 1.0 kgf/cm relative to the initial pressure of the polymerization ² , it can be carried out at a higher stirring speed, preferably, it is carried out at a stirring speed which is increased by 2 to 5 times compared with the initial stirring speed.

When the stirring speed is increased during the polymerization under these conditions, the solubility in the solvent can be increased by increasing the inhomogeneity of the monomer distribution in the polymer to be prepared, and the cohesion force can be decreased to improve the storage of the composition stability.

Preferably, when the time of increasing the stirring speed is close to the time of reaching the polymerization temperature, more particularly, coincident with the time of reaching the polymerization temperature, the stirring speed may be increased by 2 to 5 times compared to the initial stirring speed, so as to show no Excellent storage stability where phase separation occurs.

The vinyl chloride-based resin composition prepared according to the above method may exhibit excellent EVA compatibility because it includes a copolymer having a bulky and hydrophobic hydrocarbon group.

In addition, since the irregularity of the monomer distribution in the resin to be prepared increases, the vinyl chloride-based resin composition prepared according to the method can exhibit excellent dissolution in a solvent, especially in an acetate-based solvent sex. As a result, the transparency of the vinyl chloride-based resin composition and the storage stability of the solution can be improved. In addition, the use of hydroxyl monomers and polyethylene glycol-based reactive additives containing (meth)acrylate groups can result in excellent transparency and gloss.

II. Vinyl Chloride-Based Resin Compositions

According to another embodiment of the present disclosure, there is provided a vinyl chloride-based resin composition prepared by the above method, comprising a vinyl chloride-based monomer, an ethylenically unsaturated monomer, having a C10 to C20 straight chain, Copolymers of branched or cyclic alkyl (meth)acrylate monomers and hydroxyl monomers.

Since the vinyl chloride-based resin composition includes the copolymer of the monomer, it can have excellent EVA compatibility, and can be mixed with pigments to exhibit high wettability.

The vinyl chloride-based resin composition is prepared by the above method, and the components used to form the composition are as described above.

For example, the copolymer may be based on 100 parts by weight of the vinyl chloride-based monomer, 0.1 to 50 parts by weight of the ethylenically unsaturated monomer, 1 to 50 parts by weight of the linear chain having C10 to C20 , a copolymer of branched or cyclic alkyl (meth)acrylate monomers and 1 to 30 parts by weight of hydroxyl monomers.

The ethylenically unsaturated monomer may be at least one compound selected from the group consisting of vinyl ester-based monomers, such as vinyl acetate monomers and vinyl propionate monomers; olefin-based monomers, such as Ethylene, propylene, isobutyl vinyl ether, and halogenated olefins; (meth)acrylate-based monomers, such as alkyl (meth)acrylates; maleic anhydride monomers; acrylonitrile monomers; styrene monomers body; and vinylidene halide monomer.

The (meth)acrylate monomer can be selected from isodecyl acrylate, isodecyl methacrylate, isobornyl acrylate, isobornyl methacrylate, dipentyl maleate, dihexyl maleate At least one compound of ester, dioctyl maleate and dinonyl maleate.

The hydroxyl monomer can be selected from glycerol monoacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylamide, hydroxypolyethoxyallyl ether, hydroxypropyl acrylate, methyl methacrylate Hydroxypropyl acrylate, pentaerythritol triacrylate, polypropylene glycol methacrylate, acryloyloxyethoxyhydroxybenzophenone, allylhydroxyacetophenone, butoxystyrene and (methacryloyloxy group) at least one compound in hydroxybenzophenone.

In addition, the vinyl chloride-based resin composition may further include a (meth)acrylate group-containing polyethylene glycol-based reactive additive represented by the following Chemical Formula 1:

[Chemical formula 1]

Among them, in Chemical formula 1,

n is an integer from 2 to 100,

R1 and R2 are each independently hydrogen, a C1 to C10 hydrocarbon group or a (meth)acrylate group, and at least one of R1 and R2 is a (meth)acrylate group.

The polyethylene glycol-based reactive additive containing a (meth)acrylate group may be added in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the vinyl chloride-based monomer.

The (meth)acrylate group-containing polyethylene glycol-based reactive additive is a compound represented by Chemical Formula 1, and may be selected from methoxy polyethylene glycol acrylate, methoxy polyethylene glycol methyl Ethoxylated polyethylene glycol acrylates, ethoxylated polyethylene glycol acrylates, ethoxylated polyethylene glycol methacrylates, aryloxy polyethylene glycol acrylates, aryloxy polyethylene glycol methacrylates, polyethylene At least one compound of glycol diacrylate and polyethylene glycol dimethacrylate.

The vinyl chloride-based resin composition may further include an organotin compound represented by Chemical Formula 2, an initiator, a suspending agent, an emulsifier, and the like.

III. Coating ink

According to another embodiment of the present disclosure, a coating ink including the vinyl chloride-based resin composition is provided.

Since the coating ink contains the above-mentioned vinyl chloride-based resin composition, it is excellent in compatibility with EVA, excellent in wettability of pigments in the composition, and excellent in solubility in acetate-based solvents. Therefore, it has excellent coating properties and color on metals and various plastic materials.

The paint ink can be prepared by mixing the vinyl chloride-based resin composition with a solvent, pigment, beads, etc., and uniformly dispersing it using a vibrator or the like.

Here, as solvents, pigments, beads, etc., conventional components known in the art may be added to the paint ink without particular limitation.

beneficial effect

According to the present disclosure, there is provided a vinyl chloride-based resin composition, which is excellent in transparency, long-term storage stability, and gloss, especially with ethylene-vinyl acetate, and a preparation method thereof. Excellent compatibility, suitable for use as a binder for paint inks.

Detailed ways

In the following, preferred examples and comparative examples are given for better understanding of the present invention. However, the following examples are only for illustrating the present invention, and the present invention is not limited thereto or by them.

Example 1

The oxygen in the 280L reactor was removed using a vacuum pump. 45kg vinyl chloride based monomer, 1kg vinyl acetate monomer, 7kg dioctyl maleate, 0.5kg methoxy PEG600 methyl methacrylate (as a polyethylene glycol based reactive additive), 0.19kg Dioctyltin mercaptide (as organotin compound), 3.0 kg of a 3% aqueous solution of cellulose-based suspending agent and 56 g of azobisisobutyronitrile (as initiator) were added to the reactor along with 130 L of deionized water, Polymerization was then initiated while rotating the Brumagin impeller at 300 rpm.

Immediately after the reactor temperature reached 70°C, 5 kg of hydroxypropyl acrylate was continuously added over 4 hours. When the reactor pressure decreased by 1.0 kgf/ ^cm2 relative to the initial polymerization, a further addition of 45 kg of vinyl chloride-based monomer was started, and the rotational speed of the Brumagin impeller was increased to 600 rpm.

The further added vinyl chloride-based monomer was added within 6 hours, and the polymerization was stopped when the pressure of the reactor decreased by 1.0 kgf/cm ² relative to the initial polymerization after the addition of the vinyl chloride-based monomer. After that, unreacted monomers are recovered and the polymerization is terminated. The polymerized slurry was dehydrated and dried to obtain vinyl chloride-based resin composition particles having an average particle diameter of 100 μm.

Example 2

Vinyl chloride-based resin composition pellets were obtained in the same manner as in Example 1, except that 3 kg of dioctyl maleate was added in place of 7 kg of dioctyl maleate.

Example 3

Vinyl chloride-based resin composition pellets were obtained in the same manner as in Example 1, except that 7 kg of isodecyl acrylate was added in place of 7 kg of dioctyl maleate.

Comparative Example 1

The oxygen in the 280L reactor was removed using a vacuum pump. 36kg vinyl chloride based monomer, 14.5kg vinyl acetate monomer, 0.5kg methoxy PEG600 methacrylate (as polyethylene glycol based reactive additive), 0.19kg dioctyl tin mercaptide (as organotin compound), 3.0 kg of a 3% aqueous solution of a cellulose-based suspending agent, and 56 g of azobisisobutyronitrile (as an initiator) were added to the reactor along with 130 L of deionized water, and polymerization was then initiated while Rotate the Brumagin impeller at 300 rpm.

Immediately after the reactor temperature reached 68°C, 9 kg of hydroxypropyl acrylate were continuously added over a period of 6 hours. When the reactor pressure was reduced by 1.0 kgf/ ^cm2 relative to the initial polymerization, a further 36 kg of vinyl chloride-based monomer was started, and the rotational speed of the Brumagin impeller was increased to 600 rpm.

The further added vinyl chloride-based monomer was added within 5 hours, and the polymerization was stopped when the pressure of the reactor decreased by 1.0 kgf/cm ² relative to the initial polymerization after the addition of the vinyl chloride-based monomer. After that, unreacted monomers are recovered and the polymerization is terminated. The polymerized slurry was dewatered and dried to obtain vinyl chloride-based resin composition particles having an average particle diameter of 190 μm.

Comparative Example 2

Except (i) 41 kg instead of 36 kg of vinyl chloride-based monomer were added before polymerization initiation, 5 kg of vinyl acetate monomer was added instead of 14.5 kg; and (ii) 41 kg instead of 36 kg of vinyl acetate-based monomer was added during polymerization Except for the monomer of vinyl chloride, vinyl chloride-based resin composition particles were obtained in the same manner as in Comparative Example 1.

Comparative Example 3

Except (i) before polymerization initiation, 43 kg of vinyl chloride-based monomer were added instead of 36 kg, 5 kg of vinyl acetate monomer was added instead of 14.5 kg, and 5 kg of hydroxypropyl acrylate was added instead of 9 kg; and (ii) ) Vinyl chloride-based resin composition particles were obtained in the same manner as in Comparative Example 1 except that 43 kg of vinyl chloride-based monomers were added instead of 36 kg during the polymerization.

Comparative Example 4

Except (i) prior to polymerization initiation, 45 kg of vinyl chloride-based monomer was added instead of 36 kg, 1 kg of vinyl acetate monomer was added instead of 14.5 kg, and 5 kg of hydroxypropyl acrylate was added instead of 9 kg; and (ii) ) Vinyl chloride-based resin composition particles were obtained in the same manner as in Comparative Example 1, except that 45 kg of vinyl chloride-based monomers were added instead of 36 kg during the polymerization.

Comparative Example 5

A vinyl chloride-based resin composition pellet (product name: TP-400A, manufacturer: Hanwha Chemical), which is a terpolymer of vinyl chloride, vinyl acetate, and dicarboxylic acid, was prepared.

Comparative Example 6

A，制造商：Shin-Etsu MicroSi公司)，其为氯乙烯、乙烯醇和乙酸乙烯酯的三元共聚物。Preparation of saponified vinyl chloride-based resin composition pellets (product name:

A, Manufacturer: Shin-Etsu MicroSi Corporation), which is a terpolymer of vinyl chloride, vinyl alcohol and vinyl acetate.

Preparation Examples 1-A to 1-I

Prepared by mixing 20% by weight of the vinyl chloride-based resin composition pellets prepared in each of the Examples and Comparative Examples, 40% by weight of ethyl acetate and 40% by weight of toluene, followed by stirring at 50° C. for 90 minutes Mixed solutions corresponding to the preparation examples of the respective examples and comparative examples.

Preparation Examples 2-A to 2-I

42-60，制造商：Arkema)混合，并用油墨搅拌器搅拌1小时，以制备对应于各实施例和对比例的红色涂料油墨。50 g of the mixed solution according to one of Preparation Examples 1-A to 1-I, 10 g of pigment (Red 146), 35 g of beads (product name: alumina beads, manufacturer: Samwha Ceramic), and 5 g of ethylene-vinyl acetate (product name:

42-60, manufacturer: Arkema) and mixed with an ink stirrer for 1 hour to prepare red paint inks corresponding to the respective examples and comparative examples.

Preparation Examples 3-A to 3-I

42-60，制造商：Arkema)混合，并用油墨搅拌器搅拌1小时，以制备对应于各实施例和对比例的白色涂料油墨。50 g of the mixed solution according to one of Preparation Examples 1-A to 1-I, 20 g of pigment (White R-216), 35 g of beads (product name: alumina beads, manufacturer: Samwha Ceramic) and 5 g of ethylene-vinyl acetate Esters (product name:

42-60, manufacturer: Arkema) and mixed with an ink stirrer for 1 hour to prepare white paint inks corresponding to the respective examples and comparative examples.

Test Example 1

Using a Brookfield viscometer to measure the viscosity of the mixed solutions of Preparation Examples 1-A to 1-I, the red inks of Preparation Examples 2-A to 2-I and the white inks of Preparation Examples 3-A to 3-I at 25°C (cps).

Test case 2

The transparency of the mixed solutions of Preparation Examples 1-A to 1-I was measured using an ultraviolet spectrometer (475 nm).

Test case 3

After the red inks of Preparation Examples 2-A to 2-I and the white inks of Preparation Examples 3-A to 3-I were respectively coated on the PET film and dried, a gloss meter (BYK, Micro-Gloss) was used in the The gloss was measured five times at 60° and the average value was calculated.

Test Example 4

After storing each of the red inks of Preparation Examples 2-A to 2-I in a container for 10 days at room temperature, the degree of phase separation of the ink was observed. The stability was relatively evaluated as the following 5 kinds: excellent (⊚), very good (◯), good (▲), moderate (Δ) and poor (X).

When the ink is unstable, layer separation of the ink and aggregation of the pigment occurs within 1 hour after ink formulation. In addition, the gloss of the coating is relatively poor when the ink with poor stability is applied.

【Table 1】

mixture resin composition transparency(%) Viscosity (cps) Preparation Example 1-A Example 1 91 360 Preparation Example 1-B Example 2 87 542 Preparation Example 1-C Example 3 89 354 Preparation Example 1-D Comparative Example 1 93 254 Preparation Example 1-E Comparative Example 2 76 673 Preparation Example 1-F Comparative Example 3 71 891 Preparation Example 1-G Comparative Example 4 60 4322 Preparation Example 1-H Comparative Example 5 93 251 Preparation Example 1-I Comparative Example 6 76 300

【Table 2】

red ink resin composition Gloss (GU) Viscosity (cps) stability Preparation Example 2-A Example 1 22.5 116 ◎ Preparation Example 2-B Example 2 15.0 161 ○ Preparation Example 2-C Example 3 21.2 121 ◎ Preparation Example 2-D Comparative Example 1 4.1 221 X Preparation Example 2-E Comparative Example 2 6.0 187 △ Preparation Example 2-F Comparative Example 3 13.0 161 ▲ Preparation Example 2-G Comparative Example 4 16.0 140 ○ Preparation Example 2-H Comparative Example 5 3.9 224 X Preparation Example 2-I Comparative Example 6 18.7 114 ◎

【table 3】

white ink resin composition Gloss (GU) Viscosity (cps) Preparation Example 3-A Example 1 7.4 90 Preparation Example 3-B Example 2 5.1 104 Preparation Example 3-C Example 3 6.0 93 Preparation Example 3-D Comparative Example 1 2.3 191 Preparation Example 3-E Comparative Example 2 3.6 156 Preparation Example 3-F Comparative Example 3 4.7 137 Preparation Example 3-G Comparative Example 4 5.5 110 Preparation Example 3-H Comparative Example 5 2.1 195 Preparation Example 3-I Comparative Example 6 6.5 94

The vinyl chloride-based resin compositions according to Comparative Examples 1 to 4 were prepared by reducing the contents of relatively hydrophilic vinyl acetate and hydroxypropyl acrylate, and whether the compatibility with ethylene-vinyl acetate was observed when ink was prepared Improved. As a result, the stability and gloss (dispersibility) of the ink are improved due to the reduced vinyl acetate and hydroxypropyl acrylate content. However, compared with Comparative Example 6, which is a saponified vinyl chloride resin composition, the inks of Comparative Examples 1 to 4 were inferior in glossiness (dispersibility). In addition, it was confirmed that the viscosity of the solution increased rapidly from Comparative Example 1 to Comparative Example 4, making it unsuitable for use as a paint ink.

Compared with Comparative Example 6, which was a saponified vinyl chloride-based resin composition, the vinyl chloride-based resin compositions according to Examples 1 to 3 exhibited excellent transparency, and had equal or higher gloss (dispersion). properties) and stability. Therefore, they were found to have suitable viscosity for use as coating inks.

Claims (8)

1. a method for preparing a resin composition based on vinyl chloride, comprising, in the presence of an initiator, making a vinyl chloride-based monomer, an ethylenically unsaturated monomer, having C10 to C20 straight chain, branched chain or the step of polymerizing cyclic alkyl (meth)acrylate monomers and hydroxyl monomers, Wherein, based on 100 parts by weight of the vinyl chloride-based monomer, the added amount of the ethylenically unsaturated monomer is 0.1 parts by weight to 50 parts by weight; The addition amount of the alkyl-like (meth)acrylate monomer is 1 to 50 parts by weight, and the addition amount of the hydroxyl monomer is 1 to 30 parts by weight, wherein the vinyl chloride-based monomer is added for the first time before polymerization, and within 100 minutes after reaching the polymerization temperature, or when the pressure in the reactor is reduced by 0.5kgf/ ^cm2 to 1.0kgf relative to the initial pressure of the polymerization /cm ² is added for the second time, Wherein, the ethylenically unsaturated monomer includes vinyl acetate monomer, vinyl propionate monomer, ethylene, propylene, isobutyl vinyl ether, maleic anhydride monomer, acrylonitrile monomer, benzene at least one compound of vinyl monomer and vinylidene halide monomer; Wherein, the (meth)acrylate monomers with C10 to C20 linear, branched or cyclic alkyl groups include isodecyl acrylate, isodecyl methacrylate, isobornyl acrylate, methacrylic acid at least one compound selected from isobornyl, dipentyl maleate, dihexyl maleate, dioctyl maleate and dinonyl maleate; Wherein, the hydroxy monomer includes selected from glycerol monoacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylamide, hydroxypolyethoxyallyl ether, hydroxypropyl acrylate, Hydroxypropyl methacrylate, pentaerythritol triacrylate, polypropylene glycol methacrylate, acryloyloxyethoxyhydroxybenzophenone, allylhydroxyacetophenone, and (methacryloyloxy)hydroxydiphenyl at least one compound in ketone, Wherein, the polymerization is performed by further adding a (meth)acrylate group-containing polyethylene glycol-based reactive additive represented by the following Chemical Formula 1: [Chemical formula 1]

In Chemical Formula 1, n is an integer from 2 to 100, R1 and R2 are each independently hydrogen, a C1 to C10 hydrocarbon group or a (meth)acrylate group, and at least one of R1 and R2 is a (meth)acrylate group; wherein the weight average molecular weight Mw of the polyethylene glycol-based reactive additive is 200 g/mol to 5000 g/mol, and Wherein, based on 100 parts by weight of the vinyl chloride-based monomer, the addition amount of the polyethylene glycol-based reactive additive is 0.1 parts by weight to 5 parts by weight. 2. The method for preparing a vinyl chloride-based resin composition according to claim 1, Wherein, 10 wt% to 90 wt% of the total vinyl chloride-based monomer is added for the first time before polymerization, and the remaining vinyl chloride-based monomer is added for the second time when the temperature in the reactor reaches the polymerization temperature. 3. The method for preparing a vinyl chloride-based resin composition according to claim 1, Wherein, the hydroxyl monomer is added within 100 minutes after reaching the polymerization temperature, or when the pressure in the reactor decreases by 0.5 kgf/cm ² to 1.0 kgf/cm ² relative to the initial pressure of the polymerization. 4. The method for preparing a vinyl chloride-based resin composition according to claim 1, Wherein, the polyethylene glycol-based reactive additive is added before polymerization, or when the polymerization degree of the monomer is 30% to 80%. 5. The method for preparing a vinyl chloride-based resin composition according to claim 1, wherein the polymerization is carried out with stirring, and The stirring is performed by increasing the stirring speed within 100 minutes after reaching the polymerization temperature, or when the pressure in the reactor decreases by 0.5 kgf/cm ² to 1.0 kgf/cm ² relative to the initial pressure of the polymerization. 6. The method for preparing a vinyl chloride-based resin composition according to claim 1, Wherein, the polymerization is suspension polymerization or emulsion polymerization. 7. A vinyl chloride-based resin composition prepared by the method of claim 1. 8. A paint ink comprising the vinyl chloride-based resin composition of claim 7.