CN111201253B - Vinyl chloride-based resin composition and method for preparing the same - Google Patents
Vinyl chloride-based resin composition and method for preparing the same Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/06—Vinyl chloride
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- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/04—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C09D127/06—Homopolymers or copolymers of vinyl chloride
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Abstract
The present disclosure relates to a vinyl chloride-based resin composition and a method of preparing the same. According to the present disclosure, there are provided a vinyl chloride-based resin composition excellent in transparency, long-term storage stability and glossiness, particularly excellent in compatibility with ethylene-vinyl acetate, which may be suitably used as a binder for coating ink, and a method for preparing the same.
Description
Technical Field
The present disclosure relates to a vinyl chloride-based resin composition and a method of preparing the same.
Background
Binder resins are used in inks, paints, coatings, adhesives, etc. to improve pigment dispersibility and adhesion. The polymer material used as the binder resin generally includes acrylic resin, vinyl resin, and urethane resin.
Among them, a vinylchloride-based resin may be obtained in the form of fine particles by drying a vinylchloride resin slurry prepared by a suspension polymerization method using a vinylchloride-based monomer alone or by mixing a mixture of a vinylchloride-based monomer and another comonomer copolymerizable therewith, a suspending agent, a buffer, a polymerization initiator, and the like.
Specific examples of the vinyl chloride-based resin may include vinyl chloride, vinyl acetate, hydroxyl, and carboxylic acid monomers, and the vinyl chloride-based resin is widely used for gravure ink adhesives and food packaging adhesives due to its excellent adhesion to metals as well as various plastic materials.
Meanwhile, in the ink field, Polyurethane (PU), Ethylene Vinyl Acetate (EVA), and the like are blended with a vinyl chloride-based resin as a binder resin. However, unlike the vinylchloride-based resin prepared by saponification treatment, the vinylchloride-based resin prepared by non-saponification treatment is limited in application fields due to poor compatibility with EVA.
Disclosure of Invention
Technical problem
The present disclosure aims to provide a method for preparing a vinyl chloride-based resin composition having excellent compatibility with ethylene-vinyl acetate by a non-saponification treatment method.
The present disclosure is directed to provide a vinyl chloride-based resin composition prepared by the above method.
The present disclosure also provides a coating ink comprising the vinyl chloride-based resin composition.
Technical scheme
According to an embodiment of the present disclosure, there is provided a method for preparing a vinyl chloride-based resin composition including the step of polymerizing a vinyl chloride-based monomer, an ethylenically unsaturated monomer, a (meth) acrylate monomer having a C10 to C20 linear, branched, or cyclic alkyl group, and a hydroxyl monomer in the presence of an initiator.
Wherein the vinyl chloride-based monomer is added for the first time before polymerization, and within 100 minutes after the polymerization temperature is reached, or when the pressure in the reactor is reduced by 0.5kgf/cm with respect to the initial pressure of polymerization2To 1.0kgf/cm2The second addition is made.
According to another embodiment of the present disclosure, there is provided a vinyl chloride-based resin composition prepared by the above method, including a copolymer of a vinyl chloride-based monomer, an ethylenically unsaturated monomer, a (meth) acrylate monomer having a linear, branched, or cyclic alkyl group of C10 to C20, and a hydroxyl monomer.
According to another embodiment of the present disclosure, there is provided a coating ink including the vinyl chloride-based resin composition.
Hereinafter, a method for preparing a vinyl chloride-based resin composition, a vinyl chloride-based resin composition prepared by the method, and a coating ink including the vinyl chloride-based resin composition according to embodiments of the present invention will be described in detail.
Unless expressly stated otherwise, the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting of the disclosure.
Unless otherwise indicated in context, singular expressions of the present disclosure may include plural expressions.
The terms "comprises," "comprising," "including," and the like, in the present disclosure are used to recite certain features, ranges, integers, steps, operations, elements, and/or components, and these do not preclude the presence or addition of other certain features, ranges, integers, steps, operations, elements, and/or components.
As a result of the present inventors' continuous research, it was confirmed that when the content of a hydrophilic monomer such as a hydroxyl monomer is reduced and a monomer having a large volume and a hydrophobic hydrocarbon group is introduced in preparing a copolymer using a vinyl chloride-based monomer, an ethylenically unsaturated monomer, and a hydroxyl monomer, a vinyl chloride-based resin composition having excellent compatibility with ethylene-vinyl acetate (EVA) can be provided even by a non-saponification treatment method.
A vinyl chloride-based resin composition including a copolymer having a hydrophobic structure introduced into a molecule has excellent EVA compatibility and excellent wettability to a pigment in the composition, and thus is suitable for use as a coating ink having excellent coating properties and color on metals and various plastic materials.
Further, in the present disclosure, the 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. Accordingly, 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.
I. Method for preparing 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 including the step of polymerizing a vinyl chloride-based monomer, an ethylenically unsaturated monomer, a (meth) acrylate monomer having a linear, branched or cyclic alkyl group of C10 to C20, and a hydroxyl monomer in the presence of an initiator.
Wherein the vinyl chloride-based monomer is first added before polymerization, within 100 minutes after reaching the polymerization temperature, or when the pressure in the reactor is reduced by 0.5kgf/cm with respect to the initial pressure of polymerization2To 1.0kgf/cm2The second addition is made.
In the method of preparing the vinyl chloride-based resin composition, when the vinyl chloride-based monomer and the ethylenically unsaturated monomer are used to prepare the copolymer, a hydroxyl monomer and a monomer having a large-sized and hydrophobic hydrocarbon group are introduced as monomers. Therefore, the vinyl chloride-based resin composition prepared by the above method may have excellent transparency and gloss, and particularly, exhibit excellent compatibility with EVA.
A method of preparing a vinyl chloride-based resin composition according to an embodiment of the present disclosure includes the steps of: polymerizing a vinyl chloride-based monomer, an ethylenically unsaturated monomer, a (meth) acrylate monomer having a linear, branched or cyclic alkyl group of C10 to C20, and a hydroxyl monomer in the presence of an initiator.
The monomers may be added to the reactor together at the same time or may be added separately at an optimized time.
In particular, the vinyl chloride-based monomer may be added for the first time before polymerization and within 100 minutes after the polymerization temperature is reached, or when the pressure in the reactor is reduced by 0.5kgf/cm with respect to the initial pressure of polymerization2To 1.0kgf/cm2The second addition is made.
Therefore, by separately adding the vinyl chloride-based monomer, the monomer is irregularly distributed in the polymer to be produced, and as a result, excellent solubility in a solvent, particularly in an acetate-based solvent, can be exhibited. In addition, the transparency and gloss of the vinyl chloride-based resin composition may be improved.
More specifically, 10 to 90 wt%, preferably 40 to 60 wt%, and more preferably 50 wt% of the total vinyl chloride-based monomers are added for the first time before polymerization. The remaining vinyl chloride-based monomer, i.e., 10 to 90 wt%, preferably 40 to 60 wt%, more preferably 50 wt% of the total vinyl chloride-based monomer may be within 100 minutes after the polymerization temperature is reached or when the pressure in the reactor is reduced by 0.5kgf/cm with respect to the initial pressure of the polymerization2To 1.0kgf/cm2The second addition is made.
When the addition timing and the addition amount are simultaneously controlled, the irregularity of the distribution of the monomer 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 the storage stability.
Even more particularly, 10 to 90 wt%, preferably 40 to 60 wt%, more preferably 50 wt% of the total vinyl chloride-based monomers are added for the first time before polymerization. And, the remaining vinyl chloride-based monomer, i.e., 10 to 90 wt%, preferably 40 to 60 wt%, more preferably 50 wt% of the total vinyl chloride-based monomer, is added for the second time. And, when the temperature in the reactor reaches the polymerization temperature, the remaining vinyl chloride-based monomer may be added for a third time. In this case, in addition to the above-described 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 monomer; acrylonitrile monomer; a styrene monomer; and vinylidene halide monomers. Preferably, a compound having excellent solubility in water among the above ethylenically unsaturated monomers can be suitably used.
More preferably, the ethylenically unsaturated monomer may include at least one compound selected from the group consisting of a vinyl acetate monomer, a vinyl propionate monomer, ethylene, propylene, isobutyl vinyl ether, a maleic anhydride monomer, an acrylonitrile monomer, a styrene monomer, and a vinylidene halide monomer.
The ethylenically unsaturated monomer may be added in an amount of 0.1 to 50 parts by weight, based on 100 parts by weight of the vinyl chloride-based monomer.
In particular, the ethylenically unsaturated monomer may be added in an amount of 0.1 parts by weight or more, 0.5 parts by weight or more, or 1.0 parts by weight or more, based on 100 parts by weight of the vinyl chloride-based monomer; 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, it is possible to reduce the amount of unreacted monomer remaining in the resin after polymerization, thereby minimizing the change of the resulting vinyl chloride-based resin composition due to external environments.
The ethylenically unsaturated monomer may be added to the reactor simultaneously with the other monomers prior to polymerization, i.e., prior to initiating polymerization.
The method of 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 ester 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, the copolymer including a repeating unit derived from a (meth) acrylate monomer may exhibit high wettability to a pigment through a large volume and a hydrophobic hydrocarbon group.
The (meth) acrylate monomer may be at least one compound selected from the group consisting of isodecyl acrylate, isodecyl methacrylate, isobornyl acrylate, isobornyl methacrylate, diamyl maleate, dihexyl maleate, dioctyl maleate and dinonyl maleate.
And, the (meth) acrylate monomer may be added in an amount of 1 to 50 parts by weight, based on 100 parts by weight of the vinylchloride-based monomer.
In particular, the (meth) acrylate ester monomer may be added in an amount of 1.0 part 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, based on 100 parts by weight of the vinyl chloride-based monomer; and 50 parts or less, 45 parts or less, 40 parts or less, 35 parts or less, 30 parts or less, 25 parts or less, 20 parts or less, 15 parts or less, or 10 parts or less by weight.
Preferably, the (meth) acrylate monomer is added in an amount of 1.0 part by weight or more based on 100 parts by weight of the vinylchloride-based monomer in order to achieve the above-mentioned effects by the large volume of the copolymer and the hydrophobic hydrocarbon group.
However, when the bulky and hydrophobic hydrocarbon groups are excessively contained in the (meth) acrylate monomer or copolymer, the glass transition temperature (Tg) of the composition is lowered due to plasticization, and thus it becomes difficult to dry the composition in a commercial process. Therefore, it is preferable that the (meth) acrylate monomer is added in an amount of 50 parts by weight or less based on 100 parts by weight of the vinyl chloride-based monomer.
The hydroxyl monomer may be at least one compound selected from the group consisting of glycerol monoacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylamide, hydroxypolyethoxyallyl ether, hydroxypropyl acrylate, hydroxypropyl methacrylate, pentaerythritol triacrylate, poly (propylene glycol) methacrylate, acryloxyethoxyhydroxybenzophenone, allylhydroxyacetophenone, butoxystyrene, and (methacryloyloxy) 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 vinylchloride-based monomer.
Specifically, the hydroxyl monomer may be added in an amount of 1.0 part 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, based on 100 parts by weight of the vinyl chloride-based monomer; and 30 parts or less, 25 parts or less, 20 parts or less, 15 parts or less, or 10 parts or less by weight.
When the hydroxyl monomer is used within the above range, transparency and gloss may be improved by imparting hydrophilicity to the vinylchloride-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.
The hydroxyl monomer may be added simultaneously with the other monomers prior to polymerization or prior to initiation of polymerization. Further, it may be possible to decrease the pressure in the reactor by 0.5kgf/cm within 100 minutes after the polymerization temperature is reached, or when the pressure in the reactor is lowered with respect to the initial pressure of polymerization2To 1.0kgf/cm2The hydroxyl monomer is added separately.
When the hydroxyl monomer is added together with other monomers before polymerization, most molecules react at the initial stage of polymerization. However, when separately added at a specific time, the monomer is distributed throughout the vinyl chloride-based resin to be prepared, thereby uniformly improving the overall transparency and gloss.
Meanwhile, in the method of preparing the vinyl chloride-based resin composition, a polyethylene glycol-based reactive additive including 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 including a (meth) acrylate group may be a compound represented by the following chemical formula 1:
[ chemical formula 1]
Wherein, in chemical formula 1,
n is an integer of 2 to 100,
r1 and R2 are each independently hydrogen, a C1 to C10 hydrocarbyl 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 may be adjusted according to the number of ethylene glycol repeating units in chemical formula 1, i.e., the value of n.
Preferably, n may be 2 to 50, or 2 to 20.
The polyethylene glycol-based reactive additive including a (meth) acrylate group may improve compatibility with a pigment, increase a curing speed in a polymerization reaction, and impart hydrophilicity to the prepared vinyl chloride-based resin.
The weight average molecular weight (Mw) of the polyethylene glycol-based reactive additive including a (meth) acrylate group may preferably be 200g/mol to 5000 g/mol.
In particular, the weight average molecular weight (Mw) of the polyethylene glycol-based reactive additive may be 200g/mol or more, 250g/mol or more, 300g/mol or more, 350g/mol or more, 400g/mol or more, 450g/mol or more, or 500g/mol or more; and 5000g/mol or less, 4500g/mol or less, 4000g/mol or less, 3500g/mol or less, 3000g/mol or less, 2500g/mol or less, 2000g/mol or less, 1500g/mol or less, or 1000g/mol or less.
The polyethylene glycol-based reactive additive having a weight average molecular weight within the above range is excellent in compatibility with the vinyl chloride-based monomer, and can improve plasticity, dispersibility and polymerizability of the monomer mixture during polymerization. Accordingly, the transparency and gloss of the vinylchloride-based resin composition to be prepared may be improved.
The polyethylene glycol-based reactive additive including a (meth) acrylate group may be at least one compound selected from the group consisting of methoxy polyethylene glycol acrylate, methoxy polyethylene glycol methacrylate, ethoxy polyethylene glycol acrylate, ethoxy polyethylene glycol methacrylate, aryloxy polyethylene glycol acrylate, aryloxy polyethylene glycol methacrylate, polyethylene glycol diacrylate and polyethylene glycol dimethacrylate.
The polyethylene glycol-based reactive additive including 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 polyethylene glycol-based reactive additive including a (meth) acrylate group may be added in an amount of 0.1 parts by weight or more, 0.2 parts by weight or more, 0.3 parts by weight or more, 0.4 parts by weight or more, or 0.5 parts by weight or more, based on 100 parts by weight of the vinylchloride-based monomer; and 5.0 parts by weight or less, 4.5 parts by weight or less, 4.0 parts by weight or less, 3.5 parts by weight or less, 3.0 parts by weight or less, 2.5 parts by weight or less, 2.0 parts by weight or less, or 1.0 parts by weight or less.
In order to obtain the above-mentioned effects by adding the components, the addition amount of the polyethylene glycol-based reactive additive is preferably 0.1 parts by weight or more based on 100 parts by weight of the vinyl chloride-based monomer.
However, when the component is used in excess, unreacted additives may remain after polymerization, thereby reducing the physical properties of the copolymer. Therefore, it is preferable that the addition amount of the polyethylene glycol-based reactive additive is 5 parts by weight or less based on 100 parts by weight of the vinylchloride-based monomer.
The polyethylene glycol-based reactive additive may be added simultaneously with the other monomers prior to polymerization or prior to initiation of polymerization. In addition, when the polymerization degree of the other monomer is 30% to 80%, the polyethylene glycol-based reactive additive may be separately added.
According to an embodiment of the present disclosure, when the monomer is added, an organotin compound represented by the following chemical formula 2 may be optionally further added:
[ chemical formula 2]
Wherein, in chemical formula 2,
sn is tin, and
r11 to R14 are each independently hydrogen, a mercapto group (-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 polymerization, and can improve transparency and gloss, prevent discoloration, and improve storage stability of a solution of a vinylchloride-based resin to be prepared.
The organotin compound may be contained in an amount of 0.1 parts by weight to 5 parts by weight, based on 100 parts by weight of the vinylchloride-based monomer.
In particular, the organotin compound may be contained in an amount of 0.1 parts by weight or more, 0.15 parts by weight or more, or 0.2 parts by weight or more, based on 100 parts by weight of the vinylchloride-based monomer; 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 in the above range, it is possible to prevent the delay of polymerization reaction and the decrease in productivity due to the change in the content of molecules used as a polymerization inhibitor.
The organotin compound may be added before the polymerization, i.e., before the 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 at least one compound selected from the group consisting of t-butyl peroxyneodecanoate, diisopropyl peroxydicarbonate, methyl ethyl ketone peroxide, di-2-ethylhexyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, t-butyl peroxypivalate, t-amyl peroxypivalate, and t-hexyl peroxypivalate.
The oil-soluble initiator may 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, based on 100 parts by weight of a monomer mixture including a vinyl chloride-based monomer, an ethylenically unsaturated monomer, a (meth) acrylate monomer having a C10 to C20 linear, branched or cyclic alkyl group, and a hydroxyl monomer. When the oil-soluble initiator is used within the above range, polymerization reactivity is excellent and the heat of polymerization reaction 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 bisulfate, and sodium dithionite.
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, productivity can be improved by appropriately adjusting the polymerization time.
According to embodiments of the present disclosure, the polymerization may be a suspension polymerization or an 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 dehydrated and dried. The components are added in the manner described above.
In the suspension polymerization, polymerization water at room temperature or at an elevated temperature may be used as a reaction medium. Specifically, the monomer and the dispersant are uniformly dispersed in polymerization water, and the oil-soluble initiator is decomposed at a specific temperature, for example, 50 ℃ to 70 ℃, so that polymerization is performed by a chain reaction with the vinyl chloride-based monomer. Thereafter, when the reaction conversion of the monomer mixture reaches a certain point, the polymerization may be terminated.
According to embodiments of the present disclosure, one or more additives of suspending agents and emulsifying agents may optionally be 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 the suspending agent, polyvinyl alcohol, cellulose, gelatin, acrylic acid polymer, methacrylic acid polymer, itaconic acid polymer, fumaric acid polymer, maleic acid polymer, succinic acid polymer, or a mixture thereof in which polyvinyl acetate is partially saponified and the saponification degree is 40% or more, more particularly 40% to 90%, can be used.
The suspending agent may be used in an amount of 0.01 to 5 parts by weight, 0.03 to 5 parts by weight, or 0.05 to 2.5 parts by weight, based on 100 parts by weight of the monomer mixture. When the suspending agent is used within the above range, uniform vinyl chloride-based resin particles may be produced.
Anionic emulsifiers, nonionic emulsifiers or mixtures thereof may be used as emulsifiers.
The anionic emulsifier may be an alkali metal or ammonium salt of a C6 to C20 fatty acid, an alkali metal or ammonium salt of a C6 to C20 alkyl sulfonic acid, an alkali metal or ammonium salt of a C6 to C20 alkyl benzene sulfonic acid, an alkali metal or ammonium salt of a C6 to C20 alkyl sulfuric acid, an alkali metal or ammonium salt of a C6 to C20 alkyl disulfonic diphenyl ether, or mixtures thereof.
The non-ionic emulsifier may be a C6 to C20 alcohol, polyethylene oxide, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, sorbitan monolaurate, polyvinyl alcohol, polyethylene glycol, or a mixture thereof.
The emulsifier may be added in an amount of 0.005 to 1.0 part by weight, 0.01 to 0.5 part by weight, or 0.01 to 0.1 part by weight, based on 100 parts by weight of the monomer mixture. When the emulsifier is used within the above range, the polymerization conversion rate and particle stability of the ethylenically unsaturated monomer and the hydroxyl monomer having water solubility higher than that of the vinyl chloride-based monomer can be improved.
When the anionic emulsifier and the nonionic emulsifier are used in combination, the anionic emulsifier and the nonionic emulsifier 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 within the above content range.
When the anionic emulsifier and the nonionic emulsifier are mixed in this weight ratio range, the stability of the slurry can be secured and the reaction conversion rate of the ethylenically unsaturated compound can be increased 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 the additive and a water-soluble initiator is used as the initiator, the emulsifier and the water-soluble initiator may be mixed in a weight ratio of 1:50 to 50:1, 1:20 to 20:1, 1:1 to 20:1, or 2:1 to 15: 1.
An emulsifier or a water-soluble initiator may be located on the surface of the polymerized vinyl chloride-based resin to prevent heat transfer to the inside of the resin and minimize the change of the resin. In particular, ethylenically unsaturated monomers have a higher solubility in water than vinyl chloride and are therefore more likely to be distributed in the external or aqueous phase of the vinyl chloride droplets than the internal parts of the vinyl chloride droplets in suspension polymerization using an oil-soluble initiator. At this time, the ethylenically unsaturated monomer distributed outside the vinyl chloride droplets or in the aqueous phase due to hydrophilicity is collected and induced to participate in polymerization, thereby increasing the reaction conversion rate of the compound. The water-soluble initiator may also increase the reaction conversion of the ethylenically unsaturated monomer. In addition, the emulsifier and the water-soluble initiator may induce the formation of particle morphology distributed on the surface of the polymerized vinyl chloride-based resin to minimize the change of molecular structure caused by heat. 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 adhesive force due to the use of the emulsifier.
Meanwhile, the polymerization reaction may be performed while stirring.
The stirring process may be performed according to a conventional method.
According to an embodiment of the present disclosure, the pressure in the reactor may be reduced by 0.5kgf/cm within 100 minutes after reaching the polymerization temperature, or when the pressure in the reactor is reduced with respect to the initial pressure of the polymerization2To 1.0kgf/cm2The stirring is carried out by increasing the stirring speed.
In particular, the stirring may be performed at 100 to 500rpm in the initial stage of the polymerization, and within 100 minutes after the polymerization temperature is reached, or when the pressure in the reactor is lowered by 0.5kgf/cm with respect to the initial pressure of the polymerization2To 1.0kgf/cm2In this case, the stirring may be performed at a higher stirring speed, preferably at a stirring speed increased by 2 to 5 times as compared with the initial stirring speed.
When the stirring speed is increased during the polymerization under such conditions, the solubility in a solvent can be increased by increasing the nonuniformity of the distribution of the monomer in the polymer to be produced, and the cohesive force can be decreased to improve the storage stability of the composition.
Preferably, when the timing of increasing the stirring speed is close to the timing of reaching the polymerization temperature, more particularly, coincides with the timing of reaching the polymerization temperature, the stirring speed may be increased by 2 to 5 times as compared to the initial stirring speed, in order to exhibit excellent storage stability in which no 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 large volume and a hydrophobic hydrocarbon group.
In addition, since irregularity in distribution of monomers in the resin to be prepared increases, the vinyl chloride-based resin composition prepared according to the method may show excellent solubility in a solvent, particularly, in an acetate-based solvent. As a result, the transparency of the vinyl chloride-based resin composition and the storage stability of the solution may be improved. In addition, the use of a hydroxyl monomer and a polyethylene glycol-based reactive additive including a (meth) acrylate group may result in excellent transparency and gloss.
Vinyl chloride-based resin composition
According to another embodiment of the present disclosure, there is provided a vinyl chloride-based resin composition prepared by the above method, including a copolymer of a vinyl chloride-based monomer, an ethylenically unsaturated monomer, a (meth) acrylate monomer having a C10 to C20 linear, branched, or cyclic alkyl group, and a hydroxyl monomer.
Since the vinyl chloride-based resin composition includes the copolymer of the monomer, it may have excellent EVA compatibility, and may be mixed with a pigment to exhibit high wettability.
The vinyl chloride-based resin composition is prepared by the above-described method, and the components for forming the composition are as described above.
For example, the copolymer may be a copolymer of 0.1 to 50 parts by weight of an ethylenically unsaturated monomer, 1 to 50 parts by weight of a (meth) acrylate monomer having a C10 to C20 linear, branched or cyclic alkyl group, and 1 to 30 parts by weight of a hydroxyl monomer, based on 100 parts by weight of a vinyl chloride-based monomer.
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 monomer; acrylonitrile monomer; a styrene monomer; and vinylidene halide monomers.
The (meth) acrylate monomer may be at least one compound selected from the group consisting of isodecyl acrylate, isodecyl methacrylate, isobornyl acrylate, isobornyl methacrylate, diamyl maleate, dihexyl maleate, dioctyl maleate and dinonyl maleate.
The hydroxyl monomer may be at least one compound selected from the group consisting of glycerol monoacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylamide, hydroxypolyethoxyallyl ether, hydroxypropyl acrylate, hydroxypropyl methacrylate, pentaerythritol triacrylate, polypropylene glycol methacrylate, acryloyloxyethoxy hydroxybenzophenone, allyl hydroxyacetophenone, butoxystyrene, and (methacryloyloxy) hydroxybenzophenone.
In addition, the vinyl chloride-based resin composition may further include a polyethylene glycol-based reactive additive including a (meth) acrylate group shown in the following chemical formula 1:
[ chemical formula 1]
Wherein, in chemical formula 1,
n is an integer of 2 to 100,
r1 and R2 are each independently hydrogen, a C1 to C10 hydrocarbyl 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 including 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 polyethylene glycol-based reactive additive including a (meth) acrylate group is a compound represented by chemical formula 1, and may be at least one compound selected from the group consisting of methoxy polyethylene glycol acrylate, methoxy polyethylene glycol methacrylate, ethoxy polyethylene glycol acrylate, ethoxy polyethylene glycol methacrylate, aryloxy polyethylene glycol acrylate, aryloxy polyethylene glycol methacrylate, polyethylene 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, etc.
Coating inks
According to another embodiment of the present disclosure, there is provided a coating ink including the vinyl chloride-based resin composition.
Since the coating ink includes the above vinyl chloride-based resin composition, compatibility with EVA is excellent, wettability of a pigment in the composition is excellent, and solubility in an acetate-based solvent is excellent. Therefore, it has excellent coating properties and color on metals and various plastic materials.
The coating ink may be prepared by mixing the vinylchloride-based resin composition with a solvent, a pigment, beads, etc., and uniformly dispersing them using a vibrator, etc.
Herein, as the solvent, the pigment, the bead, etc., conventional components known in the art may be added to the coating ink without particular limitation.
Advantageous effects
According to the present disclosure, there are provided a vinyl chloride-based resin composition excellent in transparency, long-term storage stability and glossiness, particularly excellent in compatibility with ethylene-vinyl acetate, which can be suitably used as a binder for coating inks, and a method for preparing the same.
Detailed Description
Hereinafter, preferred examples and comparative examples are given to better understand the present invention. However, the following examples are only for illustrating the present invention, and the present invention is not limited thereto or thereby.
Example 1
Oxygen was removed from the 280L reactor using a vacuum pump. 45kg of vinyl chloride-based monomer, 1kg of vinyl acetate monomer, 7kg of dioctyl maleate, 0.5kg of methoxy PEG600 methyl methacrylate (as a reactive additive based on polyethylene glycol), 0.19kg of dioctyltin mercaptide (as an organotin compound), 3.0kg of a 3% aqueous solution of cellulose-based suspending agent and 56g of azobisisobutyronitrile (as an initiator) were added to the reactor together with 130L of deionized water, and then polymerization was initiated while rotating a Brumagin impeller at 300 rpm.
Immediately after the reactor temperature reached 70 ℃, 5kg of hydroxypropyl acrylate was continuously added over 4 hours. When the reactor pressure was reduced by 1.0kgf/cm with respect to the initial polymerization2At this time, further addition of 45kg of vinyl chloride-based monomer was started, and the rotation speed of the Brumagin impeller was increased to 600 rpm.
Further added vinyl chloride-based monomer was added over 6 hours, and the pressure of the reactor after the addition of the vinyl chloride-based monomer was reduced by 1.0kgf/cm with respect to the initial polymerization2When the polymerization is stopped. Thereafter, the unreacted monomer was recovered and the polymerization was 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
Pellets of a vinyl chloride-based resin composition were obtained in the same manner as in example 1, except that 3kg of dioctyl maleate was added instead of 7kg of dioctyl maleate.
Example 3
Pellets of a vinyl chloride-based resin composition were obtained in the same manner as in example 1, except that 7kg of isodecyl acrylate was added instead of 7kg of dioctyl maleate.
Comparative example 1
Oxygen was removed from the 280L reactor using a vacuum pump. 36kg of vinyl chloride-based monomer, 14.5kg of vinyl acetate monomer, 0.5kg of methoxy PEG600 methacrylate (as a reactive additive based on polyethylene glycol), 0.19kg of dioctyltin mercaptide (as an organotin compound), 3.0kg of a 3% aqueous solution of a cellulose-based suspending agent, and 56g of azobisisobutyronitrile (as an initiator) were added to the reactor together with 130L of deionized water, followed by initiation of polymerization while rotating a Brumagin impeller at 300 rpm.
When the reactor is warmImmediately after the temperature reached 68 ℃, 9kg of hydroxypropyl acrylate was continuously added over 6 hours. When the reactor pressure was reduced by 1.0kgf/cm with respect to the initial polymerization2At this time, further addition of 36kg of vinyl chloride-based monomer was started, and the rotation speed of the Brumagin impeller was increased to 600 rpm.
Further added vinyl chloride-based monomer was added over 5 hours, and the pressure of the reactor after the addition of the vinyl chloride-based monomer was reduced by 1.0kgf/cm with respect to the initial polymerization2When the polymerization is stopped. Thereafter, the unreacted monomer was recovered and the polymerization was terminated. The polymerized slurry was dehydrated and dried to obtain vinyl chloride-based resin composition particles having an average particle diameter of 190 μm.
Comparative example 2
Except that (i) 41kg instead of 36kg of vinyl chloride-based monomer was added and 5kg instead of 14.5kg of vinyl acetate monomer was added before initiation of polymerization; and (ii) pellets of a vinyl chloride-based resin composition were obtained in the same manner as in comparative example 1, except that 41kg, instead of 36kg, of a vinyl chloride-based monomer was added during the polymerization.
Comparative example 3
Except that (i) 43kg instead of 36kg of vinyl chloride-based monomer was added, 5kg instead of 14.5kg of vinyl acetate monomer was added, and 5kg instead of 9kg of hydroxypropyl acrylate was added before initiation of polymerization; and (ii) vinyl chloride-based resin composition pellets were obtained in the same manner as in comparative example 1, except that 43kg, instead of 36kg, of vinyl chloride-based monomer was added during the polymerization.
Comparative example 4
Except that (i) 45kg instead of 36kg of vinyl chloride-based monomer was added, 1kg instead of 14.5kg of vinyl acetate monomer was added, and 5kg instead of 9kg of hydroxypropyl acrylate was added before initiation of polymerization; and (ii) pellets of a vinyl chloride-based resin composition were obtained in the same manner as in comparative example 1, except that 45kg, instead of 36kg, of a vinyl chloride-based monomer was added during the polymerization.
Comparative example 5
Pellets of a vinyl chloride-based resin composition (product name: TP-400A, manufacturer: Hanwha Chemical) which is a terpolymer of vinyl chloride, vinyl acetate and dicarboxylic acid were prepared.
Comparative example 6
A saponified vinyl chloride-based resin composition particle (product name:
a, manufacturer: Shin-Etsu MicroSi Co.), which is a terpolymer of vinyl chloride, vinyl alcohol and vinyl acetate.
Preparation examples 1-A to 1-I
A mixed solution corresponding to the preparation examples of each example and comparative example was prepared by mixing 20 wt% of the vinyl chloride-based resin composition particles prepared in each example and comparative example, 40 wt% of ethyl acetate, and 40 wt% of toluene, and then stirring at 50 ℃ for 90 minutes.
Preparation examples 2-A to 2-I
50g of the mixed solution according to one of preparation examples 1-A to 1-I, 10g of a pigment (Red 146), 35g of beads (product name: alumina beads, manufacturer: Samwha Ceramic), and 5g of ethylene-vinyl acetate (product name:
42-60, manufacturer: arkema) and stirred 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
50g of the mixed solution according to one of preparation examples 1-A to 1-I, 20g of a pigment (White R-216), 35g of beads (product name: alumina beads, manufacturer: Samwha Ceramic) and 5g of ethylene-vinyl acetate (product name:
42-60，the manufacturer: arkema) and stirred with an ink stirrer for 1 hour to prepare white paint inks corresponding to the respective examples and comparative examples.
Test example 1
The viscosity (cps) 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 ℃ was measured using a Brookfield viscometer.
Test example 2
The transparency of the mixed solutions of preparation examples 1-A to 1-I was measured using an ultraviolet spectrometer (475 nm).
Test example 3
After the red inks of production examples 2-a to 2-I and the white inks of production examples 3-a to 3-I were respectively coated on a PET film and dried, the glossiness was repeatedly measured five times at 60 ° using a glossmeter (BYK, Micro-Gloss) and an average value thereof was calculated.
Test example 4
After the red inks of preparation examples 2-A to 2-I were stored in a container at room temperature for 10 days, the degree of phase separation of the inks was observed. The stability was relatively evaluated as the following 5: excellent (. circleincircle.), good (. smallcircle.), good (. tangle-solidup.), medium (. DELTA.) and poor (. X).
When the ink is unstable, layer separation of the ink and aggregation of the pigment may occur within 1 hour after the ink is formulated. In addition, when inks with poor stability are applied, the gloss of the coating is relatively poor.
[ TABLE 1]
| Mixed solution | 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 examples 1 to D | Comparative example 1 | 93 | 254 |
| Preparation examples 1 to E | Comparative example 2 | 76 | 673 |
| Preparation example 1-F | Comparative example 3 | 71 | 891 |
| Preparation examples 1-G | Comparative example 4 | 60 | 4322 |
| Preparation example 1-H | Comparative example 5 | 93 | 251 |
| Preparation examples 1 to I | Comparative example 6 | 76 | 300 |
[ TABLE 2]
| Red ink | Resin composition | Glossiness (GU) | Viscosity (cps) | Stability of |
| 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 examples 2-D | Comparative example 1 | 4.1 | 221 | X |
| Preparation examples 2 to 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 | Glossiness (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 examples 3-D | Comparative example 1 | 2.3 | 191 |
| Preparation examples 3 to E | Comparative example 2 | 3.6 | 156 |
| Preparation example 3-F | Comparative example 3 | 4.7 | 137 |
| Preparation examples 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 it was observed whether the compatibility with ethylene-vinyl acetate was improved when preparing the ink. As a result, the stability and gloss (dispersibility) of the ink are improved due to the reduced vinyl acetate and hydroxypropyl acrylate content. However, the inks of comparative examples 1 to 4 were inferior in glossiness (dispersibility) compared with comparative example 6, which is a saponified vinyl chloride resin composition. Further, it was confirmed that the viscosity of the solution rapidly increased from comparative example 1 to comparative example 4, making it unsuitable for use as a coating ink.
The vinyl chloride-based resin compositions according to examples 1 to 3 showed excellent transparency, as well as equivalent or higher glossiness (dispersibility) and stability, as compared to comparative example 6, which is a saponified vinyl chloride-based resin composition. Thus, they were found to have suitable viscosity for use as coating inks.
Claims (8)
1. A method for preparing a vinyl chloride-based resin composition, comprising the step of polymerizing a vinyl chloride-based monomer, an ethylenically unsaturated monomer, a (meth) acrylate monomer having a C10 to C20 linear, branched or cyclic alkyl group, and a hydroxyl monomer in the presence of an initiator,
wherein the ethylenically unsaturated monomer is added in an amount of 0.1 to 50 parts by weight, the (meth) acrylate monomer having a C10 to C20 linear, branched or cyclic alkyl group is added in an amount of 1 to 50 parts by weight, and the hydroxyl monomer is added in an amount of 1 to 30 parts by weight, based on 100 parts by weight of the vinylchloride-based monomer,
wherein the vinyl chloride-based monomer is added for the first time before polymerization, and within 100 minutes after the polymerization temperature is reached, or when the pressure in the reactor is reduced by 0.5kgf/cm with respect to the initial pressure of polymerization2To 1.0kgf/cm2When the mixture is added for the second time,
wherein the ethylenically unsaturated monomer includes at least one compound selected from the group consisting of a vinyl acetate monomer, a vinyl propionate monomer, ethylene, propylene, isobutyl vinyl ether, a maleic anhydride monomer, an acrylonitrile monomer, a styrene monomer, and a vinylidene halide monomer;
wherein the (meth) acrylate monomer having a C10 to C20 linear, branched, or cyclic alkyl group includes at least one compound selected from isodecyl acrylate, isodecyl methacrylate, isobornyl acrylate, isobornyl methacrylate, dipentyl maleate, dihexyl maleate, dioctyl maleate, and dinonyl maleate;
wherein the hydroxyl monomer comprises at least one compound selected from the group consisting of glycerol monoacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylamide, hydroxypolyethoxyallyl ether, hydroxypropyl acrylate, hydroxypropyl methacrylate, pentaerythritol triacrylate, polypropylene glycol methacrylate, acryloxyethoxyhydroxybenzophenone, allylhydroxyacetophenone, and (methacryloyloxy) hydroxybenzophenone,
wherein the polymerization is performed by further adding a polyethylene glycol-based reactive additive comprising a (meth) acrylate group represented by the following chemical formula 1:
[ chemical formula 1]
In the chemical formula 1, the first and second,
n is an integer of 2 to 100,
r1 and R2 are each independently hydrogen, a C1 to C10 hydrocarbyl group, or a (meth) acrylate group, and at least one of R1 and R2 is a (meth) acrylate group;
wherein the polyethylene glycol-based reactive additive has a weight average molecular weight Mw of 200 to 5000g/mol, and
wherein the polyethylene glycol-based reactive additive is added in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the vinylchloride-based monomer.
2. The method for preparing a vinyl chloride-based resin composition according to claim 1,
wherein 10 to 90% by weight 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 pressure in the reactor is decreased by 0.5kgf/cm within 100 minutes after the polymerization temperature is reached or when the pressure in the reactor is lowered with respect to the initial pressure of polymerization2To 1.0kgf/cm2The hydroxyl monomer is added.
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 degree of polymerization of the monomer is 30% to 80%.
5. The method for preparing vinyl chloride-based resin composition according to claim 1,
wherein the polymerization is carried out with stirring, and
within 100 minutes after the polymerization temperature is reached, or when the pressure in the reactor is lowered by 0.5kgf/cm relative to the initial pressure of polymerization2To 1.0kgf/cm2The stirring is performed by increasing the stirring speed.
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 coating ink comprising the vinyl chloride-based resin composition of claim 7.
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| WO2023089453A1 (en) | 2021-11-16 | 2023-05-25 | SCG Chemicals Public Company Limited | Vinyl chloride copolymer and copolymer composition, and an article comprising the same |
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| CN103865326A (en) * | 2014-02-27 | 2014-06-18 | 安徽颍美彩印包装有限公司 | Printing ink for surface of light-resistant metal and preparation method thereof |
| KR101759719B1 (en) * | 2016-12-05 | 2017-07-20 | 한화케미칼 주식회사 | Method for preparing vinylchloride based resin composition |
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| JP2991570B2 (en) * | 1992-07-09 | 1999-12-20 | 日信化学工業株式会社 | Magnetic recording media |
| DE19531849A1 (en) * | 1994-08-31 | 1996-03-07 | Henkel Kgaa | Polystyrene binders, used in adhesives, coatings and sealants, |
| JPH1143517A (en) * | 1997-05-27 | 1999-02-16 | Denki Kagaku Kogyo Kk | Vinyl chloride-vinyl acetate copolymer, binder for magnetic recording medium and magnetic recording medium |
| JP5019778B2 (en) * | 2006-04-14 | 2012-09-05 | 新第一塩ビ株式会社 | Method for producing vinyl chloride polymer |
| JP5729286B2 (en) * | 2010-12-24 | 2015-06-03 | 日信化学工業株式会社 | Vinyl chloride resin, method for producing the same, and ink |
| WO2012147625A1 (en) * | 2011-04-27 | 2012-11-01 | 旭硝子株式会社 | Water-repellent and oil-repellent agent compound, manufacturing method therefor, and article |
| DE112013000162B4 (en) * | 2012-09-20 | 2018-04-26 | Lg Chem. Ltd. | Process for producing a vinyl chloride resin latex with low energy consumption |
| JP2014114380A (en) * | 2012-12-10 | 2014-06-26 | Taiyo Vinyl Corp | Vinyl chloride-based resin composition for hard calender molding |
| KR102345704B1 (en) * | 2013-11-26 | 2021-12-30 | 에이지씨 가부시키가이샤 | Water- and oil-repellent composition, article and process for producing article |
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| CN103865326A (en) * | 2014-02-27 | 2014-06-18 | 安徽颍美彩印包装有限公司 | Printing ink for surface of light-resistant metal and preparation method thereof |
| KR101759719B1 (en) * | 2016-12-05 | 2017-07-20 | 한화케미칼 주식회사 | Method for preparing vinylchloride based resin composition |
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