KR101253814B1 - Acrylic type polymer composition, method for preparing the same, and vinyl chloride resin composition comprising the same - Google Patents

Abstract

The present invention relates to an acrylic polymer composition, a method for preparing the same, and a vinyl chloride resin composition including the same. According to the present invention, at least one monomer selected from the group consisting of a methyl methacrylate monomer and an alkyl acrylate monomer is polymerized to be formed. Provided is an acrylic polymer composition having a glass transition temperature of 10 to 55 ° C. and a relative viscosity of 2 to 12, a preparation method thereof, and a vinyl chloride resin composition including the same.

Acrylic resin, vinyl chloride resin, plasticizer, filler, glass transition temperature

Description

ACRYLIC TYPE POLYMER COMPOSITION, METHOD FOR PREPARING THE SAME, AND VINYL CHLORIDE RESIN COMPOSITION COMPRISING THE SAME}

The present invention relates to an acrylic polymer composition, a method for preparing the same, and a vinyl chloride resin composition including the same, and more particularly, to provide an acrylic polymer composition having a glass transition temperature and a relative viscosity in a predetermined range, and an acrylic polymer according to the present invention. When it is added to the vinyl chloride resin can provide an excellent foaming vinyl chloride resin, when added to the vinyl chloride resin composition using a plasticizer can provide a vinyl chloride resin that does not appear fish-eye, When added to a vinyl chloride resin using a large amount of filler can provide a vinyl chloride resin with further improved processability and mechanical properties.

Vinyl chloride-based resin is inexpensive, easy to control the hardness, and can be applied to most processing equipment has a variety of applications. In addition, the present invention is widely used in various fields because it provides a molded article having excellent physical and chemical properties.

This widely used vinyl chloride resin has several disadvantages in impact strength, processability, thermal stability, and heat deflection temperature. Therefore, additives to compensate for this have been developed and used. The additives of such vinyl chloride-based resins include impact modifiers, processing aids, stabilizers, fillers, and the like, and are appropriately selected and used depending on the intended use.

In recent years, interest in foam molding is increasing as a means for reducing the weight of vinyl chloride resins and lowering the cost of molded products. However, when foaming with only vinyl chloride resin, sufficient stretching and melt strength cannot be obtained, and thus the appearance of the molded product is poor, and the foaming cell is large and uneven, so that the foaming ratio is low. Therefore, in order to compensate for these disadvantages, a method of adding a processing aid mainly containing methyl methacrylate to a vinyl chloride resin mixed with a blowing agent has been generally used.

US Pat. No. 6,221,966 adjusts the size of the latex particle size to improve the processability, transparency, and foamability of the vinyl chloride resin.

In addition, US Patent No. 6,391,976 discloses a method of adding a small amount of a processing aid consisting of methyl methacrylate and alkyl methacrylate having 3 to 5 carbon atoms, but does not satisfy the processability and foaming properties. In addition, the vinyl chloride resin composition containing the plasticizer does not sufficiently exhibit dispersibility, processability, and mechanical properties. For example, protrusion may occur in the vinyl chloride resin composition having a plasticizer content of 100 parts by weight or more, and satisfactory mechanical properties may not be obtained when applied to a vinyl chloride resin tile composition that uses a large amount of calcium carbonate.

In order to solve the above problems, the present invention is added to the vinyl chloride resin to provide an excellent foaming vinyl chloride resin composition, and added to the vinyl chloride resin composition with a high plasticizer content, there is no fish-eye, tile flooring An object of the present invention is to provide an acrylic polymer composition which is added to a vinyl chloride resin composition containing a large amount of calcium carbonate to further improve mechanical properties.

Moreover, an object of this invention is to provide the vinyl chloride type resin composition excellent in foamability containing the said polymer.

In addition, an object of the present invention is to provide a vinyl chloride-based resin composition containing a plasticizer that does not generate a fish-eye including the polymer.

In addition, an object of the present invention is to provide a vinyl chloride-based resin composition for tiles mechanical properties containing the polymer.

The present invention provides an acrylic polymer composition having a glass transition temperature of 10 to 55 ° C. and a relative viscosity of 2 to 12 formed by polymerization of at least one monomer selected from the group consisting of a methyl methacrylate monomer and an alkyl acrylate monomer. .

Here, the acrylic polymer composition is formed by polymerizing at least one member selected from the group consisting of methyl methacrylate monomer and alkyl acrylate monomer, based on 100 parts by weight of the acrylic polymer composition, having a glass transition temperature of -10 ° C. or less and a relative viscosity. 0.1 to 30 parts by weight of the first polymer of 1.2 to 10; And 70 to 99.9 parts by weight of the second polymer formed by polymerizing one or more selected from the group consisting of a methyl methacrylate monomer and an alkyl acrylate monomer; it can provide an acrylic polymer composition comprising a.

The acrylic polymer composition of the present invention is based on 100 parts by weight of the methyl methacrylate monomer and the alkyl acrylate monomer (the linear, branched or cyclic alkyl group having 1 to 18 carbon atoms), methyl methacrylate monomer 25 To 45 parts by weight; And 55 to 75 parts by weight of an alkyl acrylate monomer (linear, branched or cyclic alkyl group having 1 to 18 carbon atoms) may be polymerized to provide an acrylic polymer composition.

In addition, the alkyl acrylate monomer of the present invention may be linear, branched or cyclic having 1 to 18 carbon atoms of the alkyl group.

Further, the first polymer of the present invention is from the group consisting of methyl acrylate monomer, ethyl acrylate, n-butyl acrylate, lauryl acrylate, stearyl acrylate, 2-ethylhexyl acrylate, and cyclohexyl acrylate. It may be one or more monomers selected.

There is provided a method for producing an acrylic polymer composition, wherein the acrylic polymer composition according to the present invention is prepared by a polymerization method of emulsion polymerization, suspension polymerization or solution polymerization.

Here, the polymerization method of the emulsion polymerization of the present invention is based on 100 parts by weight of the acrylic polymer composition formed, at least one monomer selected from the group consisting of methyl methacrylate monomer and alkyl acrylate monomer having 1 to 18 carbon atoms of the reactor reactor (A) 0.1 to 30 parts by weight of the first polymer having a glass transition temperature of −10 ° C. or less and a relative viscosity of 1.2 to 10; And one or more selected from the group consisting of a methyl methacrylate monomer and an alkyl acrylate monomer having 1 to 18 carbon atoms in the reactor or in the reactor of step (a) in which the reactor or the first polymer is present before or after step (a). (B) polymerizing the above monomers to emulsion polymerization of 70 to 99.9 parts by weight of the second polymer;

And a glass transition temperature of the acrylic polymer composition including the first polymer and the second polymer may be 10 to 55 ° C., and a relative viscosity of 2 to 12.

In addition, another emulsion polymerization method of the present invention is based on 100 parts by weight of the acrylic polymer composition formed, the polymerization of the alkyl acrylate monomer having 1 to 18 carbon atoms of the alkyl group in the reactor by the glass transition temperature is -10 ℃ or less and relative Emulsion polymerization of 0.1 to 30 parts by weight of the first polymer having a viscosity of 1.2 to 10 (a); And one or more selected from the group consisting of a methyl methacrylate monomer and an alkyl acrylate monomer having 1 to 18 carbon atoms in the reactor or in the reactor of step (a) in which the reactor or the first polymer is present before or after step (a). 70 to 99.9 parts by weight of the second monomer is polymerized by emulsion polymerization; and the glass transition temperature of the acrylic polymer composition including the first polymer and the second polymer is 10 to 55 ° C. and the relative viscosity. 2 to 12 may be a method for producing an acrylic polymer composition.

In addition, the alkyl acrylate monomer having 1 to 18 carbon atoms in the alkyl group of step (a) may be methyl acrylate, ethyl acrylate, n-butyl acrylate, lauryl acrylate, stearyl acrylate, 2-ethylhexyl acrylate. And at least one monomer selected from the group consisting of cyclohexyl acrylate.

In addition, at the time of forming the polymer of steps (a) and (b) of the present invention, the polymer may be formed by including one or more selected from the group consisting of an emulsifier, a polymerization initiator, and a redox catalyst.

The present invention is 100 parts by weight of vinyl chloride resin; And 0.1 to 30 parts by weight of the acrylic polymer; provides a vinyl chloride-based resin composition comprising a.

Here, the vinyl chloride resin composition may further include a filler of 1,200 parts by weight or less.

The filler is at least one member selected from the group consisting of calcium carbonate, talc, clay, silica, mica, titanium dioxide, aluminum hydroxide, bentonite, and aluminum oxide.

The present invention is 100 parts by weight of vinyl chloride resin; 0.1-20 parts by weight of acrylic polymer; It provides a vinyl chloride-based resin composition comprising; and 1 to 100 parts by weight of a plasticizer.

Here, the plasticizer is dibutyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, tricresyl phosphate, tri-2-ethylhexyl phosphate, cresyl diphenyl phosphate, triaryl phosphate, di- It may be at least one selected from the group consisting of 2-ethylhexyl adipate, diisodecyl adipate, and paraffin having 5 to 200 carbon atoms.

As described above, the present invention provides an acrylic polymer composition having a glass transition temperature of 10 to 55 ° C. and a relative viscosity of 2 to 12, and when the acrylic polymer is added to the vinyl chloride resin, it is possible to provide an excellent foamable vinyl chloride resin. It can be, and when added to a vinyl chloride resin composition using a plasticizer can provide a vinyl chloride resin that does not appear fish-eye, when added to a vinyl chloride resin using a filler processability and mechanical properties Further improved vinyl chloride resin can be provided.

Hereinafter, the present invention will be described in detail with reference to examples.

The present invention provides an acrylic polymer composition having a glass transition temperature of 10 to 55 ° C. and a relative viscosity of 2 to 12 formed by polymerization of at least one monomer selected from the group consisting of a methyl methacrylate monomer and an alkyl acrylate monomer. .

It is preferable that the glass transition temperature of the acrylic polymer of the present invention is 10 to 55 ℃, when the glass transition temperature is less than 10 ℃, it is difficult to mass-produce stability and difficulty in recovering in the form of powder during the polymerization, 55 ℃ If it exceeds, the present invention does not provide an excellent effect on the resin composition using the foaming properties, fish eye, a large amount of fillers.

In addition, it is preferable that the relative viscosity of the acrylic polymer of the present invention is 2 to 12, and when the relative viscosity is less than 2, it is not preferable because a sufficient elastic body is not provided, and when it exceeds 12, the fluidity is too small to be undesirable.

The acrylic polymer composition of the present invention is formed by polymerizing at least one member selected from the group consisting of methyl methacrylate monomers and alkyl acrylate monomers based on 100 parts by weight of the acrylic composition, and has a glass transition temperature of -10 ° C. or less. 0.1 to 30 parts by weight of the first polymer having a relative viscosity of 1.2 to 10; And 70 to 99.9 parts by weight of the second polymer formed by polymerizing one or more selected from the group consisting of a methyl methacrylate monomer and an alkyl acrylate monomer.

Here, when the first polymer and the second polymer are polymerized, a polymerizable monomer may be added by adding a methyl methacrylate monomer and an alkyl acrylate monomer. A monomer capable of polymerizing with a methyl methacrylate monomer and an alkyl acrylate monomer is a monomer capable of radical reaction including a double bond such as styrene, styrene derivatives and acrylonitrile.

In addition, the glass transition temperature of the first polymer is preferably -10 ° C or less and the relative viscosity is 1.2 to 10. If the glass transition temperature is higher than -10 ℃ it is not preferable because it does not provide uniform dispersibility. In addition, when the relative viscosity is less than 1.2, the fluidity is large and the function of the lubricant increases, which is not preferable. If the relative viscosity is more than 10, the fluidity is low, which may inhibit uniform dispersion, which is not preferable.

In addition, when the content of the first polymer is less than 0.1 part by weight based on 100 parts by weight of the total amount of the acrylic composition, the present invention does not provide an excellent effect on the resin composition using the foamable, fish eye, and a large amount of filler. If it exceeds the weight part, the lubricant function is strong, which is detrimental to the processability, it is difficult to recover in the form of powder, which is not suitable for mass production. The content of the second polymer 70 to 99.9 parts by weight is an amount determined according to the content of the first polymer.

The acrylic polymer composition according to the present invention is more preferably methyl based on 100 parts by weight of the total content of the methyl methacrylate monomer and the alkyl acrylate monomer (the alkyl group is linear, branched or cyclic having 1 to 18 carbon atoms). 25 to 45 parts by weight of methacrylate monomer; And 55 to 75 parts by weight of an alkyl acrylate monomer (linear, branched or cyclic, having 1 to 18 carbon atoms in the alkyl group); may be an acrylic polymer composition formed by polymerization.

The acrylic polymer composition having the composition has a glass transition temperature (Tg) of 10 to 55 ° C and a relative viscosity of 2 to 12. In addition, when a monomer having a very low glass transition temperature is used, a monomer having a relatively high glass transition temperature may be used in place of the methyl methacrylate monomer.

The alkyl acrylate monomer may be linear, branched or cyclic having 1 to 18 carbon atoms in the alkyl group.

Here, as the alkyl acrylate monomer, methyl acrylate, ethyl acrylate, n-butyl acrylate, lauryl acrylate, stearyl acrylate, 2-ethylhexyl acrylate, or cyclohexyl acrylate alone or two or more in combination It can be used by, but not limited to.

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Further, the first polymer may be used alone or in combination of methyl acrylate, ethyl acrylate, n-butyl acrylate, lauryl acrylate, stearyl acrylate, 2-ethylhexyl acrylate, or cyclohexyl acrylate. It can polymerize.

In the production method of the acrylic polymer composition, the polymerization method is not particularly limited, and polymerization methods such as emulsion polymerization, suspension polymerization and solution polymerization can be used.

Emulsion polymerization is emulsification of a monomer having a certain composition in a non-solvent (generally water), followed by polymerization and production using an initiator and a redox catalyst. Suspension polymerization is a monomer of a certain composition in a non-solvent (usually water). After dispersing using a dispersant, the polymerization is carried out using an initiator and a redox catalyst. Solution polymerization, unlike emulsification and suspension polymerization, dissolves a monomer having a predetermined composition in a solvent to produce a polymerization using an initiator and a redox catalyst. . Preferred among the polymerization methods are emulsion polymerization methods.

The method for producing an acrylic polymer composition of the present invention prepared by emulsion polymerization is selected from the group consisting of methyl methacrylate monomer and alkyl acrylate monomer having 1 to 18 carbon atoms based on 100 parts by weight of the formed acrylic polymer composition. Polymerizing one or more monomers in a reactor to form a polymer once or several times so as to emulsify and polymerize 0.1 to 30 parts by weight of the first polymer having a glass transition temperature of −10 ° C. or less and a relative viscosity of 1.2 to 10 (a); And one or more selected from the group consisting of a methyl methacrylate monomer and an alkyl acrylate monomer having 1 to 18 carbon atoms in the reactor or in the reactor of step (a) in which the reactor or the first polymer is present before or after step (a). Performing a step of polymerizing the monomers to form a polymer once or several times to perform emulsion polymerization of 70 to 99.9 parts by weight of the second polymer; an acrylic polymer composition comprising a first polymer and a second polymer The glass transition temperature of 10 to 55 ℃ and the relative viscosity is characterized in that 2 to 12.

According to the present invention, the monomer to be polymerized in the reactor of step (a) may be used alone or in combination of two or more alkyl acrylate monomers having 1 to 18 carbon atoms in the alkyl group.

In addition, in step (a), it is preferable that the content of the first polymer having a glass transition temperature of −10 ° C. or less and a relative viscosity of 1.2 to 10 is 0.1 to 30 parts by weight based on 100 parts by weight of the acrylic polymer composition. The acrylic polymer composition of the same as described above.

Step (a) is carried out to the monomer containing the first polymer formed in step (b) to form a second polymer, in this case an acrylic polymer composition in which the first polymer and the second polymer is uniformly mixed You can get it. Alternatively, irrespective of the order of steps (a) and (b), first, a monomer may be added to a reactor containing a second polymer formed by performing step (b) to form a first polymer. In this case, it is also possible to obtain an acrylic polymer composition in which the second polymer and the first polymer are uniformly mixed.

In the present invention, the content of the second polymer is preferably 70 to 99.9 parts by weight based on 100 parts by weight of the acrylic polymer composition to be formed, for the same reason as described above with respect to the acrylic polymer composition of the present invention.

In the present invention, the alkyl acrylate monomer having 1 to 18 carbon atoms of the alkyl group is methyl acrylate, ethyl acrylate, n-butyl acrylate, lauryl acrylate, stearyl acrylate, 2-ethylhexyl acrylate, or cyclo Hexyl acrylate can be used individually or in combination of 2 or more types.

In the present invention, in step (a) and (b) it may further comprise one or more selected from the group consisting of an emulsifier, a polymerization initiator, and a redox catalyst to form a polymer.

The emulsifier is preferably 0.5 to 5% by weight in all of the components used to prepare the acrylic copolymer. In addition, the type of emulsifier is not particularly limited, and examples thereof include aliphatic ester, alkyl benzene sulfonate, alkyl phosphate salt, and alkyl sulfosuccinate. It is preferable to use nonionic emulsifiers such as anionic emulsifiers, polyoxyethylene alkyl ethers, and alkylamine esters alone or in combination of two or more kinds thereof.

The polymerization initiator is preferably 0.001 to 0.1% by weight of all the components used to prepare the acrylic copolymer. As the type of polymerization initiator, water-soluble initiators such as potassium persulfate, ammonium persulfate, sodium persulfate, t-butyl hydroperoxide, and di- Fat-soluble initiators such as isopropylbenzene hydroperoxide, cumene hydroperoxide, benzoyl peroxide, organic peroxides such as lauryl peroxide, redox initiator, etc. This is preferred.

The redox catalyst is preferably 0.001 to 0.1% by weight of all the components used to prepare the acrylic copolymer. As a kind of redox catalyst, disodium ethylenediaminetetraacetate (EDTA), formaldehyde sodium sulfoxylate (SFS), ferrous sulfate, copper bisulfate, etc. are preferable. .

The latex-based acrylic copolymer prepared by fusion polymerization may be prepared into a powdery acrylic copolymer through agglomeration, dehydration and drying steps.

Vinyl chloride-based resin is a polymer containing 50% by weight or more of vinyl chloride, it is inexpensive, easy to control the hardness, and can be applied to most processing equipment has a variety of applications. In addition, the present invention is widely used in various fields because it provides a molded article having excellent physical and chemical properties.

The present invention is 100 parts by weight of vinyl chloride resin; It provides a vinyl chloride-based resin composition excellent foaming properties, including; 0.1 to 30 parts by weight of the acrylic polymer of the present invention.

Herein, the content of the acrylic polymer of the present invention includes 0.1 to 30 parts by weight based on 100 parts by weight of the vinyl chloride resin. When the content of the acrylic polymer is less than 0.1, the effect of the acrylic copolymer does not appear, and when it exceeds 30 parts by weight, workability is inhibited.

Here, the vinyl chloride-based resin composition is 1,200 based on 100 parts by weight of the vinyl chloride-based resin alone or two or more of calcium carbonate, talc, clay, silica, mica, titanium dioxide, aluminum hydroxide, bentonite, or aluminum oxide as a filler. It provides a vinyl chloride resin composition for tiles excellent in mechanical properties further included in parts by weight or less.

The present invention is 100 parts by weight of vinyl chloride resin; 0.1 to 20 parts by weight of the acrylic polymer of the present invention; And a plasticizer 1 to 100 parts by weight; provides a vinyl chloride-based resin composition that does not generate projections.

Here, when the acrylic polymer content of the present invention is less than 0.1 based on 100 parts by weight of the vinyl chloride resin, the contribution to the improvement of the physical properties of the soft vinyl chloride resin is small, and when it exceeds 20 parts by weight, workability may be inhibited.

Further, as a plasticizer, dibutyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, butylbenzyl phthalate, tricresyl phosphate, tri-2-ethylhexyl phosphate, cresyl diphenyl phosphate, triaryl phosphate, di- 2-ethylhexyl adipate, diisodecyl adipate, or paraffin having 5 to 200 carbon atoms may be used alone or in combination of two or more thereof.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

Example  One

(1) Preparation of Polymer

To a 3-liter four-necked flask reactor equipped with a stirrer, thermometer, nitrogen inlet, and circulation condenser, an emulsion was prepared by adding 420 g of ion-exchanged water, 10 g of 8% sodium lauryl sulfate solution (3% diluent), and 90 g of n-butyl acrylate. . After making the emulsion, the reactor was maintained at 40 ° C., replaced with a nitrogen atmosphere, and then 0.45 g of t-butyl hydroperoxide (10% diluent) and 12 g of an activation solution were added thereto. The activation solution was 0.017 g of disodium ethylenediaminetetraacetate (EDTA), 0.04 g of formaldehyde sodium sulfoxylate (SFS), 0.001 g of ferrous sulfate and 1.406 g of ion-exchanged water. Was used.

After completion of the first reaction, the mixture was stirred at 60 ° C. for 1 hour, and after adjusting the internal temperature of the reactor to 40 ° C., 162 g of ion-exchanged water, 25 g of 8% sodium lauryl sulfate solution (3% diluent), and methyl methacrylate An emulsion was prepared by adding a monomer mixture of 210 g and 60 g of n-butyl acrylate. After the emulsion was prepared, the reactor was maintained at 40 ° C. and replaced with a nitrogen atmosphere. Then, 0.3 g of t-butyl hydroperoxide (10% diluent) and 6.7 g of the same activation solution as used in the first batch reaction were added. Secondary batch reactions were performed.

After completion of the secondary reaction, the mixture was further stirred at 60 ° C. for 1.5 hours, and after adjusting the internal temperature of the reactor to 40 ° C., 162 g of ion-exchanged water, 25 g of 8% sodium lauryl sulfate solution (3% diluent), and methyl methacryl An emulsion was prepared by adding a monomer mixture of 210 g of rate and 60 g of n-butyl acrylate. After making the emulsion, the internal temperature of the reactor was maintained at 40 ° C., replaced with a nitrogen atmosphere, and 0.3 g of t-butyl hydroperoxide (10% diluent) and 6.7 g of the same activating solution as used in the first batch reaction were added. The third batch reaction was carried out.

After terminating the third reaction, the mixture was further stirred at 60 ° C. for 1 hour to prepare a latex polymer. The latex prepared polymer was agglomerated, dehydrated and dried in calcium chloride to prepare a powder. The relative viscosity thereof was measured, and the results are shown in Table 2.

Relative Viscosity Measurement

3 g of the powdered sample was dissolved in 50 ml of THF solvent, and the relative viscosity was measured using a Uberod viscometer.

Relative viscosity = TIME _Solution / TIME _THF

The main components in each reaction step for preparing the polymer of Example 1, Examples 2 to 6 and Examples 8 to 10, Comparative Examples 1 to 2, and Comparative Examples 4 to 7 to be described later in Table 1 Indicated.

Example  2

Except that ethyl acrylate was used instead of n-butyl acrylate in the first batch reaction, the polymer was prepared in the same manner as in Example 1, and the relative viscosity was measured. The results are shown in Table 2.

Example  3

Except that 2-ethyl hexyl acrylate was used instead of n-butyl acrylate in the first batch reaction, the polymer was prepared in the same manner as in Example 1, and the relative viscosity was measured, and the results are shown in Table 2.

Example  4

The monomer mixture of methyl methacrylate and n-butyl acrylate in the secondary and tertiary batch reactions was added 180 g of methyl methacrylate and 90 g of n-butyl acrylate in the second reaction, 210 g of methyl methacrylate and n in the third reaction. A polymer was prepared in the same manner as in Example 1 except that 60 g of butyl acrylate and the mixed monomer mixture were used, and the relative viscosity was measured. The results are shown in Table 2.

Example  5

The monomer mixture of methyl methacrylate and n-butyl acrylate in the secondary and tertiary batch reactions was added 180 g of methyl methacrylate and 90 g of n-butyl acrylate in the second reaction, 180 g and n of methyl methacrylate in the third reaction. A polymer was prepared in the same manner as in Example 1 except that 90 g of butyl acrylate and the mixed monomer mixture were used, and the relative viscosity was measured. The results are shown in Table 2.

Example  6

A polymer was prepared in the same manner as in Example 4 except that 50% of n-butyl acrylate and ethyl acrylate were used instead of n-butyl acrylate in the first batch reaction. Table 2 shows.

Example  7

In a 3-liter four-necked flask reactor equipped with a stirrer, thermometer, nitrogen inlet and circulation condenser, 532 g of ion-exchanged water, 25 g of 8% sodium lauryl sulfate solution (3% diluent), 210 g of methyl methacrylate and n-butyl acrylate The monomer mixture mixed with 60 g was added to make an emulsion. After making into an emulsion, the internal temperature of the reactor was maintained at 40 ° C. and replaced with a nitrogen atmosphere. Then, 0.3 g of t-butyl hydroperoxide (10% diluent) and 6.7 g of the same activation solution used in Example 1 were added to the first batch. The reaction was carried out.

After completion of the first reaction, the mixture was stirred for 1 hour at 60 ° C., and 50 g of ion-exchanged water, 10 g of 8% sodium lauryl sulfate solution (3% diluent), and 90 g of n-butyl acrylate were added to form an emulsion. After the emulsion was prepared, the reactor was kept at 40 ° C. and replaced with a nitrogen atmosphere. Then, 0.45 g of t-butyl hydroperoxide (10% diluent) and 12 g of the same activating solution as used in Example 1 were added. The next batch reaction was carried out.

After completion of the secondary reaction, the mixture was further stirred at 60 ° C. for 1.5 hours, and after adjusting the internal temperature of the reactor to 40 ° C., 162 g of ion-exchanged water, 25 g of 8% sodium lauryl sulfate solution (3% diluent), and methyl methacryl An emulsion was prepared by adding a monomer mixture of 210 g of rate and 60 g of n-butyl acrylate. After the emulsion was prepared, the internal temperature of the reactor was maintained at 40 ° C., replaced with a nitrogen atmosphere, and then 0.3 g of t-butyl hydroperoxide (10% diluent) and 6.7 g of the same activating solution as used in Example 1 were added thereto. The third batch reaction was carried out.

After terminating the third reaction, the mixture was further stirred for 1 hour at 60 ° C. to prepare a latex polymer. The latex polymer prepared was agglomerated, dehydrated and dried with calcium chloride to prepare a powder, and then the relative viscosity was measured. The results are shown in Table 2 below.

Table 1 shows the main components of each of the reaction steps for preparing the polymer of Example 7 and the polymer of Comparative Example 3 described later.

Example  8

The polymer was polymerized in the same manner as in Example 1, except that 180 g of n-butyl acrylate in the first batch reaction, 140 g of methyl methacrylate and 40 g of n-butyl acrylate in the third batch reaction were used. After preparing the relative viscosity was measured and the results are shown in Table 2.

Example  9

The polymer was polymerized in the same manner as in Example 1, except that 30 g of n-butyl acrylate in the first batch reaction, 257 g of methyl methacrylate and 73 g of n-butyl acrylate in the third batch reaction were used. After preparing the relative viscosity was measured and the results are shown in Table 2.

Example  10

A polymer was prepared in the same manner as in Example 1, except that 30 g of ethyl acrylate in the first batch reaction, 257 g of methyl methacrylate, 73 g of n-butyl acrylate, and a mixed monomer mixture were used in the third batch reaction. The relative viscosity was measured and the results are shown in Table 2.

Comparative example  One

A polymer was prepared in the same manner as in Example 1 except that 70 g of methyl methacrylate and 20 g of n-butyl acrylate were used in the first batch reaction. The relative viscosity was measured, and the results are shown in Table 2.

Comparative example  2

The monomer mixture of methyl methacrylate and n-butyl acrylate in the secondary and tertiary batch reactions was added 250 g of methyl methacrylate and 20 g of n-butyl acrylate in the secondary reaction, 250 g of methyl methacrylate and n in the tertiary reaction. A polymer was prepared in the same manner as in Example 1 except that 20 g of butyl acrylate and a mixed monomer mixture were used, and the relative viscosity was measured. The results are shown in Table 2 below.

Comparative example  3

250 g of methyl methacrylate in the first batch reaction, 20 g of n-butyl acrylate, 90 g of n-butyl acrylate in the second batch reaction, 250 g of methyl methacrylate and 20 g of n-butyl acrylate in the third batch reaction Except that one monomer mixture was used, the polymer was prepared in the same manner as in Example 7, the relative viscosity was measured, and the results are shown in Table 2.

Comparative example  4

A polymer was prepared in the same manner as in Example 1, except that a reaction temperature of 60 ° C., 0.9 g of t-butyl hydroperoxide (10% diluent), and 24 g of an activation solution were added in the first batch reaction. The relative viscosity was measured and the results are shown in Table 2.

Comparative example  5

The relative viscosity was measured by preparing a polymer in the same manner as in Example 1, except that 0.009 g of t-butyl hydroperoxide (10% diluent) and 4 g of an activation solution were added in the first batch reaction. After the results are shown in Table 2.

Comparative example  6

Reaction temperature 70 ℃ in 2nd batch reaction, 0.6g t-butyl hydroperoxide (10% diluent) and 13.4g activating solution were added and reaction temperature 70 ℃ in 3rd batch reaction, t-butyl A polymer was prepared in the same manner as in Example 1 except that 0.6 g of t-butyl hydroperoxide (10% diluent) and 13.4 g of an activation solution were added. Shown in

Comparative example  7

The polymer was polymerized in the same manner as in Example 1, except that 220 g of n-butyl acrylate in the first batch reaction, 110 g of methyl methacrylate and 30 g of n-butyl acrylate in the third batch reaction were used. After preparing the relative viscosity was measured and the results are shown in Table 2.

Examples 11 to 30 and Comparative Examples 8 to 21: Preparation of vinyl chloride resin having excellent foaming properties using a polymer and preparation of vinyl chloride resin having excellent dispersibility

Example  11

(1) Preparation of vinyl chloride resin containing polymer (including filler)

To 100 g of vinyl chloride resin (LS080, manufactured by LG Chemical), after adding 6.4 g of composite stabilizer KD-105 (a composite heat stabilizer and foam stabilizer of uniformly mixed heat stabilizer and lubricant) and 13 g of filler (CaCO ₃ ) 6 g of the polymer prepared in Example 1 and 0.9 g of azodicarbonamide were further added and kneaded while heating up to 115 ° C. using a Henschel mixer to prepare a vinyl chloride resin including an acrylic polymer. .

(2) Foamability Measurement of Vinyl Chloride Resin Containing Polymer

The vinyl chloride resin prepared in (1) above was 5 mm at a cylinder temperature of 180 ° C. and a screw speed of 30 rpm using a 30 mm single spindle extruder equipped with a rectangular slit die. The foam density of the foamed molded product obtained by cutting out a rectangular rod of thickness) x30 mm (width) and cutting it to a length of 5 mm was measured using a specific gravity meter and the results are shown in Table 2. The lower the foam density, the higher the foamability. This is an excellent thing.

In addition, the cross section of the foamed molded product obtained above was observed by an optical microscope and evaluated as 5 points when the foam cells were uniform, 3 points when the foam cells were slightly uneven, and 1 point when the foam cells were not uniform. The results are shown in Table 2 below.

Example  12

After preparing a vinyl chloride resin in the same manner as in Example 11 using the polymer prepared in Example 2 to evaluate the degree of foamability, the results are shown in Table 2.

Example  13

The vinyl chloride resin was prepared in the same manner as in Example 11 using the polymer prepared in Example 3 to evaluate the degree of foamability, and the results are shown in Table 2 below.

Example  14

After preparing a vinyl chloride resin in the same manner as in Example 11 using the polymer prepared in Example 4 to evaluate the degree of foamability, the results are shown in Table 2.

Example  15

The vinyl chloride resin was prepared in the same manner as in Example 11 using the polymer prepared in Example 5 to evaluate the degree of foamability, and the results are shown in Table 2 below.

Example  16

After preparing a vinyl chloride resin in the same manner as in Example 11 using the polymer prepared in Example 6 to evaluate the degree of foamability, the results are shown in Table 2.

Example  17

The vinyl chloride resin was prepared in the same manner as in Example 11 using the polymer prepared in Example 7 to evaluate the degree of foamability, and the results are shown in Table 2 below.

Example  18

The vinyl chloride resin was prepared in the same manner as in Example 11 using the polymer prepared in Example 8 to evaluate the degree of foamability, and the results are shown in Table 2 below.

Example  19

The vinyl chloride resin was prepared in the same manner as in Example 11 using the polymer prepared in Example 9 to evaluate the degree of foamability, and the results are shown in Table 2 below.

Example  20

After preparing a vinyl chloride resin in the same manner as in Example 11 using the polymer prepared in Example 10 to evaluate the degree of foamability, the results are shown in Table 2.

Comparative example  8

A vinyl chloride resin was prepared in the same manner as in Example 11 using the polymer prepared in Comparative Example 1 to evaluate the degree of foamability, and the results are shown in Table 2 below.

Comparative example  9

A vinyl chloride resin was prepared in the same manner as in Example 11 using the polymer prepared in Comparative Example 2 to evaluate the degree of foamability, and the results are shown in Table 2 below.

Comparative example  10

A vinyl chloride resin was prepared in the same manner as in Example 11 using the polymer prepared in Comparative Example 3 to evaluate the degree of foamability, and the results are shown in Table 2 below.

Comparative example  11

A vinyl chloride resin was prepared in the same manner as in Example 11 using the polymer prepared in Comparative Example 4 to evaluate the degree of foamability, and the results are shown in Table 2 below.

Comparative example  12

A vinyl chloride resin was prepared in the same manner as in Example 11 using the polymer prepared in Comparative Example 5 to evaluate the degree of foamability, and the results are shown in Table 2 below.

Comparative example  13

A vinyl chloride resin was prepared in the same manner as in Example 11 using the polymer prepared in Comparative Example 6 to evaluate the degree of foamability, and the results are shown in Table 2 below.

Comparative example  14

A vinyl chloride resin was prepared in the same manner as in Example 11 using the polymer prepared in Comparative Example 7 to evaluate the degree of foamability, and the results are shown in Table 2 below.

Example  21

(3) of vinyl chloride resin containing polymer Undispersed ( fish - eye A) measurement

50 g of polyvinyl chloride resin (LS080, manufactured by LG Chemical) 6.4 g of composite stabilizer KD-105 (combined thermal stabilizer and foam stabilizer of uniformly mixed thermal stabilizer and lubricant) and 50 g of plasticizer (DINP) in Example 1 4 g of the prepared polymer was added and mixed at room temperature using a mixer to prepare a vinyl chloride resin composition including a plasticizer. Roll-milling the vinyl chloride resin composition at 175 ° C to prepare sheet-shaped specimens, and then observing the number of microdispersions (microgelates) present in a predetermined area of the sheet surface. When the product is slightly produced 3 points, when a lot of undispersed product is evaluated as 1 point, the results are shown in Table 2.

Example  22

A vinyl chloride resin was prepared in the same manner as in Example 21 using the polymer prepared in Example 2 to evaluate the degree of undispersed product, and the results are shown in Table 2 below.

Example  23

A vinyl chloride resin was prepared in the same manner as in Example 21 using the polymer prepared in Example 3 to evaluate the degree of undispersed product, and the results are shown in Table 2 below.

Example  24

A vinyl chloride resin was prepared in the same manner as in Example 21 using the polymer prepared in Example 4 to evaluate the degree of undispersed product, and the results are shown in Table 2 below.

Example  25

A vinyl chloride resin was prepared in the same manner as in Example 21 using the polymer prepared in Example 5 to evaluate the degree of undispersed product, and the results are shown in Table 2 below.

Example  26

A vinyl chloride resin was prepared in the same manner as in Example 21 using the polymer prepared in Example 6 to evaluate the degree of undispersed product, and the results are shown in Table 2 below.

Example  27

A vinyl chloride resin was prepared in the same manner as in Example 21 using the polymer prepared in Example 7 to evaluate the extent of the undispersed product, and the results are shown in Table 2 below.

Example  28

A vinyl chloride resin was prepared in the same manner as in Example 21 using the polymer prepared in Example 8 to evaluate the degree of undispersed product, and the results are shown in Table 2 below.

Example  29

A vinyl chloride resin was prepared in the same manner as in Example 21 using the polymer prepared in Example 9 to evaluate the degree of undispersed product, and the results are shown in Table 2 below.

Example  30

A vinyl chloride resin was prepared in the same manner as in Example 21 using the polymer prepared in Example 10, and the results of evaluating the degree of undispersed product were shown in Table 2 below.

Comparative example  15

A vinyl chloride resin was prepared in the same manner as in Example 21 using the polymer prepared in Comparative Example 1 to evaluate the degree of undispersed product, and the results are shown in Table 2 below.

Comparative example  16

A vinyl chloride resin was prepared in the same manner as in Example 21 using the polymer prepared in Comparative Example 2 to evaluate the degree of undispersed product, and the results are shown in Table 2 below.

Comparative example  17

A vinyl chloride resin was prepared in the same manner as in Example 21 using the polymer prepared in Comparative Example 3 to evaluate the degree of undispersed product, and the results are shown in Table 2 below.

Comparative example  18

A vinyl chloride resin was prepared in the same manner as in Example 21 using the polymer prepared in Comparative Example 4 to evaluate the degree of undispersed product, and the results are shown in Table 2 below.

Comparative example  19

A vinyl chloride resin was prepared in the same manner as in Example 21 using the polymer prepared in Comparative Example 5 to evaluate the degree of undispersed product, and the results are shown in Table 2 below.

Comparative example  20

A vinyl chloride resin was prepared in the same manner as in Example 21 using the polymer prepared in Comparative Example 6 to evaluate the degree of undispersed product, and the results are shown in Table 2 below.

Comparative example  21

A vinyl chloride resin was prepared in the same manner as in Example 21 using the polymer prepared in Comparative Example 7 to evaluate the extent of the undispersed product, and the results are shown in Table 2 below.

Examples 31 to 40 and Comparative Examples 22 to 28: Preparation of a vinyl chloride resin composition for tiles having excellent mechanical properties using a polymer

Example  31

After preparing the compounding compound of the vinyl chloride resin composition containing the polymer of Example 1, the mechanical properties were evaluated and the results are shown in Table 3.

1) of vinyl chloride resin composition Compounder  Produce

800 parts by weight of calcium carbonate, 45 parts by weight of plasticizer (DINP), 2.5 parts by weight of rosin, 1 part by weight of epoxy, 2 parts by weight of glycerin, 3 parts by weight of processing aid, Ba-Zn-based A raw material containing 2 parts by weight of the stabilizer and 8 g of the polymer of Example 1 was kneaded at room temperature to prepare a compounder having an acrylic composition.

2) Mechanical Properties

After processing 64 g of the composition under conditions of 120 ° C and 40 rpm for 10 minutes, the melt compounder was collected, placed in a mold of 1 mm x 150 mm x 150 mm, preheated (0.5 kg) for 4 minutes with a 195 ° C heating press, A press specimen of 1 mm thickness was prepared by compression (10 kg) for 4 minutes.

Tensile strength and tensile elongation of the press specimens were measured according to ASTM D-638.

Example  32

The polymer of Example 2 was used and evaluated in the same manner as in Example 31, and the results are shown in Table 3.

Example  33

The polymer of Example 3 was used and evaluated in the same manner as in Example 31, and the results are shown in Table 3.

Example  34

The polymer of Example 4 was used and evaluated in the same manner as in Example 31, and the results are shown in Table 3.

Example  35

The polymer of Example 5 was used and evaluated in the same manner as in Example 31, and the results are shown in Table 3.

Example  36

The polymer of Example 6 was used and evaluated in the same manner as in Example 31, and the results are shown in Table 3.

Example  37

The polymer of Example 7 was evaluated in the same manner as in Example 31, and the results are shown in Table 3.

Example  38

The polymer of Example 8 was used and evaluated in the same manner as in Example 31, and the results are shown in Table 3.

Example  39

The polymer of Example 9 was used and evaluated in the same manner as in Example 31, and the results are shown in Table 3.

Example  40

The polymer of Example 10 was used and evaluated in the same manner as in Example 31, and the results are shown in Table 3.

Comparative example  22

The polymers of Comparative Example 1 were evaluated in the same manner as in Example 31, and the results are shown in Table 3.

Comparative example  23

The polymers of Comparative Example 2 were evaluated in the same manner as in Example 31, and the results are shown in Table 3.

Comparative example  24

The polymers of Comparative Example 3 were evaluated in the same manner as in Example 31, and the results are shown in Table 3.

Comparative example  25

The polymers of Comparative Example 4 were evaluated in the same manner as in Example 31, and the results are shown in Table 3.

Comparative example  26

The polymers of Comparative Example 5 were evaluated in the same manner as in Example 31, and the results are shown in Table 3.

Comparative example  27

The polymers of Comparative Example 6 were evaluated in the same manner as in Example 31, and the results are shown in Table 3.

Comparative example  28

After evaluating in the same manner as in Example 31 using the polymer of Comparative Example 7, the results are shown in Table 3.

The glass transition temperature was obtained by the following Fox Equation.

Fox Equation: 1 / Tg = w ₁ / Tg ₁ + w ₂ / Tg ₂ + ‥‥

W _i : weight fraction of component i

Tg _i : Glass transition temperature of i component (Tg, K)

Relative viscosity I of Example 7, Comparative Example 3 is the relative viscosity of the secondary reaction.

Relative viscosity I: Relative viscosity of the first polymer having a glass transition temperature of -10 ° C. or less.

Relative viscosity II: Relative viscosity of the final acrylic polymer composition

In Tables 1 and 2, the vinyl chloride-based resin compositions of Examples 11 to 20 prepared using the acrylic polymer compositions of Examples 1 to 10 and vinyl chloride-based resins were used in the vinyl chloride-based resin compositions of Comparative Examples 8 to 14. Compared to the foam density and the uniformity of the foam cell it can be seen that the foamability is good.

In addition, the vinyl chloride-based resin composition of Examples 21 to 30 prepared using the acrylic polymer composition, the plasticizer and the vinyl chloride-based resin of Examples 1 to 10 was compared with the vinyl chloride-based resin composition of Comparative Examples 15 to 21. It can be seen that there is little fish-eye.

In Table 3, the vinyl chloride-based resin compositions of Examples 31 to 40 prepared using the acrylic polymer compositions, the fillers, and the vinyl chloride-based resins of Examples 1 to 10 were compared with those of the vinyl chloride-based resin compositions of Comparative Examples 22 to 28. It can be seen that the tensile strength and tensile elongation are excellent.

As described above, the polymer composition according to the present invention is added to the vinyl chloride resin composition at a constant ratio to improve the processability of the vinyl chloride resin and to provide an excellent molded foam, and is added to the vinyl chloride resin composition having a high plasticizer content. It is a useful invention that has no effect (Fish-eye), and is added to the vinyl chloride resin composition containing a large amount of calcium carbonate, such as tile flooring, to further improve mechanical properties.

While the invention has been described in detail above with reference to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope and spirit of the invention, and such modifications and variations fall within the scope of the appended claims. It is also natural.

Claims (14)

An acrylic polymer composition having a glass transition temperature of 10 to 55 ° C. and a relative viscosity of 2 to 12 formed by polymerization of at least one monomer selected from the group consisting of a methyl methacrylate monomer and an alkyl acrylate monomer, The acrylic polymer composition is based on 100 parts by weight of the acrylic polymer composition, 0.1 to 30 parts by weight of a first polymer having a glass transition temperature of -10 ° C. or less and a relative viscosity of 1.2 to 10, formed by polymerizing at least one selected from the group consisting of a methyl methacrylate monomer and an alkyl acrylate monomer; And 70 to 99.9 parts by weight of the second polymer formed by polymerizing one or more selected from the group consisting of methyl methacrylate monomers and alkyl acrylate monomers. delete The polymer composition of claim 1, wherein the acrylic polymer composition comprises a total of methyl methacrylate monomers and alkyl acrylate monomers (the alkyl group is linear having 1 to 18 carbon atoms, branched form having 4 to 18 carbon atoms or cyclic type having 3 to 18 carbon atoms). Based on 100 parts by weight of content, 25 to 45 parts by weight of methyl methacrylate monomer; And 55 to 75 parts by weight of an alkyl acrylate monomer (an alkyl group is linear having 1 to 18 carbon atoms, a branched form having 4 to 18 carbon atoms or a cyclic type having 3 to 18 carbon atoms); and an acrylic polymer composition formed by polymerization. The acrylic polymer composition of claim 1, wherein the alkyl acrylate monomer is linear having 1 to 18 carbon atoms, branched form having 4 to 18 carbon atoms or cyclic type having 3 to 18 carbon atoms. The method of claim 1 wherein the first polymer is from the group consisting of methyl acrylate, ethyl acrylate, n-butyl acrylate, lauryl acrylate, stearyl acrylate, 2-ethylhexyl acrylate, and cyclohexyl acrylate Acrylic polymer composition, characterized in that formed by polymerizing at least one monomer selected. A method for producing an acrylic polymer composition, wherein the acrylic polymer composition of claim 1 is prepared by a polymerization method of emulsion polymerization, suspension polymerization or solution polymerization. The method of claim 6, wherein the polymerization method of emulsion polymerization is based on 100 parts by weight of the acrylic polymer composition formed. One or more monomers selected from the group consisting of methyl methacrylate monomers and alkyl acrylate monomers having 1 to 18 carbon atoms in the alkyl group are polymerized in a reactor, and have a glass transition temperature of -10 ° C. or lower and a relative viscosity of 1.2 to 10. Emulsion polymerizing 0.1 to 30 parts by weight of one polymer (a); And At least one selected from the group consisting of a methyl methacrylate monomer and an alkyl acrylate monomer having 1 to 18 carbon atoms in the reactor or in the reactor of step (a) in which the reactor or first polymer is present before or after step (a) (B) polymerizing a monomer to emulsion-polymerize 70 to 99.9 parts by weight of the second polymer; And a glass transition temperature of the acrylic polymer composition including the first polymer and the second polymer is 10 to 55 ° C. and a relative viscosity of 2 to 12. 8. The alkyl acrylate monomer according to claim 7, wherein the alkyl acrylate monomer having 1 to 18 carbon atoms in step (a) is methyl acrylate, ethyl acrylate, n-butyl acrylate, lauryl acrylate, stearyl acrylate, 2- Ethyl hexyl acrylate, and cyclohexyl acrylate method of producing an acrylic polymer composition, characterized in that at least one monomer selected from the group consisting of. 8. The preparation of an acrylic polymer composition according to claim 7, further comprising one or more selected from the group consisting of an emulsifier, a polymerization initiator, and a redox catalyst in steps (a) and (b). Way. 100 parts by weight of vinyl chloride resin; And 0.1 to 30 parts by weight of the acrylic polymer of claim 1; Vinyl chloride-based resin composition comprising. The vinyl chloride resin composition of claim 10, wherein the vinyl chloride resin composition further comprises 1,200 parts by weight or less of a filler. 12. The vinyl chloride resin composition according to claim 11, wherein the filler is at least one selected from the group consisting of calcium carbonate, talc, clay, silica, mica, titanium dioxide, aluminum hydroxide, bentonite, and aluminum oxide. 100 parts by weight of vinyl chloride resin; 0.1 to 20 parts by weight of the acrylic polymer of claim 1; And 1 to 100 parts by weight of plasticizer; Vinyl chloride-based resin composition comprising. The method of claim 13, wherein the plasticizer is dibutyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, butylbenzyl phthalate, tricresyl phosphate, tri-2-ethylhexyl phosphate, cresyl diphenyl phosphate, triaryl Vinyl chloride-based resin composition, characterized in that at least one selected from the group consisting of phosphate, di-2-ethylhexyl adipate, diisodecyl adipate, and paraffin having 5 to 200 carbon atoms.