KR101131250B1 - Transparent resin, method of preparing the same and transparent resin composition containing the same - Google Patents

Abstract

The present invention relates to a transparent resin having excellent impact resistance, a method for preparing the same, and a transparent resin composition comprising the same, and more particularly, in preparing a transparent resin including a seed, a core, and a shell, The present invention relates to a transparent resin, a method for preparing the same, and a transparent resin composition comprising the same, wherein the ionic surfactant is used together, a core is prepared in the presence of a fat-soluble initiator, and a shell is prepared in the presence of a water-soluble initiator. According to the present invention, since the refractive index between the seed, core and shell layers of the transparent resin is constantly controlled and has two kinds of particle size distribution, the transparent resin of the present invention is an impact modifier of polymethyl methacrylate (PMMA) resin. When used as, there is an effect of providing a transparent resin, such as excellent transparency and improved impact strength.

Seed, core, shell, transparent resin, surfactant, initiator, impact modifier, polymethylmethacrylate

Description

Transparent resin, a manufacturing method thereof, and a transparent resin composition comprising the same {TRANSPARENT RESIN, METHOD OF PREPARING THE SAME AND TRANSPARENT RESIN COMPOSITION CONTAINING THE SAME}

The present invention relates to a transparent resin having excellent impact resistance, a method for preparing the same, and a transparent resin composition comprising the same, and more particularly, in preparing a transparent resin including a seed, a core, and a shell, The present invention relates to a transparent resin, a method for preparing the same, and a transparent resin composition comprising the same, wherein the ionic surfactant is used together, a core is prepared in the presence of a fat-soluble initiator, and a shell is prepared in the presence of a water-soluble initiator.

Polymethyl methacrylate (PMMA) resin is not only excellent in transparency and weather resistance but also excellent in hardness, chemical resistance, surface gloss, adhesiveness, etc., and thus is widely used as a substitute for glass. However, PMMA resins have a lower impact resistance than other plastic materials to increase the thickness of the product or are used only for limited applications.

In order to improve the impact resistance of such a PMMA resin, a method of modifying using an impact modifier has been proposed.

Japanese Laid-Open Patent Publication No. 2006-131803 (published May 25, 2006) discloses a modified PMMA resin using an impact modifier using an acrylic rubber. Although the impact resistance of the PMMA resin was improved by the above method, it was not satisfactory, and when a large amount of impact modifiers were used to improve the impact resistance, the hardness and transparency of the PMMA resin were lowered.

US Patent No. 4,999,402 discloses a method of improving the processability by adding a molecular weight modifier to the shell layer in preparing a transparent resin composed of a polymethyl methacrylate shell layer on an acrylic rubber core. The transparent resin prepared by the above method can be processed alone, but due to its structural problems, satisfactory impact strength has not been obtained, and transparency is reduced because the refractive index of the layers is not controlled, and the use thereof has a film level. There is a problem that is limited only to thickness.

In Japanese Patent Publication No. 1980-148729, etc., the structure of the impact modifier is a core-shell structure with two to three stages of emulsion polymerization, and during the final emulsion polymerization, a hard polymer having good compatibility with the matrix resin is applied to the outer layer. A method of polymerization is presented. However, such a method has a problem in that the amount of rubber in the impact modifier is small, so that the amount of the impact modifier is increased, and when the shell is thick, a problem occurs that the impact strength is lowered.

On the other hand, Japanese Patent Application Publication No. 1981-96862 proposes a method of using a graft copolymer having a high content of rubber components by highly crosslinking a rubbery polymer. However, highly crosslinked polymers have a low elasticity of rubber, a shock absorbing effect, a decrease in compatibility (mixability) with the matrix resin, resulting in processing difficulties.

In addition, since the conventional impact modifier is not uniformly dispersed during molding, transparency of the molded article is lowered. As a result, there is a problem in that the thickness of the molding is limited in order to maintain transparency.

In order to solve the problems of the prior art as described above, the present invention provides a transparent resin having excellent transparency and improved impact strength, a method of manufacturing the same and a transparent resin composition comprising the transparent resin and polymethyl methacrylate (PMMA) resin. For the purpose of

These and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention

(a) a seed consisting of an alkyl (meth) acrylate-based polymer;

(b) a core surrounding the seed and comprising a copolymer of an alkyl acrylate compound and an aromatic vinyl compound; And

(c) a shell surrounding the core and composed of a copolymer of an alkyl methacrylate compound and an alkyl acrylate compound; Including but not limited to,

It provides a transparent resin, characterized in that the particles are in a bimodal form.

It is preferable that the said seed contains the copolymer of the alkyl acrylate type compound and the aromatic vinyl type compound which are a component of the said core.

It is preferable that the refractive indices of the seed, the core and the shell are respectively 1.48 to 1.50.

In addition,

(a) polymerizing an alkyl (meth) acrylate compound to prepare a seed;

(b) polymerizing an alkyl acrylate compound and an aromatic vinyl compound in the presence of the seed and a fat soluble initiator to prepare a core surrounding the seed; And

(c) polymerizing an alkyl methacrylate compound and an alkyl acrylate compound in the presence of the core and the water-soluble initiator to prepare a shell surrounding the core; It provides a method for producing a transparent resin comprising a.

It is preferable to perform superposition | polymerization of said (b) and (c) using anionic surfactant and a nonionic surfactant together.

The manufacturing method of the transparent resin

(a) polymerizing an alkyl (meth) acrylate compound to prepare a seed;

(b) surrounding the seed, polymerizing an alkyl acrylate compound and an aromatic vinyl compound in the presence of an anionic surfactant, a nonionic surfactant, and a fat-soluble initiator to prepare an acrylic rubber core; And

(c) wrapping the core and polymerizing an alkyl methacrylate compound and an alkyl acrylate compound in the presence of an anionic surfactant, a nonionic surfactant, and a water-soluble initiator to prepare a shell. Do.

In addition, the transparent resin according to the present invention is used as an impact modifier of polymethyl methacrylate (PMMA) resin to provide a transparent resin composition having excellent transparency, impact strength, and the like.

As described above, according to the present invention, since the refractive index between the seed, core, and shell layers of the transparent resin is constantly adjusted, and has two kinds of particle size distribution, the transparent resin of the present invention may be made of polymethyl methacrylate ( When used as an impact modifier of PMMA) resin, there is an effect of providing a transparent resin having excellent transparency and improved impact strength.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Transparent resin according to the present invention

(a) a seed consisting of an alkyl (meth) acrylate-based polymer;

(b) a core surrounding the seed and comprising a copolymer of an alkyl acrylate compound and an aromatic vinyl compound; And

(c) a shell surrounding the core and composed of a copolymer of an alkyl methacrylate compound and an alkyl acrylate compound; Including but not limited to,

The particles are characterized in that they are in a bimodal form.

It is preferable that the said seed contains the copolymer of the alkyl acrylate type compound and the aromatic vinyl type compound which are a component of the said core.

The seed is 1 to 30% by weight, the core is 10 to 70% by weight, the shell is preferably 10 to 80% by weight.

It is preferable that the refractive indices of the seed, the core and the shell are respectively 1.48 to 1.50.

Moreover, the manufacturing method of the transparent resin which concerns on this invention is

(a) polymerizing an alkyl (meth) acrylate compound to prepare a seed;

(b) polymerizing an alkyl acrylate compound and an aromatic vinyl compound in the presence of the seed and a fat soluble initiator to prepare a core surrounding the seed; And

(c) polymerizing an alkyl methacrylate compound and an alkyl acrylate compound in the presence of the core and the water-soluble initiator to prepare a shell surrounding the core; Characterized in that comprises a.

The manufacturing method of the said transparent resin

(a) polymerizing an alkyl (meth) acrylate compound to prepare a seed;

(b) surrounding the seed, polymerizing an alkyl acrylate compound and an aromatic vinyl compound in the presence of an anionic surfactant, a nonionic surfactant, and a fat-soluble initiator to prepare an acrylic rubber core; And

(c) surrounding the core and polymerizing an alkyl methacrylate compound and an alkyl acrylate compound in the presence of an anionic surfactant, a nonionic surfactant, and a water-soluble initiator to prepare a shell. desirable.

(a) Preparation of Seed

(A) Seed according to the present invention may be prepared by emulsion polymerization of an alkyl (meth) acrylate-based compound, and at this time, a surfactant, an initiator, a crosslinking agent, and ion-exchanged water, etc. which are commonly used in emulsion polymerization may be used. .

As the alkyl (meth) acrylate-based compound, an alkyl (meth) acrylate-based compound having 2 to 8 carbon atoms of alkyl may be used, and specifically, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, or the like. May be used, and preferably methyl methacrylate may be used.

The seed according to the present invention may be polymerized further including a grafting agent to further improve impact strength and processability.

The grafting agent is 3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, allyl acrylate, allyl methacrylate, trimethyl One or more types selected from the group consisting of all propane triacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, and divinylbenzene can be used.

The grafting agent may be included in the amount of 0.05 to 5 parts by weight based on 100 parts by weight of the transparent resin, and may be polymerized. Preferably, the grafting agent may be included in the amount of 0.1 to 1 parts by weight. The improvement effect is great.

It is preferable that the seed has an average particle diameter of 800 to 1600 mm 3, and more preferably 800 to 1300 mm 3. When the average particle diameter falls within the above range, there is an effect of improving transparency and impact strength.

For reference, in the present invention, the average particle diameter refers to the average value of the measured latex particle diameter.

In addition, the seed preferably has a refractive index of 1.48 to 1.50 in order to maintain transparency.

The seed is preferably contained in 1 to 30% by weight based on the transparent resin. If the content is less than 1% by weight, there is a problem of lowering the impact strength, and if the content exceeds 30% by weight, there is a problem of lowering the impact strength.

A water-soluble initiator or a fat-soluble initiator can be used as an initiator used at the time of seed production, specifically, potassium persulfate (KPS) etc. which are water-soluble initiators can be used.

In preparing the seed, an anionic surfactant and a nonionic surfactant may be used together.

Here, the anionic surfactant and the non-ionic surfactant are preferably used in a weight ratio of 1: 9 to 9: 1. In this case, the total amount of the surfactant may be 0.001 to 1.5 parts by weight based on 100 parts by weight of the transparent resin total monomers.

Examples of the anionic surfactant include alkyl aryl ether sulfate having 6 to 16 carbon atoms or alkyl ether sulfate having 6 to 16 carbon atoms, sodium dodecyl sulfate (SLS), sodium dodecyl benzene sulfonate, and alkyl disulfonated die. Phenyl oxide, sodium dihexyl sulfosuccinate, etc. can be used.

The nonionic surfactant may be an octylphenoxypolyethoxyethanol compound, a glycerol ester compound, an alkanol amide compound, an aliphatic ester compound, or the like, and an octylphenoxypolyethoxyethanol nonionic interface As the activator, Triton CF10, Triton N101, Triton X-45, Triton X-100, Triton X-405, etc. of Rohm and Haas can be used.

(b) preparation of the core

The core according to the present invention surrounds the seed (a) and is formed by polymerizing an alkyl acrylate compound and an aromatic vinyl compound in the presence of an anionic surfactant, a nonionic surfactant, and a fat-soluble initiator.

The core is formed by polymerizing 9 to 58 parts by weight of an alkyl acrylate compound and 1 to 12 parts by weight of an aromatic vinyl compound based on 100 parts by weight of the total monomers constituting the transparent resin.

The alkyl acrylate compound is an alkyl acrylate compound having 1 to 8 carbon atoms of alkyl, preferably methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, At least one selected from the group consisting of octyl acrylate, and 2-ethylhexyl acrylate.

As the aromatic vinyl compound, at least one selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, and vinyltoluene may be used.

The core according to the present invention may be prepared by emulsion polymerization of an alkyl acrylate compound and an aromatic vinyl compound in the presence of the seed.

When the core is prepared, when a large amount of anionic surfactant and non-ionic surfactant are used together and a fat-soluble initiator is used together, the core to be manufactured is bimodal. It is possible to make the dispersed particles of the final transparent resin into a bimodal form, in which large particles are advantageous for impact strength and small particles are advantageous for transparency.

The bimodal form of the present invention is substantially included in the generally accepted bimodal form, but also includes a case where only the expression thereof is different (for example, multimodal or the like).

Figure 1 shows a SEM image showing the bimodal form of the transparent resin (prepared in Example 1) according to the present invention, it can be confirmed that the bimodal from the shape and size of the particles, each particle is a core-shell structure It can be confirmed that it has (the core is visible inside the particle).

The bimodal form is preferably composed of particles having an average particle diameter of 1100 to 2000 mm 3 and particles having an average particle diameter of 2000 to 3500 mm 3, more preferably particles having an average particle diameter of 1500 to 2000 mm 3 and an average particle diameter of 2500 to 3000 mm 3. It is made of particles, there is an effect excellent in impact strength and formability within this range.

Here, the anionic surfactant and the non-ionic surfactant are preferably used in a weight ratio of 1: 9 to 9: 1. In this case, the total amount of the surfactant may be 0.5 to 5 parts by weight based on 100 parts by weight of the total monomers forming the transparent resin.

Examples of the anionic surfactant include alkyl aryl ether sulfate having 6 to 16 carbon atoms or alkyl ether sulfate having 6 to 16 carbon atoms, sodium dodecyl sulfate (SLS), sodium dodecyl benzene sulfonate, and alkyl disulfonated die. Phenyl oxide, sodium dihexyl sulfosuccinate, etc. can be used.

The nonionic surfactant may be an octylphenoxypolyethoxyethanol compound, a glycerol ester compound, an alkanol amide compound, an aliphatic ester compound, or the like, and an octylphenoxypolyethoxyethanol nonionic surfactant Examples include Rohm Hass' Triton CF10, Triton N101, Triton X-45, Triton X-100 and Triton X-405.

As the fat-soluble initiator, benzoyl peroxide, cumin hydroperoxide (CHP), insoluble peroxide compound, hydroperoxide compound, azobisisobutyronitrile, azobismethylbutyronitrile, azobiscyclohexane Carbonnitrile, and the like, and specific examples thereof include 3,5-diisopropylbenzine hydroperoxide (DIPHP), peroxyester, peroxydicarbonate, azoisobutyrodimethyl ester, azobisisobutyrodimethyl Azo derivatives, such as ester and azobisisobutyodidiethyl ester, etc. are mentioned.

The oil-soluble initiator is easy to penetrate into the seed, thereby greatly improving the size and shape (bimodal) and impact strength of the seed and the core by controlling the degree of monomer polymerization by penetrating into the seed during core polymerization.

In addition, the fat-soluble initiator may be used in an amount of 0.01 to 2 parts by weight based on 100 parts by weight of the total monomers used for preparing the core.

The core preferably has an average particle diameter (including seeds) of 2100 to 2800 mm 3, more preferably 2200 to 2800 mm 3. The average particle diameter at this time means the average particle diameter of all cores. If the average particle diameter is less than 2200 mm 3, the impact strength is lowered. If the average particle diameter is more than 2 800 mm 3, there is a problem that deformation occurs easily during processing.

In addition, the core has a refractive index of 1.48 to 1.50 to maintain transparency, and preferably the same as the refractive index of the seed.

The core is preferably contained in 10 to 70% by weight relative to the transparent resin of the present invention. If the content is less than 10% by weight, there is a problem of lowering the impact strength, and if the content exceeds 70% by weight, there is a problem of deterioration of processing.

The core according to the invention can be polymerized further comprising a grafting agent to make the impact strength and workability more constant. The grafting agent is 3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, allyl acrylate, allyl methacrylate, trimethyl One or more types selected from the group consisting of all propane triacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, and divinylbenzene can be used.

It is preferable that the grafting agent included in the core is included in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the total monomers constituting the transparent resin and polymerized.

(c) Preparation of the Shell

The shell according to the present invention surrounds the core (b) and is formed by polymerizing an alkyl methacrylate compound and an alkyl acrylate compound in the presence of an anionic surfactant, a nonionic surfactant and a water-soluble initiator.

The shell is preferably formed by polymerization of 9 to 79 parts by weight of the alkyl methacrylate compound and 1 to 8 parts by weight of the alkyl acrylate compound with respect to 100 parts by weight of the total monomer constituting the transparent resin.

As the alkyl methacrylate compound, an alkyl (meth) acrylate compound having 1 to 4 carbon atoms of alkyl may be used, and specifically, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, or the like may be used. Can be.

The alkyl acrylate compound is an alkyl acrylate compound having 1 to 8 carbon atoms of alkyl, specifically, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, One or more selected from the group consisting of octyl acrylate, and 2-ethylhexyl acrylate can be used.

In the preparation of the shell, it can be polymerized by adding a molecular weight regulator.

The molecular weight modifier may be used one or more selected from the group consisting of t-dodecyl mercaptan (tertiary-dodecyl mercaptan) and n-octyl mercaptan (n-octyl mercaptan).

When the shell is prepared, when an anionic surfactant and a non-ionic surfactant are used together in a large amount and a water-soluble initiator is used together, the particles dispersed in the transparent resin Can be maintained in a bimodal form, where large particles are advantageous for impact strength and small particles are advantageous for transparency.

Here, the anionic surfactant and the non-ionic surfactant are preferably used in a weight ratio of 1: 9 to 9: 1. In this case, the total amount of the surfactant may be used from 0.05 to 5 parts by weight based on 100 parts by weight of the total monomer constituting the transparent resin.

Examples of the anionic surfactant include alkyl aryl ether sulfate having 6 to 16 carbon atoms of alkyl or alkyl ether sulfate having 6 to 16 carbon atoms of alkyl, sodium dodecyl sulfate (SLS), sodium dodecyl benzenesulfonate, and alkyl disulfonated die. Phenyl oxide, sodium dihexyl sulfosuccinate, etc. can be used.

The nonionic surfactant may be an octylphenoxypolyethoxyethanol compound, a glycerol ester compound, an alkanol amide compound, an aliphatic ester compound, or the like, and an octylphenoxypolyethoxyethanol nonionic surfactant The furnace may include Rohm Hass' Triton CF10, Triton N101, Triton X-45, Triton X-100, Triton X-405 and the like.

Since the water-soluble initiator is not easy to penetrate into the core, grafting occurs well on the surface of the core during shell formation by graft polymerization.

The water-soluble initiators include sodium persulfate, potassium persulfate (KPS), ammonium persulfate, t-butyl hydroperoxide (tBHP), or 4.4'-azobis (4 Azo derivatives such as -cyanovalic acid), 2,2'-azobis (2-amidinopropane) dihydrochloride, and the like.

In addition, the water-soluble initiator may be used in an amount of 0.01 to 2 parts by weight based on 100 parts by weight of the total monomers used for preparing the shell.

The shell preferably has an average particle diameter (including seeds and cores) of 2400 to 3100 mm 3, more preferably 2600 to 3100 mm 3. The average particle size at this time means the average particle diameter of all shells (the same as the average particle diameter of the transparent resin particles), and there is an effect of improving transparency and impact strength within this range.

The shell has a bimodal form due to the core of the bimodal form, preferably a particle having an average particle diameter of 1400 ~ 2300 mm 3 and particles having an average particle diameter of 2300 ~ 3800 mm 3, more preferably an average particle diameter It is composed of particles of 1800 ~ 2300 Å particles and particles having an average particle diameter of 2800 ~ 3300 Å, excellent impact strength, transparency and weather resistance improvement within this range.

The shell is 10 to 10 with respect to the transparent resin It is preferably included in 80% by weight. If the content is less than 10% by weight, the workability is lowered, and if the content exceeds 80% by weight, there is a problem that the impact strength is lowered.

In addition, the shell has a refractive index of 1.48 to 1.50 in order to maintain transparency, preferably the same as the refractive index of the seed, the core, a transparent resin composition prepared in combination with a polymethyl methacrylate (PMMA) resin within this range The transparency is excellent effect.

The refractive index between the seed, core and shell layers is constantly adjusted to allow single processing, thereby improving the impact strength without decreasing transparency.

(d) Preparation of Transparent Resin Composition

When the transparent resin according to the present invention is used as an impact modifier of a polymethyl methacrylate (PMMA) resin, a transparent resin composition having excellent transparency and improved impact strength can be prepared.

25 to 85% by weight of the polymethyl methacrylate (PMMA) resin can be prepared by including a transparent resin 15 to 75% by weight of the present invention.

It will be apparent to those skilled in the art that the transparent resin composition of the present invention may further include dyes, pigments, lubricants, antioxidants, ultraviolet stabilizers, thermal stabilizers, reinforcing agents, fillers and light stabilizers which are commonly used according to the use.

Hereinafter, the present invention will be described in more detail with reference to Examples, which are intended to help a specific understanding of the present invention, and the present invention is not limited to the following Examples.

[Example]

Example 1

(a) seed production

1052.7 g of ion-exchanged water was introduced into the reactor and the temperature was raised to 70 ° C with nitrogen washing. When the temperature of the ion-exchanged water reached 70 ° C., 148.5 g of methyl methacrylate (MMA), 20 g of sodium dodecyl sulfate (SLS, 3 wt% solution), 180 g of Triton X-100 (3 wt% solution), and 1.5 g of allyl methacrylate (AMA) was added at once. When the temperature in the reactor was stabilized at 70 ° C., 70 g of potassium persulfate (KPS, 3 wt% solution) was added to initiate the polymerization. Nitrogen washing was performed continuously until the reaction was complete.

At this time, the seed was 5 weight% with respect to the transparent resin of this invention.

The average particle diameter of the polymerized seed latex was measured using a laser light scattering device, NICOMP, and as a result, it was 1115 GPa, and the refractive index was 1.4903.

(b) core manufacturing

First, 0.19 g of ferros sulfate (FES), 25.75 g of sodium formaldehyde sulfoxylate (SFS), and 3.50 g of disodium ethylenediaminetetraacetate (EDTA) were dissolved in 706.8 g of ion-exchanged water to prepare an activation solution. 939.0 g of ion-exchanged water, 30 g of sodium dodecyl sulfate (SLS, 3 wt% solution), 270 g of Triton X-100 (3 wt% solution), 1525.8 g of butyl acrylate, 366 g of styrene, 13.2 g of allyl methacrylate Was stirred to emulsify the monomers. The emulsified monomer was added dropwise to the reactor in which the seed polymerization was completed for 2 hours at a temperature of 70 ° C. and a nitrogen atmosphere, and at the same time, the polymerization was carried out by adding 300 g of an activation solution and 9.4 g of cumin hydroperoxide (CHP, 80 wt% solution). Started. 75 g of the activating solution and 3 g of cumin hydroperoxide (CHP, 80 wt% solution) were added thereto to undergo a aging step for 1 hour after the reaction was terminated. At this time, the formed core was 65% by weight with respect to the transparent resin of the present invention.

The conversion rate of the polymerized core latex was 99%, the average particle diameter was 2230 GPa, and the refractive index was 1.4903.

(c) shell manufacturing

At the end of the core polymerization, 314.2 g of ion-exchanged water, 14 g of sodium dodecyl sulfate (3% by weight solution), 126 g of methyl methacrylate (712.5 g of methyl methacrylate), 37.5 g of methyl acrylate, and 3.6 g of n-octyl mercaptan was added dropwise for 2 hours. When the temperature in the reactor was stabilized at 70 ° C., polymerization was started by adding 90 g of activating solution and 3 g of t-butyl hydroperoxide. After completion of the reaction, 30 g of activating solution and 1.7 g of t-butyl hydroperoxide (t-BHP, 70 wt% solution) were added to allow the maturation step for 1 hour. It was carried out continuously until. At this time, the shell was 30% by weight of the transparent resin of the present invention.

The conversion rate of the final polymerized transparent resin latex was 99%, the average particle diameter was 2600 mm 3, and the refractive index was 1.4903.

Ion-exchanged water was added to the final transparent resin latex prepared as described above to lower the final solid content to 10% by weight or less, and the temperature was raised to 80 ° C while slowly stirring with a stirrer. 22 wt% aqueous calcium chloride solution was added thereto to prepare a mixture in the form of a slurry. The mixture was cooled to 90 ° C. or more, and then cooled. The cooled mixture was washed with ion-exchanged water, filtered and dried to obtain a transparent resin in powder form.

(d) Preparation of transparent resin composition

40 parts by weight of the obtained transparent resin in powder form, 0.2 parts by weight of lubricant, 0.1 parts by weight of antioxidant, and 0.01 parts by weight of light stabilizer were kneaded and kneaded to 60 parts by weight of polymethyl methacrylate resin (LG MMA, IH830). Pellets were prepared using a twin screw extruder, and the pellets were injected again to prepare specimens.

Example 2

As shown in Table 1 below, except that the type and amount of the surfactant, initiator used in the preparation of the seed, core and shell, and the composition of each of the seed, core and shell were different It was carried out.

To 40 parts by weight of the transparent resin in the form of powder, 60 parts by weight of polymethyl methacrylate resin (LG MMA, IH830), 0.2 parts by weight of lubricant, 0.1 parts by weight of antioxidant, and 0.01 parts by weight of light stabilizer were added and kneaded. Pellets were prepared using a twin screw extruder, and the pellets were injected again to prepare specimens.

Example 3

As shown in Table 1 below, except that the type and amount of the surfactant, initiator used in the preparation of the seed, core and shell, and the composition of each of the seed, core and shell were different It was carried out.

To 40 parts by weight of the transparent resin in the form of powder, 60 parts by weight of polymethyl methacrylate resin (LG MMA, IH830), 0.2 parts by weight of lubricant, 0.1 parts by weight of antioxidant, and 0.01 parts by weight of light stabilizer were added and kneaded. Pellets were prepared using a twin screw extruder, and the pellets were injected again to prepare specimens.

Example 4

As shown in Table 1 below, except that the type and amount of the surfactant, initiator used in the preparation of the seed, core and shell, and the composition of each of the seed, core and shell were different It was carried out.

To 40 parts by weight of the transparent resin in the form of powder, 60 parts by weight of polymethyl methacrylate resin (LG MMA, IH830), 0.2 parts by weight of lubricant, 0.1 parts by weight of antioxidant, and 0.01 parts by weight of light stabilizer were added and kneaded. Pellets were prepared using a twin screw extruder, and the pellets were injected again to prepare specimens.

Comparative Example 1

(a) seed production

It carried out similarly to Example 1 above.

(b) core manufacturing

Except for using Triton X-100 in Example 1 and only 300 g of sodium dodecyl sulfate (SLS) was carried out in the same manner as in Example 1.

The conversion of the polymerized core latex was 99% and the refractive index was 1.4900.

(c) shell manufacturing

Example 1 was the same as in Example 1 except for using 140 g of sodium dodecyl sulfate (SLS) instead of Triton X-100.

The conversion rate of the final polymerized transparent resin latex was 99% and the refractive index was 1.4901.

(d) Preparation of transparent resin composition

40 parts by weight of the obtained transparent resin in powder form, 0.2 parts by weight of lubricant, 0.1 parts by weight of antioxidant, and 0.01 parts by weight of light stabilizer were kneaded and kneaded to 60 parts by weight of polymethyl methacrylate resin (LG MMA, IH830). Pellets were prepared using a twin screw extruder, and the pellets were injected again to prepare specimens.

Comparative Example 2

(a) Preparation of Seed

It carried out similarly to Example 1 above.

(b) preparation of the core

Except for using sodium dodecyl sulfate (SLS) in Example 1, except that only 300 g of Triton X-100 was used in the same manner as in Example 1.

The conversion of the polymerized core latex was 99% and the refractive index was 1.4898.

(c) shell manufacturing

Except for using sodium dodecyl sulfate (SLS) in Example 1 was carried out in the same manner as in Example 1 except that only 140 g of Triton X-100.

The conversion rate of the final polymerized transparent resin latex was 99% and the refractive index was 1.4903.

(d) Preparation of transparent resin composition

40 parts by weight of the obtained transparent resin in powder form, 0.2 parts by weight of lubricant, 0.1 parts by weight of antioxidant, and 0.01 parts by weight of light stabilizer were kneaded and kneaded to 60 parts by weight of polymethyl methacrylate resin (LG MMA, IH830). Pellets were prepared using a twin screw extruder, and the pellets were injected again to prepare specimens.

Comparative Example 3

(a) Preparation of Seed

It carried out similarly to Example 2 above.

(b) preparation of the core

Example 2 was carried out in the same manner as in Example 2, except that 250 g of potassium persulfate (KPS, 3% by weight solution) was used instead of 3,5-diisopropylbenzine hydroperoxide (DIPHP). It was.

(c) shell manufacturing

Example 2 was carried out in the same manner as in Example 2, except that 40 g of potassium persulfate (KPS, 3 wt% solution) was used without tBHP.

(d) Preparation of transparent resin composition

40 parts by weight of the obtained transparent resin in powder form, 0.2 parts by weight of lubricant, 0.1 parts by weight of antioxidant, and 0.01 parts by weight of light stabilizer were kneaded and kneaded to 60 parts by weight of polymethyl methacrylate resin (LG MMA, IH830). Pellets were prepared using a twin screw extruder, and the pellets were injected again to prepare specimens.

Comparative Example 4

A specimen was prepared by injecting an acrylonitrile-butadiene-styrene transparent resin (LG Chemical, TR-558A) pellets.

[Test Example]

The physical properties of the transparent resins prepared in Examples 1 to 4 and Comparative Examples 1 to 4 were measured by the following methods, and the results are shown in the following [Table 2].

* Refractive Index-After the transparent resin was prepared into a thin film having a thickness of 0.2 mm, it was measured using an Abbe refractometer at 25 ° C in accordance with ASTM D1298.

* Impact Strength-Izod impact strength was measured according to ASTM D256 using a 1/8 ”specimen.

* Transparency, haze-It was measured according to ASTM D1003 using an injection molded square molded article having a thickness of 3 mm.

* Weather Resistance-Color Quest II after leaving the transparent resin for 200 hours in a weather-o-meter (ATLAS Ci35A) at 83 ° C and water spray cycle 18 minutes / 120 minutes. Δb value (difference in yellowness) was measured using (color quest II, Hunter Lab).

Hardness—measured using a Rockwell hardness tester (Rockwell 2000, Instron).

[Table 1]

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 article
castle Seed 5 10 10 5 5 5 10 core 65 60 60 65 65 65 60 Shell 30 30 30 30 30 30 30 Interface
Active agent Seed SLS:
Triton X-
100
= 1: 9 SLS:
Triton X-
100
= 2: 8 SLS:
Triton X-
100
= 5: 5 SLS:
Triton X-
100
= 7: 3 SLS Triton
X-100 SLS:
Triton X-
100
= 2: 8 core Shell dog
city
My Seed KPS KPS KPS KPS KPS KPS KPS core CHP DIPHP CHP DIPHP CHP CHP Shell tBHP tBHP tBHP tBHP tBHP tBHP Latex
Particle diameter
Å (medium
Part)
Seed 1115 (100) 1490 (100) 1503 (100) 1090 (100) 1150
(100) 960 (100) 1530
(100) core 1535 (25)
/ 2414 (75) 1590 (31)
/ 2540 (69) 1455 (18)
/ 2701 (82) 1307 (15)
/ 2771 (85) 2700
(100) 2420
(100) 2834
(100) Shell 1790 (26)
/ 2660 (74) 1860 (30)
/ 2830 (74) 1689 (30)
/ 2880 (80) 1500 (14)
/ 2920 (86) 3050
(100) 2610
(100) 3100
(100)

* The particle size of the latex was measured using a laser light scattering device NICOMP.

 TABLE 2

division transparency(%) Haze (%) Impact Strength (kg? Cm / cm) Hardness Weatherability room
city
Yes One 92.0 1.6 6.9 100.2 1.0 2 93.4 1.3 7.4 99.8 1.4 3 93.1 1.4 7.5 100.0 1.6 4 93.4 1.8 6.7 100.7 1.8 ratio
School
Yes One 92.8 2.0 6.0 99.3 2.3 2 93.4 1.8 5.6 101.1 2.0 3 93.1 2.3 6.4 98.7 1.9 4 90.3 2.0 10.2 99.8 5.3

As shown in Table 2, Examples 1 to 4 according to the present invention have transparency compared to Comparative Example 1 using only anionic surfactants or Comparative Example 2 using only nonionic surfactants when preparing seeds, cores, and shells. It can be seen that the impact strength is excellent. In addition, comparing Example 2, which uses a fat-soluble initiator in the manufacture of the core and a water-soluble initiator in the manufacture of the shell, with Comparative Example 3, the transparent resin composition according to Example 2 had better transparency, impact strength, etc. than Comparative Example 3. Able to know.

Although the present invention has been described in detail 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 present invention, and such modifications and modifications fall within the scope of the appended claims. It is also natural.

1 is a SEM photograph showing the bimodal form of the transparent resin (prepared in Example 1) according to the present invention.

Claims (21)

 (a) a seed consisting of an alkyl (meth) acrylate-based polymer; (b) a bimodal core covering the seed and comprising a copolymer of an alkyl acrylate compound and an aromatic vinyl compound; And (c) a shell surrounding the core and composed of a copolymer of an alkyl methacrylate compound and an alkyl acrylate compound; ≪ / RTI > Characterized in that the particles are in bimodal form Transparent resin. delete The method of claim 1, The seed comprises a copolymer of an alkyl acrylate compound and an aromatic vinyl compound, which are components of the core. Transparent resin. The method of claim 1, The seed is 1 to 30% by weight, the core is 10 to 70% by weight, the shell is characterized in that 10 to 80% by weight Transparent resin. The method of claim 1, The seed has an average particle diameter of 800 ~ 1600 mm 3, the core has an average particle diameter of 2100 ~ 2800 mm 3, and the shell has an average particle diameter of 2400 ~ 3100 mm 3 Transparent resin. The method of claim 1, Refractive index of the seed, core and shell are characterized in that each of 1.48 ~ 1.50 Transparent resin. The method of claim 1, The seed, characterized in that made further comprising a grafting agent Transparent resin. The method of claim 1, The core is characterized in that it further comprises a grafting agent Transparent resin. The method of claim 1, The particles, characterized in that the bimodal form consisting of particles having an average particle diameter of 1400 ~ 2300 mm 3 and particles having an average particle diameter of 2300 ~ 3800 mm 3 Transparent resin. The method of claim 1, The core is characterized in that the bimodal form consisting of particles having an average particle diameter of 1100 ~ 2000 Å and particles having an average particle diameter of 2000 ~ 3500 Å Transparent resin. (a) polymerizing an alkyl (meth) acrylate compound to prepare a seed; (b) polymerizing an alkyl acrylate compound and an aromatic vinyl compound in the presence of the seed, anionic surfactant, fat soluble initiator and nonionic surfactant to prepare a core surrounding the seed; And (c) polymerizing an alkyl methacrylate compound and an alkyl acrylate compound using a water-soluble initiator in the presence of the core to prepare a shell surrounding the core; Characterized in that comprises a Method for producing a transparent resin. The method of claim 11, The polymerization of the above (c) is carried out including an anionic surfactant and a nonionic surfactant. Method for producing a transparent resin. delete The method of claim 11, The polymerization of the above (a) is an emulsion polymerization, characterized in that Method for producing a transparent resin. The method of claim 11 or 12, The weight ratio of the anionic surfactant and the nonionic surfactant is 1: 9 to 9: 1, characterized in that Method for producing a transparent resin. The method of claim 11 or 12, The anionic and nonionic surfactants are 0.5 to 5 parts by weight based on 100 parts by weight of the total monomers forming the transparent resin, respectively, when the core and shell are used. Method for producing a transparent resin. The method of claim 11, The fat-soluble initiator, 3,5-diisopropyl benzine hydroperoxide (DIPHP), benzoyl peroxide, cumin hydroperoxide (CHP), peroxy ester, peroxy dicarbonate, azoisobutyrodimethyl ester, At least one member selected from the group consisting of azobisisobutyrodimethyl ester, azobisisobutyronidiethyl ester, azobisisobutyronitrile, azobismethylbutyronitrile and azobiscyclohexanecarbonitrile. Method for producing a transparent resin. The method of claim 11, The water-soluble initiator, sodium persulfate, potassium persulfate (KPS), ammonium persulfate, t-butyl hydroperoxide (tBHP), 4.4'-azobis (4- Cyanobalic acid) and 2,2'-azobis (2-amidinopropane) dihydrochloride, characterized in that at least one member selected from the group consisting of Method for producing a transparent resin. The method of claim 11 or 12, The anionic surfactants include alkyl aryl ether sulfate having 6 to 16 carbon atoms of alkyl, alkyl ether sulfate having 6 to 16 carbon atoms of alkyl, sodium dodecyl sulphate (SLS), sodium dodecyl benzenesulfonate and alkyl disulfonated compounds. At least one member selected from the group consisting of diphenyl oxide and sodium dihexyl sulfosuccinate Method for producing a transparent resin. The method of claim 11 or 12, The nonionic surfactant, It is at least one member selected from the group consisting of octylphenoxy polyethoxy ethanol compound, glycerol ester compound, alkanol amide compound and aliphatic ester compound Method for producing a transparent resin. 15 to 75% by weight of the transparent resin of any one of claims 1 or 3 to 10 and 25 to 85% by weight of polymethyl methacrylate (PMMA) resin Transparent resin composition.

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