WO2015016677A1

WO2015016677A1 - Resin

Info

Publication number: WO2015016677A1
Application number: PCT/KR2014/007135
Authority: WO
Inventors: 유흥식; 류진영; 최은주; 이종원; 최현
Original assignee: 주식회사 엘지화학
Priority date: 2013-08-02
Filing date: 2014-08-01
Publication date: 2015-02-05

Abstract

The present invention relates to a resin, a preparation method therefor, a resin mixture containing the resin, a pellet, a method for preparing a resin molded product by using the same, and a resin molded product. A resin exemplified in the present invention can provide the resin molded product having a surface with improved mechanical properties and surface hardness. In addition, when using the resin, an additional surface coating step with respect to the surface of a resin molded product can be omitted and the aforementioned effects can be exhibited, thereby reducing production time and costs and increasing productivity.

Description

Suzy

The present application relates to a resin, a method for producing the same, a resin mixture containing the resin, a pellet, a method for producing a resin molded article using the same, and a resin molded article.

Plastic resins are easy to process and have excellent properties such as tensile strength, elastic modulus and heat resistance, and thus are used in various applications such as automobile parts, helmets, electric machine parts, spinning machine parts, toys, or pipes.

In particular, the resin used in home appliances, automobile parts and toys should have an excellent surface hardness.

For example, in order to increase the surface hardness of the extruded or injected resin molded article, a high hardness coating process was required after the extrusion or injection process, and since such a coating process includes a spray process, environmentally harmful substances are generated. Was present.

The present application provides a resin, a method for producing the same, a resin mixture containing the resin, a pellet, a method for producing a resin molded article using the same, and a resin molded article.

One embodiment of the present application provides a resin comprising particles comprising a seed, a core and a shell. For example, the resin may comprise a seed comprising a polymer derived from an alkyl (meth) acrylate monomer and a crosslinkable monomer; A core surrounding the seed and comprising a polymer derived from an alkyl (meth) acrylate monomer, an aryl (meth) acrylate monomer and a crosslinkable monomer; And particles surrounding the core and comprising a shell comprising an alkyl (meth) acrylate monomer, an aryl (meth) acrylate monomer and a polymer derived from a compound of formula (I).

[Formula 1]

In Formula 1, R ₁ represents hydrogen or alkyl having 1 to 5 carbon atoms, R ₂ represents a compound of Formula 2,

[Formula 2]

In Formula 2, R ₃ represents alkylene having 1 to 8 carbon atoms, R ₄ and R ₅ each independently represent hydrogen and alkyl having 1 to 8 carbon atoms, and n is an integer of 1 to 100.

Another embodiment of the present application provides a method of preparing the resin. For example, the method of preparing the resin is carried out in the presence of an anionic surfactant and a water-soluble polymerization initiator, (a) polymerizing an alkyl (meth) acrylate monomer and a crosslinkable monomer to prepare a seed; (b) further polymerizing an alkyl (meth) acrylate monomer, an aryl (meth) acrylate monomer and a crosslinkable monomer in the presence of the seed to produce a core surrounding the seed; And (c) polymerizing an alkyl (meth) acrylate monomer, an aryl (meth) acrylate monomer, and the compound of Formula 1 using a water-soluble initiator in the presence of the core to produce a shell surrounding the core. Include.

Another embodiment of the present application is a first resin; And a second resin having a difference in surface energy or melt viscosity with the first resin, wherein the second resin comprises a polymer derived from an alkyl (meth) acrylate monomer and a crosslinkable monomer; A core surrounding the seed and comprising a polymer derived from an alkyl (meth) acrylate monomer, an aryl (meth) acrylate monomer and a crosslinkable monomer; And a particle surrounding the core, the particle comprising a shell comprising an alkyl (meth) acrylate monomer, an aryl (meth) acrylate monomer, and a polymer derived from a compound of Formula 1 below.

[Formula 1]

[Formula 2]

Another embodiment of the present application is a core formed of a first resin; And a cell formed of the first resin and the second resin having a difference in surface energy or melt viscosity.

Another embodiment of the present application to melt the resin mixture to form a molten mixture; And processing the melted mixture to form a layered structure.

Another embodiment of the present application is to melt the pellets to form a molten mixture; And processing the melted mixture to form a layered structure.

Another embodiment of the present application is the first resin layer; A second resin layer formed on the first resin layer; And an interface layer formed between the first resin layer and the second resin layer, wherein the second resin is derived from an alkyl (meth) acrylate monomer and a crosslinkable monomer. Seeds comprising a polymer to be formed; A core surrounding the seed and comprising a polymer derived from an alkyl (meth) acrylate monomer, an aryl (meth) acrylate monomer and a crosslinkable monomer; And a particle surrounding the core, the particle including a shell including an alkyl (meth) acrylate monomer, an aryl (meth) acrylate monomer, and a polymer derived from the compound represented by Formula 1 below.

[Formula 1]

[Formula 2]

Hereinafter, a resin according to a specific embodiment, a method for preparing the resin, a resin mixture, pellets, a method for preparing a resin molded article using the same, and a resin molded article will be described in detail.

In one example, the resin may be a resin including particles having a triple structure of seed-core-shell. For example, the resin polymerizes a seed from an alkyl (meth) acrylate monomer and a crosslinkable monomer, and polymerizes an alkyl (meth) acrylate monomer, an aryl (meth) acrylate monomer and a crosslinkable monomer to the seed. It may be prepared by polymerizing the core surrounding the seed, by graft polymerizing an alkyl (meth) acrylate monomer, an aryl (meth) acrylate monomer and a compound of formula 1 to the core to polymerize the shell surrounding the core. have.

In the above, "seed" means the portion existing inside the triple structure, "core" means the portion existing between the seed and the shell of the triple structure surrounding the seed, "Shell" means the outermost part of the triple structure surrounding the core.

In addition, "wrap" means that the outer circumferential surface of the particles is substantially covered, wherein the outer circumferential surface is formed to substantially cover, for example, 50% or more, 60% or more of the outer circumferential surface At least 70%, at least 80%, at least 90%, at least 95%, or at least 99%.

In one example, the main monomer for polymerizing the polymer included in the seed, core and shell may use an alkyl (meth) acrylate monomer. As such alkyl (meth) acrylate, For example, C1-C40 alkyl (meth) acrylate, C1-C30 alkyl (meth) acrylate, C1-C20 alkyl (meth) acrylate, C1-C10 alkyl (meth) acrylates, C1-C5 alkyl (meth) acrylates, C1-C3 alkyl (meth) acrylates or C1-C2 alkyl (meth) acrylates can be used. have. As said alkyl (meth) acrylate monomer, methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate , Hexyl acrylate, octyl acrylate, and 2-ethylhexyl acrylate may include one or more selected from the group consisting of, but is not limited thereto.

The content of alkyl (meth) acrylates forming the main polymerized units of the polymer can be appropriately controlled according to the use of the resin and the physical properties required for the seed, core and shell. For example, the content of the alkyl (meth) acrylate is 50 to 97 parts by weight, 60 to 95 parts by weight, 65 parts based on 100 parts by weight of the total monomers contained in the monomer mixture for preparing the polymer included in the resin To 90 parts by weight, 50 to 80 parts by weight, 50 to 75 parts by weight, 50 to 70 parts by weight, 55 to 80 parts by weight, 60 to 80 parts by weight, 55 to 75 parts by weight or 60 to 70 parts by weight.

In one example, the polymer unit of the polymer included in the seed, core and shell may include a monomer having a bulky functional group, in addition to the alkyl (meth) acrylate monomer described above. The polymers formed from monomer mixtures containing monomers having bulky functional groups can increase the hydrodynamic volume to provide a resin with a lower melt viscosity and increase the glass transition temperature of the polymer, It is possible to provide a resin having a high hardness.

In one example, the monomer having a bulky functional group included in the polymerized unit of the polymer included in the seed may be an alkyl (meth) acrylate. Accordingly, the monomer mixture for forming the polymer included in the seed may be, for example, an alkyl (meth) acrylate forming a main polymerized unit of the aforementioned polymer; And two or more alkyl (meth) acrylates including alkyl (meth) acrylates having a bulky alkyl group. As an alkyl (meth) acrylate which has a bulky alkyl group, it is C3-C20, C3-C12, C3-C6, C5-C20, C4-C20, C10-C20 or C12, for example. Alkyl (meth) acrylates of from 20 to 20; Or alicyclic (meth) acrylate having 5 to 40 carbon atoms, 5 to 25 carbon atoms, 5 to 16 carbon atoms, 6 to 40 carbon atoms, 10 to 40 carbon atoms, 12 to 40 carbon atoms, or 16 to 40 carbon atoms. Etc. can be mentioned. Specifically, as said C3-C20 alkyl (meth) acrylate, For example, isopropyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, or 2-ethyl Hexyl (meth) acrylate etc. are mentioned, As said C5-C40 alicyclic (meth) acrylate, For example, cyclohexyl (meth) acrylate or isobornyl (meth) acrylate Etc. can be mentioned.

The content of the alkyl (meth) acrylate having such a bulky alkyl group can be appropriately controlled according to the melt viscosity of the resin and the physical properties required for the seed. For example, the content of alkyl (meth) acrylate having a bulky alkyl group is 10 to 40 parts by weight, 15 to 40 based on 100 parts by weight of the total monomers included in the monomer mixture for preparing the polymer included in the seed. It can be adjusted to 10 parts by weight, 20 to 40 parts by weight, 10 to 35 parts by weight, 10 to 30 parts by weight, 15 to 35 parts by weight or 20 to 30 parts by weight.

In another example, as the monomer having a bulky functional group, aryl (meth) acrylate may be used. In one example, the bulky monomer included in the polymerized unit of the polymer included in the core and the shell may be used. The monomer having a functional group may be aryl (meth) acrylate. As said aryl (meth) acrylate, C6-C40, C6-C25 or C6-C16 aryl (meth) acrylate etc. are mentioned, for example. Specifically, as the aryl (meth) acrylate having 6 to 40 carbon atoms, for example, naphthyl (meth) acrylate, phenyl (meth) acrylate, anthracenyl (meth) Acrylate or benzyl (meth) acrylate and the like can be used.

The content of such aryl (meth) acrylate can also be appropriately controlled according to the purpose of use of the resin and the physical properties required for the core and the shell, like the (meth) acrylate having the bulky alkyl group described above. For example, the content of aromatic (meth) acrylate is 10 to 40 parts by weight, 15 to 40 parts by weight, based on 100 parts by weight of the total monomers contained in the monomer mixture for preparing the polymer included in the core or shell, 20 to 40 parts by weight, 10 to 35 parts by weight may be adjusted to 10 to 30 parts by weight, 15 to 35 parts by weight or 20 to 30 parts by weight.

Hereinafter, each part of the seed, the core, and the shell of the particle having the triple structure will be described.

The seed may be a polymer that is derived from an alkyl (meth) acrylate monomer and a crosslinkable monomer as the innermost part of the particle having the triple structure.

The alkyl (meth) acrylate monomers are the main monomers for preparing the aforementioned polymers, and the details thereof are the same as described above.

In addition, the polymer included in the seed may be polymerized by further including a crosslinkable monomer in order to further improve impact strength and processability in addition to the alkyl (meth) acrylate monomer. In one example, the crosslinkable monomer is 3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, allyl acrylate, One or more selected from the group consisting of allyl methacrylate, trimethylolpropane triacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, and divinylbenzene may be used, but is not particularly limited. .

In one example, the polymer included in the seed may include polymerized units polymerized in an amount of 5 to 99.5 parts by weight of the alkyl (meth) acrylate monomer and 0.5 to 5 parts by weight of the crosslinkable monomer.

The particle diameter of the particle including the seed may be variously adjusted according to the total particle diameter of the particle having the triple structure, and is not particularly limited. For example, the average particle diameter of the particle including the seed may be 10 nm or more. 1,000 nm, for example, 50 nm to 900 nm or 100 nm to 500 nm.

In one example, the seed may be present in the glass phase at room temperature.

The core is a part that improves the hardness of the resin, and surrounds the seed and includes a polymer derived from a whole alkyl (meth) acrylate monomer, an aryl (meth) acrylate monomer and a crosslinkable monomer.

The alkyl (meth) acrylate monomer contained in the polymerized unit of the polymer contained in the core is the main monomer of the polymer, the aryl (meth) acrylate monomer is the monomer having the bulky functional group described above, and the crosslinkable monomer is Since the same monomer as the crosslinkable monomer applied in the seed, the content thereof is the same as described above.

In one example, the polymer included in the core, 10 to 80 parts by weight of the alkyl (meth) acrylate monomer, 20 to 40 parts by weight of the aryl (meth) acrylate monomer and 0.01 to 5 parts by weight of the crosslinkable monomer And polymerized polymerized units by content. In addition, the crosslinkable monomer in the polymer unit of the polymer included in the core may be included in an amount of 0.01 to 5 parts by weight, or 0.05 to 3 parts by weight with respect to 100 parts by weight of the content of the remaining monomers other than the crosslinkable monomer, When the content of the crosslinkable monomer is less than 0.01 part by weight, the effect of improving the surface hardness of the resin is insignificant, and when the content exceeds 5 parts by weight, the impact strength of the resin may be lowered.

The particle diameter of the core may be variously adjusted according to the total particle diameter of the particle having the triple structure, and is not particularly limited. For example, the average particle diameter of the core is 10 nm to 5,000 nm, for example, 50 nm to 4,000 nm or 100 nm to 2,000 nm.

In one example, the core may be present on a rubber at room temperature.

The shell is present at the outermost part of the particles having the triple structure, and is a part for increasing the layer separation efficiency in the resin mixture to be described later, and surrounds the core, and includes an alkyl (meth) acrylate monomer, an aryl ( Meta) acrylate monomers and particles comprising a shell comprising a polymer derived from a compound of formula (1).

[Formula 1]

[Formula 2]

The alkyl (meth) acrylate monomer included in the polymerized unit of the polymer contained in the shell is the main monomer of the polymer, and the aryl (meth) acrylate monomer is the monomer having the bulky functional group described above. Same as one.

In one example, the hydrophobic functional group at the R ₂ position of the compound of formula I is (meth) acrylate monomers, for example, polydimethyl as the siloxane functional group is introduced into the compound, for example, the compounds of the R ₂ The compound of formula 2 may be a methacrylate including a poly dimethyl siloxane unit, by the hydrophobic functional group, it is possible to increase the layer separation efficiency with the first resin in the resin mixture to be described later.

In one example, the polymer included in the shell is 10 to 90 parts by weight of the alkyl (meth) acrylate monomer, 20 to 30 parts by weight of the aryl (meth) acrylate monomer and 1 to 50 parts by weight of the compound of Formula 1 May comprise polymerized units polymerized by content

The particle diameter of the particle including the shell may be, for example, the total particle diameter of the particle having the triple structure, and is not particularly limited. For example, the average particle diameter of the particle including the shell may be 10 nm or more. 10,000 nm, for example, 100 nm to 7,000 nm or 50 nm to 5,000 nm. When the particle diameter is less than 10 nm, the surface hardness of the produced resin may be lowered, and when the particle diameter exceeds 10,000 nm, the impact strength of the resin may be lowered.

In one example, the shell may be present in the glass phase at room temperature.

The content of the core in the particle having the triple structure of the seed-core-shell included in the exemplary resin of the present application is 1 to 150 parts by weight, for example, 1 to 120 parts by weight, based on 10 parts by weight of the seed. To 130 parts by weight or 5 to 110 parts by weight.

In addition, the content of the shell in the particles may be 5 to 100 parts by weight, for example 5 to 80 parts by weight, 7 to 70 parts by weight, 10 to 80 parts by weight based on 10 parts by weight of the seed.

The present application also relates to a method for producing the resin.

In one example, the manufacturing method may be a method for preparing particles having a triple structure of the seed-core-shell described above, the method comprising: preparing a seed; Manufacturing a core surrounding the seed; And manufacturing a shell surrounding the core.

For example, the preparation method may comprise the steps of: a) preparing a seed by polymerizing an alkyl (meth) acrylate monomer and a crosslinkable monomer; (b) further polymerizing an alkyl (meth) acrylate monomer, an aryl (meth) acrylate monomer and a crosslinkable monomer in the presence of the seed to produce a core surrounding the seed; And (c) polymerizing an alkyl (meth) acrylate monomer, an aryl (meth) acrylate monomer and a compound of formula 1 using a water-soluble initiator in the presence of the core to prepare a shell surrounding the core. And the effects thereof are the same as described above, and thus will be omitted.

[Formula 1]

[Formula 2]

In one example, the preparation method is carried out in the presence of an anionic surfactant and a water soluble polymerization initiator.

In one example, the anionic surfactant may use a variety of anionic surfactants known in the art, for example, alkyl aryl ether sulfate having 6 to 16 carbon atoms of alkyl, alkyl ether sulfate having 6 to 16 carbon atoms of alkyl. At least one selected from the group consisting of sodium dodecyl sulfate (SLS), sodium dodecylbenzenesulfonate, alkyl disulfonated diphenyl oxide, sodium lauryl sulfate and sodium dihexyl sulfosuccinate, It is not particularly limited.

The water-soluble polymerization initiator may also be used without limitation as long as it is a variety of water-soluble polymerization initiators known in the art, for example, sodium persulfate, potassium persulfate, ammonium persulfate, t-butyl hydroperoxide (tBHP) , 4.4'-azobis (4-cyanobalic acid) and 2,2'-azobis (2-amidinopropane) dihydrochloride may be used.

In the above production method, the monomer mixture comprising the above-mentioned monomers can generally provide a polymer in such a manner as to prepare a resin through polymerization of the monomers. For example, the monomer mixture may be polymerized by a method such as bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization to provide a polymer having a triple structure of seed-core-shell.

In one example, preparing the seed comprises dispersing a dispersant in a solvent; Dispersing the aforementioned alkyl (meth) acrylate monomer and crosslinkable monomer in the solvent; Adding and mixing additives such as the aforementioned anionic surfactant and water-soluble polymerization initiator to the solvent; And a polymerization step of reacting at a temperature of 40 ° C. or higher. Here, the order of each step can be changed arbitrarily, and two or more steps can proceed to one step.

The solvent can be used without limitation as long as it is a medium known to be commonly used to prepare the seed. As such a solvent, methyl ethyl ketone, ethanol, methyl isobutyl ketone, distilled water, etc. can be used, for example, 2 or more types can also be mixed and used.

As a dispersing agent which can be added to the said solvent, For example, organic dispersing agents, such as a polyvinyl alcohol, poly olifin maleic acid, or cellulose; Or inorganic dispersants such as tricalcium phosphate.

In addition, in preparing the acrylic polymer, additives conventionally used in the polymer industry may be used, and a process that is commonly performed may be further performed.

Further, in one example, preparing the core may include dispersing the aforementioned alkyl (meth) acrylate monomer, aryl (meth) acrylate monomer and crosslinkable monomer in a solution containing the seed; Adding and mixing additives such as the aforementioned anionic surfactant and water-soluble polymerization initiator to the solvent; And a polymerization step of reacting at a temperature of 40 ° C. or higher. Here, the order of each step can be changed arbitrarily, and two or more steps can proceed to one step.

In addition, preparing the shell may include dispersing the aforementioned alkyl (meth) acrylate monomer and the compound of Formula 1 in a solution containing the seed-core polymer; Adding and mixing additives such as chain transfer agents, anionic surfactants, and water-soluble polymerization initiators to the solvent; And a polymerization step of reacting at a temperature of 40 ° C. or higher. Here, the order of each step can be changed arbitrarily, and two or more steps can proceed to one step.

Examples of the chain transfer agent include alkyl mercaptans such as n-butyl mercaptan, n-dodecyl mercaptan, tertiary dodecyl mercaptan or isopropyl mercaptan; Aryl mercaptans such as phenyl mercaptan, naphthyl mercaptan or benzyl mercaptan; Halogen compounds such as carbon tetrachloride; Aromatic compounds, such as alpha-methylstyrene dimer and alpha-ethylstyrene dimer, etc. can be used.

The present application also relates to a resin mixture containing the resin, pellets, a method for producing a resin molded article using the same, and a resin molded article. The resin may be used in various fields in the form of a mixture mixed with heterogeneous resins having different physical properties. Hereinafter, a resin mixture including the resin, pellets, a method of manufacturing a resin molded article using the same, and a resin molded article may be used. Explain. Resin of this application is defined as "2nd resin" in the following resin mixture, The said heterogeneous resin which has a physical property different from resin of this application is defined as "1st resin" in the following resin mixture.

In the above, the "mixture" may be a mixture of two or more different resins. The type of the mixture is not particularly limited, but may include a case in which two or more resins are mixed in one matrix, or a case in which two or more pellets are mixed. Each of the resins may have different physical properties, for example, the physical properties may be surface energy, melt viscosity, or solubility parameter.

"Melt processing" means a process of melting a resin mixture at a temperature above the melting temperature (Tm) to form a melt blend, and forming a desired molded article using the melt mixture, for example, injection Molding, extrusion molding, blow molding, transfer molding, film blowing, fiber spinning, calendering thermoforming or foam molding.

"Resin molded article" means a pellet or product formed from a resin mixture, and the resin molded article is not particularly limited, but may be, for example, an automobile part, an electronic device part, a mechanical part, a functional film, a toy, or a pipe. have.

"Layer separation" may mean that a layer formed substantially by one resin is positioned or arranged on a layer formed substantially by another resin. Substantially, the layer formed by one resin may mean that one type of resin does not form a sea-island structure and is continuously present throughout one layer. The sea-level structure means that the phase separated resin is partially distributed in the whole resin mixture. In addition, "substantially formed" may mean that only one resin is present in one layer, or that one resin is rich.

In one example, the resin mixture may be separated by melt processing. As a result, a resin molded article having a specific function, for example, a high hardness function, can be manufactured without a separate process such as coating and plating. Therefore, the resin molded article can have improved mechanical properties and surface properties, and the production cost and time of the resin molded article can be reduced when using the resin mixture.

Layer separation of the resin mixture may occur due to the difference in physical properties between the first resin and the second resin and / or the molecular weight distribution of the second resin. Here, the physical properties may be, for example, surface energy, melt viscosity or solubility parameter. In the present specification, a mixture of resins including two kinds of resins will be described, but it will be apparent to those skilled in the art that three or more kinds of resins having different physical properties can be mixed and separated by melt processing.

According to one embodiment, the resin mixture may include a first resin and a second resin having a surface energy difference of 0.1 to 35 mN / m at 25 ° C. from the first resin.

The surface energy difference between the first resin and the second resin is 0.1 to 35 mN / m, 0.1 to 30 mN / m, 0.1 to 20 mN / m, 0.1 to 15 mN / m, 0.1 to 7 mN / m at 25 ℃ , 1 to 35 mN / m, 1 to 30 mN / m, 2 to 20 mN / m, 3 to 15 days. In the case of using the first and second resins having a surface energy difference in this range, the second resin can easily move to the surface without the first and second resins peeling off, and the delamination phenomenon can easily occur.

The resin mixture of the first resin and the second resin having a surface energy difference of 0.1 to 35 mN / m at 25 ° C. may be layer separated by melt processing. As one example, when the resin mixture of the first resin and the second resin is melt processed and exposed to air, the first resin and the second resin may be separated by a hydrophobic difference. In particular, since the second resin having a lower surface energy than the first resin has high hydrophobicity, the second resin can be moved in contact with air to form a second resin layer located on the air side. In addition, the first resin may be placed on the side opposite to the air while contacting the second resin. Thus, layer separation occurs between the first resin and the second resin of the resin mixture.

The resin mixture may be separated into two or more layers. As one example, the resin mixture comprising the first resin and the second resin may have three layers, for example, a second resin layer, when two opposite surfaces of the melt processed resin mixture are exposed to air. It can be separated into a / first resin layer / a second resin layer. On the other hand, when only one side of the melt processed resin mixture is exposed to air, the resin mixture may be separated into two layers, for example, a second resin layer / first resin layer. In addition, when the resin mixture comprising the first resin, the second resin and the third resin having a surface energy difference is melt processed, the melt processed resin mixture has five layers, for example, a third resin layer / agent. The layer can be separated into two resin layers / first resin layer / second resin layer / third resin layer. In addition, when all surfaces of the melt-processed resin mixture are exposed to air, the resin mixture may be layered in all directions to form a core-shell structure.

According to another embodiment, the resin mixture comprises a first resin; And a second resin having a melt viscosity difference of 0.1 to 3000 pa * s at a shear rate of 100 to 1000 s ⁻¹ and a processing temperature of the resin mixture.

The difference in melt viscosity of the first resin and the second resin is 0.1 to 3000 pa * s, 1 to 2000 pa * s, 1 to 1000 pa * at a shear rate of 100 to 1000 s ⁻¹ and a processing temperature of the resin mixture. s, 1 to 500 pa * s, 50 to 500 pa * s, 100 to 500 pa * s, 200 to 500 pa * s or 250 to 500 pa * s. In the case of using the first and second resins having a difference in melt viscosity in this range, the second resin can easily move to the surface and the layer separation phenomenon can easily occur without the first and second resins peeling off.

The resin mixture of the first resin and the second resin having a melt viscosity difference of 0.1 to 3000 pa * s at a shear rate of 100 to 1000 s ⁻¹ and a processing temperature of the resin mixture is layered due to the difference in melt viscosity after melt processing. Can be separated. As one example, when the resin mixture of the first resin and the second resin is melt processed and exposed to air, the first resin and the second resin may be separated by the fluidity difference. In particular, since the second resin having a lower melt viscosity than the first resin has high fluidity, the second resin can be moved in contact with air to form a second resin layer located on the air side. In addition, the first resin may be placed on the side opposite to the air while contacting the second resin. Thus, layer separation occurs between the first resin and the second resin of the resin mixture.

The melt viscosity can be measured by capillary flow, which means shear viscosity (pa * s) depending on the specific processing temperature and shear rate (/ s).

The "shear rate" means a shear rate applied when the resin mixture is processed, and the shear rate can be adjusted between 100 and 1000 s ^-1 depending on the processing method. Control of the shear rate according to the processing method will be apparent to those skilled in the art.

The said "processing temperature" means the temperature which processes the said resin mixture. For example, when the resin mixture is used for melt processing such as extrusion or injection, it means a temperature applied to the melt processing step. The processing temperature can be adjusted according to the resin applied to melt processing such as extrusion or injection. For example, in the case of the resin mixture including the first resin of the ABS resin and the second resin obtained from the acrylic monomer, the processing temperature may be 210 to 270 ° C.

According to another embodiment of the invention, the first resin; And a second resin having a difference in solubility parameters from 0.001 to 10.0 (J / cm ³ ) ^1/2 at 25 ° C., may be provided.

The difference between the solubility parameters of the first resin and the second resin is 0.001 to 10.0 (J / cm ³ ) ^1/2 , 0.01 to 5.0 (J / cm ³ ) ^1/2 , 0.01 to 3.0 ( J / cm ³ ) ^1/2 , 0.01 to 2.0 (J / cm ³ ) ^1/2 , 0.1 to 1.0 (J / cm ³ ) ^1/2 , 0.1 to 10.0 (J / cm ³ ) ^1/2 , 3.0 to 10.0 (J / cm ³ ) ^1/2 , 5.0 to 10.0 (J / cm ³ ) ^1/2 or 3.0 to 8.0 (J / cm ³ ) ^1/2 . These solubility parameters are inherent properties of the resins which show the solubility according to the polarity of each resin molecule, and solubility parameters for each resin are generally known. When the difference in solubility parameter is ^less than 0.001 (J / cm ³ ) ^1/2 , the first resin and the second resin are easily mixed, so that the layer separation phenomenon is difficult to occur easily, and the difference in solubility parameter is 10.0 (J / cm ³ ) If greater than ^1/2 , the first resin and the second resin may not be bonded and may be peeled off.

The upper limit and / or lower limit of the difference in solubility parameters may be any value within the range of 0.001 to 10.0 (J / cm ³ ) ^1/2 , and may be dependent on the physical properties of the first resin. In particular, when the first resin is used as the base resin and the second resin is used as a functional resin for improving the surface properties of the first resin, the second resin has a difference in solubility parameter between the first resin and the second resin at 25 ° C. Can be selected to be from 0.001 to 10.0 (J / cm ³ ) ^1/2 . As one example, the difference in solubility parameter may be selected in consideration of the miscibility of the second resin in the melt mixture of the first resin and the second resin.

At 25 ° C., the resin mixture of the first resin and the second resin having a solubility parameter difference of 0.001 to 10.0 (J / cm ³ ) ^1/2 may be layer separated after melt processing due to the difference in solubility parameters. As one example, when the resin mixture of the first resin and the second resin is melt processed and exposed to air, the first resin and the second resin may be separated by the degree of miscibility. In particular, the second resin having a difference in solubility parameter of 0.001 to 10 (J / cm ³ ) ^1/2 at 25 ° C. relative to the first resin may not be mixed with the first resin. Therefore, if the second resin additionally has a lower surface tension or lower melt viscosity than the first resin, the second resin can be moved in contact with air to form a second resin layer located on the air side. In addition, the first resin may be placed on the side opposite to the air while contacting the second resin. Thus, layer separation occurs between the first resin and the second resin of the resin mixture.

In the resin mixture, the first resin is a resin mainly determining the physical properties of the desired molded article, and may be selected according to the type of the desired molded article and the process conditions used. As such a first resin, a general synthetic resin can be used without particular limitation.

As a 1st resin, For example, Styrene-type resins, such as an acrylonitrile butadiene styrene (ABS) resin, a polystyrene resin, an acrylonitrile styrene acrylate (ASA) resin, or a styrene-butadiene-styrene block copolymer; Polyolefin resins such as high density polyethylene resin, low density polyethylene resin or polypropylene resin; Thermoplastic elastomers such as ester-based thermoplastic elastomers or olefin-based thermoplastic elastomers; Polyoxyalkylene resins such as polyoxymethylene resin or polyoxyethylene resin; Polyester resins such as polyethylene terephthalate resins or polybutylene terephthalate resins; Polyvinyl chloride resins; Polycarbonate resins; Polyphenylene sulfide resin; Vinyl alcohol-based resins; Polyamide-based resins; Acrylate resins; Engineering plastics; These copolymers or mixtures thereof are mentioned. As the engineering plastics, plastics exhibiting excellent mechanical and thermal properties may be used. For example, polyetherketone, polysulfone, polyimide and the like can be used as the engineering plastics. In one example, as the first resin, a copolymer obtained by polymerizing acrylonitrile, butadiene, styrene and an acrylic monomer may be used.

In the resin mixture, the second resin may use a resin including particles having a triple structure of an exemplary seed-core-shell of the present application, and the description thereof is the same as described above.

In one example, the weight average molecular weight (Mw) of the second resin may be about 5,000 to 200,000. In another example, the weight average molecular weight of the second resin is 10,000 to 200,000, 1.50,000 to 200,000, 20,000 to 200,000, 0.50,000 to 180,000, 0.50,000 to 150,000, 0.50,000 to 120,000, 10,000 to 180,000, 1.50,000 to 150,000, or 20,000 to 120,000. When the second resin having a weight average molecular weight in this range is applied to, for example, a resin mixture for melt processing, the second resin may have appropriate fluidity and layer separation may easily occur.

In addition, in one example, the molecular weight distribution (PDI) of the second resin may be controlled in the range of 1 to 2.5, 1 to 2.2, 1.5 to 2.5, or 1.5 to 2.2. When the second resin having a molecular weight distribution in this range is applied to, for example, a resin mixture for melt processing, the content of low molecular weight and / or high molecular weight which prevents occurrence of delamination in the second resin is reduced, thereby making layer separation easier. Can happen.

In one example, the resin mixture may include 0.1 to 50 parts by weight of the second resin based on 100 parts by weight of the first resin. In another example, the resin mixture may include 1 to 30 parts by weight, 1 to 20 parts by weight, or 1 to 15 parts by weight based on 100 parts by weight of the first resin. When the content includes the first resin and the second resin, it is possible to induce a layer separation phenomenon, it is possible to provide an economical resin mixture by appropriately controlling the content of the second resin that is relatively expensive compared to the first resin.

The above resin mixture can be prepared into pellets by extrusion. In the pellet manufactured using the resin mixture, the first resin may form a core, and the second resin may be separated from the first resin to form a shell.

According to one embodiment, the pellet is a core formed of a first resin; And a cell comprising particles having a triple structure of seed-core-shell and comprising a second resin having a difference in surface energy, melt viscosity or solubility parameter from the first resin.

In addition, as described above, the first resin and the second resin may have different surface energy, melt viscosity, or solubility parameters. For example, the first resin and the second resin may have a surface energy difference of 0.1 to 35 mN / m at 25 ° C .; Or at a shear rate of 100 to 1000 s ⁻¹ and a melt temperature of 0.1 to 3000 pa * s at the processing temperature of the pellets.

Since the type and physical properties of the first resin and the second resin have already been described in detail, specific details will be omitted.

On the other hand, the resin mixture or pellets described above may be melt processed to provide a resin molded article having a layered structure.

According to one embodiment, melting the resin mixture to form a melt blend (melt blend); And processing the melted mixture to form a layered structure.

As described above, due to the difference in physical properties between the first resin and the second resin, a layer separation phenomenon may occur in the process of melt processing the resin mixture, and due to this layer separation phenomenon, pellets or It can have the effect of selectively coating the surface of the molded article.

In particular, when using a resin having a triple-structured particle of seed-core-shell as the second resin, a shell portion having a relatively low surface energy or melt viscosity during the melt processing process is located on the surface of the resin molded article and It is possible to provide a resin molded article having improved characteristics and surface properties.

Melt processing the resin mixture may be performed under shear stress. For example, the melt processing step may be performed by an extrusion and / or injection processing method.

In addition, the step of melt processing the resin mixture may vary the temperature applied according to the type of the first resin and the second resin used. For example, when styrene resin is used as the first resin and acrylic resin is used as the second resin, the melt processing temperature may be controlled to about 210 to 270 ° C.

The method of manufacturing a resin molded article may further include curing the resultant obtained by melt processing the resin mixture, that is, the melt processed product of the resin mixture. The curing can be, for example, thermosetting or UV curing. In addition, the resin molded article may be further subjected to chemical or physical treatment.

In one example, the method of manufacturing a resin molded article may further include preparing a second resin before melting the resin mixture to form a molten mixture. 2nd resin can provide a specific function, for example, high hardness, to the surface layer of a resin molded article. Since the contents related to the preparation of the second resin have already been described, specific details are omitted.

According to another embodiment, the method for producing a resin molded article may include melting a pellet to form a molten mixture; And processing the melt mixture to form a layered structure.

In one example, the pellet may be prepared by melt processing such as extrusion of the resin mixture described above. For example, when extruding a resin mixture comprising the first resin and the second resin, the second resin having a higher hydrophobicity than the first resin moves in contact with air to form a surface layer of the pellet. One resin may be located in the center of the pellet to form a core. The pellets thus prepared can be manufactured into a resin molded article by melt processing such as injection. However, the present invention is not limited thereto, and in another example, the resin mixture may be manufactured into a resin molded article by melt processing such as direct injection or the like.

On the other hand, according to another embodiment, the resin molded article is a first resin layer, a second resin layer formed on the first resin layer and an interface layer formed between the first resin layer and the second resin layer. It may include. The interface layer may include first and second resins.

As for the resin molded article manufactured from the resin mixture containing the specific 1st resin and the said 2nd resin which has a physical property difference with the said 1st resin, a 1st resin layer is located inside and a 2nd resin layer is resin It may be a layered structure formed on the surface of the molded article.

In particular, when using a resin containing particles having the triple structure of the seed-core-shell polymer described above as the second resin, the molded article can further improve the surface hardness.

The first resin layer mainly includes the first resin, determines physical properties of the molded article, and may be located inside the resin molded article. In addition, the said "2nd resin layer" mainly contains the said 2nd resin, can be located in the outer edge of a resin molded article, and can provide a fixed function to the surface of a molded article.

Since specific details of the first resin and the second resin have been described above, the description of the related contents will be omitted.

The resin molded article may include an interfacial layer formed between the first resin layer and the second resin layer and containing a mixture of the first resin and the second resin. The interfacial layer may be formed between the separated first resin layer and the second resin layer to serve as an interface, and may include a mixture of the first resin and the second resin. The blend may be in a state in which the first resin and the second resin are physically or chemically bonded, and the first resin layer and the second resin layer may be bonded through the blend.

The resin molded article may be formed in a structure in which the first resin layer and the second resin layer are divided by such an interface layer, and the second resin layer is exposed to the outside. For example, the molded article may include the first resin layer; Interfacial layer; And a structure in which the second resin layer is sequentially stacked, and may have a structure in which an interface and a second resin are stacked on upper and lower ends of the first resin. In addition, the resin molded article may include a structure in which the interface and the second resin layer sequentially surround the first resin layer having various three-dimensional shapes, for example, spherical, circular, polyhedral, sheet, and the like.

The layer separation phenomenon appearing in the resin molded article seems to be due to the production of a resin molded article by applying a specific first resin and a second resin having different physical properties. Examples of such different physical properties include surface energy or melt viscosity. Details of such differences in physical properties are as described above.

In one example, the first resin layer, the interfacial layer, and the second resin layer may be identified using an SEM after etching the fracture surface using THF vapor after the specimen is subjected to a low temperature impact test. For the measurement of the thickness of each layer, the specimen is cut with a diamond knife using a microtoming device to make a smooth cross section, and then the smooth cross section is etched using a solution that can selectively dissolve the second resin better than the first resin. The etched cross-section is different in the degree of melting depending on the content of the first resin and the second resin, and when the cross-section is viewed from the surface at 45 degrees using the SEM, the first resin layer, the second resin layer, The interfacial layer and the surface can be observed and the thickness of each layer can be measured. In one example, 1,2-dichloroethane solution (10% by volume, in EtOH) was used as a solution for selectively dissolving the second resin, but this is illustrative and the solubility of the second resin is higher than that of the first resin. The solution is not particularly limited, and those skilled in the art can appropriately select and apply a solution according to the type and composition of the second resin.

The interfacial layer is 1 to 95%, 10 to 95%, 20 to 95%, 30 to 95%, 40 to 95%, 50 to 95%, 60 to 95%, or the total thickness of the second resin layer and the interface layer, or It may have a thickness of 60 to 90%. If the interfacial layer is 0.01-95% of the total thickness of the second resin layer and the interfacial layer, the interfacial bonding force between the first resin layer and the second resin layer is excellent, so that peeling of both layers does not occur, and the second resin layer Due to this, the surface properties can be greatly improved. On the contrary, if the interface layer is too thin as compared to the second resin layer, the bonding force between the first resin layer and the second resin layer is low, so that peeling of both layers may occur. The effect of the improvement of properties may be insignificant.

The second resin layer may have a thickness of 0.01 to 30%, 0.01 to 20%, 0.01 to 10%, 0.01 to 5%, 0.01 to 3%, 0.01 to 1% or 0.01 to 0.1% relative to the total resin molded article. . As the second resin layer has a range of thicknesses, it is possible to impart improved surface hardness or scratch resistance to the surface of the molded article. If the thickness of the second resin layer is too thin, the surface properties of the molded article are sufficiently improved. It may be difficult to, and if the thickness of the second resin layer is too thick, the mechanical properties of the functional resin itself may be reflected in the resin molded article to change the mechanical properties of the first resin.

In the resin molded article of the structure mentioned above, the component of a 1st resin layer can be detected by the infrared spectroscopy IR on the surface of a 2nd resin layer.

In the above, the surface of the second resin layer means a surface exposed to the outside (for example, air) rather than the first resin layer.

Details of the first resin, the second resin, and the difference in physical properties of the first resin and the second resin have already been described above, and thus description of the related content will be omitted. In addition, in the present specification, the difference in physical properties between the first resin and the second resin may mean a difference in physical properties between the first resin and the second resin or a difference in physical properties between the first resin layer and the second resin layer.

In one example, the resin molded article may be used to provide automobile parts, helmets, electric machine parts, spinning machine parts, toys, pipes, and the like.

Exemplary resins of the present application can provide resin molded articles having improved mechanical properties and surface hardness. In addition, in the case of using the resin, it is possible to omit an additional surface coating step on the surface of the resin molded article can achieve the above-described effect can reduce the production time and cost, and increase the productivity.

Figure 1 shows a layered cross-sectional SEM picture of the resin molded article prepared in Example 2.

Figure 2 shows a cross-sectional SEM image of the resin molded article prepared in Comparative Example 3.

Hereinafter, the resin mixture will be described in detail with reference to Examples and Comparative Examples, but the scope of the resin mixture is not limited to the examples given below.

Physical properties in Examples and Comparative Examples were evaluated in the following manner.

1. 표면 에너지의 측정1. Measurement of surface energy

According to the Owens-Wendt-Rabel-Kaelble method, surface energy was measured using a Drop Shape Analyzer (DSA100 manufactured by KRUSS).

Specifically, the resin obtained in Example or Comparative Example is dissolved in 15% by weight of methyl ethyl ketone solvent, the precipitate is removed using a centrifuge, and then bar coating on LCD glass. ). Then, the coated LCD glass was pre-dried for 2 minutes in an oven at 60 ℃, and dried for 1 minute in an oven at 90 ℃.

After drying (or curing), deionized water and diiodomethane were dropped 10 times on the coated surface to obtain an average value of the contact angle, and the surface energy was obtained by substituting numerical values into the Owens-Wendt-Rabel-Kaelble method.

2. 단면 형상 관찰2. Observation of cross section shape

The specimens of Examples and Comparative Examples were subjected to a low temperature impact test, and then the fracture surfaces were etched using THF vapor and the cross-sectional shapes separated by SEM (manufacturer: Hitachi, model name: S-4800) were observed.

The observed cross-sectional shape was evaluated according to the following criteria.

(Circle): The state in which complete delamination was observed

△: not enough layer separation

×: No delamination

3. 강도 실험 측정3. Strength Experiment Measurement

The strength of the specimens obtained in Examples and Comparative Examples was measured based on ASTM D256. Specifically, the weight (kg * cm / cm) required to break the specimen cut the V-shaped groove (Notch) by lifting the pendulum tip was measured using an impact tester (Impact 104, Tinius Olsen). Five measurements were taken on 1/8 "and 1/4" specimens and averaged.

4. 연필 경도 측정 실험4. Pencil hardness measurement experiment

The surface pencil hardness of the specimens obtained in Examples and Comparative Examples was measured under a constant load of 500 g using a pencil hardness tester (Chungbuk Tech). The rate of change of the surface was observed by applying a scratch at an angle of 45 degrees while changing the standard pencil (Mitsubishi Co., Ltd.) from 6B to 9H (ASTM 3363-74). The measurement result is an average value of five replicate experiments.

5. 적외선 분광기(IR)에 의한 표면 분석5. Surface analysis by infrared spectroscopy (IR)

A UMA-600 infrared microscope equipped with a Varian FTS-7000 spectrometer (Varian, USA) and a mercury cadmium telluride (MCT) detector was used, and spectral measurements and data processing were performed using Win-IR PRO 3.4 software (Varian, USA). , Conditions are as follows.

Germanium (Ge) ATR crystals with a refractive index of 4.0

-The mid-infrared spectrum is scanned from 4000cm ^-1 to 600cm ^-1 with spectral resolution of 8cm ^-1 and 16 scans by attenuated total reflection (ATR) method

Internal reference band: carbonyl group of acrylate (C = O str., ˜1725 cm ⁻¹ )

Intrinsic component of the first resin: butadiene compound [C = C str. (˜1630 cm ⁻¹ ) or = CH out-of-plane vib. (˜970 cm ⁻¹ )]

The peak intensity ratios [I _BD (C = C) / I _A (C = O)] and [I _BD (out-of-plane) / I _A (C = O)] are calculated and the spectral measurements are measured within one specimen. Five runs in each of the different regions were used to calculate the mean and standard deviation.

제조예 - 제 2 수지의 제조Preparation Example-Preparation of Second Resin

제조예 1Preparation Example 1

a. 시드의 중합 a. Polymerization of seeds

A reactor of a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet, and a circulation condenser was prepared, and 546.4 g of deionized water (DDI water) was added to a 3 L vessel, and the reactor was heated to 80 ° C. in a nitrogen atmosphere. Then, 29.4 g of methyl methacrylate (MMA), 0.6 g of allyl methacrylate (AMA), 3% sodium lauryl sulfate (hereinafter, AMA), an anionic surfactant, 6 g of SLS) was added to the reactor and stirred for 15 minutes. Thereafter, 10 g of a potassium persulfate (PPS) solution as a 3% water-soluble polymerization initiator was added thereto, followed by stirring for 120 minutes. After completion of the reaction, an emulsion of a glassy seed polymer having an average particle diameter of 110 nm was prepared, and the conversion was measured at 98%.

b. 코어의 중합 b. Polymerization of the core

20 g of a 3% PPS solution was added to the emulsion, followed by stirring for 15 minutes. A mixed solution of 251.1 g of MMA, 107.6 g of phenyl methacrylate (hereinafter, referred to as PHMA), 7.3 g of AMA, and 61 g of 3% SLS was prepared. It was added dropwise to the reactor at a rate of 3 g per minute. After dropping, 20 g of 3% PPS solution was added and further polymerized for 30 minutes to prepare an emulsion of particles grafted with a rubbery core polymer to the seed. The conversion of the prepared rubbery latex polymer was measured at 97% and the average diameter of the particles was measured at 275 nm.

c. 쉘의 중합 c. Polymerization of shell

20 g of 3% PPS solution was added to the emulsion, followed by stirring for 15 minutes, and 3% SLS 60 g, MMA 147 g, PHMA 52.5 g, and a methacryloxypentyl terminated polydimethylsiloxane (PDMS, M _w : 420). A mixed solution of 10.5 g and 0.6 g of n-dodecyl mercaptan, a chain transfer agent, was prepared and added dropwise to the reactor at a rate of 3 g per minute. After completion of the dropwise addition, 20 g of a 3% PPS solution was added thereto, followed by polymerization for 30 minutes to complete the polymerization, thereby preparing an emulsion of particles grafted with a glassy shell polymer on the core. The average particle diameter of the particles was measured at 300 nm.

d. 제 2 수지의 제조d. Preparation of Second Resin

The emulsion was added dropwise to a 1% magnesium sulfate solution preheated to 80 ° C. while stirring to prepare a solid powder. The powder was filtered, washed with distilled water at 70 ° C. three times, and dried in a vacuum oven at 80 ° C. for 24 hours to prepare a functional resin including 5 parts by weight of a seed, 60 parts by weight of a core, and 35 parts by weight of a cell.

제조예 2Preparation Example 2

a. 시드의 중합 a. Polymerization of seeds

A reactor of a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet, and a circulation condenser was prepared, and 1647.6 g of deionized water (DDI water) was added to a 3 L vessel, and the reactor internal temperature was heated to 80 ° C. in a nitrogen atmosphere. Then, MMA 294g, AMA 6g, SLS 40g was added to the reactor and stirred for 15 minutes. Thereafter, 20 g of a 3% PPS solution was added thereto, followed by stirring for 120 minutes. After completion of the reaction, an emulsion of a glassy seed polymer having an average particle diameter of 100 nm was prepared, and the conversion was measured at 98%.

b. 코어의 중합 b. Polymerization of the core

120 g of 3% PPS solution was added to the emulsion, followed by stirring for 15 minutes. A mixed solution of 62.8 g of MMA, 26.9 g of PHMA, 1.8 g of AMA, and 20.3 g of 3% SLS was prepared and added dropwise to the reactor at a rate of 3 g per minute. After dropping, 10 g of a 3% PPS solution was added and further polymerized for 30 minutes to prepare an emulsion of particles grafted with a rubbery core polymer to the seed. The conversion rate of the prepared rubber latex core latex polymer was measured to be 97%, and the average diameter of the particles was measured to be 110 nm.

c. 쉘의 중합 c. Polymerization of shell

20 g of 3% PPS solution was added to the emulsion, followed by stirring for 15 minutes, and 3% SLS 60 g, MMA 147 g, PHMA 52.5 g, and a methacryloxypentyl terminated polydimethylsiloxane (PDMS, M _w : 420). A mixed solution of 10.5 g and 0.6 g of n-dodecyl mercaptan, a chain transfer agent, was prepared and added dropwise to the reactor at a rate of 3 g per minute. After completion of the dropwise addition, 20 g of a 3% PPS solution was added thereto, followed by polymerization for 30 minutes to complete the polymerization, thereby preparing an emulsion of particles grafted with a glassy shell polymer on the core. The average particle diameter of the particles was measured at 126 nm.

d. 제 2 수지의 제조d. Preparation of Second Resin

The emulsion was added dropwise to a 1% magnesium sulfate solution preheated to 80 ° C. while stirring to prepare a solid powder. The powder was filtered, washed three times with distilled water at 70 ° C., and dried in a vacuum oven at 80 ° C. for 24 hours to prepare a functional resin including 50 parts by weight of the seed, 15 parts by weight of the core, and 35 parts by weight of the cell.

실시예 1Example 1

90 parts by weight of the first resin (60 parts by weight of methyl methacrylate, 7 parts by weight of acrylonitrile, 10 parts by weight of butadiene and 23 parts by weight of styrene) and 10 parts by weight of the second resin prepared in Preparation Example 1 were mixed. After the extrusion, the pellet was extruded at a temperature of 240 ° C. in a twin screw extruder (Leistritz). Then, the pellets were injected at a temperature of 240 ° C. in an EC100Φ 30 injection machine (ENGEL) to prepare a resin molded product specimen.

In the molded product specimen, a layer separation phenomenon occurred in which a first resin layer, a second resin layer, and an interface layer having a thickness of 10 μm between the first resin layer and the second resin layer were separated.

The surface energy of the second resin layer was measured at 30 mN / m, the difference in surface energy of the first resin layer and the second resin layer was measured at 13 mN / m.

In addition, the strength for the 1/8 "and 1/4" specimens was measured at 9, respectively, and the pencil hardness of the specimens was measured at 2H, and IR analysis showed I _BD (C = C) / I _PMMA (C = O). ) = 0.0119 ± 0.0005, I _BD (out-of-plane) / I _PMMA (C = O) = 0.402 ± 0.0029.

실시예 2Example 2

A resin molded article specimen was produced in the same manner as in Example 1, except that 10 parts by weight of the second resin obtained in Production Example 2 was mixed with 90 parts by weight of the first resin.

In the molded product specimen, a layer separation phenomenon occurred in which a first resin layer, a second resin layer, and an interface layer having a thickness of 3 μm between the first resin layer and the second resin layer were separated.

The surface energy of the second resin layer was measured to be 29 mN / m, and the surface energy difference between the first resin layer and the second resin layer was measured to be 14 mN / m.

In addition, the strength for the 1/8 "and 1/4" specimens was measured at 9, respectively, and the pencil hardness of the specimens was measured at H.

비교예 1Comparative Example 1

100 parts by weight of the first resin pellets used in Example 1 were dried in an oven and injected at a temperature of 240 ° C. with an EC100Φ 30 injection machine (ENGEL) to prepare a resin molded article specimen.

The surface energy of the first resin layer was measured at 43 mN / m.

In addition, the strength for the 1/8 "and 1/4" specimens was measured at 10, respectively, and the pencil hardness of the specimens was measured at F.

비교예 2Comparative Example 2

Resin molded article specimens were prepared in the same manner as in Example 1, except that PMMA (LGMMA IF870) was used as the second resin.

In the molded article specimens, no delamination occurred.

The surface energy of the second resin layer was measured to be 43 mN / m, it was found that there is no difference in the surface energy of the first resin layer and the second resin layer.

In addition, the strength for the 1/8 "and 1/4" specimens was measured at 5, respectively, and the pencil hardness of the specimens was measured at H.

비교예 3Comparative Example 3

Resin molded product specimens were prepared in the same manner as in Example 1, except that PMMA (Sekisui XX-110BQ) crosslinked with the second resin was used.

In the molded article specimens, no delamination occurred.

In addition, the strengths for the 1/8 "and 1/4" specimens were measured at 3 and 4, respectively, and the pencil hardness of the specimens was measured at HB.

비교예 4Comparative Example 4

Contaminated hard coating solution containing self-made polyfunctional acrylate on the specimen (DPHA 17.5 parts by weight, PETA 10 parts by weight, perfluorohexylethyl methacrylate 1.5 parts by weight, SK cytech's urethane acrylate EB 1290 5 Parts by weight, 45 parts by weight of methyl ethyl ketone, 20 parts by weight of isopropyl alcohol and 1 part by weight of Ciba's UV initiator, IRGACURE184), were coated with May bar # 9 and dried at 60 to 90 ° C. for 4 minutes to form a film. Then, ultraviolet rays were irradiated at an intensity of 3,000 mJ / cm ² to cure the coating liquid composition to form a hard coating film.

The pencil hardness of the specimen was measured by 3H, IR analysis _{I BD (C = C) /} I PMMA (C = O) = 0, I BD (out-of-plane) / I PMMA (C = O) = Measured to zero.

When the resin mixture of the above embodiment is used, a layer separation phenomenon occurs between the resins during extrusion and injection, and the high hardness resin is positioned on the surface of the resin molded article according to the layer separation phenomenon. Excellent surface hardness without

On the other hand, the resin mixture of the comparative example did not show a delamination phenomenon between the resins as in the example, and the resin molded product produced also has a relatively low surface hardness, which makes it difficult to use in general electronic products, automotive parts, etc. without additional coating or painting process. Appeared.

Claims

Seeds comprising polymers derived from alkyl (meth) acrylate monomers and crosslinkable monomers;

A core surrounding the seed and comprising a polymer derived from an alkyl (meth) acrylate monomer, an aryl (meth) acrylate monomer and a crosslinkable monomer; And

Resin comprising particles surrounding the core and comprising a shell comprising an alkyl (meth) acrylate monomer, an aryl (meth) acrylate monomer and a polymer derived from a compound of formula (I):

[Formula 1]

In Formula 1, R 1 represents hydrogen or alkyl having 1 to 5 carbon atoms, R 2 represents a compound of Formula 2,

[Formula 2]

In Formula 2, R 3 represents alkylene having 1 to 8 carbon atoms, R 4 and R 5 each independently represent hydrogen and alkyl having 1 to 8 carbon atoms, and n is an integer of 1 to 100.
The method of claim 1 wherein the alkyl (meth) acrylate monomers are methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, iso A resin comprising at least one member selected from the group consisting of butyl acrylate, hexyl acrylate, octyl acrylate, and 2-ethylhexyl acrylate.
The aryl (meth) acrylate monomer according to claim 1, wherein the aryl (meth) acrylate monomer is one selected from the group consisting of naphthyl (meth) acrylate, phenyl (meth) acrylate, anthracenyl (meth) acrylate and benzyl (meth) acrylate. Resin containing the above.
The method of claim 1, wherein the crosslinkable monomer is 3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, allyl acrylate, A resin containing at least one member selected from the group consisting of allyl methacrylate, trimethylolpropane triacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, and divinylbenzene.
The resin of claim 1 wherein the average particle diameter of the particles comprising seeds is 10 to 1,000 nm.
The resin of claim 1 wherein the seed comprises a polymer derived from 5 to 99.5 parts by weight of alkyl (meth) acrylate monomer and 0.5 to 5 parts by weight of crosslinkable monomer.
The resin according to claim 1, wherein the particle containing the core has an average particle diameter of 10 to 5,000 nm.
The polymer composition of claim 1, wherein the core comprises a polymer derived from 10 to 80 parts by weight of an alkyl (meth) acrylate monomer, 20 to 40 parts by weight of an aryl (meth) acrylate monomer and 0.01 to 5 parts by weight of a crosslinkable monomer. Suzy.
The resin of claim 1 wherein the average particle diameter of the particles comprising the shell is from 10 nm to 10,000 nm.
The polymer composition of claim 1, wherein the shell comprises 10 to 90 parts by weight of an alkyl (meth) acrylate monomer, 20 to 30 parts by weight of an aryl (meth) acrylate monomer, and 1 to 50 parts by weight of a polymer derived from the compound of Formula 1. Resin containing.
The resin according to claim 1, wherein the content of the core in the particles is 1 to 150 parts by weight based on 10 parts by weight of the seed.
The resin according to claim 1, wherein the content of the shell in the particles is 5 to 100 parts by weight based on 10 parts by weight of the seed.
Is carried out in the presence of an anionic surfactant and a polymerization initiator,

(a) polymerizing an alkyl (meth) acrylate monomer and a crosslinkable monomer to prepare a seed;

(b) further polymerizing an alkyl (meth) acrylate monomer, an aryl (meth) acrylate monomer and a crosslinkable monomer in the presence of the seed to produce a core surrounding the seed; And

(c) polymerizing an alkyl (meth) acrylate monomer, an aryl (meth) acrylate monomer, and a compound of formula (I) using a water-soluble initiator in the presence of the core to prepare a shell surrounding the core: Manufacturing Method of Resin

[Formula 1]

In Formula 1, R 1 represents hydrogen or alkyl having 1 to 5 carbon atoms, R 2 represents a compound of Formula 2,

[Formula 2]

In Formula 2 R 3 represents an alkylene group having 1 to 8, R 4 and R 5 are, each independently, a hydrogen, an alkyl group having 1 to 8, n is an integer from 1 to 100.
The method of claim 13, wherein the anionic surfactant is 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, A method for producing a resin which is at least one member selected from the group consisting of alkyl disulfonated diphenyl oxide, sodium lauryl sulfate and sodium dihexyl sulfosuccinate.
The method of claim 13, wherein the polymerization initiator is sodium persulfate, potassium persulfate, ammonium persulfate, t-butyl hydroperoxide (tBHP), 4.4'-azobis (4-cyanovalic acid) and 2,2 A process for producing a resin which is at least one member selected from the group consisting of '-azobis (2-amidinopropane) dihydrochloride.
First resin; And

A second resin which is an acrylic polymer having a difference in surface energy, melt viscosity or solubility parameter from the first resin,

The second resin is

Seeds comprising polymers derived from alkyl (meth) acrylate monomers and crosslinkable monomers;

A core surrounding the seed and comprising a polymer derived from an alkyl (meth) acrylate monomer, an aryl (meth) acrylate monomer and a crosslinkable monomer; And

A resin mixture comprising particles surrounding a core comprising a shell comprising an alkyl (meth) acrylate monomer, an aryl (meth) acrylate monomer and a polymer derived from a compound of formula:

[Formula 1]

In Formula 1, R 1 represents hydrogen or alkyl having 1 to 5 carbon atoms, R 2 represents a compound of Formula 2,

[Formula 2]

In Formula 2, R 3 represents alkylene having 1 to 8 carbon atoms, R 4 and R 5 each independently represent hydrogen and alkyl having 1 to 8 carbon atoms, and n is an integer of 1 to 100.
The resin mixture according to claim 16, wherein the second resin has a surface energy difference of 0.1 to 35 mN / m from the first resin at 25 ° C.
17. The resin mixture of claim 16, wherein the second resin has a difference in melt viscosity of 0.1 to 3000 pa * s at a shear rate of 100 to 1000 s -1 and a processing temperature of the resin mixture.
17. The resin mixture of claim 16, wherein the second resin has a Solubility Parameter difference between 0.001 and 10.0 (J / cm 3 ) 1/2 at 25 ° C.
The method of claim 16, wherein the first resin is a styrene resin, a polyolefin resin, a thermoplastic elastomer, a polyoxyalkylene resin, a polyester resin, a polyvinyl chloride resin, a polycarbonate resin, a polyphenylene sulfide resin, A resin mixture, which is a vinyl alcohol resin, a polyamide resin, an acrylate resin, an engineering plastic, a copolymer thereof, or a mixture thereof.
The method of claim 16 wherein the alkyl (meth) acrylate monomers are methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, iso A resin mixture comprising at least one member selected from the group consisting of butyl acrylate, hexyl acrylate, octyl acrylate, and 2-ethylhexyl acrylate.
17. The aryl (meth) acrylate monomer of claim 16, wherein the aryl (meth) acrylate monomer is selected from the group consisting of naphthyl (meth) acrylate, phenyl (meth) acrylate, anthracenyl (meth) acrylate, and benzyl (meth) acrylate. Resin mixtures containing more than one species.
The method of claim 16 wherein the crosslinkable monomer is 3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, allyl acrylate, A resin mixture comprising at least one member selected from the group consisting of allyl methacrylate, trimethylolpropane triacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, and divinylbenzene.
The resin mixture according to claim 16, wherein the average particle diameter of the particles comprising seeds is 10 to 1,000 nm.
The resin mixture according to claim 16, wherein the seed comprises a polymer derived from 5 to 99.5 parts by weight of alkyl (meth) acrylate monomer and 0.5 to 5 parts by weight of crosslinkable monomer.
The resin mixture according to claim 16, wherein the average particle diameter of the particles comprising the core is 10 to 5,000 nm.
17. The polymer of claim 16 wherein the core comprises a polymer derived from 10 to 80 parts by weight of alkyl (meth) acrylate monomer, 20 to 40 parts by weight of aryl (meth) acrylate monomer and 0.01 to 5 parts by weight of crosslinkable monomer. Resin mixture.
The resin mixture according to claim 16, wherein the particle including the shell has an average particle diameter of 10 nm to 10,000 nm.
The polymer of claim 16 wherein the shell comprises 10 to 90 parts by weight of an alkyl (meth) acrylate monomer, 20 to 30 parts by weight of an aryl (meth) acrylate monomer and 1 to 50 parts by weight of a polymer derived from the compound of Formula 1 Resin mixture containing.
The resin mixture according to claim 16, wherein the content of the core in the particles is 1 to 150 parts by weight based on 10 parts by weight of the seed.
The resin mixture according to claim 16, wherein the content of the shell in the particles is 5 to 100 parts by weight based on 10 parts by weight of the seed.
The resin mixture according to claim 16, wherein the second resin has a molecular weight distribution of 1 to 2.5.
The resin mixture according to claim 16, wherein the second resin has a weight average molecular weight of 5,000 to 200,000.
The resin mixture according to claim 16, comprising 0.1 to 50 parts by weight of the second resin based on 100 parts by weight of the first resin.
A core formed of a first resin; And a cell formed of the first resin and a second resin having a difference in surface energy, melt viscosity or solubility parameter,

The second resin is

Seeds comprising polymers derived from alkyl (meth) acrylate monomers and crosslinkable monomers;

A core surrounding the seed and comprising a polymer derived from an alkyl (meth) acrylate monomer, an aryl (meth) acrylate monomer and a crosslinkable monomer; And

A pellet surrounding the core and comprising particles comprising a shell comprising an alkyl (meth) acrylate monomer, an aryl (meth) acrylate monomer and a polymer derived from a compound of formula (I):

[Formula 1]

In Formula 1, R 1 represents hydrogen or alkyl having 1 to 5 carbon atoms, R 2 represents a compound of Formula 2,

[Formula 2]

In Formula 2, R 3 represents alkylene having 1 to 8 carbon atoms, R 4 and R 5 each independently represent hydrogen and alkyl having 1 to 8 carbon atoms, and n is an integer of 1 to 100.
Melting the resin mixture of claim 16 to form a melt mixture; And processing the melt mixture to form a layered structure.
37. The method of claim 36, wherein the step of melting and processing is performed under shear stress.
37. The method of claim 36, further comprising curing the layered structure of the resin mixture.
The method for producing a resin molded article according to claim 38, wherein the curing is thermal curing or UV curing.
Melting the pellets of claim 35 to form a melt mixture; And processing the melt mixture to form a layered structure.
A first resin layer; A second resin layer formed on the first resin layer; And an interfacial layer comprising a first resin and a second resin, the interfacial layer being formed between the first resin layer and the second resin layer,

The second resin is

Seeds comprising polymers derived from alkyl (meth) acrylate monomers and crosslinkable monomers;

A core surrounding the seed and comprising a polymer derived from an alkyl (meth) acrylate monomer, an aryl (meth) acrylate monomer and a crosslinkable monomer; And

A resin molded article comprising particles surrounding the core and comprising a shell comprising an alkyl (meth) acrylate monomer, an aryl (meth) acrylate monomer and a polymer derived from a compound of formula (I):

[Formula 1]

In Formula 1, R 1 represents hydrogen or alkyl having 1 to 5 carbon atoms, R 2 represents a compound of Formula 2,

[Formula 2]

In Formula 2, R 3 represents alkylene having 1 to 8 carbon atoms, R 4 and R 5 each independently represent hydrogen and alkyl having 1 to 8 carbon atoms, and n is an integer of 1 to 100.
42. The resin molded article according to claim 41, wherein the first resin layer component is detected by an infrared spectrometer on the surface of the second resin layer.