KR20150028018A - Method for preparing resin cotaining inorganic particle - Google Patents

Abstract

Provided in the present invention is a method for preparing a composite resin and a composite resin prepared by the method. The composite resin as an example of the present invention has excellent surficial strength. Therefore, the composite resin for example, can provide resin molded article having excellent scratch resistance in case of being applied to the surficial layer of the resin molded article. Provided in an embodiment of the present invention is a method for preparing a composite resin, which comprises the step of reaction-extruding a linear polymer and inorganic particles and inducing the inorganic particles into the linear polymer.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for producing a composite resin,

The present application relates to a process for producing a composite resin and a composite resin produced by the process.

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

In particular, resins used for household appliances, automobile parts and toys should have excellent surface hardness.

The present application provides a method for producing a composite resin and a composite resin produced by the method.

One embodiment of the present application provides a method for producing a composite resin in which an inorganic particle is introduced into the linear polymer by reactive extrusion of a linear polymer and an inorganic particle.

As used herein, the term " composite resin " means a resin containing an organic resin and an inorganic particle. The organic resin and the inorganic particles are covalently bonded to each other by a reaction between a functional group of the organic resin and a reactive group of the inorganic particles during the reaction extrusion process.

The above production method can provide a composite resin capable of improving surface hardness due to the inclusion of inorganic particles. In addition, the composite resin produced by the above production method is not a structure in which the inorganic particles are dispersed in the resin but is covalently bonded to the functional group of the linear polymer to deteriorate the physical properties of the resin such as aggregation of the resin itself, A resin having improved surface hardness can be provided.

The linear polymer has a functional group, and the inorganic particle has a functional group capable of reacting with the functional group. By properly controlling the functional groups of the linear polymer and the functional groups of the inorganic particles and subjecting them to the reactive extrusion process, a composite resin having a structure in which the inorganic particles are bonded to the linear polymer can be provided.

The functional groups of the linear polymer and the functional groups of the inorganic particles can be composed of pairs that can react with each other in the reactive extrusion process. The functional groups of the linear polymer and the functional groups of the inorganic particles may be composed of, for example, a pair of a carboxyl group, a hydroxyl group, an amino group and an anhydride group, which can react with each other. In one example, when the functional group of the linear polymer is a carboxyl group, the functional group of the inorganic particle may be an amino group. Further, in another example, when the functional group of the linear polymer is a hydroxy group, the functional group of the inorganic particle may be an anhydride group.

In the above, the reactive extrusion process may mean, for example, a process in which a reaction takes place inside an extruder during an extrusion process. This reaction extrusion process can be carried out using a commonly used extruder. In one example, the twin screw extruder can be used as the extruder, and when the twin screw extruder is used, the first resin and the second resin can be uniformly mixed as compared with the case of using a single screw extruder.

In the reactive extrusion process, the temperature condition of the process can be adjusted according to the kind of the linear polymer used. In one example, when an acrylic polymer is used as the linear polymer, a reactive extrusion process may be performed at a temperature of at least about 150 degrees, at least about 200 degrees, or at least about 220 degrees.

In the reactive extrusion process, the shear rate can also be adjusted depending on the type of linear polymer used. In one example, when an acrylic polymer is used as the linear polymer, a reactive extrusion process may be performed at a shear rate of from about 100 to 1000 s < ^-1 >, but is not limited thereto.

The content of the linear polymer and the inorganic particles can be appropriately adjusted in consideration of the intended use of the composite resin and the like. In one example, in order to provide a composite resin exhibiting scratch resistance suitable for use as a surface layer of a resin molded article, the inorganic particles may be used in an amount of 1 to 20 parts by weight, 1 to 15 parts by weight, 1 to 12 parts by weight, By weight or 3 to 12 parts by weight.

Hereinafter, linear polymers and inorganic particles suitable for providing a composite resin will be described.

As used herein, the term " linear polymer " refers to a polymer in which structural units are linked one-dimensionally.

In one example, as the linear polymer, those prepared by polymerizing a mixture of an acrylic monomer having a functional group and a monomer containing an alkyl (meth) acrylate may be used. The linear polymer produced by this method may have functional groups capable of reacting with the functional groups of the inorganic particles along the main chain.

The acrylic monomer having a functional group can be used as a monomer for introducing the inorganic particles into the linear polymer. Examples of the acrylic monomer having such a functional group include an acrylic monomer having a carboxyl group, an acrylic monomer having a hydroxyl group, an acrylic monomer having an amino group, or an acrylic monomer having an anhydride group.

Specific examples of the acrylic monomer having a functional group include (meth) acrylic acid, 2- (meth) acryloyloxyacetic acid, 3- (meth) acryloyloxypropyl acid, 4- (meth) acryloyloxybutyric acid , An acrylic monomer having a carboxyl group such as itaconic acid or maleic acid; (Meth) acrylamide or N-substituted (meth) acrylamide; Acrylic monomers having a hydroxyl group such as hydroxyalkyl (meth) acrylate; Or an acrylic monomer having an anhydride group such as maleic anhydride.

The content of the acrylic monomer having a functional group can be controlled according to the content of the inorganic particles to be introduced into the resin. For example, in order to apply the composite resin to the surface layer of the resin molded article and to exhibit excellent scratch resistance, the acrylic monomer having a functional group is added in an amount of 3 to 20 parts by weight, 3 to 18 parts by weight based on 100 parts by weight of the total monomer mixture, 3 to 16 parts by weight, 3 to 12 parts by weight, 5 to 20 parts by weight, 7 to 20 parts by weight, 5 to 18 parts by weight, 5 to 16 parts by weight, 7 to 14 parts by weight, 12 parts by weight.

The alkyl (meth) acrylate may be a monomer that forms the predominant polymerization unit of the linear polymer. Examples of such alkyl (meth) acrylates include alkyl of 1 to 40 carbon atoms, alkyl of 1 to 30 carbon atoms, alkyl of 1 to 20 carbon atoms, alkyl of 1 to 10 carbon atoms, alkyl of 1 to 5 carbon atoms, Alkyl of 1 to 3 carbon atoms or alkyl (meth) acrylate of 1 to 2 carbon atoms can be used. The content of the alkyl (meth) acrylate forming the main polymerized unit of the linear polymer can be appropriately controlled depending on the use of the composite resin. For example, the content of the alkyl (meth) acrylate is 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 mixture of monomers for polymerizing the linear polymer may further comprise monomers having bulky functional groups. A linear polymer formed from a mixture of monomers containing a monomer having a bulky functional group may increase the hydrodynamic volume to provide a composite resin having a lower melt viscosity.

In one example, the monomer having a bulky functional group may be an alkyl (meth) acrylate. Thus, the mixture of monomers may include, for example, alkyl (meth) acrylates forming the predominant polymerization units of the linear polymers described above; And (meth) acrylates having a bulky alkyl group. Examples of the (meth) acrylate having a bulky alkyl group include a vinyl group having 3 to 20 carbon atoms, 3 to 12 carbon atoms, 3 to 6 carbon atoms, 5 to 20 carbon atoms, 7 to 20 carbon atoms, 10 to 20 carbon atoms, Alkyl (meth) acrylate of 20 to 20 carbon atoms; Or an 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, And the like. Specific examples of the alkyl (meth) acrylate having 3 to 20 carbon atoms include isopropyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) Examples of the alicyclic (meth) acrylate having 5 to 40 carbon atoms include cyclohexyl (meth) acrylate or isobornyl (meth) acrylate, And the like. The content of (meth) acrylate having such a bulky alkyl group can be appropriately controlled depending on the melt viscosity and purpose of use of the composite resin. For example, the content of the (meth) acrylate having a bulky alkyl group is 10 to 40 parts by weight, 15 to 40 parts by weight, 20 to 40 parts by weight, 10 to 35 parts by weight 10 to 40 parts by weight based on 100 parts by weight of the total monomer mixture To 30 parts by weight, 15 to 35 parts by weight, or 20 to 30 parts by weight.

In another example, aromatic (meth) acrylate may be used as the monomer having a bulky functional group. Examples of the aromatic (meth) acrylate include aromatic (meth) acrylates having 6 to 40 carbon atoms, 6 to 25 carbon atoms, and 6 to 16 carbon atoms. Examples of the aromatic (meth) acrylate having 6 to 40 carbon atoms include naphthyl (meth) acrylate, phenyl (meth) acrylate, anthracenyl (meth) Acrylate or benzyl (meth) acrylate can be used. The content of such aromatic (meth) acrylates can be appropriately controlled in accordance with the intended use of the composite resin such as (meth) acrylate having the aforementioned bulky alkyl group. For example, the content of aromatic (meth) acrylate is 10 to 40 parts by weight, 15 to 40 parts by weight, 20 to 40 parts by weight, 10 to 35 parts by weight 10 to 30 parts by weight, based on 100 parts by weight of the total monomer mixture , 15 to 35 parts by weight or 20 to 30 parts by weight.

Mixtures of monomers comprising the abovementioned monomers can generally provide a linear polymer in a manner that produces the resin through polymerization of the monomers. For example, a mixture of monomers can be polymerized by a method such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization to provide a linear polymer.

In one example, a method of making a linear polymer comprises dispersing a dispersant in a solvent; Dispersing a mixture of the above-mentioned monomers in the solvent; Adding an additive such as a chain transfer agent and / or an initiator to the solvent and mixing them; And a polymerization step of reacting at a temperature of 40 DEG C or higher. Herein, the order of each step can be changed arbitrarily, and it is also possible to carry out two or more steps to one step.

The solvent can be used without limitation as long as it is a medium known to be routinely usable for preparing polymers. As such a solvent, for example, methyl ethyl ketone, ethanol, methyl isobutyl ketone, or distilled water may be used, or two or more kinds thereof may be mixed and used.

Examples of the dispersing agent that can be added to the solvent include organic dispersing agents such as polyvinyl alcohol, polyolin-maleic acid or cellulose; Or an inorganic dispersant such as tricalcium phosphate.

Examples of the chain transfer agent include alkyl mercaptans such as n-butylmercaptan, n-dodecylmercaptan, tertiary dodecylmercaptan or isopropylmercaptan; Arylmercaptan such as phenylmercaptan, naphthylmercaptan or benzylmercaptan; Halogen compounds such as carbon tetrachloride; Alpha-methylstyrene dimer, and alpha-ethyl styrene dimer.

Examples of the initiator include peroxides such as octanoyl peroxide, decanoyl peroxide and lauroyl peroxide; azo compounds such as azobisisobutyronitrile and azobis- (2,4-dimethyl) -valeronitrile; Azo compounds and the like.

In addition, in the production of the linear polymer, additives commonly used in the polymer industry can be used, and a conventionally performed process may be further performed.

The inorganic particles to be introduced into the linear polymer may be appropriately selected depending on the intended use of the composite resin. In one example, when used for the purpose of improving the surface hardness, silicon oxide, titanium oxide, or a mixture thereof may be used as the inorganic particles. The average particle size of the inorganic particles may be adjusted to 10 to 200 nm, 10 to 160 nm, 10 to 120 nm, 20 to 200 nm, 30 to 200 nm, 20 to 160 nm or 30 to 120 nm. If the average particle size of the inorganic particles is too large, the impact strength and other mechanical properties may be significantly reduced. In addition, if the average particle size of the inorganic particles is less than 10 nm, Surface area is considerably increased, and agglomeration between particles may occur.

In one example, the inorganic particles having a functional group may be prepared by reacting an inorganic particle with a compound represented by the following formula (1).

[Chemical Formula 1]

(R ¹ X) _n -Si- (R ² -Q) _4-n

Wherein R ¹ is an alkyl group having 1 to 16 carbon atoms, R ² is a single bond or an alkylene group having 1 to 16 carbon atoms, X is a single bond or -O-, Q is -NH ₂ , -OH, -COOH, maleic anhydride or succinic anhydride, and n is an integer of 1 to 3.

In Formula 1, R ¹ may be an alkyl group having 1 to 16 carbon atoms, an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. In one example, R ¹ may be a methyl group, an ethyl group, a propyl group, a butyl group or a pentyl group, and when n is 2 or more, R ¹ may be the same or different from each other.

In Formula 1, X may be a single bond or -O-. In the above, a single bond means a case where there is no atom separately in a portion represented by X. In one example, when n is 1, X is -O-, and when n is 2 or more, at least one X is -O-, and X may be the same as or different from each other.

In Formula 1, R ² may be a single bond, an alkylene group having 1 to 16 carbon atoms, an alkylene group having 1 to 12 carbon atoms, an alkylene group having 1 to 8 carbon atoms, or an alkylene group having 1 to 5 carbon atoms. In the above, a single bond means a case where no atom exists separately at a portion represented by R ² . When R < ^{2 >} is, for example, a single bond, it may mean a compound wherein Si of formula (1) is covalently bonded to Q. In one example, R ² may be a single bond, a methylene group, an ethylene group, a propylene group, a butylene group or a pentylene group, and when n is 2 or less, R ² may be the same or different from each other.

In the above formula (1), Q may be a functional group of an inorganic particle. In one example, when n is 2 or less, Q can be the same or different from each other. Further, Q may be selected to be a bondable pair depending on the functional group of the linear polymer.

In one example, compounds of Formula 1 that are suitable for use in a reactive extrusion process include aminopropyltrimethoxysilane, aminopropyltriethoxysilane, trimethoxysilylpropylsuccinic anhydride, or triethoxysilylpropylsuccinic anhydride. .

The content of the compound represented by the formula (1) can be appropriately controlled depending on the kind of the compound, the kind of the inorganic particles and / or the kind of the linear polymer. For example, the compound may be used in an amount of 5 to 50 parts by weight, 5 to 45 parts by weight, 5 to 40 parts by weight, 5 to 35 parts by weight, 10 to 50 parts by weight, 15 to 50 parts by weight, 50 to 50 parts by weight, 10 to 45 parts by weight, 15 to 40 parts by weight, 20 to 35 parts by weight or 25 to 35 parts by weight may be used. When a compound is used in this range, it is possible to provide a surface-modified inorganic particle having one compound bonded to one inorganic particle. As a result, it is possible to provide a resin which is not agglomerated and has a high surface hardness with a site where the inorganic particles are bonded to the functional group of the linear polymer. That is, it is possible to prevent a structure in which two or more linear polymers are connected due to the surface-modified inorganic particles, thereby preventing the resin from aggregating.

In one example, a method of making a surface modified inorganic particle comprises: drying an inorganic particle; Dispersing the dried inorganic particles in a solvent; And adding a surface modifying agent to the solvent and reacting. Here, one or more of the steps may be arbitrarily omitted, and two or more steps may be performed in a single step. The inorganic particles and the surface modifier may be those described above, and as the solvent, a suitable solvent capable of dispersing the inorganic particles may be used. Examples of such solvents include toluene and the like.

Another embodiment of the present application provides a composite resin comprising a linear polymer into which inorganic particles have been introduced. The composite resin is produced by the above-described production method and has a structure in which inorganic particles are bonded along the main chain of the linear polymer, so that the surface hardness is excellent without aggregation of the resin itself.

In one example, the structure in which the inorganic particles are bonded along the main chain of the linear polymer may be represented by a polymerization unit represented by the following formula (2).

(2)

In Formula 2, R ³ , R ⁴ and R ⁵ are each independently hydrogen, a carboxyl group, an alkyl group having 1 to 4 carbon atoms or a carboxyalkyl group having 1 to 5 carbon atoms, L is a divalent organic linker containing O or N, and, D is a single bond or an alkylene group having 1 to 16, Y is a single bond or -O-, R ⁶ is an alkyl group having 1 to 16, a is an inorganic particle, m is any of 1 to 3 It is an integer.

The polymerization unit of Formula 2 shows a structure in which a plurality of inorganic particles A are bonded along the main chain of one linear polymer. That is, the polymerization unit of the formula (2) shows a structure in which one inorganic particle A binds to the linear polymer only at one site.

However, the above description explains the relationship between the inorganic particles and the linear polymer in the polymerization unit of formula (2), and most of the polymerization units combined with the inorganic particles of the composite resin mean the polymerization unit represented by formula (2) It does not mean that the structure in which the particles are bonded to the plurality of linear polymers at two or more sites is completely excluded. In one example, the polymerization unit represented by the general formula (2) may be, for example, 80 parts by weight or more, 85 parts by weight or more, 90 parts by weight or more, or 95 parts by weight or more based on 100 parts by weight of the polymerized units combined with the entire inorganic particles .

In one example, R ³ , R ^4, and R ⁵ in Formula 2 may each independently be hydrogen, a carboxyl group, a methyl group, an ethyl group, a carboxymethyl group, or a carboxyethyl group.

In one example, L in formula (2) is _a bivalent organic group containing -CONH-, -CONR _a -, -COOCO-, -OCONH-, -OCONR _a -, -COO-, -NH- or -NR _a - Linker. Wherein R < _a > may be an alkyl group having 1 to 16 carbon atoms.

In one example, D in Formula 2 may be a single bond, an alkylene group having 1 to 16 carbon atoms, an alkylene group having 1 to 12 carbon atoms, an alkylene group having 1 to 8 carbon atoms, or an alkylene group having 1 to 4 carbon atoms. For example, D may be a single bond, a methylene group, an ethylene group, a propylene group, a butylene group or a pentylene group.

In one example, R ⁶ in formula (2) may be an alkyl group having 1 to 16 carbon atoms, an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. For example, R ¹ may be a methyl group, an ethyl group, a propyl group, a butyl group or a pentyl group, and when n is 1, R ⁶ may be the same or different from each other.

In one example, the above-mentioned composite resin is mixed with a resin having properties different from those of the above-mentioned composite resin to provide a resin mixture capable of forming a pellet or a resin molded product having a layered structure due to occurrence of layer separation during the melt processing .

In the present specification, a resin having a property different from that of a composite resin may be referred to as a " first resin ", and a composite resin may be referred to as a " second resin ".

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 where two or more resins are mixed in one matrix, or a case where two or more kinds of pellets are mixed. The resins may have different physical properties, for example, the physical properties may be surface energy or melt viscosity.

&Quot; 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 the desired molded article using the melt mixture, Molding, extrusion molding, blow molding, transfer molding, film blowing, fiber spinning, car-rendering thermoforming or foam molding.

The term " resin molded product " means a pellet or product formed from a resin mixture, and the resin molded product is not particularly limited, and examples thereof include automobile parts, electronic device parts, machine parts, functional films, have.

&Quot; Layer separation " may mean that the layer formed by substantially one resin is located or arranged on a layer formed by substantially different resins. A layer formed by substantially one resin may mean that one kind of resin does not form a sea-island structure but exists continuously over one layer. This solution 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 exists in one layer or that one resin is rich.

In one example, the resin mixture can be layered by melt processing. Thus, it is possible to produce a resin molded article whose surface has a specific function, for example, a high hardness function, without a separate process such as coating and plating. Therefore, the resin molded article can have improved mechanical properties and surface characteristics, and when the resin mixture is used, the production cost and time of the resin molded article can be reduced.

The layer separation of the resin mixture may be caused by a difference in physical properties between the first resin and the second resin and / or a molecular weight distribution of the second resin. Here, the physical properties may be, for example, surface energy or melt viscosity. Although a mixture of resins containing two kinds of resins is described in this specification, it will be apparent to those skilled in the art that three or more kinds of resins having different physical properties may be mixed and subjected to melt processing.

In one example, the composite resin (second resin) may be mixed with another resin (first resin) having a difference in surface energy to provide a resin mixture in which the layer separation occurs during the melt processing.

Where the second resin has a lower surface energy than the first resin, the second resin during the melt processing process may constitute a surface layer of the melt processing product. The difference in surface energy between the first resin and the second resin is, for example, 0.1 to 35 mN / m, 0.1 to 30 mN / m, 0.1 to 20 mN / m, 0.1 to 10 mN / M, 1 to 35 mN / m, 1 to 30 mN / m, 1 to 20 mN / m, 1 to 10 mN / m, 1 to 7 mN / m or 2 to 6 mN / m. When the first and second resins having a surface energy difference in this range are used, the first resin and the second resin can not easily peel off, and the second resin can easily move to the surface, and the layer separation phenomenon can easily occur.

When the second resin has a sufficiently low surface energy, it can be combined with various first resins to provide a resin mixture for melt processing. In addition, the first and second resins can be more easily layered during melt processing. In one example, the second resin having a low surface energy may be a resin produced by the aforementioned method for producing a composite resin.

Further, in another example, the second resin may be mixed with a first resin having a difference in melt viscosity to provide a resin mixture in which layer separation occurs during the melt processing process.

In the above, when the second resin has a lower melt viscosity than the first resin, the second resin during the melt processing process may constitute the surface layer of the melt processing product. The first resin and the melt viscosity difference between the second resin is, for example, from 100 to 1000 s ^-1 shear rate, and the first and second processing temperature of the resin mixture of from 0.1 to 3000 pa * s, 1 to about 2000 pa s, 1 to 1000 pa * 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 first resin and the second resin can not easily peel off, and the second resin can easily move to the surface and the layer separation phenomenon can easily occur.

When the second resin has a sufficiently low melt viscosity, it can be combined with various first resins to provide a resin mixture for melt processing. In addition, the first and second resins can be more easily layered during melt processing. In one example, as the second resin having a low melt viscosity, a composite resin prepared by using a monomer having a bulky functional group can be used.

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

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

The " processing temperature " means the temperature at which the resin mixture is processed. 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 controlled according to the resin used for melt processing such as extrusion or injection molding. For example, when an ABS resin is used as the first resin and a resin obtained from the acrylic monomer is used as the second resin, the processing temperature may be 210 to 270 캜.

In the resin mixture, the first resin is a resin which mainly determines the physical properties of a desired molded article, and may be selected according to the type of the desired molded article and the process conditions to be used. As the first resin, a general synthetic resin can be used without any particular limitation. Examples of the first resin include styrene resins such as ABS (acrylonitrile butadiene styrene) resin, polystyrene resin, acrylonitrile styrene acrylate (ASA) resin and styrene-butadiene-styrene block copolymer; A polyolefin-based resin such as a high-density polyethylene-based resin, a low-density polyethylene-based resin, or a polypropylene-based resin; A thermoplastic elastomer such as an ester-based thermoplastic elastomer or an olefin-based thermoplastic elastomer; Polyoxyalkylene resins such as polyoxymethylene resins and polyoxyethylene resins; Polyester resins such as polyethylene terephthalate resin or polybutylene terephthalate resin; Polyvinyl chloride resins; Polycarbonate resin; Polyphenylene sulfide type resin; Vinyl alcohol type resin; Polyamide based resin; Acrylate resins; Engineering plastics; Copolymers thereof, and mixtures thereof. As the engineering plastics, plastics exhibiting excellent mechanical and thermal properties can be used. For example, polyether ketone, polysulfone, and polyimide may be used as engineering plastics. In one example, the first resin may be a copolymer obtained by polymerizing acrylonitrile, butadiene, styrene, and acrylic monomers.

As the second resin in the resin mixture, it is possible to use a resin which exhibits a difference in physical properties as described above in relation to the first resin and can impart excellent mechanical properties and high surface hardness to the surface of a desired molded article. In one example, the above-mentioned composite resin can be used as the second resin so as to impart a high surface hardness to the surface of the molded article.

In one example, the weight average molecular weight of the second resin can range from about 5,000 to 200,000. In another example, the weight average molecular weight of the second resin is from 10,000 to 200,000, from 150,000 to 200,000, from 20,000 to 200,000, from 0.5 million to 180,000, from 0.5 million to 150,000, from 0.5 million to 120,000, From 150,000 to 150,000, or from 20,000 to 120,000. When a 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 has an appropriate fluidity so that layer separation can easily occur.

Further, in one example, the molecular weight distribution of the second resin can 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 the low molecular weight compound and / or the high molecular weight material which impedes the occurrence of layer separation in the second resin is reduced, Can happen.

In one example, the resin mixture may comprise 0.1 to 50 parts by weight of the second resin based on 100 parts by weight of the first resin. Further, 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 first resin and the second resin are included in such a content, the layer separation phenomenon can be induced, and the content of the second resin, which is relatively high compared to the first resin, can be appropriately controlled to provide an economical resin mixture.

The resin mixture described above can be made into pellets by extrusion. In the pellet produced using the resin mixture, the first resin forms a core and the second resin separates from the first resin to form a shell.

According to one embodiment, the pellet comprises a core formed of a first resin; And a cell formed of a second resin containing a polymerization unit represented by the following formula (2) and having a physical property different from that of the first resin.

(2)

In Formula 2, R ³ , R ⁴ and R ⁵ are each independently hydrogen, a carboxyl group, an alkyl group having 1 to 4 carbon atoms or a carboxyalkyl group having 1 to 5 carbon atoms, L is a divalent organic linker containing O or N, and, D is a single bond or an alkylene group having 1 to 16, Y is a single bond or -O-, R ⁶ is an alkyl group having 1 to 16, a is an inorganic particle, m is any of 1 to 3 It is an integer.

Further, as described above, the first resin and the second resin may have different surface energies or melt viscosities. For example, the first resin and the second resin may have a surface energy difference of from 0.1 to 35 mN / m at 25 占 폚; Or a melt viscosity difference of from 0.1 to 3000 pa * s at a shear rate of from 100 to 1000 s < ^-1 > and a processing temperature of the pellet.

The types and physical properties of the first resin and the second resin have already been described in detail, and the detailed description thereof will be omitted.

On the other hand, the above-mentioned resin mixture or pellet can be melt-processed to provide a resin molded article having a layer separation structure.

According to one embodiment, there is provided a method for producing a melt blend, comprising: melting a resin mixture to form a melt blend; And a step of processing the molten mixture to form a layer separation 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 during the melt-processing of the resin mixture. Due to such layer separation phenomenon, The effect of selectively coating the surface of the molded article can be obtained.

Particularly, when the above-mentioned composite resin is used as the second resin, a composite resin having a relatively low surface energy or melt viscosity during the melt processing step is placed on the surface of the resin molded article to provide a resin molded article having improved mechanical characteristics and surface characteristics can do.

The step of melt-working the resin mixture can be carried out under shear stress. For example, the step of melt-working can be carried out by an extrusion and / or an injection-molding method.

Further, in the step of melt-processing the resin mixture, the applied temperature may be different depending on the kind of the first resin and the second resin used. For example, when a styrene resin is used as the first resin and an acrylic resin is used as the second resin, the melt processing temperature can be controlled to about 210 to 270 degrees.

The method may further include the step of curing the resulting product obtained by melt-processing the resin mixture, that is, the melt-processed product of the resin mixture. The curing may be, for example, thermal curing or UV curing. The resin molded article may further be subjected to chemical or physical treatment.

In one example, the manufacturing method of the resin molded article may further include the step of producing the second resin before the step of melting the resin mixture to form the molten mixture. The second resin can be selected in accordance with the first resin as described above, and the selected second resin can impart a specific function, for example, high hardness, to the surface layer of the resin molded article. The contents related to the production of the second resin have already been described, and a detailed description thereof will be omitted.

According to another embodiment, a method of manufacturing a resin molded article includes melting a pellet to form a molten mixture; And processing the molten mixture to form a layered structure.

In one example, the pellets may be prepared by melt-processing the above-mentioned resin mixture, such as extrusion. For example, when a resin mixture comprising the first resin and the second resin is extruded, a second resin having a higher hydrophobicity than the first resin moves to contact with the air to form a shell of the pellet, 1 < / RTI > resin may be located at the center of the pellet to form a core. The pellets thus produced can be made into a resin molded article by melt processing such as injection molding. However, the present invention is not limited thereto. In another example, the resin mixture may be directly molded into a resin molded product by melt processing such as injection molding or the like.

On the other hand, according to another embodiment, the resin molded article has 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 . ≪ / RTI > The interface layer may include first and second resins, and the second resin may include a polymerization unit represented by the following formula (2).

(2)

In Formula 2, R ³ , R ⁴ and R ⁵ are each independently hydrogen, a carboxyl group, an alkyl group having 1 to 4 carbon atoms or a carboxyalkyl group having 1 to 5 carbon atoms, L is a divalent organic linker containing O or N, and, D is a single bond or an alkylene group having 1 to 16, Y is a single bond or -O-, R ⁶ is an alkyl group having 1 to 16, a is an inorganic particle, m is any of 1 to 3 It is an integer.

A resin molded product produced from a resin mixture comprising a specific first resin and the second resin having a difference in physical properties from the first resin is obtained by, for example, a method in which a first resin layer is located inside and a second resin layer is a resin Or may be a layered structure formed on the surface of the molded article.

Particularly, when the above-mentioned composite resin is used as the second resin, the molded article can further improve the surface hardness.

The " first resin layer " mainly includes the first resin, determines the physical properties of the molded article, and can be located inside the resin molded article. The " second resin layer " mainly contains the second resin, and can be located outside the resin molded article to give a certain function to the surface of the molded article.

The details of the first resin and the second resin have already been described above, and a description of the related contents will be omitted.

The resin molded article may include an interface layer formed between the first resin layer and the second resin layer and including a mixture of the first resin and the second resin. The interface layer may be formed between the layered 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 first resin and the second resin may be physically or chemically bonded to each other, and the first resin layer and the second resin layer may be bonded to each other through the mixture.

The resin molded article may be formed in such a structure that the first resin layer and the second resin layer are separated by the 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 the second resin layer may be sequentially stacked, and may be a structure in which the interface and the second resin are laminated on the 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 a first resin layer having various shapes, for example, spherical, circular, polyhedral, sheet or the like.

Layer separation phenomenon appearing in the resin molded article appears to be due to the production of resin molded articles by applying specific first and second resins having different physical properties. Examples of such different physical properties include surface energy or melt viscosity. The details of the difference in physical properties are as described above.

In one example, the first resin layer, the interface layer and the second resin layer can be confirmed by SEM after etching the specimen using a THF vapor after the low-temperature impact test. To measure the thickness of each layer, the specimen is cut with a diamond knife using a microtoming machine to obtain a smooth cross-section, and then a smooth cross-section is etched using a solution that can selectively melt the second resin compared to the first resin. The cross-sectional area of the etched section differs depending on the content of the first resin and the second resin. When the cross section is observed at 45 degrees from the surface using SEM, the first resin layer, the second resin layer, The interface layer and the surface can be observed, and the thickness of each layer can be measured. In one example, a 1,2-dichloroethane solution (10 vol%, in EtOH) was used as a solution for selectively dissolving the second resin, but this is illustrative only and is not intended to limit the solubility of the second resin Solution is not particularly limited, and those skilled in the art can appropriately select and apply the solution according to the type and composition of the second resin.

The interfacial layer may comprise from 1 to 95%, from 10 to 95%, from 20 to 95%, from 30 to 95%, from 40 to 95%, from 50 to 95%, from 60 to 95% of the total thickness of the second resin layer and interfacial layer And may have a thickness of 60 to 90%. If the interface layer has a thickness of 0.01 to 95% of the total thickness of the second resin layer and the interface layer, the interfacial bonding force between the first resin layer and the second resin layer is excellent so that the peeling of both layers does not occur, Can be greatly improved. On the other hand, if the interface layer is too thin as compared with 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. If the interface layer is too thick, The effect of improving the characteristics 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% . When the thickness of the second resin layer is too small, the surface properties of the molded article can be sufficiently improved. [0051] [52] If the thickness of the second resin layer is too large, the mechanical properties of the functional resin itself may be reflected in the resin molded article, and the mechanical properties of the first resin may be changed.

In the resin molded article having the above-described structure, the component of the first resin layer can be detected by the infrared ray spectroscope (IR) at the surface of the second resin layer.

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

The details of the first resin, the second resin, and the difference in physical properties between the first resin and the second resin have already been described above, and a description of the relevant contents will be omitted. In this specification, a 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 can be used for providing automobile parts, helmets, electric appliance parts, spinning machine parts, toys, pipes, and the like.

Exemplary composite resins of the present application can exhibit excellent surface hardness. Thus, the composite resin can provide a resin molded article having excellent scratch resistance when applied to, for example, a surface layer of a resin molded article.

Fig. 1 is a SEM photograph showing a layered sectional shape of the resin molded article produced in Example 1. Fig.
Fig. 2 is a SEM photograph of a sectional shape of the resin molded article produced in Comparative Example 1. Fig.

Hereinafter, the method for producing the composite resin will be described in detail with reference to Examples and Comparative Examples, but the scope of the method is not limited by the following Examples.

The physical properties in the following examples and comparative examples were evaluated in the following manner.

1. Molecular weight distribution ( PDI ) And a weight average molecular weight ( Mw )

The molecular weight distribution was measured using GPC (Gel Permeation Chromatography). The conditions were as follows.

- Appliance: 1200 series from Agilent Technologies

- Column: Using 2 PLgel mixed B from Polymer laboratories

- Solvent: THF

- Column temperature: 40 degrees

- Sample concentration: 1 mg / mL, 100 L injection

Standard: Polystyrene (Mp: 3900000, 723000, 316500, 52200, 31400, 7200, 3940, 485)

The analysis program was a ChemStation of Agilent Technologies. The weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined by GPC and the molecular weight distribution (PDI) was calculated from the weight average molecular weight / number average molecular weight Respectively.

2. Measurement of surface energy

Based on the Owens-Wendt-Rabel-Kaelble method, the surface energy was measured using a Drop Shape Analyzer (DSA100 from KRUSS).

Specifically, the resin obtained in Example or Comparative Example was dissolved in methyl ethyl ketone solvent in an amount of 15% by weight, followed by bar coating on LCD glass. The coated LCD glass was preliminarily dried in an oven at 60 DEG C for 2 minutes and dried in an oven at 90 DEG C for 1 minute.

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

3. Measurement of melt viscosity

The melt viscosity was measured using a capillary rheometer (Capillary Rheometer 1501, Gottfert).

Specifically, a capillary die was attached to a barrel, and then the resin obtained in Example or Comparative Example was divided into three portions. Shear viscosity (pa * s) was measured at a processing temperature of 240 ° C according to a shear rate of 100 to 1000 s ^-1 .

4. 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). A standard pencil (manufactured by Mitsubishi) was changed from 6B to 9H while maintaining an angle of 45 degrees, and scratches were applied to observe the rate of change of the surface (ASTM 3363-74). The measurement result is the average value of the results of five repeated experiments.

5. Strength measurement experiment

The strengths of the specimens obtained in Examples and Comparative Examples were measured according to ASTM D256. Specifically, the energy (kg * cm / cm) required to break the V-shaped groove of the pendulum was measured by using an impact tester (Impact 104, Tinius Olsen). The 1/8 "and 1/4" specimens were each measured five times and the average value was determined.

6. Observing cross-sectional shape

After the low-temperature impact test of the specimens of Examples and Comparative Examples, the fractured surface was etched by using dichloroethane vapor (or plasma) and the layered cross-sectional shape was measured using SEM (Hitachi, model: S-4800) Were observed.

In order to measure the thicknesses of the layered first resin layer, the second resin layer and the interface layer, the specimens of the following examples and comparative examples were cut with a diamond knife using a microtoming machine (Leica EM FC6) at -120 ° C to obtain a smooth cross section Lt; / RTI > The section of the specimen containing the microtomed smooth section is immersed in a 1,2-dichloroethane solution (10 vol%, in EtOH), etched for 10 seconds, and washed with distilled water. The portion of the etched cross-section is different according to the content of the first resin and the second resin, and the degree of melting can be observed and can be observed using an SEM. That is, when the cross section is 45 degrees from the surface, the first resin layer, the second resin layer, and the interface layer can be observed due to the difference in shade, and the thicknesses of the first resin layer, the second resin layer, and the interface layer can be measured.

7. Infrared spectroscopy ( IR )

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

- Germanium (Ge) ATR crystal with a refractive index of 4.0

- ATR (attenuated total reflection) IR spectra of this method by the scan from 4000cm ^-1 to spectral resolution and 16 scans of 8cm ^-1 to 600cm ^-1

- Internal reference band: Carbonyl group of acrylate (C = O str., ~ 1725 cm ^-1 )

- inherent 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 ratio [I _BD (C = C) / I _A (C = O)] and [I _BD (out-of-plane) / I _A Five runs were performed in different regions, and mean values and standard deviations were calculated.

Manufacturing example  One

A 3-liter reactor was charged with 1500 parts by weight of distilled water and 24 parts by weight of a 2% aqueous solution of polyvinyl alcohol as a dispersant. Subsequently, 520 parts by weight of methyl methacrylate, 200 parts by weight of cyclohexyl methacrylate, 80 parts by weight of methacrylic acid, 11.2 parts by weight of n-dodecylmercaptan as chain transfer agent, and azobisdimethyl valeronitrile 2.4 Was further added, and the mixture was stirred at 400 rpm. The mixture was reacted at 60 DEG C for 3 hours to polymerize, and cooled to 30 DEG C to obtain a bead-shaped linear polymer (A). Then, the linear polymer (A) was washed three times with distilled water, dehydrated and then dried in an oven.

Manufacturing example  2

(B) was prepared in the same manner as in Production Example 1, except that 2.4 parts by weight of n-dodecylmercaptan was used instead of 11.2 parts by weight of n-dodecylmercaptan.

Manufacturing example  3

Put into the average particle size was more than 12 hours of drying at 90 ℃ oven of 100 nm of silicon dioxide (SiO ₂₎ particles of 100 parts by weight Toluene 450 parts by weight and the mixture was stirred over an hour. Subsequently, 30 parts by weight of aminopropyltrimethoxysilane was added to the dispersion, and the mixture was stirred in a nitrogen atmosphere for 24 hours. The surface-modified inorganic particles (A) obtained above were washed five times or more in the order of toluene, ethyl acetate and methanol, and dried using a vacuum oven at room temperature.

Manufacturing example  4

(B) was prepared in the same manner as in Production Example 3, except that silicon dioxide particles having an average particle size of 40 nm were used instead of the silicon dioxide particles having an average particle size of 100 nm.

Example  One

(1) Preparation of composite resin and measurement of physical properties

90 parts by weight of the linear polymer (A) prepared in Preparation Example 1 and 10 parts by weight of the surface-modified inorganic particles (A) prepared in Preparation Example 3 were mixed and extruded at a temperature of 240 DEG C in a twin screw extruder (Leistritz) To prepare a composite resin.

The weight average molecular weight of the resin measured by GPC was 25K and the molecular weight distribution was 1.8, and the melt viscosity of the composite resin was 485 pa * s.

(2) Preparation of resin mixture and measurement of physical properties

60% by weight of methyl methacrylate, 7% by weight of acrylonitrile, 10% by weight of butadiene and 23% by weight of styrene were polymerized to prepare a thermoplastic resin. The melt viscosity of the thermoplastic resin was 810 pa * s. 90 parts by weight of the thermoplastic resin prepared above and 10 parts by weight of the composite resin were mixed to prepare a resin mixture.

The difference in surface energy between the thermoplastic resin and the composite resin was 12 mN / m and the melt viscosity difference was 325 pa * s. (3) Production of resin molded article and measurement of physical properties

The resin mixture was extruded in a twin screw extruder (Leistritz) at a temperature of 240 DEG C to obtain a pellet. Then, these pellets were injected by an EC100? 30 extruder (manufactured by ENGEL) at a temperature of 240 占 폚 to prepare a specimen 1 of resin molded article having a thickness of 3200 占 퐉. The pencil hardness of the specimen was 2H, and the intensities were 8 kg · cm / cm for both IZOD 1/8 "and IZOD 1/4", and layer separation was observed in the specimen. A cross-sectional SEM photograph of the specimen is shown in Fig. The thickness of the composite resin layer of the specimen was 5 占 퐉, and the thickness of the interface layer was 21 占 퐉. The peak intensity ratio measured by infrared spectroscopy _{[I BD (C = C)} / I A (C = O)] The mean 0.0118 with a standard deviation of 0.0005, and peak intensity ratio _{[I BD (out-of-} plane) / I _A (C = O)] had an average of 0.407 and a standard deviation of 0.0031.

Example  2

(1) Preparation of composite resin and measurement of physical properties

95 parts by weight of the linear polymer (A) prepared in Preparation Example 1 and 5 parts by weight of the surface-modified inorganic particles (A) prepared in Preparation Example 3 were mixed and extruded at a temperature of 240 DEG C in a twin screw extruder (Leistritz) To prepare a composite resin.

The weight average molecular weight of the resin measured by GPC was 25K and the molecular weight distribution was 1.8, and the melt viscosity of the composite resin was 460 pa * s.

(2) Preparation of resin mixture and measurement of physical properties

A resin mixture was prepared in the same manner as in Example 1, except that the composite resin prepared in (1) of Example 2 was used.

The difference in surface energy between the thermoplastic resin and the composite resin was 15 mN / m and the melt viscosity difference was 350 pa * s.

(3) Production of resin molded article and measurement of physical properties

A specimen 2 having a thickness of 3200 탆 was prepared in the same manner as in Example 1, except that the resin mixture prepared in (2) of Example 2 was used. The pencil hardness of the specimen was 1.5H, and the strength was 9 kg · cm / cm for both IZOD 1/8 "and IZOD 1/4", and layer separation was observed in the specimen. The thickness of the composite resin layer of the specimen was 4 占 퐉, and the thickness of the interface layer was 18 占 퐉.

Example  3

(1) Preparation of composite resin and measurement of physical properties

90 parts by weight of the linear polymer (B) prepared in Preparation Example 2 and 10 parts by weight of the surface-modified inorganic particles (A) prepared in Preparation Example 3 were mixed and extruded at a temperature of 240 DEG C in a twin screw extruder (Leistritz) To prepare a composite resin.

The weight-average molecular weight of the resin measured by GPC was 100 K, the molecular weight distribution was 2.0, and the melt viscosity of the composite resin was 470 pa * s.

(2) Preparation of resin mixture and measurement of physical properties

A resin mixture was prepared in the same manner as in Example 1, except that the composite resin prepared in (1) of Example 3 was used.

The difference in surface energy between the thermoplastic resin and the composite resin was 14 mN / m, and the melt viscosity difference was 340 pa * s.

(3) Production of resin molded article and measurement of physical properties

A specimen 3 having a thickness of 3200 탆 was prepared in the same manner as in Example 1, except that the resin mixture prepared in (2) of Example 3 was used. The pencil hardness of the specimen was 2H, and the intensity was 7 kg · cm / cm for both IZOD 1/8 "and IZOD 1/4", and layer separation phenomenon was observed in the specimen. The thickness of the composite resin layer of the specimen was 2.5 탆, and the thickness of the interface layer was 17 탆.

Example  4

(1) Preparation of composite resin and measurement of physical properties

90 parts by weight of the linear polymer (A) prepared in Preparation Example 1 and 10 parts by weight of the surface-modified inorganic particles (B) prepared in Production Example 4 were mixed and extruded at a temperature of 240 DEG C in a twin screw extruder (Leistritz) To prepare a composite resin.

The weight-average molecular weight of the resin measured by GPC was 25 K, the molecular weight distribution was 1.8, and the melt viscosity of the composite resin was 480 pa * s.

(2) Preparation of resin mixture and measurement of physical properties

A resin mixture was prepared in the same manner as in Example 1, except that the composite resin prepared in (1) of Example 4 was used.

The difference in surface energy between the thermoplastic resin and the composite resin was 12 mN / m and the melt viscosity difference was 330 pa * s. (3) Production of resin molded article and measurement of physical properties

A specimen 4 having a thickness of 3200 탆 was prepared in the same manner as in Example 1, except that the resin mixture prepared in (4) of Example 4 was used. The pencil hardness of the specimen was 2H, and the intensities were 8 kg · cm / cm for both IZOD 1/8 "and IZOD 1/4", and layer separation was observed in the specimen. The thickness of the composite resin layer of the specimen was 3 mu m and the thickness of the interface layer was 17 mu m.

Comparative Example  One

(1) Production of resin molded article and measurement of physical properties

A specimen 5 having a thickness of 3200 탆 was prepared in the same manner as in Example 1, except that a composite resin was not used.

The pencil hardness of the specimen 5 was F, and the strength was 10 kg · cm / cm for both IZOD 1/8 "and IZOD 1/4", and no layer separation phenomenon was observed in the specimen. A cross-sectional SEM photograph of the specimen is shown in Fig.

Comparative Example  2

(1) Preparation of resin containing no inorganic particles and measurement of physical properties

Polymethyl methacrylate (LGMMA IF870) was used instead of the composite resin of Example 1.

The weight average molecular weight of the resin measured by GPC was 73 K, the molecular weight distribution was 1.9, and the melt viscosity of the PMMA resin was 540 pa * s.

(2) Preparation of resin mixture and measurement of physical properties

A resin mixture was prepared in the same manner as in Example 1, except that polymethylmethacrylate (LGMMA IF870) was used in place of the composite resin of Example 1.

The difference in surface energy between thermoplastic resin and polymethylmethacrylate was 1 mN / m and the difference in melt viscosity was 270 pa * s. (3) Production of resin molded article and measurement of physical properties

A specimen 6 having a thickness of 3200 탆 was prepared in the same manner as in Example 1, except that the resin mixture prepared in (2) of Comparative Example 2 was used. The pencil hardness of the specimen 6 was H, and the intensities were 5 kg · cm / cm for both IZOD 1/8 "and IZOD 1/4", and no layer separation phenomenon was observed in the specimen.

Comparative Example  3

(1) Preparation of resin containing no inorganic particles and measurement of physical properties

The linear polymer (A) prepared in Preparation Example 1 was used in place of the composite resin of Example 1.

The weight-average molecular weight of the resin measured by GPC was 25 K, the molecular weight distribution was 1.8, and the melt viscosity of the linear polymer was 415 pa * s.

(2) Preparation of resin mixture and measurement of physical properties

A resin mixture was prepared in the same manner as in Example 1, except that the linear polymer (A) prepared in Preparation Example 1 was used.

The difference in surface energy between the thermoplastic resin and the linear polymer (A) was 6 mN / m and the melt viscosity difference was 395 pa * s

(3) Production of resin molded article and measurement of physical properties

A specimen 7 having a thickness of 3200 탆 was prepared in the same manner as in Example 1, except that the resin mixture prepared in (2) of Comparative Example 3 was used. The pencil hardness of the specimen was H, and the strength was 9 kg · cm / cm for both IZOD 1/8 "and IZOD 1/4", and layer separation was observed in the specimen. The thickness of the composite resin layer of the specimen was 14 占 퐉, and the thickness of the interface layer was 12 占 퐉.

Comparative Example  4

(1) Preparation and physical property measurement of resin in which nanoparticles are dispersed

In a 1 L reactor, 664 g of distilled water and 17 g of 1% PVA aqueous solution as a dispersant were dissolved and the temperature of the reactor was raised to 60 ° C. Then, 110 g of methyl methacrylate (MMA), 42 g of cyclohexyl methacrylate (N-dodecyl mercaptan, n-DDM), which is a chain transfer agent, and 5 g of a polymerization initiator, 2,2 Azobis-2,4-dimethylvaleronitrile (ADVN) was added thereto, and the mixture was stirred at 350 rpm for 4 hours to form a core-shell. The resin of the structure was polymerized. After the polymerization, the resulting product was washed and dehydrated three times or more and then dried in an oven at 70 ° C.

The weight-average molecular weight of the resin measured by GPC was 100 K and the molecular weight distribution was 2.0.

(2) Preparation of resin mixture and measurement of physical properties

A resin mixture was prepared in the same manner as in Example 1, except that the resin prepared in (1) of Comparative Example 4 was used.

(3) Production of resin molded article and measurement of physical properties

A specimen 8 having a thickness of 3200 탆 was prepared in the same manner as in Example 1, except that the resin mixture prepared in (2) of Comparative Example 4 was used. The pencil hardness of the specimen was 0.5H, and the intensities were 5.6 to 6.5 kg · cm / cm for both IZOD 1/8 "and IZOD 1/4", and no layer separation phenomenon was observed in the specimen. Further, in the cross section of the specimen observed through the SEM, a phenomenon of aggregation of the resin was observed.

Comparative Example  5

(1) Production of resin molded article and measurement of physical properties

On the specimen 5 of Comparative Example 1, 17.5 wt% of dipentaerythritol hexyl acrylate (DPHA), 10 wt% of pentaerythritol triacrylate (PETA), 10 wt% of perfluorohexyl 5 wt% of ethyl methacrylate, 5 wt% of EB 1290, urethane acrylate of SK cytech, 45 wt% of methyl ethyl ketone, 20 wt% of isopropyl alcohol, and 1 wt% of UV initiator IRGACURE 184 of Ciba Co.) The coating was dried at 60 to 90 ° C. for about 4 minutes to form a film. Then, UV was irradiated at a dose of 3,000 mJ / cm 2 to cure the coating liquid composition to form a hard coating film.

The pencil hardness of the hard coating film is 3H and the peak intensity ratio [I _BD (C = C) / I _A (C = O)] and the peak intensity ratio [I _BD (out-of- plane) / I _A (C = O)] had an average and standard deviation of zero.

Claims (20)

A linear polymer having a functional group; And
A step of reacting and extruding an inorganic particle having a functional group capable of reacting with the functional group of the linear polymer to introduce inorganic particles into the linear polymer. The method for producing a composite resin according to claim 1, wherein the inorganic particles are used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the linear polymer. The method for producing a composite resin according to claim 1, wherein the linear polymer is obtained by polymerizing a mixture of an acrylic monomer having a functional group and a monomer containing an alkyl (meth) acrylate. The method for producing a composite resin according to claim 3, wherein the acrylic monomer having a functional group comprises an acrylic monomer having a carboxyl group, an acrylic monomer having a hydroxyl group, an acrylic monomer having an amino group or an acrylic monomer having an anhydride group. The method for producing a composite resin according to claim 3, wherein the acrylic monomer having a functional group is contained in an amount of 3 to 20 parts by weight based on 100 parts by weight of the total monomer mixture. The method for producing a composite resin according to claim 3, wherein the alkyl (meth) acrylate is an alkyl (meth) acrylate having 1 to 40 carbon atoms. The method for producing a composite resin according to claim 3, wherein the mixture of monomers comprises two or more alkyl (meth) acrylates. The method for producing a composite resin according to claim 7, wherein at least one of the two or more alkyl (meth) acrylates is an alkyl (meth) acrylate having 3 to 20 carbon atoms or an alicyclic (meth) acrylate having 5 to 40 carbon atoms Way. The process according to claim 8, wherein the alkyl (meth) acrylate having 3 to 20 carbon atoms or the alicyclic (meth) acrylate having 5 to 40 carbon atoms is contained in an amount of 10 to 40 parts by weight based on 100 parts by weight of the total monomer mixture Way. The method for producing a composite resin according to claim 3, wherein the mixture of monomers further comprises an aromatic (meth) acrylate having 6 to 40 carbon atoms. The method for producing a composite resin according to claim 10, wherein the aromatic (meth) acrylate having 6 to 40 carbon atoms is contained in an amount of 10 to 40 parts by weight based on 100 parts by weight of the total monomer mixture. The method for producing a composite resin according to claim 1, wherein the inorganic particles are silicon oxide, titanium oxide or a mixture thereof. The method for producing a composite resin according to claim 1, wherein the inorganic particles have an average particle diameter of 10 to 200 nm. The method for producing a composite resin according to claim 1, wherein the inorganic particles having a functional group are prepared by reacting an inorganic particle with a compound represented by the following formula
[Chemical Formula 1]
(R ¹ X) _n -Si- (R ² -Q) _4-n
Wherein R ¹ is an alkyl group having 1 to 16 carbon atoms, R ² is a single bond or an alkylene group having 1 to 16 carbon atoms, X is a single bond or -O-, Q is -NH ₂ , -OH, -COOH, maleic anhydride or succinic anhydride, and n is an integer of 1 to 3. 15. The method for producing a composite resin according to claim 14, wherein the inorganic particles are surface-modified with a compound represented by the formula (1) in an amount of 5 to 50 parts by weight based on 100 parts by weight of the inorganic particles. Wherein the polymer comprises a polymerized unit represented by the following formula (2): < EMI ID =
(2)

In Formula 2, R ³ , R ⁴ and R ⁵ are each independently hydrogen, a carboxyl group, an alkyl group having 1 to 4 carbon atoms or a carboxyalkyl group having 1 to 5 carbon atoms, L is a divalent organic linker containing O or N, and, D is a single bond or an alkylene group having 1 to 16, Y is a single bond or -O-, R ⁶ is an alkyl group having 1 to 16, a is an inorganic particle, m is any of 1 to 3 It is an integer. 17. The method of claim 16, L of Formula 2 is -CONH-, -CONR _a - 2 comprising the combination _{-, -COOCO-, -OCONH-, -OCONR a} -, -COO- -NH- or -NR _a Wherein R < _a > is an alkyl group having 1 to 16 carbon atoms. The composite resin according to claim 16, wherein the polymerization unit represented by the formula (2) is contained in an amount of 3 to 20 parts by weight based on 100 parts by weight of the total composite resin. 17. The composite resin according to claim 16, having a weight average molecular weight of 5,000 to 200,000. 17. The composite resin of claim 16, having a molecular weight distribution of from 1 to 2.5.

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