KR20230083785A - A polymer resin composition, preparing method of molded article using the same, and resin molded article - Google Patents

Abstract

The present invention relates to a polymer resin composition having excellent stain resistance and impact resistance, a method for manufacturing a molded article using the same, and a resin molded article.

Description

Polymer resin composition, manufacturing method of molded article using the same, and resin molded article

The present invention relates to a polymer resin composition, a method for manufacturing a molded article using the same, and a resin molded article.

Plastic resins are easy to process and have excellent properties such as tensile strength, modulus of elasticity, heat resistance, and impact resistance, so they are used for various purposes such as automobile parts, helmets, electrical equipment parts, spinning machine parts, toys, or pipes.

In particular, in the case of resins used in home appliances, automobile parts, toys, etc., since they come into direct contact with the human body, they must be environmentally friendly and have excellent surface hardness. However, in general, when a resin is exposed to the outside for a certain period of time or longer, it is easily discolored as it is decomposed by oxygen in the air, ozone, light, and the like. Accordingly, in order to improve weak weatherability and strength of the resin, it is common to apply an additional painting or plating process to the resin. However, such a painting or plating process not only reduces the efficiency and economic efficiency of the plastic resin manufacturing process, but also solves the problem of generating a large amount of harmful substances during the process itself or the disposal of the product when the painting or plating process is applied. Have.

Accordingly, various methods have been proposed for improving properties such as scratch resistance, heat resistance, and weather resistance of the resin while omitting the painting or plating process.

For example, a method of improving physical properties such as wear resistance and rigidity by adding inorganic particles to a resin has been proposed. However, according to this method, the processability of the plastic resin is lowered, and the impact strength and gloss may be lowered due to the addition of inorganic particles. In addition, for example, in order to increase the surface hardness of an extruded or injected resin molded product, a separate high-hardness coating process is required after the extrusion or injection process, and since this coating process includes a spray process, environmental harmful substances are generated. A problem existed.

The present invention is to provide a polymer resin composition having excellent stain resistance and impact resistance.

In addition, the present invention is to provide a method for manufacturing a molded article using the polymer resin composition.

In addition, the present invention is to provide a resin molded article using the polymer resin composition.

In order to solve the above problems, in the present specification, at least two or more different polymer resins are included, and at least one of the polymer resins is 1 weight of a repeating unit represented by Formula 1 based on 100 parts by weight of the total repeating unit. It provides a polymeric resin composition comprising a (meth)acrylate-based resin containing at least 50 parts by weight.

[Formula 1]

In Formula 1, R ₁ to R ₆ are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms, and L ₁ is a direct bond, an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, or a carbon atom having 1 to 10 carbon atoms. It is either an oxyalkylene group of 10, an arylene group of 6 to 30 carbon atoms, or an oxyarylene group of 6 to 30 carbon atoms, and n is an integer of 50 or more.

In the present specification, the step of melting the polymer resin composition to form a molten mixture; and forming a layer separation structure by processing the molten mixture.

In the present specification, it also includes at least two or more different polymer resins, and at least one of the polymer resins contains 1 part by weight or more and 50 parts by weight or less of the repeating unit represented by Formula 1 based on 100 parts by weight of the total repeating units. There is provided a resin molded article comprising a (meth) acrylate-based resin containing and having a polymer layer containing 50% by weight or more of the (meth) acrylate-based resin.

Hereinafter, a polymer resin composition according to specific embodiments of the present invention, a method for manufacturing a molded article using the same, and a resin molded article will be described in more detail.

Unless explicitly stated herein, terminology is used only to refer to specific embodiments and is not intended to limit the present invention.

As used herein, the singular forms also include the plural forms unless the phrases clearly dictate the contrary.

As used herein, the meaning of 'comprising' specifies a particular property, domain, integer, step, operation, element, and/or component, and other particular property, domain, integer, step, operation, element, component, and/or group. does not exclude the presence or addition of

In this specification, terms including ordinal numbers such as 'first' and 'second' are used for the purpose of distinguishing one component from another component, and are not limited by the ordinal number. For example, within the scope of the present invention, a first element may also be termed a second element, and similarly, a second element may be termed a first element.

In this specification, the weight average molecular weight was measured using an Agilent mixed B column using an Aters alliance 2695 instrument, the evaluation temperature was 40 ° C, and Tetrahydrofuran was used as a solvent. The flow rate was 1.0 mL/min, the sample was prepared at a concentration of 1 mg/10 mL, and then supplied in an amount of 100 μL, and the value of Mw was obtained using a calibration curve formed using a polystyrene standard. Nine kinds of molecular weight of polystyrene standards were used: 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000.

In this specification, the term "substitution" means that another functional group is bonded instead of a hydrogen atom in a compound, and the position to be substituted is not limited as long as the position where the hydrogen atom is substituted, that is, the position where the substituent can be substituted, and when two or more are substituted , Two or more substituents may be the same as or different from each other.

In this specification, the term "substituted or unsubstituted" means deuterium; halogen group; cyano group; nitro group; hydroxy group; carbonyl group; ester group; imide group; amide group; primary amino group; carboxy group; sulfonic acid group; sulfonamide group; phosphine oxide group; alkoxy group; aryloxy group; Alkyl thioxy group; Arylthioxy group; an alkyl sulfoxy group; aryl sulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; Aralkenyl group; Alkyl aryl group; an alkoxysilylalkyl group; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing at least one of N, O, and S atoms, or substituted or unsubstituted with two or more substituents linked to each other among the substituents exemplified above. . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, the alkyl group is a monovalent functional group derived from an alkane, and may be straight-chain or branched-chain, and the number of carbon atoms of the straight-chain alkyl group is not particularly limited, but is preferably 1 to 20. In addition, the number of carbon atoms of the branched chain alkyl group is 3 to 20. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl- propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, 2,6-dimethylheptan-4-yl, and the like, but is not limited thereto. The alkyl group may be substituted or unsubstituted.

In the present specification, a haloalkyl group means a functional group in which a halogen group is substituted for the aforementioned alkyl group, and examples of the halogen group include fluorine, chlorine, bromine, or iodine. The haloalkyl group may be substituted or unsubstituted.

In the present specification, the aryl group is a monovalent functional group derived from arene, and may be a monocyclic aryl group or a polycyclic aryl group. The monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, and the like, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto. The aryl group may be substituted or unsubstituted.

In the present specification, the alkylene group is a divalent functional group derived from an alkane, and the description of the above-described alkyl group may be applied except that they are a divalent functional group.

In the present specification, the arylene group is a divalent functional group derived from arene, and the description of the aryl group described above can be applied except that they are a divalent functional group. For example, it may be a phenylene group, a biphenylene group, a terphenylene group, a naphthalene group, a fluorenyl group, a pyrenyl group, a phenanthrenyl group, a perylene group, a tetracenyl group, an anthracenyl group, and the like. The arylene group may be substituted or unsubstituted.

, 또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

, or

means a bond connected to another substituent.

In the present specification, a direct bond or a single bond means that no atom or group of atoms is present at the corresponding position and is connected by a bond line.

In this specification, a blend may be a mixture of two or more different resins. The type of 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 types of pellets are mixed. In particular, when two or more resins are mixed in one matrix, the pellets 10 may include a composition of two or more resins 11. On the other hand, when two or more types of pellets are mixed, it may include a case where two or more types of pellets 20 and 21 containing one resin are mixed in one pellet. The resins may have different physical properties, and for example, the physical properties may be surface energy, melt viscosity, solubility parameter or glass transition temperature.

In the present specification, melt processing means a process of melting a resin mixture at a temperature higher than the melting temperature (Tm) to form a melt blend, and forming a desired molded article using the melt blend, for example For example, there are injection molding, extrusion molding, blow molding, transfer molding, film blowing, fiber spinning, calendering thermoforming or foam molding.

In the present specification, a resin molded product means a pellet or product formed from a resin composition, and the resin molded product is not particularly limited, but, for example, automobile parts, electronic device parts, mechanical parts, functional films, toys or It can be a pipe.

In this specification, layer separation may mean that a layer substantially formed by one resin is positioned or arranged on a layer substantially formed by another resin. A layer substantially formed by one resin may mean that one type of resin continuously exists throughout one layer without forming a sea-island structure. The sea-island structure means that the phase separated resin is partially distributed in the entire resin mixture. Also, "substantially formed" may mean that only one resin is present in one layer or that one resin is rich.

Hereinafter, the present invention will be described in more detail.

According to one embodiment of the invention, it includes at least two or more different polymer resins, and at least one of the polymer resins contains 1 part by weight or more of 50 parts by weight of the repeating unit represented by Formula 1 based on 100 parts by weight of the total repeating units. A polymeric resin composition including a (meth)acrylate-based resin containing less than parts by weight may be provided.

In the case of the polymer resin composition of the embodiment, the present inventors include a (meth)acrylate-based resin containing 1 part by weight or more and 50 parts by weight or less of the repeating unit represented by Formula 1 based on 100 parts by weight of the total repeating unit. As a result, it was confirmed through experimentation that surface properties such as stain resistance and impact resistance can be improved by layer separation in the finally manufactured resin molded product by showing different migration patterns between resins with respect to applied heat and external force. and completed the invention.

Specifically, a (meth)acrylate-based resin containing 1 part by weight or more and 50 parts by weight or less of the repeating unit represented by Formula 1 based on 100 parts by weight of the total repeating unit has excellent flowability and low viscosity, When manufacturing a molded article using the polymer resin composition, the (meth)acrylate-based resin may move towards the outer surface of the molded article to be finally manufactured, and in this way, the (meth)acrylate-based resin moves to the surface and is positioned therefor, thereby making the manufactured article Surface properties such as excellent stain resistance and impact resistance can be secured.

The at least two or more types of polymer resins may be classified according to physical properties such as weight average molecular weight and intrinsic viscosity, or differences in types of polymer backbones.

The (meth)acrylate-based resin includes both acrylate-based resins and methacrylate-based resins.

The polymer resin composition may be separated into two or more layers. As an example, the polymer resin composition comprising at least two or more types of polymer resins, when two surfaces facing each other of the melt-processed polymer resin composition are exposed to air, three layers, for example, (meth) The layer may be separated into an acrylate-based resin layer/other type of resin layer/(meth)acrylate-based resin layer. On the other hand, when only one side of the melt-processed polymer resin composition is exposed to air, the polymer resin composition may be separated into two layers, for example, a (meth)acrylate-based resin layer/another type of resin layer. can In addition, when all surfaces of the melt-processed polymer resin composition are exposed to air, the polymer resin composition may separate layers in all directions to form a core-shell structure.

The (meth)acrylate-based resin refers to a resin capable of imparting excellent mechanical properties and high surface hardness to the surface of a desired molded article.

As described above, the (meth)acrylate-based resin may include a repeating unit represented by Chemical Formula 1.

As the (meth)acrylate-based resin includes the repeating unit represented by Chemical Formula 1, the repeating unit having excellent water repellency may be included, so that the finally produced resin molded article may also have excellent water repellency.

Specifically, the (meth)acrylate-based resin may include 1 part by weight or more and 50 parts by weight or less of the repeating unit represented by Formula 1 based on 100 parts by weight of the total repeating units.

More specifically, the (meth)acrylate-based resin contains 1 part by weight or more of the repeating unit represented by Formula 1 based on 100 parts by weight of the total repeating unit. It may contain 3 parts by weight or more, 5 parts by weight or more, 50 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 1 part by weight or more and 50 parts by weight or less, 1 part by weight or more 30 1 part by weight or more and 20 parts by weight or less, 1 part by weight or more and 10 parts by weight or less, 3 parts by weight or more and 50 parts by weight or less, 3 parts by weight or more and 30 parts by weight or less, 3 parts by weight or more and 20 parts by weight or less, 3 10 parts by weight or less, 5 parts by weight or more and 50 parts by weight or less, 5 parts by weight or more and 30 parts by weight or less, 5 parts by weight or more and 20 parts by weight or less, 5 parts by weight or more and 10 parts by weight or less.

As the (meth)acrylate-based resin includes 1 part by weight or more and 50 parts by weight or less of the repeating unit represented by Formula 1 based on 100 parts by weight of the total repeating unit, the fluidity of the repeating unit represented by Formula 1 Since the content is adjusted, excellent handling is realized and compatibility with other polymer resins is excellent, so that layer separation occurs in the finally manufactured resin molded article, so that excellent surface properties such as stain resistance and impact resistance can be realized.

When the (meth)acrylate-based resin contains less than 1 part by weight of the repeating unit represented by Formula 1 with respect to 100 parts by weight of the total repeating unit, the fluidity is disadvantageous and compatibility with other polymer resins is disadvantageous. However, it may exhibit inferior surface properties, and when it is included in an amount of more than 50 parts by weight, technical problems such as poor handling may occur.

The repeating unit represented by Chemical Formula 1 may be a repeating unit derived from a polysiloxane-based (meth)acrylic monomer.

The polysiloxane-based (meth)acrylic monomer is a compound in which a polysiloxane functional group is bonded to a (meth)acrylic monomer, for example, (meth)acryloxymethyl-terminated polydimethylsiloxane, (meth)acryloxyethyl-terminated polydimethylsiloxane, (meth)acryloxyethyl-terminated polydimethylsiloxane, Acryloxypropyl-terminated polydimethylsiloxane, (meth)acryloxybutyl-terminated polydimethylsiloxane, (meth)acryloxypentyl-terminated polydimethylsiloxane, (meth)acryloxyhexyl-terminated polydimethylsiloxane, (meth)acryloxyheptyl-terminated polydimethylsiloxane Siloxanes or (meth)acryloxyalkyl terminated polydimethylsiloxanes such as (meth)acryloxyoctyl terminated polydimethylsiloxanes may be used.

In Formula 1, R ₁ to R ₆ are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms, and L ₁ is a direct bond, an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, or a carbon atom having 1 to 10 carbon atoms. It is either an oxyalkylene group of 10, an arylene group of 6 to 30 carbon atoms, or an oxyarylene group of 6 to 30 carbon atoms, and n is an integer of 50 or more.

Specifically, in Formula 1, n may be 50 or more, 60 or more, 150 or less, 135 or less, or 50 or more and 150 or less, 50 or more and 135 or less, 60 or more and 150 or less, or 60 or more and 135 or less.

In Formula 1, when n exceeds 150, polymerization stability may be poor due to reactivity due to bulky side chains, and when n is less than 50, surface properties such as water contact angle may be poor.

In addition, the polysiloxane-based (meth)acrylic monomer has a weight average molecular weight of 3000 g/mol or more, 5000 g/mol or more, 20000 g/mol or less, 15000 g/mol or less, or 3000 g/mol or more and 20000 g/mol or less. , 3000 g/mol or more and 15000 g/mol or less, 5000 g/mol or more and 20000 g/mol or less, and 5000 g/mol or more and 15000 g/mol or less.

When the weight average molecular weight of the polysiloxane-based (meth)acrylic monomer exceeds 20000 g/mol, polymerization stability may be poor due to reactivity due to bulky side chains, and the weight average of the polysiloxane-based (meth)acrylic monomer Surface properties such as water contact angle with a molecular weight of less than 3000 g/mol may be poor.

On the other hand, the (meth) acrylate-based resin of the embodiment has a weight average molecular weight of 5000 g / mol or more, 10000 g / mol or more, 15000 g / mol or more, 20000 g / mol or less, 16000 g / mol or less, or 5000 g /mol or more and 20000 g/mol or less, 10000 g/mol or more and 20000 g/mol or less, 15000 g/mol or more and 20000 g/mol or less, 5000 g/mol or more and 16000 g/mol or less, 10000 g/mol or more 16000 g/mol It may be mol or less, 15000 g/mol or more and 16000 g/mol or less.

When the weight average molecular weight of the (meth) acrylate-based resin exceeds 20000 g / mol, the fluidity of the (meth) acrylate-based resin is lowered, making it difficult to easily cause layer separation, resulting in poor surface properties. There is a problem, and when the weight average molecular weight of the (meth)acrylate-based resin is 5000 g/mol or less, mechanical properties of the resin itself are deteriorated, and mechanical properties of a finally formed molded article may also be deteriorated.

The polymer resin composition of one embodiment may include a (meth)acrylate-based resin including a repeating unit represented by Formula 2 below in addition to the repeating unit represented by Formula 1 above.

[Formula 2]

In Formula 2, R ₇ is hydrogen or an alkyl group having 1 to 10 carbon atoms, and R ₈ is an alkyl group having 4 to 20 carbon atoms including an alicyclic ring.

The repeating unit represented by Chemical Formula 2 may be a repeating unit derived from a (meth)acrylic monomer including an alkyl group having 4 to 20 carbon atoms including an alicyclic ring.

Specifically, the alkyl group having 4 to 20 carbon atoms including the alicyclic ring may include an alkyl group having 1 to 10 carbon atoms bonded to a cycloalkyl group having 3 to 20 carbon atoms.

More specifically, the alkyl group having 4 to 20 carbon atoms including the alicyclic ring may include a substituent represented by Formula 2-1 below.

[Formula 2-1]

In Formula 2-1, R ₁₁ is a direct bond or an alkylene group having 1 to 10 carbon atoms, and R ₁₁ may be a cycloalkyl group having 3 to 20 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms.

The cycloalkyl group represents a monovalent mono or bicyclic hydrocarbon moiety of 3 to 20 cyclic carbons, usually saturated, non-aromatic. The cycloalkyl may be optionally substituted with one or more substituents. When substituted, the cycloalkyl generally contains one, two, or three substituents within the ring structure. When two or more substituents are present in the cycloalkyl group, each substituent is selected independently. A cycloalkyl group may also contain one or more unsaturated (eg, olefinic and/or acetylenic) moieties. Preferred cycloalkyls include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl groups and the like. Preferred substituents for cycloalgyl groups include, but are not limited to, alkyl, haloalkyl, halo, heteroalkyl, aryl, -ORa where Ra is hydrogen or alkyl is), etc.

More specifically, the cycloalkyl group is a cycloalkyl group having 3 or more carbon atoms, 5 or more carbon atoms, 20 or less carbon atoms, 15 or less carbon atoms, 10 or less carbon atoms, 3 to 20 carbon atoms, 5 to 20 carbon atoms, 5 to 15 carbon atoms, or 5 to 10 carbon atoms. It may be an alkyl group, for example, a cyclohexyl group.

As the (meth)acrylate-based resin contains the repeating unit represented by Formula 2, it exhibits excellent fluidity and is advantageous in handling, resulting in layer separation in the resin molded product to be finally manufactured, thereby improving stain resistance and impact resistance. can improve surface properties

Meanwhile, the (meth)acrylate-based resin may include 50 parts by weight or more and 99 parts by weight or less of the repeating unit represented by Formula 2 based on 100 parts by weight of the total repeating units.

Specifically, the (meth)acrylate-based resin contains 50 parts by weight or more of the repeating unit represented by Formula 2 based on 100 parts by weight of the total repeating unit. 60 parts by weight or more, may include 70 parts by weight or more, 99 parts by weight or less, 80 parts by weight or less, or 50 parts by weight or more and 99 parts by weight or less, 60 parts by weight or more and 99 parts by weight or less, 70 parts by weight or more 99 parts by weight parts by weight or less, 50 parts by weight or more and 80 parts by weight or less, 60 parts by weight or more and 80 parts by weight or less, and 70 parts by weight or more and 80 parts by weight or less.

As the (meth)acrylate-based resin contains 50 parts by weight or more and 99 parts by weight or less of the repeating unit represented by Formula 2 based on 100 parts by weight of the total repeating unit, it exhibits excellent fluidity and is advantageous in handling, Layer separation occurs in the resin molded product to be finally manufactured, so that excellent surface properties such as stain resistance and impact resistance can be realized.

When the (meth)acrylate-based resin contains less than 50 parts by weight of the repeating unit represented by Formula 2 based on 100 parts by weight of the total repeating units, the fluidity of the (meth)acrylate-based resin is excessively increased, making handling difficult. In addition, compatibility with other types of resins may decrease, resulting in deterioration of surface properties, and when included in an amount exceeding 99 parts by weight, water repellency may decrease, resulting in deterioration of surface properties such as stain resistance and impact resistance. there is.

Meanwhile, the (meth)acrylate-based resin may include 5 parts by weight or more and 20 parts by weight or less of the repeating unit represented by Formula 1 based on 100 parts by weight of the repeating unit represented by Formula 2.

Specifically, the (meth)acrylate-based resin includes 5 parts by weight or more, 6 parts by weight or more, or 6.5 parts by weight or more of the repeating unit represented by Formula 1 based on 100 parts by weight of the repeating unit represented by Formula 2. 20 parts by weight or less, 15 parts by weight or less, 5 parts by weight or more and 20 parts by weight or less, 5 parts by weight or more and 15 parts by weight or less, 6 parts by weight or more and 20 parts by weight or less, 6 parts by weight or more and 15 parts by weight or less, It may include 6.5 parts by weight or more and 20 parts by weight or less, or 6.5 parts by weight or more and 15 parts by weight or less.

As the (meth)acrylate-based resin contains 5 parts by weight or more and 20 parts by weight or less of the repeating unit represented by Formula 1 based on 100 parts by weight of the repeating unit represented by Formula 2, it not only exhibits excellent fluidity, but also It is advantageous in handling, and layer separation occurs in the resin molded product to be finally manufactured, so surface properties such as stain resistance and impact resistance can be improved, and excellent water repellency properties can be implemented.

When the (meth)acrylate-based resin contains less than 5 parts by weight of the repeating unit represented by Chemical Formula 1 with respect to 100 parts by weight of the repeating unit represented by Chemical Formula 2, the water repellency is lowered, resulting in poor stain resistance and impact resistance. The surface properties of the back may be deteriorated, and if it is included in an amount exceeding 20 parts by weight, the fluidity of the (meth)acrylate-based resin is excessively increased, making handling difficult, and compatibility with other types of resins is lowered, so that the surface characteristics may deteriorate.

The polymer resin composition of one embodiment may include a (meth)acrylate-based resin including a repeating unit represented by Chemical Formula 3 in addition to the repeating unit represented by Chemical Formula 1 and the repeating unit represented by Chemical Formula 2.

[Formula 3]

In Formula 3, R ₉ is hydrogen or an alkyl group having 1 to 10 carbon atoms, and R ₁₀ is a linear or branched chain alkyl group having 1 to 20 carbon atoms.

The repeating unit represented by Chemical Formula 3 may be a repeating unit derived from a (meth)acrylic monomer containing a linear or branched alkyl group having 1 to 20 carbon atoms.

The alkyl group usually represents a saturated non-aromatic monovalent hydrocarbon functional group. The alkyl group may be optionally substituted with one or more substituents.

As the (meth)acrylate-based resin includes the repeating unit represented by Chemical Formula 3, the (meth)acrylate-based resin is partially mixed with other polymer resins, thereby finally producing the (meth)acrylate-based resin. The compatibility between the resin and other polymer resins can be adjusted.

Meanwhile, the (meth)acrylate-based resin may include 5 parts by weight or more and 20 parts by weight or less of the repeating unit represented by Chemical Formula 3 based on 100 parts by weight of the total repeating units.

Specifically, the (meth)acrylate-based resin contains 5 parts by weight or more of the repeating unit represented by Formula 3 based on 100 parts by weight of the total repeating unit. 10 parts by weight or more, may include 15 parts by weight or more, 20 parts by weight or less, 19 parts by weight or less, or 5 parts by weight or more and 20 parts by weight or less, 10 parts by weight or more and 20 parts by weight or less, 15 parts by weight or more 20 parts by weight parts by weight or less, 5 parts by weight or more and 19 parts by weight or less, 10 parts by weight or more and 19 parts by weight or less, or 15 parts by weight or more and 19 parts by weight or less.

As the (meth)acrylate-based resin contains 5 parts by weight or more and 20 parts by weight or less of the repeating unit represented by Formula 3 based on 100 parts by weight of the total repeating units, the (meth)acrylate-based resin is a polymer other than the other polymers. It is partially mixed with the resin, and thereby the compatibility between the finally prepared (meth)acrylate-based resin and other polymer resins can be adjusted.

When the (meth)acrylate-based resin contains less than 5 parts by weight of the repeating unit represented by Formula 3 with respect to 100 parts by weight of the total repeating units, compatibility between the finally prepared (meth)acrylate-based resin and other polymer resins Peeling may occur due to poor properties, and when included in an amount exceeding 20 parts by weight, the finally prepared (meth)acrylate-based resin and other polymer resins may be completely mixed and layer separation may not occur.

Meanwhile, the (meth)acrylate-based resin may include 20 parts by weight or more and 60 parts by weight or less of the repeating unit represented by Formula 1 based on 100 parts by weight of the repeating unit represented by Formula 3.

Specifically, the (meth)acrylate-based resin may include 20 parts by weight or more, 25 parts by weight or more of the repeating unit represented by Formula 1 based on 100 parts by weight of the repeating unit represented by Formula 3, and 56 parts by weight or less, 20 parts by weight or more and 60 parts by weight or less, 25 parts by weight or more and 60 parts by weight or less, 20 parts by weight or more and 56 parts by weight or less, 25 parts by weight or more and 56 parts by weight or less.

As the (meth)acrylate-based resin contains 20 parts by weight or more and 60 parts by weight or less of the repeating unit represented by Formula 1 based on 100 parts by weight of the repeating unit represented by Formula 3, the (meth)acrylate The based resin is partially mixed with other polymer resins, and thus the compatibility between the (meth)acrylate based resin and other polymer resins finally prepared can be adjusted.

When the (meth)acrylate-based resin contains less than 20 parts by weight of the repeating unit represented by Formula 1 with respect to 100 parts by weight of the repeating unit represented by Formula 3, the finally prepared (meth)acrylate-based resin and other polymer resins may be completely mixed so that layer separation may not occur, and if it is included in an amount exceeding 60 parts by weight, the compatibility between the finally prepared (meth)acrylate-based resin and other polymer resins may be poor and peeling may occur. .

Meanwhile, one type of polymer resin other than the (meth)acrylate-based resin is a resin that 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 used. For example, a thermoplastic resin can be used as another type of polymer resin. General synthetic resins can be used as the thermoplastic resin without particular limitation, but specifically, ABS (acrylonitrile butadiene styrene)-based resin, polystyrene-based resin, ASA ( styrene-based resins such as acrylonitrilestyrene acrylate)-based resins or styrene-butadiene-styrene block copolymer-based resins; polyolefin-based resins such as high-density polyethylene-based resins, low-density polyethylene-based resins, or polypropylene-based resins; thermoplastic elastomers such as ester-based thermoplastic elastomers or olefin-based thermoplastic elastomers; polyoxyalkylene-based resins such as polyoxymethylene-based resins or polyoxyethylene-based resins; polyester-based resins such as polyethylene terephthalate-based resins or polybutylene terephthalate-based resins; polyvinyl chloride-based resins; polycarbonate-based resin; polyphenylene sulfide-based resins; vinyl alcohol-based resins; polyamide-based resin; acrylate-based resins; engineering plastics; copolymers thereof or mixtures thereof. The engineering plastics are plastics exhibiting excellent mechanical and thermal properties. For example, polyether ketone, polysulfone, and polyimide may be used as engineering plastics. For example, a styrenic resin can be used as the thermoplastic resin.

Meanwhile, the polymer resin composition may include 5 parts by weight or more and 50 parts by weight or less of the (meth)acrylate-based resin based on 100 parts by weight of the total polymer resin.

Specifically, the polymer resin composition contains 5 parts by weight or more, or 50 parts by weight or less, 30 parts by weight or less, 25 parts by weight or less, or 20 parts by weight of the (meth)acrylate-based resin, based on 100 parts by weight of the total polymer resin. 10 parts by weight or less, or 5 parts by weight or more and 50 parts by weight or less, 5 parts by weight or more and 30 parts by weight or less, 5 parts by weight or more and 25 parts by weight or less, 5 parts by weight or more and 20 parts by weight or less, 5 parts by weight or more 10 parts by weight may include the following.

When the polymer resin composition contains less than 5 parts by weight of the (meth)acrylate-based resin based on 100 parts by weight of the total polymer resin, layer separation may not occur, and when it is included in more than 50 parts by weight ( Manufacturing costs may increase due to the high price of meth)acrylate-based resins.

Meanwhile, the polymer resin composition may include 500 parts by weight or more and 3000 parts by weight or less of another type of polymer resin based on 100 parts by weight of the (meth)acrylate-based resin.

Specifically, the polymer resin composition contains 500 parts by weight or more, 700 parts by weight or more, 850 parts by weight or more, 900 parts by weight or more of the other type of polymer resin based on 100 parts by weight of the (meth)acrylate-based resin, or 3000 parts by weight or less, 2500 parts by weight or less, 2200 parts by weight or less, 2000 parts by weight or less, or 500 parts by weight or more and 3000 parts by weight or less, 700 parts by weight or more and 3000 parts by weight or less, 700 parts by weight or more and 2500 parts by weight or less, 850 parts by weight 2500 parts by weight or less, 850 parts by weight or more and 2200 parts by weight or less, 900 parts by weight or more and 2200 parts by weight or less, or 900 parts by weight or more and 2000 parts by weight or less.

When the polymer resin composition contains less than 500 parts by weight of the other type of polymer resin with respect to 100 parts by weight of the (meth)acrylate-based resin, the manufacturing cost may increase due to the high price of the (meth)acrylate-based resin. When it is included in an amount of more than 3000 parts by weight, layer separation may not occur.

Meanwhile, according to another embodiment of the present invention, a method of manufacturing a resin molded article having a layer separation structure may be provided.

Specifically, the manufacturing method of the molded article of the embodiment includes the steps of melting the polymer resin composition to form a molten mixture; and forming a layer separation structure by processing the molten mixture.

As described above, due to the difference in physical properties between the other type of polymer resin and the (meth)acrylate-based resin, layer separation may occur during melt processing of the polymer resin composition, and due to this layer separation, The effect of selectively coating the surface of a pellet or molded product can be achieved without a separate additional process.

In particular, by introducing a hydrogen bond donor and acceptor into the (meth)acrylate-based resin of the present invention, a high-hardness resin is located on the surface during layer separation, thereby providing a molded article with improved mechanical and surface properties.

Meanwhile, the melt processing may be performed under shear stress, for example, extrusion and/or injection processing, but is not limited thereto.

According to another embodiment of the present invention, the polymer resin composition may be manufactured into pellets by melt processing such as extrusion. For example, as described above, in the polymer resin composition including other types of polymer resins and (meth)acrylate-based resins, the (meth)acrylate-based resins are more hydrophobic than other types of polymer resins in the melt processing process. Because of its size, it moves in contact with air to form a surface layer of the pellet, and another type of polymer resin can be located in the center of the pellet to form a core. In addition, the polymer resin composition may be manufactured into pellets by extrusion and then manufactured into molded articles by melt processing such as injection of the pellets. Meanwhile, the polymer resin composition may be directly manufactured into a molded article by melt processing such as injection.

In the step of melting and processing the polymer resin composition, the applied temperature may vary depending on the type of different polymer resins and (meth)acrylate-based resins used.

The method of manufacturing the molded product may further include curing a product obtained by melt-processing the polymer resin composition, that is, a melt-processed product of the polymer resin composition. The curing may be, for example, thermal curing or UV curing. In addition, it will be apparent to those skilled in the art that additional chemical or physical treatment may be performed.

Meanwhile, the manufacturing method of the molded article may further include preparing at least two or more different polymer resins prior to melting and processing the resin mixture. Information about at least two or more different polymer resins includes all of the above.

The (meth)acrylate-based resin may impart a specific function, for example, high hardness, to the surface layer of a resin molded article. For the production of (meth)acrylate-based resin, there is no particular limitation as long as the resin is generally prepared through polymerization of monomers. For example, methods such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization may be used. there is.

Preparing the (meth)acrylate-based resin may include dispersing a monomer in a reaction solvent; Adding and mixing at least one additive selected from the group consisting of a chain transfer agent, an initiator, and a dispersion stabilizer to the reaction solvent; and a polymerization step of reacting the mixture at a temperature of 40° C. or higher.

As the reaction medium, any medium known to be commonly used for preparing synthetic resins, polymers or copolymers may be used without any other limitation. As examples of such a reaction medium, methyl ethyl ketone, ethanol, methyl isobutyl ketone, or distilled water may be used, or a mixture of two or more may be used.

Chain transfer agents that may be added to the reaction solvent 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 may be used, but are not limited to the above examples.

As the initiator, a polymerization initiator known to be commonly used in suspension polymerization, for example, peroxides such as octanoyl peroxide, decanoyl peroxide, and lauroyl peroxide, or azobisisobutyronitrile, azobis-( Azo-based compounds such as 2,4-dimethyl)-valeronitrile may be used without particular limitation.

Examples of the dispersion stabilizer that may be included in the reaction medium include organic dispersants such as polyvinyl alcohol, polyolefin-maleic acid, and cellulose, or inorganic dispersants such as tricalcium phosphate, but are not limited thereto.

On the other hand, according to another embodiment of the present invention, at least two or more different polymer resins are included, and at least one of the polymer resins contains 1 weight of the repeating unit represented by Formula 1 based on 100 parts by weight of the total repeating units. A resin molded product including a (meth)acrylate-based resin containing at least 50 parts by weight and having a polymer layer containing at least 50% by weight of the (meth)acrylate-based resin may be provided.

As described above, in a resin molded product manufactured from a resin mixture containing at least two or more different types of specific polymer resins, for example, different types of polymer resins are located inside and a (meth)acrylate-based resin layer is formed of a resin molded product. It may be a layer separation structure formed on the surface.

That is, in the resin molded article of the embodiment, a polymer layer containing 50% by weight or more of the (meth)acrylate-based resin may be located on the surface of the resin molded article.

As described above, the (meth)acrylate-based resin containing 1 part by weight or more and 50 parts by weight or less of the repeating unit represented by Formula 1 with respect to 100 parts by weight of the total repeating units has excellent flowability and low viscosity. , When manufacturing a molded article using the polymer resin composition of another embodiment including the same, the (meth)acrylate-based resin may move toward the outer surface of the molded article to be finally manufactured, and thus the (meth)acrylate-based resin is formed on the surface As it moves to and is located, the manufactured molded article can secure surface properties such as excellent stain resistance and impact resistance.

The structure of the resin molded product, that is, the structure in which the different types of resin layers and the (meth)acrylate-based resin layer are separated by an interface layer and the (meth)acrylate-based resin layer is exposed to the outside is a novel, previously unknown structure. As one, it is possible to omit a coating process or a painting process for improving surface properties, reduce production process time and production cost, and increase productivity of a final product. Such a structure cannot be formed by extruding or injecting a general resin, and it is difficult to realize the effect according to the structure.

In particular, the surface hardness of the resin molded article may be additionally increased by using the above-described (meth)acrylate-based resin.

The polymer layer containing 50% by weight or more of the (meth)acrylate-based resin mainly contains the (meth)acrylate-based resin, and is located outside the resin molded article to impart a certain function to the surface of the molded article.

Specifically, the polymer layer containing 50% by weight or more of the (meth)acrylate-based resin contains 50% by weight or more, 60% by weight or more, 70% by weight or more, 99% by weight or less, 95% by weight or more of the (meth)acrylate-based resin. 50% by weight or more and 99% by weight or less, 60% by weight or more and 99% by weight or less, 70% by weight or more and 99% by weight or less, 50% by weight or more and 95% by weight or less, 60% by weight or more and 95% by weight or less, It may contain 70% by weight or more and 95% by weight or less.

The resin molded article may further include a polymer layer containing 50% by weight or more of the other type of polymer resin.

The polymer layer containing 50% by weight or more of the other type of polymer resin may mainly include a type of polymer resin other than the (meth)acrylate-based resin. For example, when the other type of polymer resin is a thermoplastic resin, the polymer layer containing 50% by weight or more of the different type of polymer resin may be a polymer layer mainly containing the thermoplastic resin.

Specifically, the polymer layer containing 50% by weight or more of the other type of polymer resin contains 50% by weight or more, 60% by weight or more, 70% by weight or more, 99% by weight or less, 95% by weight or less, or 50 wt% or more and 99 wt% or less, 60 wt% or more and 99 wt% or less, 70 wt% or more and 99 wt% or less, 50 wt% or more and 95 wt% or less, 60 wt% or more and 95 wt% or less, 70 wt% or more It may contain 95% by weight or less.

The at least two or more types of polymer resins may be classified according to physical properties such as weight average molecular weight and intrinsic viscosity, or differences in types of polymer backbones.

The (meth)acrylate-based resin includes both acrylate-based resins and methacrylate-based resins.

Information about the at least two or more different polymer resins includes all of the above.

Specifically, at least one of the polymer resins includes a (meth)acrylate-based resin containing 1 part by weight or more and 50 parts by weight or less of the repeating unit represented by Formula 1 based on 100 parts by weight of the total repeating units. can do.

In addition, one type of polymer resin other than the (meth)acrylate-based resin is a resin that 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 used. For example, a thermoplastic resin can be used as another type of polymer resin. General synthetic resins can be used as these thermoplastic resins without particular limitations,

For example, ABS (acrylonitrile butadiene styrene) resin, polystyrene resin, ASA (acrylonitrilestyrene acrylate) resin or styrene-butadiene-styrene block copolymer resin as one type of polymer resin other than the (meth)acrylate-based resin. styrenic resins such as; polyolefin-based resins such as high-density polyethylene-based resins, low-density polyethylene-based resins, or polypropylene-based resins; thermoplastic elastomers such as ester-based thermoplastic elastomers or olefin-based thermoplastic elastomers; polyoxyalkylene-based resins such as polyoxymethylene-based resins or polyoxyethylene-based resins; polyester-based resins such as polyethylene terephthalate-based resins or polybutylene terephthalate-based resins; polyvinyl chloride-based resins; polycarbonate-based resin; polyphenylene sulfide-based resins; vinyl alcohol-based resins; polyamide-based resin; acrylate-based resins; engineering plastics; copolymers thereof or mixtures thereof. The engineering plastics are plastics exhibiting excellent mechanical and thermal properties. For example, polyether ketone, polysulfone, and polyimide may be used as engineering plastics. For example, a styrenic resin can be used as the thermoplastic resin.

On the other hand, the resin molded article is formed between the other type of polymer resin layer and the (meth) acrylate-based resin layer and includes an interface layer containing a mixture of another type of polymer resin and (meth) acrylate-based resin. can do. The interface layer may be formed between the layer-separated polymer resin layer of another type and the (meth)acrylate-based resin layer to serve as an interface, and a mixture of different types of polymer resin and (meth)acrylate-based resin may be formed. can include The mixture may be in a state in which the different kinds of polymer resin and the (meth)acrylate-based resin are physically or chemically bonded, and the other kinds of polymer resin layer and the (meth)acrylate-based resin may be in a state in which the mixture is physically or chemically bonded. Strata can be combined.

As described above, the resin molded product has a structure in which the other type of polymer resin layer and the (meth)acrylate-based resin layer are separated by this interface layer, and the (meth)acrylate-based resin layer is exposed to the outside. can include For example, the molded article may include the polymer resin layer of the other type; interface layer; And (meth) acrylate-based resin layers may include a structure in which layers are sequentially laminated, and may have a structure in which interfaces and (meth) acrylate-based resins are laminated on top and bottom of different types of polymer resins. In addition, the resin molded product has a structure in which the interface and the (meth)acrylate-based resin layer sequentially surround different types of polymer resin layers having various three-dimensional shapes, for example, spherical, circular, polyhedron, sheet, etc. can include

The layer separation phenomenon appearing in the resin molded article seems to be caused by manufacturing the resin molded article by applying at least two or more different polymer resins having different physical properties.

On the other hand, the other types of polymer resin layer, (meth) acrylate-based resin layer and interface layer can be confirmed by etching the fracture surface using THF vapor and using SEM after a low temperature impact test on the specimen, To measure the thickness of each layer, the specimen was cut with a diamond knife using microtoming equipment to make a smooth section, and then a solution that could selectively dissolve (meth)acrylate-based resin better than other types of polymer resin was used to obtain a smooth surface. Etch the cross section. The degree of melting of the etched cross section varies depending on the content of different types of polymer resins and (meth)acrylate-based resins. The resin layer, the (meth)acrylate-based resin layer, the interface layer and the surface can be observed, and the thickness of each layer can be measured. As an example of a solution that can selectively dissolve the (meth)acrylate-based resin better, a 1,2-dichloroethane solution (10% by volume, in EtOH) can be used, and compared to other types of resins, (meth)acrylate-based Any solution having a high solubility of the resin 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 (meth)acrylate-based resin.

The (meth)acrylate-based resin layer is 0.01 to 60%, 0.01 to 40%, 0.01 to 20%, 0.01 to 10%, 0.01 to 5%, 0.01 to 3%, 0.1 to 3%, or 1 to It may have a thickness of 3%. As the (meth)acrylate-based resin layer has a thickness within a certain range, it is possible to impart improved surface hardness or scratch resistance to the surface of a molded article, but the thickness of the (meth)acrylate-based resin layer is too thin. It may be difficult to sufficiently improve the surface properties of the molded article, and if the thickness of the (meth)acrylate-based resin layer is too thick, the mechanical properties of the functional resin itself are reflected in the resin molded article, changing the mechanical properties of other types of polymer resin. It can be.

In the resin molded article, other types of polymer resin layer components may be detected from the surface of the (meth)acrylate-based resin layer by infrared spectroscopy. The structure of the molded article, that is, the structure in which different types of polymer resin layer components are detected by infrared spectroscopy on the surface of the (meth)acrylate-based resin layer is a novel, previously unknown, and generally in the coating process, etc. (meth) It is difficult to detect other types of polymer resin layer components on the surface of the acrylate-based resin layer.

In addition, the surface water contact angle at 25 ° C. on the surface of the resin molded article may be 92 ° or more and 120 ° or less.

Specifically, the surface water contact angle at 25 ° C. on the surface of the resin molded article may be 92 ° or more, 94 ° or more, 120 ° or less, 110 ° or less, 105 ° or less, or 92 ° or more, 120 ° or less, 94 ° or less ° or more and 120 ° or less, 92 ° or more and 110 ° or less, 94 ° or more and 110 ° or less, 92 ° or more and 105 ° or less, and 91 ° or more and 105 ° or less.

The surface energy is a value measured by a known surface energy measurement method, and may be, for example, a value measured by the Owens-Wendt method through static contact angle measurement. As a specific example, surface energy (γ surface , mN/m) can be calculated as γ surface = γ dispersion + γ polar, and can be measured using a drop shape analyzer (DSA100 product of KRUSS).

Specifically, the surface energy and surface water contact angle are obtained by dropping deionized water and a solvent such as diiodomethane or hexadecane whose surface tension is known on the surface of the target sample to be measured and obtaining the contact angle It is possible to measure the surface water contact angle by repeating 5 times and obtaining an average value of the obtained 5 contact angle values.

In addition, the surface energy can be obtained by substituting a numerical value (Strom value) related to the surface tension of the solvent by the Owens-Wendt-Rabel-Kaelble method from the surface water contact angle.

Meanwhile, the impact strength on the surface of the 1/4" inch specimen of the resin molded article measured at room temperature may be 6.0 kJ/m ² or more and 30 kJ/m ² or less.

Specifically, the impact strength at the surface measured at room temperature for the 1/4" inch specimen of the resin molded product is 6.0 kJ/m ² or more, 9.0 kJ/m ² or more, 30 kJ/m ² or less, 25 kJ/m ² or less, or 6.0 kJ/m ² or more and 30 kJ/m ² or less, 9.0 kJ/m ² or more and 30 kJ/m ² or less, 6.0 kJ/m ^{2 or} more and 25 kJ/m ² or less, 9.0 kJ/m ² or more and 25 kJ/m ² or less.

The method of measuring the impact strength is not particularly limited, but may mean an average value measured 5 times for each 1/4" inch specimen according to the ASTM D256 test method at room temperature of 25 ° C.

The resin molded article is not particularly limited, but may be, for example, automobile parts, electronic device parts, mechanical parts, functional films, toys, or pipes.

According to the present invention, a polymer resin composition having excellent stain resistance and impact resistance, a method for manufacturing a molded article using the same, and a resin molded article may be provided.

1 shows an exemplary schematic diagram of a layer separation structure formed of a resin mixture including at least two or more different polymer resins as an example of the present invention.

The invention is explained in more detail in the following examples. However, the following examples are merely illustrative of the present invention, and the contents of the present invention are not limited by the following examples.

<Production Example: Preparation of (meth)acrylate-based resin>

Preparation Example 1

935 g of distilled water was put into a 3-liter reactor, and 380 g (2.26 mol) of cyclohexyl methacrylate, 95 g (0.95 mol) of methyl methacrylate, and polydimethylsiloxane represented by Formula A (n= 64±5, Mw: 5,000 g/mol) 25 g (0.005 mol), 12 g of n-dodecylmercaptan as a chain transfer agent) and 1.5 g of azobisdimethylvaleronitrile as an initiator were additionally added and stirred at 500 rpm did The mixture was reacted at 75 °C for 3 hours to polymerize, and cooled to 30 °C to obtain a bead-type (meth)acrylate-based resin (weight average molecular weight: 16,000 g/mol). Subsequently, the (meth)acrylate-based resin was washed with distilled water three times, dehydrated, and dried in an oven.

[Formula A]

Preparation Example 2

Cyclohexyl methacrylate 360 g (2.14 mol), methyl methacrylate 90 g (0.90 mol), polydimethylsiloxane represented by Formula A (n = 64, Mw: 5,000 g / mol) 50 g (0.01 mol) A bead-type (meth)acrylate-based resin (weight average molecular weight: 16,000 g/mol) was obtained in the same manner as in Preparation Example 1, except for using.

Preparation Example 3

935 g of distilled water was put into a 3-liter reactor, and 380 g (2.26 mol) of cyclohexyl methacrylate, 95 g (0.95 mol) of methyl methacrylate, and polydimethylsiloxane represented by Formula B (n= 131±5, Mw: 10,000 g/mol) 25 g (0.0025 mol), 12 g of n-dodecylmercaptan as a chain transfer agent, and 1.5 g of azobisdimethylvaleronitrile as an initiator were additionally added, and the mixture was stirred at 500 rpm. . The mixture was reacted at 75 °C for 3 hours to polymerize, and cooled to 30 °C to obtain a bead-type (meth)acrylate-based resin (weight average molecular weight: 16,000 g/mol). Subsequently, the (meth)acrylate-based resin was washed with distilled water three times, dehydrated, and dried in an oven.

[Formula B]

Production Example 4

Cyclohexyl methacrylate 360 g (2.14 mol), methyl methacrylate 90 g (0.90 mol), polydimethylsiloxane represented by Formula B (n = 131 ± 5, Mw: 10,000 g / mol) 50 g (0.005 mol), a bead-type (meth)acrylate-based resin (weight average molecular weight: 16,000 g/mol) was obtained in the same manner as in Preparation Example 3, except that mol) was used.

Comparative Preparation Example 1

A (meth)acrylate-based resin (meth)acrylate-based resin ( Weight average molecular weight: 16,000 g/mol) was obtained. Subsequently, the (meth)acrylate-based resin was washed with distilled water three times, dehydrated, and dried in an oven.

<Examples and Comparative Examples: Preparation of Polymer Resin Compositions and Resin Molded Articles>

Example 1

After mixing 90 parts by weight of a thermoplastic resin (HF380, LG Chem) and 10 parts by weight of the (meth)acrylate-based resin prepared in Preparation Example 1, extruded at a temperature of 240 ° C. in a twin screw extruder (Bautek) to form pellets ( pellet) was obtained. In addition, after setting the temperature of the upper and lower plates to 180 ° C using Carver's 4122 model machine, the pellets were filled in the mold between the upper and lower plates, and a 3 ton force was applied to a resin molded product with a thickness of 3 mm. was manufactured. Layer separation was observed in the prepared resin molded article.

Example 2

After mixing 95 parts by weight of a thermoplastic resin (HF380, LG Chem) and 5 parts by weight of the (meth)acrylate-based resin prepared in Preparation Example 2, a resin molded product having a thickness of 3 mm was prepared in the same manner as in Example 1. . Layer separation was observed in the prepared resin molded article.

Example 3

After mixing 90 parts by weight of a thermoplastic resin (HF380, LG Chem) and 10 parts by weight of the (meth)acrylate-based resin prepared in Preparation Example 3, a resin molded article having a thickness of 3 mm was prepared in the same manner as in Example 1. . Layer separation was observed in the prepared resin molded article.

Example 4

After mixing 95 parts by weight of a thermoplastic resin (HF380, LG Chem) and 5 parts by weight of the (meth)acrylate-based resin prepared in Preparation Example 4, a resin molded article having a thickness of 3 mm was prepared in the same manner as in Example 1. . Layer separation was observed in the prepared resin molded article.

Comparative Example 1

A resin molded article was manufactured in the same manner as in Example 1, except that the (meth)acrylate-based resin prepared in Preparation Example 1 was not included and only a thermoplastic resin (HF380, LG Chem) was used.

Comparative Example 2

A resin molded product was manufactured in the same manner as in Example 1, except that the (meth)acrylate-based resin prepared in Comparative Preparation Example 1 was used instead of the (meth)acrylate-based resin prepared in Preparation Example 1.

Comparative Example 3

A resin molded article was manufactured in the same manner as in Example 2, except that the (meth)acrylate-based resin prepared in Comparative Preparation Example 1 was used instead of the (meth)acrylate-based resin prepared in Preparation Example 2.

<Experimental example>

The physical properties of the polymer resin compositions and resin molded articles obtained in Examples and Comparative Examples were measured in the following manner.

1. Surface water contact angle

The surface water contact angle of the resin molded articles obtained in the above Examples and Comparative Examples was measured using a drop shape analyzer (DSA100 product of KRUSS) based on the Owens-Wendt-Rabel-Kaelble method.

Specifically, by dropping deionized water and hexadecane 10 times each on the surfaces of the resin molded articles obtained in Examples and Comparative Examples, average values of surface water contact angles were obtained and are shown in Table 1 below.

2. Impact strength

1/4" inch specimens were evaluated according to the ASTM D256 test method. At this time, the measurement was measured in a chamber maintaining room temperature (25 ℃), and 1/4" inch specimens were aged for 6 hours in each chamber. After taking out the specimen, it was measured 5 times each according to the ASTM D256 test method, and the average value was obtained.

water contact angle
(°) impact strength
(1/4" inch)
(kJ/m ² ) Example 1 94 9.3 Example 2 97 13.8 Example 3 100 20.2 Example 4 102 23.1 Comparative Example 1 87 28.4 Comparative Example 2 91 4.4 Comparative Example 3 90 5.7

As shown in Table 1, it was confirmed that the polymer resin compositions and resin compositions of Examples had excellent mechanical properties and surface properties, thereby realizing excellent stain resistance and impact resistance.

On the other hand, it was confirmed that the polymer resin composition and the resin composition of Comparative Example had poor mechanical properties or surface properties.

Claims (21)

Including at least two or more different polymer resins,
At least one of the polymer resins includes a (meth)acrylate-based resin containing 1 part by weight or more and 50 parts by weight or less of a repeating unit represented by Formula 1 based on 100 parts by weight of the total repeating unit,
Polymer Resin Composition:
[Formula 1]

In Formula 1,
R ₁ to R ₆ are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms;
L ₁ is a direct bond, an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an oxyalkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 30 carbon atoms, and an oxyarylene group having 6 to 30 carbon atoms. is one,
n is an integer greater than or equal to 50;
According to claim 1,
The (meth) acrylate-based resin has a weight average molecular weight of 5000 g / mol or more and 20000 g / mol or less, a polymeric resin composition.
According to claim 1,
The (meth) acrylate-based resin comprises a repeating unit represented by Formula 2 below, a polymeric resin composition:
[Formula 2]

In Formula 2,
R ₇ is hydrogen or an alkyl group having 1 to 10 carbon atoms;
R ₈ is an alkyl group having 4 to 20 carbon atoms including an alicyclic ring.
According to claim 3,
The (meth) acrylate-based resin comprises 50 parts by weight or more and 99 parts by weight or less of the repeating unit represented by Formula 2 based on 100 parts by weight of the total repeating unit, the polymeric resin composition.
According to claim 3,
The alkyl group having 4 to 20 carbon atoms including the alicyclic ring
A polymeric resin composition comprising a cycloalkyl group having 3 to 20 carbon atoms.
According to claim 1,
The (meth) acrylate-based resin includes a repeating unit represented by Formula 3 below, a polymeric resin composition:
[Formula 3]

In Formula 3,
R ₉ is hydrogen or an alkyl group having 1 to 10 carbon atoms;
R ₁₀ is a straight-chain or branched-chain alkyl group having 1 to 20 carbon atoms.
According to claim 6,
The (meth) acrylate-based resin comprises 5 parts by weight or more and 20 parts by weight or less of the repeating unit represented by Formula 3 based on 100 parts by weight of the total repeating unit, the polymeric resin composition.
According to claim 3,
The (meth) acrylate-based resin comprises 5 parts by weight or more and 20 parts by weight or less of the repeating unit represented by Formula 1 based on 100 parts by weight of the repeating unit represented by Formula 2.
According to claim 5,
The (meth) acrylate-based resin comprises 20 parts by weight or more and 60 parts by weight or less of the repeating unit represented by Formula 1 based on 100 parts by weight of the repeating unit represented by Formula 3.
According to claim 1,
At least one other kind of the polymer resin
Styrene-based resins, polyolefin-based resins, thermoplastic elastomers, polyoxyalkylene-based resins, polyester-based resins, polyvinyl chloride-based resins, polycarbonate-based resins, polyphenylene sulfide-based resins, vinyl alcohol-based resins, acrylate-based resins, A polymer resin composition comprising at least one polymer resin selected from the group consisting of engineering plastics and copolymers thereof.
According to claim 1,
The polymer resin composition comprises 500 parts by weight or more and 3000 parts by weight or less of another type of polymer resin based on 100 parts by weight of the (meth) acrylate-based resin.
Forming a molten mixture by melting the polymer resin composition of claim 1; and
Forming a layer separation structure by processing the molten mixture; manufacturing method of a molded product comprising a.
According to claim 12,
A method of manufacturing a molded article comprising curing the layer separation structure.
According to claim 12,
The melting and processing is a method of manufacturing a molded article performed under shear stress.
According to claim 13,
In the step of curing the layer separation structure, the curing is thermal curing or UV curing,
A method for manufacturing molded articles.
Including at least two or more different polymer resins,
At least one of the polymer resins includes a (meth)acrylate-based resin containing 1 part by weight or more and 50 parts by weight or less of a repeating unit represented by Formula 1 based on 100 parts by weight of total repeating units,
A resin molded article having a polymer layer containing 50% by weight or more of the (meth)acrylate-based resin:
[Formula 1]

In Formula 1,
R ₁ to R ₆ are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms;
L ₁ is a direct bond, an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an oxyalkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 30 carbon atoms, and an oxyarylene group having 6 to 30 carbon atoms. is one,
n is an integer greater than or equal to 50;
According to claim 16,
A resin molded article wherein the polymer layer is located on a surface of the resin molded article.
According to claim 16,
At least one other kind of the polymer resin
Styrene-based resins, polyolefin-based resins, thermoplastic elastomers, polyoxyalkylene-based resins, polyester-based resins, polyvinyl chloride-based resins, polycarbonate-based resins, polyphenylene sulfide-based resins, vinyl alcohol-based resins, acrylate-based resins, A resin molded article comprising at least one polymer resin selected from the group consisting of engineering plastics and copolymers thereof.
According to claim 16,
A resin molded article in which components of a different type of polymer resin layer are detected from the surface of a (meth)acrylate-based resin layer by infrared spectroscopy.
According to claim 16,
A resin molded product having a surface water contact angle at 25°C of 92° or more and 120° or less on the surface of the resin molded product.
According to claim 16,
A resin molded product having an impact strength of 6.0 kJ/m ² or more and 30 kJ/m ² or less at the surface measured at room temperature for a 1/4" inch specimen of the resin molded product.

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