WO2016117844A1

WO2016117844A1 - Acrylic elastomeric resin composition and file prepared using the same

Info

Publication number: WO2016117844A1
Application number: PCT/KR2015/014445
Authority: WO
Inventors: Min Lee; Seung Baik Nam
Original assignee: LG Hausys Ltd
Current assignee: LX Hausys Ltd
Priority date: 2015-01-20
Filing date: 2015-12-29
Publication date: 2016-07-28
Anticipated expiration: 2017-07-20
Also published as: KR101930986B1; EP3247746A4; CN107109025A; EP3247746A1; CN107109025B; KR20160089610A

Abstract

Disclosed is an acrylic elastomeric resin composition and a film prepared using the same. More particularly, disclosed are an acrylic elastomeric resin composition that can decrease deformation of a film, can easily control properties of a film, can enhance processability, is nontoxic and eco-friendly, exhibits superior dimensional stability, etc. due to superior elasticity and flexibility, and exhibits superior adhesion to other synthetic resin films (PVC film, etc.), and a film prepared using the same.

Description

ACRYLIC ELASTOMERIC RESIN COMPOSITION AND FILE PREPARED USING THE SAME

The present invention relates to an acrylic elastomeric resin composition and a film prepared using the same. More particularly, the present invention relates to an acrylic elastomeric resin composition that can decrease deformation of a film, can easily control properties of a film, can enhance processability, is nontoxic and eco-friendly, exhibits superior dimensional stability, etc. due to superior elasticity and flexibility, and exhibits superior adhesion to other synthetic resin films (PVC film, etc.), and a film prepared using the same.

As quality of life increases, interest in eco-friendly products as well as health is increasing. As an example, materials which are eco-friendly and can provide sound insulation are increasingly used as flooring materials closely related to living environment. In addition, regulations on materials, etc. used to produce such flooring materials are being strengthened.

In Korean Patent Application Pub. No. 10-2004-0065494, a PVC material is mainly used as a raw material of a flooring material. In particular, conventional flooring materials comprise a balance layer, a cushion layer, a dimensionally stabilizing layer, a printed layer, a transparent PVC layer and a surface-treated layer which are laminated in this order from a bottom side.

However, since a PVC material is mainly used in conventional flooring materials, a toxic phthalate-based plasticizer is included and thus toxic materials such as environmental hormones and toxic gases (hydrogen chloride) are released upon waste incineration or firing. In addition, the PVC material almost permanently remains in nature upon landfilling, thus causing great environmental burden.

In addition, since the flooring materials include a surface-treated layer on an upper side thereof, they can be protected from scratches and contamination. However, as time passes the surface-treated layer is increasingly worn and thus removed. In this case, a transparent PVC layer (transparent PVC film) laminated under the surface-treated layer is exposed to the outside. When such a transparent PVC layer as a PVC material contact the human body, toxic materials released from the PVC material negatively affect the human body.

In order to address such a problem, attempts to use a film produced using bioresin such as poly lactic acid (PLA) have been made, but, when PLA resin is used alone, there are several disadvantages as follows.

First, when a film is produced using PLA resin, dimensional stability is poor and thus deformation such as contraction, distortion, etc. may be severe. Accordingly, properties of flooring materials including the film might not be proper.

Second, when a film is produced using PLA resin, blocking easily occurs at high temperature such as in the summer and thus films adhere to each other in a rolled state. Accordingly, when flooring materials are produced using the same, productivity may be decreased.

Third, since PLA resin has a narrow process temperature range of 130 to 150℃, processability is low and thus, when a film is produced using the same, productivity may be decreased.

Fourth, as PLA resin has a narrow use temperature range of 20 to 35℃, it is difficult to apply PLA resin to flooring materials. In addition, when a use temperature is 20℃ or less, which is outside this temperature range, PLA resin is excessively hardened. Furthermore, PLA resin is easily destroyed in winter, and elasticity thereof is lost at 35℃ or more, thus tending to be excessively softened. Accordingly, required properties of a film used in flooring materials are rapidly decreased and thus functions as flooring materials may be lost.

Therefore, there is an urgent need for a resin composition having excellent processability and a film, which is nontoxic upon preparation of the film and eco-friendly and has superior dimensional stability, etc., prepared using the resin.

〔Related Art Document〕

〔Patent Document〕

(Patent Document 1) KR 10-2004-0065494 A (published on 22 July 2004)

Therefore, the present invention has been made in view of the above problems, and it is one object of the present invention to provide an acrylic elastomeric resin composition that exhibits less film deformation, enables film properties to be easily controlled, can enhance processability, are nontoxic and eco-friendly, has superior dimensional stability due to superior elasticity and flexibility, and superior adhesion to other synthetic resin films (PVC film, etc.), and a film prepared using the same.

In accordance with one aspect of the present invention, provided is an acrylic elastomeric resin composition comprising an acrylic elastomeric resin as a copolymer of a polymer of an alkyl methacrylate monomer composing a hard segment and a polymer of an alkyl acrylate monomer composing a soft segment.

In accordance with another aspect of the present invention, provided is a film prepared using the acrylic elastomeric resin composition.

As apparent from the fore-going, the present invention advantageously provides an acrylic elastomeric resin composition using an acrylic elastomeric resin having elasticity and thus exhibiting less film deformation.

In addition, the acrylic elastomeric resin composition according to the present invention is prepared by controlling a ratio between alkyl methacrylate and an alkyl acrylate monomer composing the acrylic elastomeric resin and thus film properties may be controlled.

In addition, the acrylic elastomeric resin composition according to the present invention exhibits increased processability upon calendar-molding, casting-molding, blow-molding, T-die extrusion-molding, etc. due to a wide process temperature range of the acrylic elastomeric resin.

In addition, the acrylic elastomeric resin composition according to the present invention does not require use of toxic phthalate-based plasticizers, has high fluidity due to low melt viscosity of the acrylic elastomeric resin, and emits volatile organic compounds, which may be included in the composition, in a small amount due to low solution viscosity.

Furthermore, the acrylic elastomeric resin composition according to the present invention exhibits superior adhesion to other synthetic resin films (PVC film, etc.) when used as a flooring material after being prepared into a film, due to superior compatibility and adhesive properties of the acrylic elastomeric resin with a polar resin.

Accordingly, a film prepared using the acrylic elastomeric resin composition according to the present invention having the effects described above is nontoxic and eco-friendly, has superior dimensional stability, etc. due to the superior elasticity and flexibility, and has superior adhesion to other synthetic resin films (PVC film, etc.).

The present invention relates to an acrylic elastomeric resin composition which exhibits less film deformation when prepared into a film, enables film properties to be easily controlled, can enhance processability, is nontoxic and eco-friendly, has superior dimensional stability, etc. due to the superior elasticity and flexibility, and has superior adhesion to other synthetic resin films(PVC films, etc.).

In regard to the acrylic elastomeric resin composition according to the present invention, an acrylic elastomeric resin may be a copolymer of a polymer of an alkyl methacrylate monomer composing a hard segment and a polymer of an alkyl acrylate monomer composing a soft segment. Here, the copolymer may be a core-shell-structure copolymer or a block copolymer.

The core-shell-structure copolymer has a bonding structure including a soft segment as a core and a hard segment as a shell enveloping the core.

In order to prepare the core-shell-structure copolymer, the core comprising the soft segment is prepared and then the shell including the hard segment and enveloping the core is prepared. The core and the shell may be prepared through emulsion polymerization or suspension polymerization. Preferably, suspension polymerization, permitting easy polymer separation or processing, is used.

In addition, the block copolymer may be composed of a soft segment and a hard segment, and may be a dicopolymer represented by soft-hard segments, a triblock copolymer represented by hard-soft-hard segments, or a triblock copolymer represented by soft-hard-hard segments. As the block copolymer, the triblock copolymer represented by the hard-soft-hard segments is preferred since it may enhance low-temperature impact resistance, heat resistance, etc.

The alkyl methacrylate monomer composing the hard segment may be one or more selected from the group consisting of methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxy ethyl methacrylate, 2-hydroxyethyl methacrylate, 2-methoxyethyl methacrylate, glycidyl methacrylate, and allyl methacrylate. When properties such as heat resistance are considered, the alkyl methacrylate monomer composing the hard segment is preferably one or two selected from the group consisting of methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, and isobornyl methacrylate, more preferably methyl methacrylate.

The alkyl acrylate monomer composing the soft segment may be one or more selected from the group consisting of methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, isobornyl acrylate, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-methoxyethyl acrylate, glycidyl acrylate, and allyl acrylate. When flexibility is considered, the alkyl acrylate monomer composing the soft segment is preferably one or two selected from ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and dodecyl acrylate, more preferably n-butyl acrylate.

So as to prepare the block copolymer, a method of living-polymerization of a monomer constituting each block is used. Examples of such living-polymerization include a method of polymerizing anions in the presence of a mine salt such as a salt of alkali metal or alkali earth metal, using an organic alkali metal compound as a polymerization initiator, a method of polymerizing anions in the presence of an organic aluminum compound using an organic alkali metal compound as a polymerization initiator, a method of polymerizing using an organic rear earth metal complex as a polymerization initiator, a method of radical-polymerizing in the presence of a copper compound using an α-halo ester compound as an initiator, etc. Alternatively, a method of polymerizing a monomer constituting each block using a polyvalent radical polymerization initiator or a polyvalent radical as a chain-transfer agent to prepare a mixture containing a block copolymer, etc. may be used. Preferably, a method of polymerizing anions in the presence of an organic aluminum compound using an organic alkali metal compound as a polymerization initiator, without an oligomer, which has a narrow molecular weight distribution and deteriorates impact resistance and heat resistance to obtain a high-purity block copolymer, or a substance having high molecular weight is used. Representative examples of the organic aluminum compound include isobutylbis(2,6-di-t-butyl-4-methylphenoxy) aluminum, isobutylbis(2,6-di-t-butyl phenoxy) aluminum, isobutylbis［2,2＇-methylenebis(4-methyl-6-t-butyl phenoxy)］aluminum, n-octylbis(2,6-di-t-butyl-4-methylphenoxy)aluminum, n-octylbis(2,6-di-t-butylphenoxy) aluminum, n-octylbis［2,2＇-methylenebis(4-methyl-6-t-butylphenoxy)］aluminum, tris(2,6-di-t-butyl-4-methylphenoxy)aluminum, tris(2,6-diphenylphenoxy) aluminum, etc. Thereamong, in regard to polymerization activation, block efficiency, etc., isobutylbis(2,6-di-t-butyl-4-methylphenoxy)aluminum, isobutylbis(2,4-di-t-butylphenoxy)aluminum, n-octylbis(2,6-di-t-butyl-4-methylphenoxy)aluminum or n-octylbis(2,4-di-t-butylphenoxy) aluminum is preferred.

Here, the copolymer preferably includes 20 to 90% by weight of the hard segment and 10 to 80% by weight of the soft segment. In this case, when the copolymer is used as a film applied to flooring materials, proper mechanical properties, particularly wear resistance, etc. may be provided.

Particularly, the hard segment may have a glass transition temperature of 80 to 120℃, and the soft segment may have a glass transition temperature of -60 to -20℃.

The hard segment and the soft segment may include, other than the monomers described above, structural units derived from other monomers within the range in which characteristics of each segment are not damaged (generally in a ratio of 40 mol% or less based on the total of structural units composing the polymer segments).

The structural units are not specifically limited, and examples thereof include structural units derived from unsaturated carboxylic acids such as methacrylic acid, acrylic acid, and maleic anhydride; olefins such as ethylene, propylene, 1-butene, isobutylene, and 1-octene; conjugated diene compounds such as 1,3-butadiene, isoprene and myrcene; aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene, and m-methylstyrene; vinyl acetate; vinylpyridine; unsaturated nitriles such as acrylonitrile and methacrylonitrile; vinyl ketones; halogen-containing monomers such as vinyl chloride, vinylidene chloride, and vinylidene fluoride; unsaturated amides such as acrylamide and methacrylamide; or the like. The hard segment and the soft segment may have one or more structural units derived from one or more of these monomers.

The molecular weight of each of the segments in the acrylic elastomeric resin and the total molecular weight of the acrylic elastomeric resin are not specifically limited. However, when molding characteristics and mechanical properties are considered, the weight-average molecular weight of the hard segment is 1,000 to 400,000, preferably 3,000 to 100,000, the weight-average molecular weight of the soft segment is 2,000 to 400,000, preferably 10,000 to 300,000, and the total weight-average molecular weight of the acrylic elastomeric resin is 5,000 to 500,000, preferably 20,000 to 300,000.

Although a film may be prepared using only the acrylic elastomeric resin, other relatively cheap resins may be mixed with the acrylic elastomeric resin, within the range in which properties of the film are not greatly affected, due to high cost of the acrylic elastomeric resin.

In the present invention, the acrylic elastomeric resin composition may selectively comprise a biodegradable PLA resin.

In this case, a mixed resin comprising the acrylic elastomeric resin and the PLA resin may include 10 to 99% by weight of the acrylic elastomeric resin and 1 to 90% by weight of the PLA resin, preferably 20 to 95% by weight of the acrylic elastomeric resin and 5 to 80% by weight of the PLA resin, more preferably 30 to 90% by weight of the acrylic elastomeric resin and 10 to 70% by weight of the PLA resin, most preferably 30 to 70% by weight of the acrylic elastomeric resin and 30 to 70% by weight of the PLA resin. When a mixture of the acrylic elastomeric resin and the PLA resin is used, elasticity, flexibility and sound insulation are provided, compared to the case in which the PLA resin is used alone. In addition, when compared to the case in which the acrylic elastomeric resin is used alone, unit costs are reduced and biodegradability is increased.

In addition, when the content of the acrylic elastomeric resin is below the range, drawbacks of a film due to application of the PLA resin, i.e., low dimensional stability, blocking at high temperature, a narrow process temperature range, and a use temperature range might not be sufficiently addressed. In addition, when the content of the PLA resin is above the range, a product to which the PLA resin is applied may be damaged when bent due to flexibility deficiency as a characteristic of the PLA resin.

Accordingly, when the resins are used within the ranges, a film providing superior elasticity, flexibility and sound insulation, and being useful in particularly preparing flooring materials may be obtained.

In addition, in the present invention, the acrylic elastomeric resin composition may selectively include a biodegradable PHA resin.

The PHA resin may be a single polymer including a repeat unit represented by Formula 1 below. Preferably, the PHA resin is a copolymer of a hard segment and a soft segment, wherein the hard segment includes the repeat unit represented by Formula 1 below and the soft segment includes a repeat unit represented by Formula 2 below.

[Formula 1]

wherein R₁ is hydrogen or substituted or unsubstituted C₁ to C₁₅ alkyl and n is an integer of 1 to 3.

[Formula 2]

wherein R₂ is hydrogen or substituted or unsubstituted C₁ to C₁₅ alkyl and m is an integer of 1 to 3.

In the polymer including the repeat unit represented by Formula 1 constituting the hard segment, R₁may be hydrogen or substituted or unsubstituted C₁ to C₁₅ alkyl, and n may be an integer of 1 to 3. Preferably, R₁ is C₁ to C₉ alkyl and n is an integer of 1 or 2. More preferably, R₁is methyl and n=1.

In the polymer including the repeat unit represented by Formula 2 constituting the soft segment, R₂ may be hydrogen or substituted or unsubstituted C₁ to C₁₅ alkyl and m may be an integer of 1 to 3. Preferably, R₂ is hydrogen or substituted or unsubstituted C₁ to C₉ alkyl and m is an integer of 1 or 2. More preferably, R₂ is hydrogen or C₁ to C₃ alkyl and m is an integer of 1 or 2.

The PHA resin includes 50 to 99% by weight of the hard segment and 1 to 50% by weight of the soft segment, preferably 50 to 90% by weight of the hard segment and 10 to 50% by weight of the soft segment, more preferably 60 to 90% by weight of the hard segment and 10 to 40% by weight of the soft segment. When the content of the hard segment is above this range, the resin becomes hard and thus it is difficult to perform processing. When the content of the soft segment is above this range, the resin becomes too flexible, whereby viscosity is decreased during processing and releasability is decreased. Therefore, it is preferable to use the PHA resin within the range.

When the PHA resin is included in the acrylic elastomeric resin composition, a mixed resin composed of the PHA resin and the acrylic elastomeric resin includes 10 to 90% by weight of the PHA resin and 10 to 90% by weight of the acrylic elastomeric resin, preferably 30 to 70% by weight of the PHA resin and 30 to 70% by weight of the acrylic elastomeric resin.

When the content of the acrylic elastomeric resin is below the range, flexibility of the film is decreased. In addition, when the content of the PHA resin is below the range, biodegradability is decreased. When the content of the PHA resin is above the range, properties are decreased due to thermal decomposition during processing. More particularly, proper extrusion- or calendar-processing temperature of the acrylic elastomeric resin is 160 to 180℃. In the case of the PHA resin, the temperature is 120 to 140℃. When the two materials are mixed, the content of the acrylic elastomeric resin is greater than the-above range and thus the content of the PHA resin is relatively decreased. Accordingly, biodegradability of a film is decreased. When the content of the acrylic elastomeric resin is smaller than the-above range, the content of the PHA resin is relatively increased and thus properties are deteriorated due to thermal decomposition of the PHA resin during extrusion-processing or calendar-processing into a film. Therefore, the acrylic elastomeric resin and the PHA resin are preferably used within the above ranges.

In addition, in the present invention, the acrylic elastomeric resin composition may selectively include all of a PLA resin as biodegradable resin and the PHA resin.

In this case, the mixed resin including the PHA resin, the PLA resin and the acrylic elastomeric resin may include 10 to 50% by weight of the PHA resin, 20 to 80% by weight of the acrylic elastomeric resin and 10 to 50% by weight of the PLA resin, preferably 10 to 30% by weight of the PHA resin, 30 to 60% by weight of the acrylic elastomeric resin, and 10 to 40% by weight of the PLA resin.

In addition, the acrylic elastomeric resin composition according to the present invention may further include 1 to 5 parts by weight of a lubricant based on 100 parts by weight of a mixed resin composed of the acrylic elastomeric resin or the PLA resin and/or the PHA resin. As the lubricant, hydrocarbon-based wax or commonly used high-quality fatty acids used in preparing flooring materials may be used.

The acrylic elastomeric resin composition does not contain low-molecular weight materials such as monomer remainders or oligomers and does not include a plasticizer.

Since the acrylic elastomeric resin composition according to the present invention uses the acrylic elastomeric resin having elasticity, less film deformation is exhibited.

In addition, the acrylic elastomeric resin composition according to the present invention may control film properties by adjusting a ratio between the alkyl methacrylate and alkyl acrylate monomers composing the acrylic elastomeric resin.

In addition, due to a broad process temperature range of the acrylic elastomeric resin, the acrylic elastomeric resin composition according to the present invention exhibits enhanced processability when prepared through calendar-molding, cast-molding, blow-molding, T-die extrusion-molding, etc.

In addition, the acrylic elastomeric resin composition according to the present invention does not require a toxic phthalate-based plasticizer and has high fluidity due to low melt viscosity of the acrylic elastomeric resin. In addition, due to low viscosity of a solution including the composition, volatile organic compounds that may be included in the composition are less emitted.

In addition, since the acrylic elastomeric resin of the acrylic elastomeric resin composition according to the present invention has superior compatibility and adhesive properties to a polar resin, the acrylic elastomeric resin composition exhibits superior adhesion to other synthetic resin films (PVC film, etc.) when used as a flooring material after being prepared into a film.

In addition, the present invention provides a film prepared using the acrylic elastomeric resin composition. To prepare the film, calendar-molding, cast-molding, blow-molding, extrusion-molding, etc. may be used.

The calendar-molding is a method of rolling a raw material between two or more rolls rotating in opposite directions to continuously prepare a sheet or a film. The casting molding is a method of laminating after coating a synthetic resin sol, into multiple layers, on release paper that is easily peeled and has superior heat resistance. The blow molding is a method of inserting a parison, which is prepared by continuously extruding a heated and melted thermoplastic resin into a tube shape by means of an extruder, to at least one mold and then closing and sealing the same, followed by swelling the parison by blowing air into the parison in a mandrel, thus adhering the parison to an inner wall of the mold to produce a hollow container. Extrusion-molding is a method of preparing a thermoplastic plastic material into a fluid state by heating and melting the thermoplastic plastic material on a surface of a base by means of an extruder and then continuously compressing the same into a film state using a T-die.

Preferably, the calendar-molding is used since it allows free control of the contents of ingredients such as additives, compared to other methods, and thus, a flooring material having superior flexibility, impact resistance, mechanical strength, processability, fitness and melting efficiency may be provided. Furthermore, raw material costs may be reduced. Therefore, the film is preferably prepared using the calender molding.

The thickness of the film may be 0.1 to 1.0 mm.

Particularly, the film may be transparent. Based on the fact that the acrylic elastomeric resin may be prepared to be transparent, a transparent elastic layer may provide an aesthetically pleasing flooring material, due to a printed layer, etc. under the transparent elastic layer when the transparent elastic layer is disposed on a printed layer of the flooring material. In addition, the film may provide durability to the flooring material and protect the printed layer under the transparent elastic layer.

Accordingly, the film prepared using the acrylic elastomeric resin composition according to the present invention is nontoxic and eco-friendly, exhibits superior dimensional stability, etc. due to superior elasticity and flexibility, and exhibits superior adhesion to other synthetic resin films (PVC film, etc.).

Now, the present invention will be described in more detail with reference to the following examples. These examples are provided only for illustration of the present invention and should not be construed as limiting the scope and spirit of the present invention.

[Example]

Example 1

1 part by weight of PE wax as a lubricant was mixed with an acrylic elastomeric resin, based on 100 parts by weight of the acrylic elastomeric resin, followed by calender-molding. As a result, a transparent film having a thickness of 0.2 mm was prepared.

A block copolymer was prepared using 40% by weight of methyl methacrylate(MMA), 20% by weight of n-butyl acrylate(BA), and 40% by weight of methacrylonitrile as monomers composing the acrylic elastomeric resin. So as to increase low-temperature impact resistance, heat resistance, etc., living polymerization as a copolymerization method was performed such that polymethyl methacrylate was bonded to both ends of poly n-butyl acrylate. In addition, a structural unit of methacrylonitrile was included upon polymerization of each block.

Example 2

1 parts by weight of PE wax as a lubricant was mixed with a mixed resin based on 100 parts by weight of the mixed resin including 40% by weight of PLA resin and 60% by weight of acrylic elastomeric resin. After mixing, calendar-molding was performed to prepare a transparent film having a thickness of 0.2 mm. 70% by weight of methyl methacrylate (MMA) and 30% by weight of n-butyl acrylate (BA) were used as monomers composing the acrylic elastomeric resin to prepare a block copolymer. Living polymerization as a copolymerization method was used such that polymethyl methacrylate was bonded to both ends of poly n-butyl acrylate, so as to enhance low-temperature impact resistance, heat resistance, etc.

Example 3

1 part by weight of PE wax as a lubricant was mixed with a mixed resin based on 100 parts by weight of the mixed resin composed of 40% by weight of PLA resin and 60% by weight of acrylic elastomeric resin. After mixing, calendar-molding was performed to prepare a transparent film having a thickness of 0.2 mm.

40% by weight of methyl methacrylate (MMA), 20% by weight of n-butyl acrylate (BA), and 40% by weight of methacrylonitrile were used as monomers composing the acrylic elastomeric resin to prepare a block copolymer. So as to increase low-temperature impact resistance, heat resistance, etc., living polymerization as a copolymerization method was performed such that polymethyl methacrylate was bonded to both ends of poly n-butyl acrylate. In addition, a structural unit of methacrylonitrile was included upon polymerization of each block.

[Comparative Example]

Comparative Example 1

A transparent PVC film (transparent film having thickness of 0.2 mm used as skin layer, manufactured by LG Hausys) having a thickness of 0.2 mm was used.

Comparative Example 2

1 part by weight of PE wax as a lubricant was mixed with a PLA resin based on 100 parts by weight of the PLA resin, followed by calendar-molding. As a result, transparent film having a thickness of 0.2 mm was prepared.

Comparative Example 3

1 part by weight of PE wax as a lubricant was mixed with an acrylic elastomeric resin based on 100 parts by weight of the acrylic elastomeric resin, followed by calendaring. As a result, a transparent film having a thickness of 0.2 mm was prepared. 100% by weight of methyl methacrylate (MMA) was used as a monomer composing the acrylic elastomeric resin to prepare a polymer.

Experimental Example

Using films prepared according to Examples 1 to 3 and Comparative Examples 1 to 3, emission amounts of TVOCs (total volatile organic compounds) were compared. Results are summarized in Table 1 below.

TVOC emission amounts were measured according to Notification No. 2010-24 of the Ministry of Environment, a small chamber method as a standard for an　indoor air quality test method. Particularly, a film specimen as a test material was fed into a small chamber having a volume of 20 L connected to a mass spectrometer/high-performance liquid chromatograph (MS/HPLC), and TVOC released from the specimen was collected in the small chamber. The collected TVOC was directly introduced into the mass spectrometer/high-performance liquid chromatograph to measure TVOC in the introduced air. In addition, under another test condition, i.e., a real life environment in which flooring materials including the films were applied and an ambient temperature was about 25℃, the specimens prepared according to Examples and Comparative Examples were tested for the same time and at the same temperature, so as to objectively compare TVOC emission amounts under the same conditions.

In addition, whitening degrees and adhesion of the films according to Examples 1 to 3 and Comparative Examples 1 and 2 were compared. Results are summarized in Table 1 below.

The whitening degrees were observed by bending the films 180 degrees at room temperature.

Adhesion was measured according to a 180-degree peel test as an ASTM D903 standard (sample size: width (W): 20 mm, length (H): 140 mm, device: 50 kN universal testing machine available from TA Instruments, and speed: 200 mm/min).

Classification	Used resin	TVOC (㎎/㎡ㆍh)	Whitening	Adhesion (kgf)
Comparative Example 1	PVC alone	0.298	X	5 or more
Comparative Example 2	PLA alone	0.008	O	0.54
Comparative Example3	Acrylic elastomeric resin alone(MMA 100% by weight)	0.018	O	2.19
Example 1	Acrylic elastomeric resin alone (40% by weight of MMA + 20% by weight of BA + 40% by weight of methacrylonitrile)	0.011	X	2.28
Example 2	PLA + Acrylic elastomeric resin (70% by weight of MMA + 30% by weight of BA)	0.028	X	1.80
Example 3	PLA + Acrylic elastomeric resin (40% by weight of MMA + 20% by weight of BA + 40% by weight of methacrylonitrile)	0.013	X	2.30

As shown in Table 1, it can be confirmed that the total volatile organic compound emission amount of each of the films (Examples 1 to 3) according to the present invention is reduced, compared to the conventional transparent PVC film (Comparative Examples 1). In addition, in the cases that the acrylic elastomeric resin is used as a mixture (Examples 2 and 3) or the acrylic elastomeric resin is used alone (Comparative Example 3 and Example 1), superior adhesion is exhibited, compared to the case that the PLA resin is used alone (Comparative Example 2). In addition, it can be confirmed that, when the PLA resin is used alone (Comparative Example 2) or the acrylic elastomeric resin composed of the alkyl methacrylate monomer is used alone (Comparative Example 3), whitening occurs.

Accordingly, through the experimental results, it can be confirmed that the film prepared using the acrylic elastomeric resin composition according to the present invention is nontoxic and eco-friendly, has superior elasticity and flexibility, and exhibits superior adhesion to other synthetic resin films (PVC film, etc.).

Claims

An acrylic elastomeric resin composition comprising an acrylic elastomeric resin as a copolymer of a polymer of an alkyl methacrylate monomer composing a hard segment and a polymer of an alkyl acrylate monomer composing a soft segment.
The acrylic elastomeric resin composition according to claim 1, wherein the copolymer is a core-shell-structure copolymer or a block copolymer.
The acrylic elastomeric resin composition according to claim 2, wherein the core-shell-structure copolymer is a copolymer of a core comprising a soft segment and a shell structure comprising a hard segment enveloping the core.
The acrylic elastomeric resin composition according to claim 2, wherein the block copolymer is composed of a soft segment and a hard segment and any one selected from a dicopolymer represented by soft-hard segments, a triblock copolymer represented by hard-soft-hard segments, and a triblock copolymer represented by soft-hard-hard segments.
The acrylic elastomeric resin composition according to claim 4, wherein the block copolymer is the triblock copolymer represented by the hard-soft-hard segments.
The acrylic elastomeric resin composition according to claim 1, wherein the alkyl methacrylate monomer composing the hard segment is one or more selected from the group consisting of methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxy ethyl methacrylate, 2-hydroxyethyl methacrylate, 2-methoxyethyl methacrylate, glycidyl methacrylate, and allyl methacrylate.
The acrylic elastomeric resin composition according to claim 6, wherein the alkyl methacrylate monomer composing the hard segment is one or two selected from the group consisting of methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, and isobornyl methacrylate.
The acrylic elastomeric resin composition according to claim 1, wherein the alkyl acrylate monomer composing the soft segment is one or more selected from the group consisting of methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, isobornyl acrylate, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-methoxyethyl acrylate, glycidyl acrylate, and allyl acrylate.
The acrylic elastomeric resin composition according to claim 1, wherein the copolymer comprises 20 to 90% by weight of the hard segment and 10 to 80% by weight of the soft segment.
The acrylic elastomeric resin composition according to claim 1, wherein the hard segment has a glass transition temperature of 80 to 120℃, and the soft segment has a glass transition temperature of -60 to -20℃.
The acrylic elastomeric resin composition according to claim 1, wherein the hard segment and the soft segment further comprise a structural unit derived from unsaturated carboxylic acids such as methacrylic acid, acrylic acid, and maleic anhydride; olefins such as ethylene, propylene, 1-butene, isobutylene, and 1-octene; conjugated diene compounds such as 1,3-butadiene, isoprene and myrcene; aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene, and m-methylstyrene; vinyl acetate; vinylpyridine; unsaturated nitriles such as acrylonitrile and methacrylonitrile; vinyl ketones; halogen-containing monomers such as vinyl chloride, vinylidene chloride, and vinylidene fluoride; unsaturated amides such as acrylamide and methacrylamide; or the like.
The acrylic elastomeric resin composition according to claim 1, wherein a weight-average molecular weight of the hard segment is 1,000 to 400,000, a weight-average molecular weight of the soft segment is 2,000 to 400,000, and a total weight-average molecular weight of the acrylic elastomeric resin is 5,000 to 500,000.
The acrylic elastomeric resin composition according to claim 1, wherein the acrylic elastomeric resin composition further comprises a PLA resin.
The acrylic elastomeric resin composition according to claim 13, wherein the acrylic elastomeric resin and the PLA resin are mixed to form a mixed resin, wherein the mixed resin comprises 10 to 99% by weight of the acrylic elastomeric resin and 1 to 90% by weight of the PLA resin.
The acrylic elastomeric resin composition according to claim 1, wherein the acrylic elastomeric resin composition further comprises a PHA resin.
The acrylic elastomeric resin composition according to claim 15, wherein the PHA resin is a copolymer of a hard segment and a soft segment, wherein the hard segment comprises a repeat unit represented by Formula 1 below and the soft segment comprises a repeat unit represented by Formula 2 below:

[Formula 1]

wherein R₁ is hydrogen or substituted or unsubstituted C₁ to C₁₅ alkyl and n is an integer of 1 to 3.

[Formula 2]

wherein R₂ is hydrogen or substituted or unsubstituted C₁ to C₁₅ alkyl, and m is an integer of 1 to 3.
The acrylic elastomeric resin composition according to claim 16, wherein, in Formula 1, R₁ is methyl and n=1, and, in Formula 2, R₂ is hydrogen and m=2.
The acrylic elastomeric resin composition according to claim 16, wherein, in Formula 1, R₁ is methyl and n=1, and, in Formula 2, R₂ is ethyl and m=1.
The acrylic elastomeric resin composition according to claim 16, wherein, in Formula 1, R₁ is methyl and n=1, and, in Formula 2, R₂ is methyl and m=2.
The acrylic elastomeric resin composition according to claim 16, wherein, in Formula 1, R₁ is methyl and n=1, and, in Formula 2, R₂ is propyl and m=1.
The acrylic elastomeric resin composition according to claim 16, wherein the PHA resin comprises 50 to 99% by weight of the hard segment and 1 to 50% by weight of the soft segment.
The acrylic elastomeric resin composition according to claim 15, wherein the PHA resin and the acrylic elastomeric resin are mixed to form a mixed resin, wherein the mixed resin comprises 10 to 90% by weight of the PHA resin and 10 to 90% by weight of the acrylic elastomeric resin.
The acrylic elastomeric resin composition according to claim 1, wherein the acrylic elastomeric resin composition comprises a PLA resin and a PHA resin.
The acrylic elastomeric resin composition according to claim 23, wherein the PHA resin, the PLA resin and the acrylic elastomeric resin are mixed to form a mixed resin, wherein the mixed resin comprises 10 to 50% by weight of the PHA resin, 20 to 80% by weight of the acrylic elastomeric resin, and 10 to 50% by weight of the PLA resin.
The acrylic elastomeric resin composition according to claim 1, wherein a lubricant is further comprised in an amount of 1 to 5 parts by weight based on 100 parts by weight of the acrylic elastomeric resin.
A film prepared using the acrylic elastomeric resin composition according to any one of claims 1 to 25.
The film according to claim 26, wherein a thickness of the film is 0.1 to 1.0 mm.