KR20150120810A - A resin composition comprising polylactide resin and polyhydroxyalkanoate resin, a film and a floor material prepared by using the resin composition - Google Patents

Abstract

The present invention relates to a resin composition comprising a polylactide resin and a polyhydroxyalkanoate resin, a film manufactured by using the same, and flooring manufactured by stacking the film on the upper surface of a basic material for flooring. The resin composition has an effect of enhancing processability and brittleness by mixing the polyhydroxyalkanoate resin, which has excellent elasticity and ductility, with the polylactide resin at a fixed ratio. In addition, when the resin composition of the present invention is used, the film can be easily manufactured by calendar molding, and the manufactured films do not adhere to each other even by high temperatures in the summer season, thereby being easy to use after storage. In addition, when the film manufactured by the resin composition of the present invention is used as the upper surface of the flooring, various kinds of harmful substances, which are released to a basic material layer in the case of using a PVC sheet as the basic material layer of the flooring, can be blocked. Since a user touches the film even if a surface protective layer of a top layer of the flooring is worn down, the flooring of the present invention is very eco-friendly.

Description

A resin composition comprising a polylactide resin and a polyhydroxyalkanoate resin, and a film and a bottom material prepared by using the resin composition and a polylactide alkanoate resin, a film and a floor material prepared by using the resin composition,

The present invention relates to a composition comprising a polylactide resin and a polyhydroxyalkanoate resin, a film produced using the composition, and a flooring material produced by laminating the film on a top surface of a base material layer for flooring will be.

BACKGROUND OF THE INVENTION Flooring materials produced by applying a petroleum resin such as polyvinyl chloride (PVC) to a method such as a calender are widely used in buildings such as houses, mansions, apartments, offices, and shops.

However, since the polyvinyl chloride flooring is manufactured from fossil energy resources that can not be regenerated, it is expected that difficulty in supplying and supplying the raw materials due to depletion of resources and a continuous increase in price are expected.

Flooring materials made from fossil raw materials such as polyvinyl chloride also emit large amounts of greenhouse gases (eg, CO ₂ ) during the manufacturing process. In addition, polyvinyl chloride flooring contains poisonous plasticizers such as dioctyl phthalate (DOP), etc., and releases harmful substances such as environmental hormones and toxic gas when incinerated waste or fire occurs. There is a problem that it causes a large environmental burden.

Accordingly, a method for forming a flooring material using polylactic acid which is a biodegradable resin is disclosed in Korean Patent Laid-Open Publication No. 10-2012-0127115.

  However, since polylactic acid has poor physical properties such as impact resistance, melting efficiency, melt strength and heat resistance, it is difficult to apply the calendering method, and therefore, most of the polylactic acid is produced by a press or extrusion method. However, a flooring material produced by applying polylactic acid to a press or an extrusion method has poor physical properties such as flexibility and has a disadvantage in terms of reduction of production cost.

In addition, the use of polylactic acid alone is very sensitive to heat, which causes deformation such as shrinkage and distortion, which is unsuitable for flooring.

On the other hand, there may be a method of producing a floor material by laminating a film made of poly (lactic acid) on the surface of the base layer. However, there is still a problem as described above. The film produced by using poly (lactic acid) There is a problem in that it is difficult to store.

(KR) 10-2012-0127115 (Nov 21, 2012)

In order to solve the above problems, the present invention provides a resin composition improved in workability and brittleness by using a polyhydroxyalkanoate resin having excellent elasticity and ductility characteristics mixed with polylactide resin at a certain ratio, It is an object of the present invention to provide a manufactured film and a flooring material.

In order to achieve the above object, the present invention provides a resin composition comprising a polylactide resin and a polyhydroxyalkanoate resin.

The present invention also provides a film produced using the resin composition.

In addition, the present invention provides a flooring produced by laminating the film on the top surface of a base layer.

The resin composition of the present invention has an effect of improving workability and brittleness by mixing a polyhydroxyalkanoate resin having excellent elasticity and ductility characteristics with polylactide resin at a certain ratio.

Further, when the resin composition of the present invention is used, it is easy to produce a film by calender molding, and the produced films are not adhered to each other even at a high temperature in summer, so that they are easy to use after storage.

In addition, when a film produced using the resin composition of the present invention is used as a top surface of a bottom material, when a PVC sheet is used as a bottom material layer, various harmful substances emitted therefrom can be blocked. Even if the layer is worn, the user is brought into contact with the film of the present invention, which is very eco-friendly.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an exemplary view showing a cross section of one embodiment of the flooring material of the present invention. Fig.

The present invention relates to a resin composition comprising a polylactide resin and a polyhydroxyalkanoate resin.

In the present invention, the polylactide resin is a resin containing a repeating unit represented by the following general formula (1).

[Formula 1]

Since the polylactide resin is biomass-based, unlike conventional petroleum-based resins, it is possible to utilize recycled resources, and the production of carbon dioxide, which is the main cause of global warming, And is environmentally friendly, such as biodegradation by water and microorganisms during landfilling.

The polylactide resin used in the present invention may be prepared by direct polycondensation of lactic acid or by ring-opening polymerization of lactide monomer under an organometallic catalyst, but is not necessarily limited thereto. Although the method of directly synthesizing the lactic acid by the axial condensation is inexpensive, it is difficult to obtain a polymer having a high molecular weight of 100,000 or more and a weight average molecular weight of 100,000 or more. Therefore, it is difficult to sufficiently secure the physical and mechanical properties of the polylactide resin, It is preferable to use those produced by a ring-opening polymerization method of a lactide monomer.

The polylactide resin preferably has a weight average molecular weight of 100,000 to 1,000,000. If it is outside the above range, the mechanical strength and heat resistance of the molded article are lowered than in the above range, which is not preferable.

Since the polylactide resin has a narrow working temperature range (130 to 150 ° C) and is difficult to process and has a narrow use temperature range (20 to 35 ° C), it is difficult to apply the polylactide resin to a floor material . Further, the polylactide resin has a brittleness property and has a property that the film becomes hard when the use temperature range is 20 ° C or lower, so that it tends to be easily cracked and broken when the film is impacted in winter, When the temperature is higher than 35 DEG C, the film tends to lose its elasticity and to become streaky.

Therefore, in the present invention, the polylactide resin is mixed with a polyhydroxyalkanoate resin having excellent elasticity and ductility characteristics.

In the present invention, the polyhydroxyalkanoate resin is an aliphatic polyester containing a repeating unit represented by the following general formula (2).

[Formula 2]

(In the general formula 2, R ₁ is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, and n is an integer of 1 or 2.)

Specifically, the polyhydroxyalkanoate resin may be composed of a homopolymer or a copolymer of a hydroxyalkanoate monomer. Specific examples of the hydroxyalkanoate monomer include 3-hydroxybutyrate in which n is 1 and R ₁ is a methyl group in the above formula (1), 3-hydroxybutyrate wherein n is 1 and R ₁ is an ethyl group, 3-hydroxy valerate, 3-hydroxy hexanoate wherein n is 1 and R ₁ is a propyl group, 3-hydroxy octanoate in which n is 1 and R ₁ is pentyl group, 3- hydroxy octanoate, 3-hydroxy octadecanoate wherein n is 1 and R ₁ is an alkyl group having a carbon number of 15, and 3-hydroxy butyrate or 3- 3-hydroxy valerate may preferably be used.

The mixing ratio of the polylactide resin and the polyhydroxyalkanoate resin is preferably 8: 2 to 6: 4. For example, 60 to 80 parts by weight of a polylactide resin and 20 to 40 parts by weight of a polyhydroxyalkanoate resin based on 100 parts by weight of the mixed resin.

When the content of the polyhydroxyalkanoate resin is less than 20 parts by weight based on 100 parts by weight of the mixed resin, the effect of improving the elasticity and ductility characteristics of the polylactide resin is insufficient. When the content of the polyhydroxyalkanoate resin is more than 40 parts by weight, And the physical properties of the molded product may be deteriorated. Therefore, it is preferable to use it within the above-mentioned range.

The resin composition containing the polylactide resin and the polyhydroxyalkanoate resin may further comprise a processing aid.

The processing aid serves to reinforce the melt strength, and the polylactide resin itself is preferably added with a processing aid because it has low melt strength or heat resistance. As such a processing aid, it is preferable to use an acrylic copolymer, an epoxy copolymer, a urethane copolymer or a polyolefin copolymer. This makes it possible to complement the melt strength of the polylactide resin and facilitate calendering.

The processing aid is preferably used in a proportion of 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the mixed resin obtained by mixing the polylactide resin and the polyhydroxyalkanoate resin . When the content of the processing aid is less than the above-mentioned range, the improvement of the melting efficiency and the improvement of the melt strength of the polylactide resin and the polyhydroxyalkanoate resin is insufficient. If the content exceeds the above range, the production cost increases, The physical properties of the resin may be deteriorated.

The resin composition of the present invention may further comprise a lubricant.

The lubricant is added in order to prevent the resin from adhering to the calender roll during processing such as car-rendering of the polylactide resin.

There is no limitation on the use of such lubricants such as stearic acid, wax, hydrocarbons, silicon, etc. However, in the present invention, it is particularly preferable to use environmentally friendly higher fatty acids, for example, stearic acid as a saturated fatty acid having 18 carbon atoms.

The lubricant is preferably used in a proportion of 0.1 to 8 parts by weight based on 100 parts by weight of the mixed resin obtained by mixing the polylactide resin and the polyhydroxyalkanoate resin.

When the content of the lubricant is less than 0.1 part by weight based on 100 parts by weight of the mixed resin obtained by mixing the polylactide resin and the polyhydroxyalkanoate resin, the effect of using the lubricant can not be obtained. When the amount of the lubricant is more than 8 parts by weight, The heat resistance, the gloss, and the like of the thermosetting resin composition can be deteriorated.

In addition, the resin composition of the present invention may further contain other additives. Examples of the other additives may include a crosslinking agent, an antioxidant, a dehydrating agent, and the like.

The crosslinking agent increases the molecular weight through chain extension to improve tensile strength, heat resistance, and the like.

Such a crosslinking agent may be a diisocyanate, an epoxy group copolymer, a hydroxycarboxylic acid compound or the like, but is not limited thereto.

The cross-linking agent is preferably used in a proportion of 0.01 to 10 parts by weight based on 100 parts by weight of the mixed resin obtained by mixing the polylactide resin and the polyhydroxyalkanoate resin, more preferably the polylactide resin and the poly It is preferably used in a proportion of 0.1 to 5.0 parts by weight based on 100 parts by weight of the mixed resin obtained by mixing the hydroxyalkanoate resin.

When the content of the cross-linking agent is less than the above range, there is a problem that the heat resistance is lowered, and when it exceeds the above range, there is a possibility that the flexibility is lowered.

The antioxidant serves to prevent the polylactide resin from being oxidized and deteriorating the mechanical properties such as impact resistance. Such antioxidants may be phenol-based, sulfur-based, phosphorus-based antioxidants used as antioxidants for plastics, but are not limited thereto. The antioxidant has no toxicity, is stable at the processing temperature, and does not interfere with activity and other resin processability, and has a high compatibility with the resin. The antioxidant may be used in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the mixed resin obtained by mixing the polylactide resin and the polyhydroxyalkanoate resin.

The resin composition of the present invention has an effect of improving workability and brittleness by mixing a polyhydroxyalkanoate resin having excellent elasticity and ductility characteristics with polylactide resin at a certain ratio. In addition, when the resin composition of the present invention is used, calendering is easy.

The present invention also provides a film (20) produced using the resin composition.

The above-mentioned resin composition can be applied to various methods known in the technical field of the present invention in the production of the film 20, but it can be particularly preferably applied to calendering. In the case of calendering, the content of additives such as additives can be freely controlled as compared with other production methods, and thus a flooring material or flooring material having excellent flexibility, impact resistance, mechanical strength, workability, , And further reduction of raw material costs is possible. In the present invention, the method for producing the film 20 by applying the calendering method is not particularly limited, and for example, a method may be used in which a resin composition is prepared by mixing the respective raw materials; A kneading step of heating and pressurizing the mixed raw materials under an appropriate condition to homogeneously gel; And calendering into a final film shape.

The mixing and kneading of the raw materials can be carried out, for example, by using a super mixer, an extruder, a kneader, a Banbury mixer, a double or triple roll, or the like in a liquid or powdery raw material. In this step, in order to perform more efficient mixing, the blended raw materials are kneaded at a predetermined temperature (e.g., 120 DEG C to 200 DEG C) using a Banbury mixer or the like, and the kneaded raw materials are heated at a predetermined temperature (ex 120 DEG C to 200 DEG C), the mixing and kneading steps may be repeatedly carried out in multiple steps as in the first and second mixing methods using a two-roll mill or the like.

The calendering conditions can be selected in consideration of the composition of the resin composition and can be controlled within a range of, for example, a processing temperature of 120 to 200 DEG C, preferably 130 to 190 DEG C have. If the processing temperature is too low at the time of processing the film 20, the degree of softening of the resin may be insufficient and the moldability may deteriorate. If the processing temperature is excessively high, the viscosity may become excessively low, It is preferable to process it within the above range.

The thickness of the film can be varied in a range of 0.1 to 0.5 mm and 0.5 to 1.0 mm according to the thickness of the film 20 of 0.1 to 1.0 mm and preferably the thickness of the base material layer 50.

When the resin composition of the present invention is used, it is easy to produce a film by calender molding, and the produced films are not adhered to each other even at a high temperature in summer, so that they are easy to use after storage.

Further, the present invention provides a floor material (1) produced by laminating the film (20) on the top surface of a flooring base material layer (50).

Hereinafter, the flooring of the present invention will be described in detail with reference to the drawings.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an exemplary view showing a cross section of one embodiment of the flooring material of the present invention. Fig.

The base layer 50 serves to absorb impacts on the upper or lower part of the bottom material. The base layer 50 may be made of polyvinylchloride (PVC), polypropylene (PO), polyolefin (PET), polyethlene terephthalate (PET) (Polyamide) as a main component and kneaded in a rolling roll, followed by calendaring. Preferably, the substrate layer 50 is composed of at least one selected from the top, the interlayer 51, the base layer 52, and the backside layer 53, and is rolled at a temperature of 140 캜 to 165 캜, Then, each layer was pre-heated with a heating drum at 150 DEG C, and each layer was laminated at a pressure of 5 kgf / cm < 2 > in an embossing roll for plywood, and then passed through a foaming oven at 180 to 230 DEG C to form a base layer 50 ).

The base layer 52 may further include plasticizers, stabilizers, fillers, and the like which are conventionally used in the production of the polymer resin in the production of the separable layer 51, the base layer 52 and the back layer 53, And further includes a foaming agent.

The base layer 50 is made of one or more polymer resins selected from polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), rubber, PU The cushion feeling and the soundproofing function. In particular, when the base layer 50 includes the base layer 52, the cushion feeling and the soundproofing are more excellent. Further, the base material layer 50 has an effect of preventing moisture or cool air from flowing into the bottom of the floor material 1. [

The bottom layer 1 of the present invention may be further laminated with the dimensionally stable layer 40 and the print layer 30 sequentially from the bottom between the base layer 50 and the film 20 as necessary.

The printing layer 30 may be formed by a known printing method such as digital real printing, gravure printing, screen printing, offset printing, rotary printing, or flexographic printing.

The dimension stabilizing layer 40 is preferably formed by impregnating a glass fiber scrim, a glass fiber woven fabric, or a nonwoven fabric with a synthetic resin sol, and then gelling the gel in a gelling drum.

As the synthetic resin, it is preferable to use at least one selected from PVC resin, acrylic resin, melamine resin, and PLA resin.

Here, the glass fiber may have a unit mass per unit area of 30 to 150 g / m ² . When the mass per unit area of the glass fiber is less than 30 g / m ² , the dimensional stability reinforcing effect may be insufficient. When the mass per unit area of the glass fiber exceeds 150 g / m ² , There is a problem that the adhesive strength with the adhesive layer 30 may be deteriorated.

The above-mentioned dimension-stabilizing layer 40 may be prepared by adding a plasticizer such as a citric acid plasticizer such as ATBC, a phthalate plasticizer such as DINP, a phosphate plasticizer and the like as a plasticizer to the synthetic resin, a calcium carbonate, White pigment, and titanium dioxide. These may be used singly or in combination of two or more.

The dimension-stabilizing layer 40 preferably has a thickness of 0.1 to 1.0 mm. If the thickness of the dimension stabilizing layer 40 is less than 0.1 mm, the effect of stabilizing the dimension may be insufficient. If the thickness of the dimension stabilizing layer 40 exceeds 1.0 mm, the thickness becomes thicker without any further dimension stabilizing effect, Resulting in an overall increase in manufacturing costs.

The bottom material of the present invention may further include a surface protective layer (10) on the film (20).

The surface protective layer 10 protects the film, prevents adhesion of contaminants and scratches, and imparts waterproof property. The surface protective layer 10 may be formed of at least one of urethane acrylate, epoxy acrylate, polyester acrylate, Or a mixture of at least one selected from the group consisting of a polyurethane resin, a phenol resin, a melamine resin, a urea resin, and a silicone resin is coated on the upper side of the film 20, Or the surface protective layer 10 can be formed in various manners by mixing the photocurable resin and the thermosetting resin to form the surface protective layer 10 through photo-curing and thermal curing have.

The surface protective layer 10 preferably has a thickness of 0.001 to 0.1 mm. When the surface protective layer 10 is formed to a thickness of less than 0.001 mm, the effect of improving physical properties such as scratch resistance is not expected to be expected. When the surface protective layer 10 is formed to have a thickness of more than 0.1 mm, And the appearance quality of the bottom material 1 may be deteriorated.

When a film produced using the resin composition of the present invention is used as an upper surface of a bottom material, when a PVC sheet is used as a bottom material layer, various harmful substances emitted therefrom can be blocked, and a surface protective layer Even if worn, the user is brought into contact with the film of the present invention, so that there is a very eco-friendly effect.

1: Bottom material 10: Surface protective layer
20: Film 30: Printed layer
40: dimensional stability layer 50: base layer
51: intermediate layer 52: base layer
53: backside layer

Claims (17)

A resin composition comprising a polylactide resin and a polyhydroxyalkanoate resin. The method according to claim 1,
Wherein the mixing ratio of the polylactide resin and the polyhydroxyalkanoate resin is 8: 2 to 6: 4. The method according to claim 1,
Wherein the polylactide resin has a weight average molecular weight of 100,000 to 1,000,000. The method according to claim 1,
Wherein the polyhydroxyalkanoate is a homopolymer or copolymer of a hydroxyalkanoate monomer. 5. The method of claim 4,
The hydroxyalkanoate monomer may be selected from the group consisting of 3-hydroxy butyrate, 3-hydroxy valerate, 3-hydroxy hexanoate, 3-hydroxybutanoate, Wherein the resin composition is one or two or more selected from the group consisting of 3-hydroxy octanoate and 3-hydroxy octadecanoate. The method according to claim 1,
Wherein the resin composition further comprises a processing aid. The method according to claim 6,
Wherein the processing aid is at least one selected from an acrylic copolymer, an epoxy copolymer, a urethane copolymer and a polyolefin copolymer. The method according to claim 6,
Wherein the resin composition comprises 0.1 to 20 parts by weight of a processing aid per 100 parts by weight of a mixed resin obtained by mixing a polylactide resin and a polyhydroxyalkanoate resin. The method according to claim 1,
Wherein the resin composition further comprises 0.1 to 8 parts by weight of a lubricant based on 100 parts by weight of a mixed resin obtained by mixing the polylactide resin and the polyhydroxyalkanoate resin. The method according to claim 1,
Wherein the resin composition further comprises at least one additive selected from a crosslinking agent, an antioxidant, and an iodine releasing agent. A film produced by calender molding with the resin composition of any one of claims 1 to 10. 12. The method of claim 11,
Wherein the film has a thickness of 0.1 to 1.0 mm. A flooring produced by laminating the film (20) of claim 11 on the top surface of a substrate layer (50). 14. The method of claim 13,
Characterized in that the substrate layer (50) comprises at least one layer selected from the interleaving layer (51), the base layer (52) and the backside layer (53). 14. The method of claim 13,
Wherein the base layer (50) is formed of a PVC resin. 14. The method of claim 13,
Characterized by further comprising a printing layer (30) or a dimensionally stabilizing layer (40), or a printing layer (30) and a dimensionally stabilizing layer (40) between the film (20) and the substrate layer (50). 14. The method of claim 13,
Further comprising a surface protective layer (10) formed on the top surface of the film (20) by coating at least one selected from the group consisting of urethane acrylate, epoxy acrylate, polyester acrylate and silicone acrylate, .

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