TWI534193B - Biomass polymer composite composition and interior decoration with wood structure - Google Patents

Description

Biomass polymer composite composition and wood-like structure for interior decoration

The invention relates to a raw polymer composite composition and a wood-like structure, in particular to a wood-like floor tile or a partition wall-forming biopolymer composite composition suitable for indoor use, and the composite of the biomass polymer The composition is used as a main material for the interior decoration with a wood-like structure.

Plastic products have the advantages of light weight, high design freedom, low cost, easy installation and good durability. Under the continuous innovation of formula and processing technology, they quickly penetrate into the construction field, partially replacing concrete, wood, steel and glass. Such as traditional building materials. In general, the mechanical strength of plastics is still lower than that of metals and cement. Therefore, the main applications are still concentrated on interior and exterior materials and functional materials, mainly non-structural materials. Plastic floor tiles have a very high proportion in the interior flooring market due to their cushioning, durability, low cost, no waxing and reduced maintenance.

At present, the main substrate of plastic floor tiles sold on the market is poly(vinyl chloride) (referred to as PVC). However, due to the poor thermal stability of polyvinyl chloride, it is easy to release harmful substances (plasticizers), causing serious damage to the environment. Therefore, international environmental regulations have many restrictions on the use of PVC. In addition, due to the large use of petrochemical raw materials in traditional plastic floor tiles Therefore, it will also cause environmental pollution. Especially in the wake of the aggravation of the earth's climate and the high price of oil, the alternative materials for petrochemical raw materials have been actively seeking solutions in recent years. Therefore, the development of a brick material that can reduce the use of petrochemical raw materials and can combine "energy saving", "saving resources" and "hazardous material avoidance" to replace the PVC material used in existing plastic floor tiles is the solution to be solved by the present invention. problem.

Accordingly, it is an object of the present invention to provide a biopolymer composite composition for a wood-like floor tile or a partition wall panel suitable for interior decoration.

Therefore, the green polymer composite composition of the present invention comprises: a thermoplastic polyolefin elastomer, a modified biodegradable resin, and a filler, wherein the biopolymer composite composition does not contain chlorine The modified biodegradable resin is obtained by reacting a biodegradable resin containing at least one functional group of a hydroxyl group or a carboxyl group with a modifier, and the modifier is acrylic acid acrylate. The ester functional group is added in an amount of 1 to 5% by weight based on the weight of the biodegradable resin, and the content of the modified biodegradable resin is not more than 100% by weight of the biopolymer composite composition. 25 wt%, the filler has a weight percentage of 40 to 65 wt%.

Preferably, the biopolymer composite composition is characterized in that the biodegradable resin is selected from the group consisting of polylactic acid, polyglycolic acid, and polylactic acid polyglycolic acid.

Preferably, the biopolymer composite composition, wherein the modifier is selected from the group consisting of compounds represented by formulas (I) to (III), Wherein, in the formula (I), R is selected from hydrogen or methyl, in the formula (II), x=1-20, y=1-12, and in the formula (1II), x=1-20, y=1-20, z =1-12.

Preferably, the biopolymer composite composition has a Shore D hardness of more than 45 and a tensile strength of not less than 140 kgf/cm ² .

Preferably, the biopolymer composite composition has a weight percentage of the modified biodegradable resin of between 10 and 25 wt%.

Preferably, the biopolymer composite composition has a Shore D hardness of more than 50 and a tensile strength of more than 150 kgf/cm ² .

Preferably, the biopolymer composite composition has the weight percentage of the biopolymer composite composition of 100% by weight, The sum of the content of the modified biodegradable resin and the thermoplastic polyolefin elastomer is not more than 30% by weight.

Preferably, the biopolymer composite composition further comprises a polyolefin polymer, the modified biodegradable resin, the thermoplastic polymer, based on 100% by weight of the biopolymer composite composition. The total weight of the olefin elastomer and the polyolefin polymer is not more than 30% by weight, and the weight percentage of the thermoplastic polyolefin elastomer is greater than the weight percentage of the polyolefin polymer.

Further, another object of the present invention is to provide a wood-like structure for interior decoration.

The interior wood-like structure has a body composed of the biopolymer composite composition, and a cover layer connected to one surface of the body, wherein the body has a Shore D hardness of more than 45, and The tensile strength is not less than 140 kgf/cm ² .

Preferably, the interior decorative wood structure, wherein the cover layer has an intermediate film connected to the surface of the main body, and a printing film connected to the surface of the intermediate film away from the main body, the intermediate film is The first composition comprises a polyolefin polymer, a thermoplastic polyolefin elastomer, and a filler. The weight percentage of the filler is 10% by weight based on 100% by weight of the first composition. 30 wt%, and the weight ratio of the thermoplastic polyolefin elastomer to the polyolefin polymer is between 4/1 and 1/4.

Preferably, the wood-like structure for interior decoration, wherein the cover layer further has a connection with the surface of the printing film away from the main body. a protective film comprising a second composition comprising a polyolefin polymer and a thermoplastic polyolefin elastomer, and the thermoplastic polyolefin elastomer is 100% by weight based on the weight of the second composition The weight percentage is between 50 and 90% by weight.

The utility model has the advantages that the thermoplastic polyolefin elastomer is used to replace the toxic PVC, and the raw material polymer composite material obtained by replacing the petrochemical raw material with the raw material material can not only reduce the use of the petrochemical raw material, but also has more traditional plastics. The advantages of environmental friendliness and low oil dependence.

21‧‧‧ body

22‧‧‧ Coverage

221‧‧‧Intermediate film

222‧‧‧Printing film

223‧‧‧Protective film

Other features and advantages of the present invention will be apparent from the embodiments of the present invention, wherein: FIG. 1 is a schematic diagram illustrating the preferred embodiment of the present invention; FIG. 2 is a shear viscosity diagram illustrating PLA And the shear viscosity results of M-PLA at different mixing times; Figure 3 is a torsion diagram showing the results of torque changes of PLA and M-PLA at different mixing times; Figure 4 is an SEM image showing TPO/PLA ( Electron micrograph of 75/25); Figure 5 is an SEM image showing the electron micrograph of TPO/M-PLA (75/25); Figure 6 is a DMA diagram illustrating the thermoplastic polyolefin elastomer TPO with different contents ( 5-25 wt%) M-PLA blending, and DMA measurement results of thermoplastic polyolefin elastomer and M-PLA; FIG. 7 is a DSC diagram illustrating the modified polylactic acid composition 21C for repeated DSC measurement results after processing test.

The wood-like structure composed of the biopolymer composite composition of the invention can be applied to wood-like floor tiles or partition wall panels for interior decoration/decoration, without adding a plasticizer, a heavy metal stabilizer, halogen-free, and Traditional plastic floor tiles use a smaller amount of petrochemical raw materials.

A preferred embodiment of the wood-like structure for interior decoration of the present invention is exemplified by a wood-like floor tile having the composite polymer composite composition as a main body.

A preferred embodiment of the wood-like floor tile of the present invention comprises a body 21 and a cover layer 22.

The body 21 is composed of a biopolymer composite composition. The biopolymer composite composition comprises a thermoplastic polyolefin elastomer, a modified biodegradable resin, a filler, and an auxiliary agent. Wherein the modified biodegradable resin is obtained by reacting a biodegradable resin having at least one functional group of a hydroxyl group or a carboxyl group with a modifier, and the amount of the modifier is the biodegradable The weight of the resin is 1 to 5%. And the content of the modified biodegradable resin is not more than 25% by weight based on 100% by weight of the raw polymer composite composition.

A common characteristic of general biodegradable resins is low temperature resistance and easy hydrolysis during processing. Taking polylactic acid as an example, polylactic acid is an environmentally friendly raw material. However, polylactic acid has a slow crystallization rate, low heat resistance (heat-resistant temperature below 60 ° C), and hydrolysis in the melt processing process, resulting in overall mechanical Shortcomings such as the decline in nature, therefore, the current polyemulsion Most of the acid is still used in disposable low temperature packaging materials. However, in general, plastic floor tiles are used because they are processed repeatedly. Therefore, polylactic acid cannot be directly used. In addition, the compatibility of polylactic acid in blending with other polymer plastics is also a great problem. The problem of the structure and blending of lactic acid itself is an important factor in determining whether polylactic acid can be used as a wood-like floor tile material. Therefore, the biopolymer composite composition of the present invention mainly remodifies the biodegradable resin with a modifier, and the modified biodegradable resin improves the processability of the general biodegradable resin. Mechanical strength and compatibility with other polymer plastics.

The hydroxyl group- or carboxyl group-containing biodegradable resin may be selected from the group consisting of polylactic acid (PLA), polyglycolic acid (PGA), and polylactic acid polyglycolic acid (PLGA). In the preferred embodiment, the biodegradable resin is selected. Self-polylactic acid. The modifier is a compound having a glycidyl acrylate functional group. For example, the modifier may be selected from the following formula (I), formula (II): ethylene-glycidyl methacrylate copolymer (poly ( Ethylene-co-glycidyl methacrylate)), and formula (III): 2-methyl-2-acrylic acid epoxidized methyl ester (meth) copolymer (poly(ethylene-co-glycidyl methacrylate)) a compound, wherein, formula (I): R = hydrogen or methyl, formula (II): x = 1-20, y = 1-12, formula (III): x = 1-20, y = 1-20, z=1-12. The modified biodegradable resin reacts the biodegradable resin with a modifier, and grafts the modifier to the polylactic acid to improve the processing hydrolysis of the polylactic acid and improve the heat resistance of the polylactic acid. And compatibility with thermoplastic polyolefin elastomers.

In the preferred embodiment, 1 wt% of the modifier (R = hydrogen) as shown in formula (I) and polylactic acid (PLA, Mw: 128337 Da, Weimeng/NCP0005) , MI=10-30 g/10 min 190° C. 2.16 kg) was reacted at 180° C. under a kneading condition of 60 rpm to obtain the modified biodegradable resin (expressed as M-PLA), which was obtained by the reaction. The modified biodegradable resin has a molecular weight of about 373,237 Da.

Referring to Figures 2, 3, 2, and 3, the PLA and M-PLA were observed by a capillary rheometer and a spectrometer at 200 ° C to observe the shear viscosity of different mixing times (200 ° C, shear rate: 1300(s ^-1 )) and the change in torque value (200 ° C, 50 rpm). The results show that the shear viscosity of the PLA and the torque value decrease with the increase of the mixing time (the hydrolysis occurs), while the M-PLA shows no significant change, indicating that the modified M-PLA can improve the general PLA. Hydrolysis problem of melt-kneading over a long period of time.

The thermoplastic polyolefin elastomer is selected from the group consisting of copolymers of ethylene, propylene, and a group A, which is selected from the group consisting of butene, pentene, or a combination thereof, and the modified type The sum of the weight percentage of the biodegradable resin and the thermoplastic polyolefin elastomer is not more than 30% by weight.

In order to effectively reduce the proportion of petrochemical raw materials used, and to consider the compatibility of the modified biodegradable resin with other polymer materials and the reworkability and mechanical properties of the biopolymer composite composition, The weight percent of the modified biodegradable resin is from 5 to 25 wt%, based on 100% by weight of the mass polymer composite composition; preferably, the weight percentage of the modified biodegradable resin is between 10 to 25 wt%, more preferably, the weight percent of the modified biodegradable resin is between 15 and 25 wt%. In a preferred embodiment, the thermoplastic polyolefin elastomer is selected from the group consisting of POE 840 (Mitsui, MI = 3.6 (g/10 min 190 ° C 2.16 kg)), POE 6120 (Exxon Mobil, MI = 1.3 (g/10 min 190 ° C 2.16 kg) ), and POE3000 (Exxon Mobil, MI = 3 (g/10 min 190 ° C 2.16 kg)). In addition, it should be noted that the TPO indicated in the subsequent tables and drawings refers to the results of blending POE840, POE6120, and POE3000 in the ratios in Table 1.

Refer to Table 1 and Figures 4 and 5. Table 1 shows the results of the mechanical properties of TPO/PLA and TPO/M-PLA blended with TPO, PLA, and a weight ratio of 75/25, while Figures 4 and 5 It is a scanning electron micrograph of the TPO/PLA and TPO/M-PLA. As can be seen from the results in Table 1, When TPO is blended with PLA or M-PLA, the tensile strength after blending is not very different. However, the modified M-PLA can be observed from the electron micrographs in Figs. 4 and 5. Further improve the interface compatibility with TPO, and have better compatibility with TPO.

The filler has a weight percentage of 40 to 65 wt%, and is mainly used as a filler to increase the hardness of the product, improve electrical insulation, heat resistance, and improve physical and mechanical properties. The filler material mainly has two types of fiber and powder, and may be organic powder, inorganic powder, or fiber as a main constituent material, and the filler of the present invention may be selected from calcium carbonate, wollastonite, barium sulfate, talcum powder. , clay, calcined clay, natural fiber, glass fiber, or other fillers, etc., in this embodiment the filler is selected from calcium carbonate (Anrong ore, 150 μm).

The additive may be added depending on the environment or needs of use, and is not an essential additive. Additives commonly used in imitation wood floor tiles are dyes, plasticizers, softeners, reinforcing agents, slip agents, modifiers, flame retardants, or a combination of the above, due to the type of the additives and The materials are well known to those skilled in the art and will not be further described herein. In the preferred embodiment of the present invention, the additive added to the biopolymer composite composition comprises: a flame retardant (hydrogen hydroxide) Aluminum, combined with chemistry, 100μm. ), slip agent (Jin Changyu, B-101), and white oil (good oil chemical, BF-150).

In addition, the biopolymer composite composition may further comprise an ethylene-vinyl acetate copolymer (e.g., EVA, commonly known as rubber rubber), a polyolefin polymer, or other ethylene copolymer, for the desired properties. Propylene copolymer and the like. Wherein, the polyolefin polymer has the characteristics of non-toxicity, light weight, corrosion resistance, good electrical insulation, and easy processing, and therefore, may be appropriately added to the biopolymer composite composition to improve mechanical properties, preferably The polyolefin polymer may be selected from crystalline polyolefin polymers having a stereoscopic and regular macromolecular chain, such as polyethylene (PE), polypropylene (PP), and a combination thereof.

The composition of the above-mentioned bulk (containing 21A~21J) containing different proportions of M-PLA and the polymer composite composition without M-PLA (expressed as 21K) and related test results are summarized in Table 2 and Table 3. .

It can be seen from the above Tables 2 and 3 that the Shore D of the biopolymer composite composition having a M-PLA content of 5 to 25 wt% is greater than 45 and the tensile strength (kgf/cm ² ) is greater than 140. And other related tests can meet the specifications of indoor imitation wood floor tiles, and when a small amount (2.5 wt%) of polyolefin polymer (PP) is added to replace the filler, not only the Xiao hardness D can be raised to more than 50. And the tensile strength (kgf/cm ² ) can be increased to more than 155.

Referring again to FIG. 6, FIG. 6 is a blend of the TPO shown in Table 2 with different contents (5-25 wt%) of M-PLA, and TPO and M-PLA, respectively, using a dynamic mechanical analyzer (dynamic mechanical analyzer, DMA) measurement results. As can be seen from Fig. 6, the glass transition temperature of TPO is about -7.6 ° C; the glass transition temperature of PLA is about 70.0 ° C. When TPO is blended with 5-25wt% M-PLA, it can be found that the glass transition temperature of the blended TPO/M-PLA is shifted to the high temperature side by 11.7 °C, which shows that TPO is compatible with M-PLA. Sex.

Next, the biopolymer composite composition 21C shown in the above Table 2 was subjected to a reprocessing test, and the DSC and melt flow index (g/10 min) of the biopolymer composite composition 21C having different recovery times were measured. ), density (kg/cm ³ ), hardness (shore D), and tensile strength (kgf/cm ² ), observe changes in material properties to understand the thermal properties and processing durability of the biopolymer composite composition And the situation of heat and bad solutions. The measurement results are summarized in Table 4 and Figure 7.

From the DSC results of Fig. 7, it can be seen that the biopolymer composite composition 21C has no significant change in thermal properties after different recovery processing times, and the results of Table 4 show that the tensile strength increases with the number of recycling processes. However, there is a decline; however, the retention of 85% of the tensile strength can still be maintained at the 4th time, indicating that the use of modified biodegradable resin (M-PLA) can effectively improve the heat resistance of polylactic acid and easy The problem of cracking.

The cover layer 22 has an intermediate film 221 connected to the surface of the main body 21, a printed film 222 connected to the surface of the intermediate film 221 away from the main body 21, and a protective film 223 formed on the surface of the printed film 222. The main body 21 and the intermediate film 221 are bonded to the protective film 223 so as to be heat-pressed, and the wood-like floor tile for interior decoration is obtained. The protective film 223 is transparent and permeable after being heat-bonded, so that the predetermined pattern of the printed film 222 can be clearly displayed, and at the same time, the printed film 222 can be isolated from the outside to maintain the predetermined pattern of the printed film 222. Integrity.

In detail, the interposer 221 is composed of a first composition including a polyolefin polymer, a thermoplastic polyolefin elastomer, and a filler, and the weight percentage of the first composition is 100% by weight. The weight percentage of the filler is between 10 and 30% by weight, and the weight ratio of the thermoplastic polyolefin elastomer to the polyolefin polymer is between 4/1 and 1/4; the printing film 222 is formed on the surface of the intermediate film 221 and Having a predetermined pattern, the protective film 223 is composed of a second composition including a polyolefin polymer and a thermoplastic polyolefin elastomer, and the thermoplastic polyolefin is 100% by weight based on the weight of the second composition. The weight percentage of the elastomer is between 50 and 90% by weight. In addition, the first composition may further have a processing aid, for example Such as a flame retardant, the interposer film 221 is made to have high temperature resistance and flame resistance, and the film may also include a process for improving fire resistance, abrasion resistance, scratch resistance, or strengthening to make it have better characteristics. Auxiliaries, as such processing aids are well known to those skilled in the art, are not described in detail herein. In the preferred embodiment, the first composition is 85 wt% LLDPE 3225 (MI = 2.0 g/min), and 15 wt% ethylene-octene copolymer, and the second composition is 68 wt% LLDPE 3225. (MI = 2.0 g/min), 12% by weight of an ethylene-octene copolymer, and 12% by weight of calcium carbonate.

In summary, the biopolymer composite composition of the present invention replaces PVC by using a thermoplastic polyolefin elastomer, so that it is not toxic in the conventional PVC polymer to add a plasticizer which affects the hormone content in the living body. The problem is that, by replacing the thermoplastic polyolefin elastomer with a modified biodegradable resin and controlling the hardness with the filler, the amount of the petrochemical raw material can be further reduced and at the same time, it can be used for interior decoration. The hardness and impact strength required for wood-like floor tiles can indeed achieve the object of the present invention.

The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made by the patent application scope and patent specification content of the present invention, All remain within the scope of the invention patent.

21‧‧‧ body

22‧‧‧ Coverage

221‧‧‧Intermediate film

222‧‧‧Printing film

223‧‧‧Protective film

Claims (10)

A raw polymer composite composition suitable for indoor wood-like floor tiles or partition wall panels, the raw polymer composite composition comprising: a thermoplastic polyolefin elastomer, a modified biodegradable resin, a filler, And a polyolefin polymer; the biopolymer composite composition does not contain a chlorine-containing compound, and wherein the modified biodegradable resin is a biodegradable property of at least one of a hydroxyl group or a carboxyl group a resin obtained by reacting with a modifier having a glycidyl acrylate functional group at a content of 1 to 5% by weight of the biodegradable resin; and the biopolymer composite composition The content of the modified biodegradable resin is not more than 25% by weight, the weight percentage of the filler is 40 to 65 wt%, and the content of the polyolefin polymer is not more than 2.5 wt%, the weight percentage is 100 wt%, The weight of the modified biodegradable resin, the thermoplastic polyolefin elastomer and the polyolefin polymer is not more than 30% by weight, and the weight percentage of the thermoplastic polyolefin elastomer is greater than the weight percentage of the polyolefin polymer ratio. The biopolymer composite composition according to claim 1, wherein the hydroxyl group-containing biodegradable resin is selected from the group consisting of polylactic acid, polyglycolic acid, and polylactic acid polyglycolic acid. The biopolymer composite composition according to claim 1, wherein the modifier is selected from the following formulas (I) to (III), Wherein, in the formula (I), R is selected from hydrogen or methyl, in the formula (II), x=1-20, y=1-12, and in the formula (III), x=1-20, y=1-20, z =1-12. The biopolymer composite composition according to claim 1, wherein the polymer composite composition has a Shore D hardness of more than 45 and a tensile strength of not less than 140 kgf/cm ² . The biopolymer composite composition according to claim 1, wherein the modified biodegradable resin has a weight percentage of 10 to 25 wt%. The biopolymer composite composition according to claim 5, wherein the polymer composite composition has a Shore D hardness of more than 50 and a tensile strength of more than 150 kgf/cm ² . The biopolymer composite composition according to claim 1, wherein the The weight percentage of the biopolymer composite composition is 100% by weight, and the total content of the modified biodegradable resin and the thermoplastic polyolefin elastomer is not more than 30% by weight. A wood-like structure for interior decoration, comprising: a body composed of a raw polymer composite composition according to any one of claims 1 to 7; and a cover connected to one surface of the body a layer wherein the body has a Shore D hardness of more than 45 and a tensile strength of not less than 140 kgf/cm ² . The wood-like structure for interior decoration according to claim 8, wherein the cover layer has an intermediate film connected to a surface of the main body, and a printing film connected to the surface of the intermediate film away from the main body, the intermediate film The first composition comprises a polyolefin polymer, a thermoplastic polyolefin elastomer, and a filler, and the weight percentage of the filler is 10% by weight based on 100% by weight of the first composition. ~30wt%, and the weight ratio of the thermoplastic polyolefin elastomer to the polyolefin polymer is between 4/1 and 1/4. The wood-like structure for interior decoration according to claim 9, wherein the cover layer further has a protective film connected to the surface of the printing film away from the main body, the protective film being composed of a second composition, the second composition The polymer comprises a polyolefin polymer and a thermoplastic polyolefin elastomer, and the weight percentage of the thermoplastic polyolefin elastomer is between 50 and 90% by weight based on 100% by weight of the second composition.