CN109963907A - It is a kind of to use the degradable floor of PLA resin and its production technology - Google Patents

It is a kind of to use the degradable floor of PLA resin and its production technology Download PDF

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Publication number
CN109963907A
CN109963907A CN201880003789.2A CN201880003789A CN109963907A CN 109963907 A CN109963907 A CN 109963907A CN 201880003789 A CN201880003789 A CN 201880003789A CN 109963907 A CN109963907 A CN 109963907A
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parts
weight
resin
polylactic
polylactic resin
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戴会斌
章忠飞
赵培东
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ZHEJIANG JINGTONG PLASTICS CO Ltd
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ZHEJIANG JINGTONG PLASTICS CO Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
    • C08L93/04—Rosin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F15/00—Flooring
    • E04F15/02—Flooring or floor layers composed of a number of similar elements
    • E04F15/10—Flooring or floor layers composed of a number of similar elements of other materials, e.g. fibrous or chipped materials, organic plastics, magnesite tiles, hardboard, or with a top layer of other materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
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Abstract

A kind of using the degradable floor of PLA resin and its production technology, raw material is polylactic resin mixture, is formed by granulation, extrusion, pattern printing, lamination, cutting, fluting or trimming process.The degradable floor using PLA resin is easy to degrade, it is discarded after facilitate processing.

Description

It is a kind of to use the degradable floor of PLA resin and its production technology
Technical field:
It is especially a kind of using the degradable floor of PLA resin and its production technology the present invention relates to floor field.
Background technique:
House, luxurious house, apartment, office are widely used in using the flooring board of the petroleum resinoids such as polyvinyl chloride (PVC) In the buildings such as room or shop.But with the promotion of environmental consciousness, waste and old plastic floor is treated as a problem, unifies back It receives and returns to plastic floor processing enterprise to re-use cost too high, and treatment in situ is without relevant art and equipment, therefore how to solve Certainly waste and old plastic floor becomes a urgent problem to be solved.
Summary of the invention:
The technical problem to be solved by the invention is to provide it is a kind of be easy to degrade, facilitate processing using PLA resin can Degradation floor.
The technical solution of the invention is as follows, provides a kind of degradable floor using PLA resin, and raw material is polylactic acid Resin compound.With the enhancing of environmental consciousness, polylactic acid (PLA) is as lactide or the thermoplastic polyester of lactic acid, due to tool There is good degradation property, has been used for medical, pharmaceuticals, food, (polyethylene (PE) and polypropylene used for cosmetic and industrial (PP) substitution use) etc. multiple fields.Since polylactic acid prepares the amylofermentation extracted from corn, potato etc. by polymerization Lactic acid prepare, after landfill disposal, water and carbon dioxide can be degraded at 3 months, it is very environmentally friendly.
Preferably, polylactic resin mixture in addition to polylactic resin, further include plasticizer, melt strength intensive, At least one of lubricant, hydrolysis agent and chain extender.
Preferably, filler is at least one of calcium carbonate, wood powder, titanium dioxide and pine resin.
Preferably, the polylactic resin relative to 100 parts by weight, the non-phthalic acid ester comprising 3~60 parts by weight The acrylic copolymer as melt strength intensive of class plasticizer and 0.05~12 parts by weight.
Preferably, the polylactic resin relative to 100 parts by weight, further comprises as 0.02~5 parts by weight of lubricant Higher fatty acids, 0.01~6 parts by weight chain extender, 8 parts by weight hydrolysis agent below, 600 parts by weight carbonic acid below One of calcium, 150 parts by weight wood powder below, 50 parts by weight titanium dioxide below and 25 parts by weight rosin below with On.
Preferably, it is with a thickness of 2~10mm.
Preferably, polylactic resin is noncrystalline polylactic resin.Polylactic resin can divide into crystalloid polylactic acid (c- Polylactic acid) resin and noncrystalline polylactic acid (a- polylactic acid) resin.In the case where crystalloid polylactic resin, plasticizer can produce The bleeding flowed out to the surface of thin slice, it is preferred that utilizing noncrystalline polylactic resin.Utilizing noncrystalline polylactic acid In the case where resin, has the advantages that the compatilizer that must be added without adding bleeding in order to prevent.Utilizing amorphous In the case where matter polylactic resin, most preferably, polylactic resin utilizes 100% noncrystalline polylactic resin.
The present invention also provides a kind of production technologies on degradable floor using PLA resin, include the following steps,
Step 1 is granulated, polylactic resin mixture is granulated after mixing；
Step 2 squeezes out, and by extruder extrusion molding, plate thickness is 2~10mm, and extrusion temperature is 110-230 DEG C；
Step 3, pattern printing, by 3D technology in plate upper surface print pattern；
Step 4, lamination are handled using UV curing of coatings；
Step 5, cutting, is cut by predetermined size；
Step 6, fluting or trimming.
Using after above scheme compared with prior art, the invention has the following advantages that being substituted by poly-lactic acid ester existing The PVC material of technology prepares floor, using the degradable characteristic of poly-lactic acid ester, the floor of preparation is degraded, after discarding Facilitate processing, can be voluntarily biodegradable by land-fill method, degradation cycle was generally acted at 3 months, very environmentally friendly.
Detailed description of the invention:
Fig. 1 is the structural diagram of the present invention.
Specific embodiment:
With regard to specific embodiment, the invention will be further described below:
A kind of degradable floor using PLA resin, raw material are polylactic resin mixture.Wherein, polylactic resin Mixture further includes in plasticizer, melt strength intensive, lubricant, hydrolysis agent and chain extender in addition to polylactic resin At least one.Polylactic resin can divide into crystalloid polylactic acid (c- polylactic acid) resin and noncrystalline polylactic acid (a- polylactic acid) Resin.In the case where crystalloid polylactic resin, the bleeding that plasticizer is flowed out to the surface of thin slice can produce, therefore preferably Ground utilizes noncrystalline polylactic resin.In the present invention, although it is preferred that noncrystalline polylactic resin, the type of polylactic resin It is not particularly limited.It further include at least one of calcium carbonate, wood powder, titanium dioxide and pine resin.When among these, calcium carbonate As filler, titanium dioxide is as colorant, and wood powder and rosin are respectively as native texture and aroma source.
Plasticizer can assign outstanding flexibility, impact resistance and melting to composition or from formed body prepared by composition Efficiency.As long as the type for the plasticizer that can be used in the present invention is able to carry out above-mentioned effect, just it is not particularly limited, but Preferably, using the plasticizer with environmental protection characteristic.At this moment, as above-mentioned environment-friendly plasticizer, non-phthalic acid ester class is used Plasticizer, and this softens polylactic resin, so that thermoplasticity increases, so that floor is easy to carry out molding at high temperature and adds Work.As above-mentioned non-phthalic ester plasticizer, three propyl ester of citric acid (TPC), three propyl ester of acetyl tributyl citrate can be used (ATPC), trihexyl citrate (THC) etc..
Sediment is accumulated during melt extruded etc. in order to prevent or cross-linking agent, polylactic acid resin composition contain profit Lubrication prescription, this lubricant have many types, but as long as being to execute above-mentioned effect, are just not particularly limited, for example, can be used The silicide of stearic acid, Metallic stearates (for example, calcium salt, magnesium salts or lead salt) and mineral oil etc.
It is melt strength intensive that acrylic copolymer, which uses,.For polylactic resin, itself melt strength or Heat resistance is weaker, and acrylic copolymer makes up this disadvantage of polylactic resin, thus can not only supplement melt strength, Also press process may be implemented.
Further, above-mentioned lubricant prevents the accumulation of deposit or cross-linking by-products during melt extrusion.More In kind lubricant, embodiment of the present invention application higher fatty acids is environmentally friendly lubricant.
Polylactic resin mixture is by the hydrolysis of polylactic resin in mechanical performance (such as impact resistance) in order to prevent Deterioration, polylactic resin mixture can further comprise hydrolysis agent.The example of hydrolysis agent may include carbodiimides and Oxazoline.It will be appreciated, however, that can be used any typical hydrolysis agent without limiting.
Above-mentioned chain extender, which plays the role of increasing, prolongs the molecular weight of chain based on expanding, Lai Tigao tensile strength, heat resistance etc., This chain extender can use diisocyanate, epoxy group copolymer and hydroxy carboxylic acid compound etc..
Specifically, the polylactic resin relative to 100 parts by weight, the non-phthalic acid ester class comprising 3~60 parts by weight The acrylic copolymer as melt strength intensive of plasticizer and 0.05~12 parts by weight, further comprises as lubricant The higher fatty acids of 0.02~5 parts by weight, the chain extender of 0.01~6 parts by weight, 8 parts by weight hydrolysis agent below, 600 weight Part calcium carbonate, 150 parts by weight wood powder below, 50 parts by weight titanium dioxide below and 25 parts by weight rosin below below One or more of.
Embodiment 1
A kind of degradable floor using PLA resin, according to the mass fraction, including following components, polylactic resin 100 Part, it is 18 parts of non-phthalic ester plasticizer, 3 parts of acrylic copolymer, 1 part of higher fatty acids, 2 parts of chain extender, water-fast 2 parts of agent, 360 parts of calcium carbonate, 15 parts of wood powder, 30 parts of titanium dioxide of solution.
Embodiment 2
A kind of degradable floor using PLA resin, according to the mass fraction, including with component, 100 parts of polylactic resin, 4 parts of three propyl ester of citric acid, 1 part of methyl acrylate, 2 parts of stearic acid, 0.5 part of hydroxy carboxylic acid compound, 1 part of carbodiimides, carbon 500 parts of sour calcium, 10 parts of titanium dioxide, 3 parts of rosin.In addition it can which crosslinking agent and colorant is added as needed.
Hereinafter, the group according to above-described embodiment is grouped as, prepared according to the following steps, forms degradable floor.
A kind of degradable floor using PLA resin, includes the following steps,
Step 1 is granulated, and polylactic resin mixture investment mixing machine is granulated after mixing；
Step 2 squeezes out, and by extruder extrusion molding, plate thickness 9m, extrusion temperature is 150 DEG C；
Step 3, pattern printing, by 3D printing technique in plate upper surface print pattern, pattern is set as needed；
Step 4, lamination are handled using UV curing of coatings, realize resistant, scratch resistance, wear-resisting property；
Step 5, cutting, is cut by predetermined size；
Step 6, fluting or trimming carry out fluting or trimming processing according to actual needs.
The degradable floor of above-mentioned technique preparation is after discarded, by the way that complete drop can be realized at 2-5 months under landfill Solution, it is very environmentally friendly.
Only the preferred embodiment of the present invention has been described above, but is not to be construed as limiting the scope of the invention.It is all The equivalent structure or equivalent flow shift done using description of the invention, be included in scope of patent protection of the invention it It is interior.

Claims (8)

1. a kind of degradable floor using PLA resin, it is characterised in that: its raw material is polylactic resin mixture.
2. the degradable floor according to claim 1 using PLA resin, it is characterised in that: polylactic resin mixture In addition to polylactic resin, further include in plasticizer, melt strength intensive, lubricant, hydrolysis agent and chain extender at least It is a kind of.
3. the degradable floor according to claim 2 using PLA resin, it is characterised in that: further include calcium carbonate, wood At least one of powder, titanium dioxide and rosin.
4. the degradable floor according to claim 2 or 3 using PLA resin, it is characterised in that: relative to 100 weight The polylactic resin of part, the conduct of the non-phthalic ester plasticizer comprising 3~60 parts by weight and 0.05~12 parts by weight The acrylic copolymer of melt strength intensive.
5. the degradable floor according to claim 4 using PLA resin, it is characterised in that: relative to 100 parts by weight Polylactic resin, further comprise as the higher fatty acids of 0.02~5 parts by weight of lubricant, the chain extender of 0.01~6 parts by weight, 8 parts by weight hydrolysis agent below, 600 parts by weight calcium carbonate below, 150 parts by weight wood powder below, below 50 parts by weight Titanium dioxide and one or more of 25 parts by weight rosin below.
6. the degradable floor according to claim 1 using PLA resin, it is characterised in that: it is with a thickness of 2~10mm.
7. the degradable floor according to claim 1 using PLA resin, it is characterised in that: polylactic resin is amorphous Matter polylactic resin.
8. a kind of production technology on the degradable floor using PLA resin, which is characterized in that include the following steps,
Step 1 is granulated, polylactic resin mixture is granulated after mixing；
Step 2 squeezes out, and by extruder extrusion molding, plate thickness is 2~10mm, and extrusion temperature is 110-230 DEG C；
Step 3, pattern printing, by 3D printing technique in plate upper surface print pattern；
Step 4, lamination are handled using UV curing of coatings；
Step 5, cutting, is cut by predetermined size；
Step 6, fluting or trimming.
CN201880003789.2A 2018-06-13 2018-06-13 It is a kind of to use the degradable floor of PLA resin and its production technology Pending CN109963907A (en)

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PCT/CN2018/090982 WO2019237267A1 (en) 2018-06-13 2018-06-13 Degradable floor using pla resin and production process therefor

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CN111978753A (en) * 2020-08-19 2020-11-24 安徽丰原生物新材料有限公司 Degradable polylactic acid plate and preparation method thereof
CN113683803A (en) * 2021-09-13 2021-11-23 苏州盛万达塑胶包装材料有限公司 Production process of degradable PLA mulching film

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GB2595848B (en) * 2020-06-01 2023-04-19 Altro Ltd Improvements in or relating to organic material

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CN102947521A (en) * 2010-03-15 2013-02-27 乐金华奥斯有限公司 Flooring material using pla resin
CN102791482A (en) * 2010-03-31 2012-11-21 乐金华奥斯有限公司 Board complex having a polylactic acid cover
JP2014152193A (en) * 2013-02-05 2014-08-25 Lonseal Corp Polylactic acid-based calender molding film or sheet having flexibility

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111978753A (en) * 2020-08-19 2020-11-24 安徽丰原生物新材料有限公司 Degradable polylactic acid plate and preparation method thereof
CN113683803A (en) * 2021-09-13 2021-11-23 苏州盛万达塑胶包装材料有限公司 Production process of degradable PLA mulching film

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