CN103097132A - Method for producing transparent resin laminate, molded body and resin laminate - Google Patents
Method for producing transparent resin laminate, molded body and resin laminate Download PDFInfo
- Publication number
- CN103097132A CN103097132A CN2011800405290A CN201180040529A CN103097132A CN 103097132 A CN103097132 A CN 103097132A CN 2011800405290 A CN2011800405290 A CN 2011800405290A CN 201180040529 A CN201180040529 A CN 201180040529A CN 103097132 A CN103097132 A CN 103097132A
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- Prior art keywords
- intermediate layer
- resin
- crystalline resin
- metallocene
- resin laminate
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- 229920005989 resin Polymers 0.000 title claims abstract description 126
- 239000011347 resin Substances 0.000 title claims abstract description 126
- 238000004519 manufacturing process Methods 0.000 title claims description 54
- 229920006038 crystalline resin Polymers 0.000 claims abstract description 73
- 238000001816 cooling Methods 0.000 claims abstract description 72
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 49
- 238000002425 crystallisation Methods 0.000 claims abstract description 19
- 230000008025 crystallization Effects 0.000 claims abstract description 19
- 239000012968 metallocene catalyst Substances 0.000 claims abstract description 13
- 238000002844 melting Methods 0.000 claims abstract description 5
- 230000008018 melting Effects 0.000 claims abstract description 5
- 239000004711 α-olefin Substances 0.000 claims description 48
- 238000010438 heat treatment Methods 0.000 claims description 40
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 38
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 15
- 229920001684 low density polyethylene Polymers 0.000 claims description 14
- 239000004702 low-density polyethylene Substances 0.000 claims description 14
- 238000003475 lamination Methods 0.000 claims description 13
- 239000010410 layer Substances 0.000 abstract 4
- 239000002344 surface layer Substances 0.000 abstract 3
- 239000000463 material Substances 0.000 description 87
- 230000002093 peripheral effect Effects 0.000 description 25
- 238000000137 annealing Methods 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 17
- -1 polypropylene Polymers 0.000 description 13
- 239000000498 cooling water Substances 0.000 description 12
- 238000009434 installation Methods 0.000 description 12
- 239000004743 Polypropylene Substances 0.000 description 11
- 229920001155 polypropylene Polymers 0.000 description 11
- 230000003746 surface roughness Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 9
- 239000003595 mist Substances 0.000 description 9
- 239000005060 rubber Substances 0.000 description 9
- 238000002788 crimping Methods 0.000 description 6
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- 229910052751 metal Inorganic materials 0.000 description 5
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- 239000011888 foil Substances 0.000 description 4
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/91—Heating, e.g. for cross linking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/9145—Endless cooling belts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
- B29C51/14—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor using multilayered preforms or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/06—PE, i.e. polyethylene
- B29K2023/0608—PE, i.e. polyethylene characterised by its density
- B29K2023/0633—LDPE, i.e. low density polyethylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/10—Polymers of propylene
- B29K2023/12—PP, i.e. polypropylene
Landscapes
- Mechanical Engineering (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
Abstract
An intermediate layer of a crystalline resin and a surface layer are formed, said surface layer being formed, on at least one surface of the intermediate layer, from a crystalline resin that has a higher melt flow rate and a shorter relaxation time in comparison to those of the crystalline resin that constitutes the intermediate layer. The intermediate layer and/or the surface layer contains a metallocene type ethylene-a-olefin copolymer that is produced using a metallocene catalyst. A master sheet (2) is formed by cooling laminated sheets that are obtained by extruding the crystalline resins in a molten state, and the master sheet (2) is heat-treated at a temperature not lower than the crystallization temperature but not higher than the melting point, so that a transparent resin laminate (3) is produced.
Description
Technical field
The present invention relates to manufacture method, formed body and the resin laminate of transparent resin laminate.
Background technology
The crystalline resin that the polypropylene of take is representative, due to its crystallinity high (degree of crystallinity, crystallization rate, spherulite size etc.), is opaque under common film-forming method.Obtain in the situation of transparent crystalline resin film or thin slice, example as described in Patent Document 1, generally adopts by adding additive (nucleator), manufactures in a large number fine crystal, suppresses the method that the polymer molecule of spherocrystal growth designs.
As other transparent expression method, the quench of conveyer belt technique (ベ Le ト プ ロ セ ス) of can having enumerated use that for example patent documentation 2 is put down in writing.In the quench that has used this conveyer belt technique, by polypropylene is used from molten condition, the conveyer belt and the roller that remain low temperature are pushed, the film making process of chilling is given the transparency.That is, by chilling, suppress crystalline growth to seek low crystallization and fine spherocrystallization, even do not add nucleator, also can not realize the better transparency.
In addition, in the polypropylene-based resin sheet as patent documentation 3 records, by add specific straight chain shape low density polyethylene (LDPE), chilling to polypropylene, high transparent and resistance to impact have been guaranteed.
The prior art document
Patent documentation
No. 3725955 communique of [patent documentation 1] Japan Patent
No. 4237275 communique of [patent documentation 2] Japan Patent
[patent documentation 3] Japanese Patent Laid-Open 2006-297876 communique
Summary of the invention
But the polypropylene foil containing nucleator of patent documentation 1 record, although the transparency had lifting more in the past, also do not eliminate its gonorrhoea sense fully.Therefore, for for requiring the further purposes field of the transparency, need further to promote the transparency.
Therefore in addition, because polypropylene is exactly crystalline resin originally, near fusing point, viscosity can sharply descend, and is difficult to hot forming, and the interpolation of nucleator can improve degree of crystallinity, further dwindles the scope of hot-forming property, may make hot forming more difficult.
In addition, patent documentation 2 record pass through conveyer belt technique or water cooling has been passed through the thin slice of extruding masking chilling operation, many spherocrystals are arranged near sheet surface, the existence of this spherocrystal may make the transparency descend.
In addition, even patent documentation 3 record in the situation that added specific linear shape low density polyethylene (LDPE) in polypropylene, also require its transparency further to promote.
The manufacture method, formed body and the resin laminate that the purpose of this invention is to provide the transparent resin laminate of transparency lifting.
After research with keen determination by the present inventor, find, the stress applied during by the control resin extruded, the crystallization meeting that chilling produces afterwards changes.The present invention is based on this opinion and complete.
The manufacture method of the transparent resin laminate of the present invention's record, it is characterized in that, possesses at least superficial layer formed by crystalline resin of one side that the intermediate layer formed by crystalline resin is arranged and be arranged at this intermediate layer, the crystalline resin of described superficial layer, compare to the crystalline resin that forms described intermediate layer, melt index (Melt Flow Rate: hereinafter referred to as MFR) is large, relaxation time is short, the crystalline resin that forms described intermediate layer and at least one party in the crystalline resin that forms described superficial layer contain that to use the metallocene of metallocene catalyst manufacture be ethene-alpha-olefin copolymer, the crystalline resin and the crystalline resin melting separately that forms described superficial layer in described intermediate layer will be formed, extruding, state with the sheet lamination is cooling, form the resin laminate, by this resin laminate with more than crystallization temperature, the following temperature of fusing point is heat-treated.
In addition, in the present invention, the isotactic pentad fraction that preferred described intermediate layer is above by: 80 quality %, 99.5 quality % are following 85% or more, 99% below, MFR divides above, 5.0g/10 to divide following propylene resin (a) at 0.5g/10, and 0.5 quality % is above, the manufacture of the use metallocene catalyst below 20 quality %, density is at 898kg/m
3above, 913kg/m
3below, at 0.5g/10, to divide above, 6.0g/10 to divide following metallocene be that ethene-alpha-olefin copolymer (b) forms to MFR.
In addition, in the present invention, the crystalline resin that is preferably formed described intermediate layer and described superficial layer is propylene resin.
In addition, in the present invention, preferred described metallocene is that ethene-alpha-olefin copolymer is straight chain shape low density polyethylene (LDPE).
In addition, in the present invention, the surface that the two sides of the substrate layer preferably formed at crystalline resin arranges ，Gai intermediate layer, described intermediate layer arranges described superficial layer.
In addition, in the present invention, the crystalline resin that is preferably formed described substrate layer is propylene resin.
The formed body of the present invention's record, it is characterized in that, possess the intermediate layer formed by crystalline resin and at least superficial layer formed by crystalline resin of one side that is arranged at this intermediate layer, the crystalline resin of described superficial layer, compare to the crystalline resin that forms described intermediate layer, melt index (Melt Flow Rate: hereinafter referred to as MFR) is large, relaxation time is short, the crystalline resin that forms described intermediate layer and at least one party in the crystalline resin that forms described superficial layer contain that to use the metallocene of metallocene catalyst manufacture be ethene-alpha-olefin copolymer, the crystalline resin and the crystalline resin sheet lamination under molten condition that forms described superficial layer in described intermediate layer will be formed, the resin laminate that chilling obtains, more than crystallization temperature, the following temperature of fusing point is carried out hot forming.
The resin laminate of the present invention's record, it is characterized in that, form transparent resin laminate by heat treatment, possess the intermediate layer formed by crystalline resin and at least superficial layer formed by crystalline resin of one side that is arranged at this intermediate layer, the crystalline resin in described intermediate layer contains: more than 80 quality %, 99.5 the isotactic pentad fraction below quality % is more than 85%, below 99%, MFR is more than 0.5g/10 divides, 5.0g/10 minute following propylene resin (a), and 0.5 more than quality %, the following use metallocene catalyst of 20 quality % is manufactured, density is at 898kg/m
3above, 913kg/m
3below, at 0.5g/10, to divide above, 6.0g/10 to divide following metallocene be ethene-alpha-olefin copolymer (b) to MFR, the crystalline resin of described superficial layer, compare to the crystalline resin that forms described intermediate layer, MFR is large, the relaxation time is short.
In addition, in the present invention, the two sides that the two sides of the substrate layer preferably formed at crystalline resin arranges ，Gai intermediate layer, described intermediate layer arranges described superficial layer.
In the present invention, form at least superficial layer of one side in He Gai intermediate layer, crystalline resin intermediate layer, this superficial layer by the melt index that compares to the crystalline resin that forms intermediate layer greatly and short crystalline resin of relaxation time form.In addition, the metallocene that makes at least one party in intermediate layer and superficial layer contain the manufacture of use metallocene catalyst is ethene-alpha-olefin copolymer.
Therefore, the stress applied while pushing as sheet, relaxed by superficial layer, can reduce and cause the residual stress easily resulted from apart from the spherocrystal generation of surperficial certain depth position.
But, because the words that only reduce residual stress can't suppress the generation of spherocrystal, therefore, containing metallocene by the depth location produced at spherocrystal is ethene-alpha-olefin copolymer, can suppress generation and the growth of spherocrystal, in the amount that reduces spherocrystal, the size of spherocrystal also diminishes.Therefore, can reduce the scattering of light that spherocrystal causes, promote the transparency (reduction mist degree).
In addition, each crystalline resin is pushed in molten condition, cooling under platy layer cumuliformis state, form the resin laminate, this resin laminate is heat-treated with the temperature more than crystallization temperature, below fusing point.
In the heat treatment of chilling sheet, carry out crystallization in fine higher order structure in maintaining the good resin laminate of the cooling degree of crystallinity obtained, therefore there is no the problem of damage, can form well sheet, obtain the sheet transparency resin laminate of high transparent.
The accompanying drawing explanation
[Fig. 1] shows the manufacturing installation skeleton diagram of the manufacture transparency resin laminate that the example in the manufacture method of transparent resin laminate of the present invention relates to.
[Fig. 2] shows the skeleton diagram of the acquisition unit in above-mentioned manufacturing installation.
[Fig. 3], for the chart of the relation of refractive index that demonstration polypropylene foil of the present invention is described and density, transverse axis is that density, the longitudinal axis are refractive index.
Symbol description
1 ... manufacturing installation
2 ... former material as the resin laminate
2A ... intermediate layer
2B ... superficial layer
3 ... transparency resin laminate
10 ... former material building mortion
20 ... annealing device
The specific embodiment
The manufacture method of the transparent resin laminate that an example of the present invention relates to is described referring to Fig. 1.
In addition, in this example, as transparent resin laminate, the polypropylene-based sheet transparency resin laminate of take describes as example, but is not limited thereto.For example, also can utilize the crystalline resin beyond various polypropylene, in addition, the present invention is also applicable to the heating shaping of container etc. etc.
[formation of manufacturing installation]
In Fig. 1, manufacturing installation 1 possesses and has: the former material forming device 10 that is sheet, chilling by material resin melting mixing, extruding, and the former material 2 as the resin laminate (with reference to Fig. 2) of these former material forming device 10 manufactures is heat-treated, manufacture the annealing device 20 of transparent resin laminate 3.
Herein, being described in detail later of former material 2, as shown in Figure 2, be 2 kinds of 3 layers of structures that are provided with superficial layer 2B on 2A two sides, the intermediate layer of sheet.
Former material forming device 10, possess T-shaped die head pressurizing unit 100 and cooling pressurizing unit 110 arranged.
T-shaped die head pressurizing unit 100, possess extruder 101 and T-shaped die head 102 arranged.
As extruder 101, can use such as single shaft extruder or multishaft extruder etc.The intermediate layer 2A of extruder 101 minutes and former material 2 corresponding and corresponding with superficial layer 2B, be provided with a plurality of.
T-shaped die head 102 releasably is installed on the top of each extruder 101, the molten resin 2C of extruder 101 each self compactions is shaped to the state of sheet lamination.This T-shaped die head 102, for example can enumerate, rack type die and slit die head etc.In addition, T-shaped die head 102, so long as can form the die head of multilayer tablet, be not limited to rack type die and slit die head.In addition, the formation as order from the fused raw material resin lamination of extruder, for example can enumerate feed sleeve pipe (Off イ mono-De Block ロ Star Network) mode or branch manifold die head mode.
The cooling pressurizing unit 110 of former material building mortion 10 will be former material 2 at the cooling limit, molten resin 2C limit of T-shaped die head 102 sheet laminations extrusion molding extrusion molding.This cooling pressurizing unit 110, as shown in Figure 1 and Figure 2, possess the first chill roll 111, the second chill roll 112, the 3rd chill roll 113, the 4th chill roll 114, cooling by endless belt 115, cooling water nozzle 116, tank 117, suction roll 118 and stripper roll 119.
The first chill roll 111, the second chill roll 112, the 3rd chill roll 113 and the 4th chill roll 114 are supported by axle, rotatable, are the metallic roll that the good material of heat conductivity is made.In addition, in the first chill roll 111, the 3rd chill roll 113, the 4th chill roll 114 at least any one, its rotating shaft is connected with not shown rotating driving device, by the driving of rotating driving device, rotates.
In addition, the first chill roll 111, the second chill roll 112, the 3rd chill roll 113 and the 4th chill roll 114, the angle based on the cooling durability with endless belt 115, preferably diameter dimension is larger, particularly preferably is designed to diameter 100～1500mm in practicality.
The periphery of the first chill roll 111 is covered by elastomeric material 111A.As elastomeric element, can use such as acrylonitrile-butadiene rubber (NBR), fluorubber, polysiloxane rubber, EPDM (ethylene-propylene-diene copolymer) etc.
This elastomeric material 111A, for strain and obtain good face and press, preference as hardness (measuring according to JIS K6301A method) below 80 degree, thickness is in the 10mm left and right.
The second chill roll 112 is that the surface roughness of side face is (according to the surface roughness of JIS B0601 " surface roughness-definition and mean ": the metallic roll (minute surface chill roll) that Rmax) mirro finished below 0.3 μ m is crossed.In the inside of the second chill roll 112, in order to regulate surperficial temperature, inside be provided with the cooling device of not shown water-cooled etc.The surface roughness of the second chill roll 112 (Rmax) surpasses 0.3 μ m, and glossiness and the transparency of the former material 2 obtained may descend.
This kind the second chill roll 112, the metal-made that formed by stainless steel etc. of being configured to be situated between is cooling with endless belt 115, and, between the first chill roll 111, clips intermediate layer 2A and superficial layer 2B from T-shaped die head 102 melt extruded.
Cooling with endless belt 115, by such as stainless steel, carbon steel, titanium alloy etc., formed endless belt-shapedly, reel and be arranged at the first chill roll 111, the 3rd chill roll 113, the 4th chill roll 114.This cooling outer peripheral face with endless belt 115, the face joined with intermediate layer 2A and the superficial layer 2B of T-shaped die head 102 melt extruded, form the minute surface of surface roughness (Rmax) below 0.3 μ m.
In addition, the 3rd chill roll 113 and the 4th chill roll 114, be provided with the cooling device of not shown water-cooled etc. by inside, can regulate the cooling temperature with endless belt 115.
Cooling water nozzle 116, be positioned at the below of the vertical direction of the second chill roll 112, set into to cooling with the 115 back side, endless belt ejection cooling water 116A.
Cooling water nozzle 116, by ejection cooling water 116A, when making cooling use endless belt 115 chilling, also make by the first chill roll 111 and the second chill roll 112 and being crimped as planar intermediate layer 2A and superficial layer 2B chilling.
Tank 117, be the case shape of top opening, is set to cover below the second chill roll 112 whole, reclaims and be sprayed onto the cooling cooling water 116A with 115 back sides, endless belt.
In tank 117, be provided with the discharge outlet 117B that the water 117A of recovery is discharged below tank 117.
Suction roll 118, be arranged at the side surface part of the 3rd chill roll 113 1 sides of the second chill roll 112, with cooling, with endless belt 115, joins.
Suction roll 118 is attached to the cooling unnecessary cooling water with 115 back sides, endless belt for removing.
In addition, stripper roll 119, can be configured to former material 2 is connect to the 3rd chill roll 113 1 side pressures, but preferably as shown in the figure, with the 3rd chill roll 113 from configuration, the former material 2 of not crimping.
The annealing device 20 of manufacturing installation 1, possess preheating device 210, annealing device body 220, cooling device 230.
In these first preheat rolls 211, the second preheat roll 212 and the 3rd preheat roll 213, be provided with the not shown temperature adjustment device of the steam heating type etc. of capable of regulating surface temperature.In addition, as temperature adjustment device, be not limited to directly be arranged at the formation of each preheat roll 211～213, but the roller of preheating special use also is set separately, or the formation of carrying out preheating by being arranged at outside preheating device.
In addition, preheating device 210 is not limited to the formation that these 3 preheat rolls 211～213 are set, and can be also any formation of pyrogen material 2 in advance such as one or more preheat rolls or use endless belt is set.
The annealing device body 220 of annealing device 20, while heat the former material 2 of preheating device 210 preheatings to advance.This annealing device body 220, possess the first warm-up mill 221 arranged, endless belt 227, not shown drive unit for the second warm-up mill 222, the 3rd warm-up mill 223, the 4th warm-up mill 224, the rubber rollers 225 as backer roll, guide roller 226, metal heating.
In addition, the first warm-up mill 221, the second warm-up mill 222, the 3rd warm-up mill 223, the 4th warm-up mill 224 and guide roller 226, can be used the good materials of heat conductivity such as metal.In addition, the first warm-up mill 221, the second warm-up mill 222, the 3rd warm-up mill 223 and the 4th warm-up mill 224, angle based on metal heating by the durability of endless belt 227, preferably diameter dimension is larger, particularly preferably is designed to diameter 100～1500mm in practicality.
In these first warm-up mills 221, the second warm-up mill 222, the 3rd warm-up mill 223 and the 4th warm-up mill 224, be provided with the not shown temperature adjustment device of the steam heating type etc. of capable of regulating surface temperature.In addition, as temperature adjustment device, be not limited to directly be arranged at the formation of each warm-up mill 221～224, the special-purpose roller of heating also can be set separately, or be heated by being arranged at outside heater.
In addition, the temperature that the crystallization temperature that the condition of heating is former material 2 is above, fusing point is following, for example former material 2 is ethene-alpha-olefin copolymer (b) while forming by above-mentioned propylene resin (a) and metallocene, its condition be former material 2 surface temperature more than 120 ℃, not enough fusing point.
In addition, drive unit is connected with in the first warm-up mill 221, the second warm-up mill 222 and the 3rd warm-up mill 223 at least any 1.In addition, drive unit, by driving, makes at least any 1 rotation in the first warm-up mill 221, the second warm-up mill 222 and the 3rd warm-up mill 223 connected.
Heating is formed endless belt-shaped with endless belt 227 by such as stainless steel, carbon steel, titanium alloy etc.In addition, gauge can be set arbitrarily, more than the preferred 0.3mm of intensity.
In addition, this heating is set up on the first warm-up mill 221, the second warm-up mill 222 and the 3rd warm-up mill 223 with endless belt 227, in rotary moving by the driving of drive unit.In addition, drive unit will heat to drive to control by the translational speed of endless belt 227 and be, the cooling translational speed with endless belt 115 in rotary moving with the driving of the drive unit of above-mentioned cooling pressurizing unit 110 is roughly the same.
The 4th warm-up mill 224 is configured to outer peripheral face and uses the outer peripheral face of endless belt 227 relative with heating, with the outside tangent line of the first warm-up mill 221 and the second warm-up mill 222, intersects.The 4th warm-up mill 224 sets the former material 2 into using importing preheating device 210 preheatings between the outer peripheral face of endless belt 227 in outer peripheral face and the heating of the 4th warm-up mill 224, but flexible rotating.
The outer peripheral face of rubber rollers 225 uses the outer peripheral face of endless belt 227 relative with the heating that winding stand is located at the part of the first warm-up mill 221.
In addition, rubber rollers 225, at least cover and be formed with not shown padded coaming at outer peripheral face.This padded coaming can be used the material same with the second chill roll 112 of cooling pressurizing unit 110.In addition, rubber rollers 225 can be also that padded coaming has covered the almost whole of outer peripheral face, or whole formed by padded coaming etc. almost.
In addition, rubber rollers 225 will be pressed on from the former material 2 of preheating device 210 outer peripheral face of heating with endless belt 227, make its heat adhere to.That is, rubber rollers 225, set as being situated between and use endless belt 227 through former material 2 and the heating of preheating, with the first warm-up mill 221, contacts.In addition, former material 2 is advanced with the state of endless belt 227 to be attached to heating, then by the 4th warm-up mill 224, is pushed, clamps and advance.
Thus, guide roller 226 will heat with endless belt 227 and 224 of the 4th warm-up mills and be heated and press and the transparent resin laminate 3 that obtains, guide as the outer peripheral face from the 4th warm-up mill 224 peels off, and from heating, with the outer peripheral face of endless belt 227, peel off.
The cooling device 230 of annealing device 20, will pass through the heat treated transparent resin laminate 3 of annealing device body 220 cooling.This cooling device 230, possess the first cooled guide roller 231, the second cooled guide roller 232, a pair of guide roller 233 arranged.These the first cooled guide rollers 231, the second cooled guide roller 232 and a pair of guide roller 233 can be used the material good such as heat conductivities such as metals.
The first cooled guide roller 231, the second cooled guide roller 232 and a pair of guide roller 233, set as being positioned on nearly straight line, makes to crawl and set up through the heat treated transparent resin laminate 3 of annealing device body 220.In these the first cooled guide rollers 231 and the second cooled guide roller 232, be provided with the not shown temperature adjustment device of the steam heating type etc. of capable of regulating surface temperature.In addition, as temperature adjustment device, be not limited to the formation that directly is arranged at each cooled guide roller 231,232, the roller of cooling special use also can be set separately or be undertaken cooling by being arranged at outside cooling device.
In addition, a pair of guide roller 233 is equipped on manufacture downstream one side of the second cooled guide roller 232.In addition, these guide rollers 233 also are located at the above-below direction for the moving direction intersection of transparent resin laminate 3, and outer peripheral face is relative, clips the transparent resin laminate 3 be cooled between outer peripheral face.
In addition, cooling device 230, be not limited to the formation that sets of the first cooled guide roller 231, the second cooled guide roller 232 and a pair of guide roller 233, can be also be provided with the formation of one or more rollers and use endless belt etc. can cooling transparent resin laminate 3 any formation.
[formation of former material]
Then the formation of the former material 2 of transparent resin laminate is manufactured in explanation by above-mentioned manufacturing installation 1.
Former material 2 is for for example, and the 2A two sides, intermediate layer of sheet is provided with 2 kinds of 3 layers of structures of superficial layer 2B.
Intermediate layer 2A, by crystalline resin, for example polypropylene-based resin forms.Particularly preferably intermediate layer 2A is that the polypropylene-based resin that ethene-alpha-olefin copolymer (b) is principal component forms by take propylene resin (a) and metallocene.
Propylene resin (a), preferably isotactic pentad fraction more than 85%, below 99%, melt index (MeltFlow Rate: hereinafter referred to as MFR) divides below above, 5.0g/10 divides at 0.5g/10.In addition, more preferably isotactic pentad fraction more than 90%, below 99%, divide at 2.0g/10～4.0g/10 of MFR divides.
Herein, isotactic pentad fraction refers to, the isotaxy mark of the five-tuple unit's (5 continuous isotaxy bondings of propylene monomer) in the strand that resin forms.The determination method of this mark for example 687 pages of institutes of マ Network ロ モ レ キ ユ mono-Le ズ (Macromolecules) the 8th volume (1975) is put down in writing, by
13c-NMR measures.
In addition, for the mensuration of MFR, can be according to JIS-K7210, in measuring 230 ℃ of temperature, loading 2.16kg mensuration.
In addition, the isotactic pentad fraction of propylene resin (a) is lower than 85%, and the rigidity of formed products may be not enough.On the other hand, isotactic pentad fraction is higher than 99%, and the transparency may descend.Therefore, propylene resin (a) is preferably set to isotactic pentad fraction more than 85%, below 99%.
In addition, propylene resin (a), MFR is less than 0.5g/10 and divides, and the shear stress grow of mold-slide section during extrusion molding promotes crystallization, and the transparency may descend.On the other hand, MFR is greater than 5.0g/10 and divides, and it is large that jet stretch multiple during hot forming (De ロ mono-ダ ウ Application) becomes, and formability may descend.Therefore, propylene resin (a), MFR preferably sets at 0.5g/10 and divides below above, 5.0g/10 divides.
On the other hand, metallocene is ethene-alpha-olefin copolymer (b), uses the metallocene catalyst manufacture, and density is at 898kg/m
3above, 913kg/m
3below, MFR divides below above, 6.0g/10 divides at 0.5g/10.
Herein, density is in 23 ℃ of test temperatures, measure according to JIS-K7112 " plastics-density of non-foamed plastic and the assay method of proportion ".
For the mensuration of MFR, can be according to JIS-K7210, in measuring 190 ℃ of temperature, loading 2.16kg mensuration.
In addition, as metallocene, be ethene-alpha-olefin copolymer (b), preferably with the refractive index of propylene resin equal material, particularly straight chain shape low density polyethylene (LDPE) roughly.
Metallocene is ethene-alpha-olefin copolymer (b), and density is less than 898kg/m
3or density is greater than 913kg/m
3, with the refractive index of matrix propylene resin (a), not conforming to, propylene resin (a) becomes large with the anaclasis that metallocene is the interface of ethene-alpha-olefin copolymer (b), can be detrimental to the transparency.
That is, propylene resin (a) and metallocene are that the refractive index of ethene-alpha-olefin copolymer (b) is roughly the same, and the transparency of the transparent resin laminate 3 of manufacture promotes.
Fig. 3 be show by chilling be configured as sheet, the chart of the relation of the refractive index of the polypropylene foil of crystallization and density by heat treatment.With reference to Fig. 3, during by the polypropylene foil heat treatment of chilling, crystallization, refractive index is 1.504～1.509, and density is at 900～907kg/m
3scope in.Therefore, the metallocene of interpolation is that the words of refractive index in 1.504～1.509 scope of ethene-alpha-olefin copolymer (b) just can not damaged the transparency.
Herein, the refractive index of material and the relation of density, can mean by Lorentz-Lorenz formula shown in following formula (1).The molecular weight that the density that the refractive index that n is the object material, ρ are the object material, M are the object material, N are the polarizability that Avogadro constant number, P are the object material.
[several 1]
Because Avogadro constant number N, polarizability P, molecular weight M are constant, so the following formula (2) that refractive index n can be parameter in order to density p shows.
[several 2]
Wherein,
As shown in above formula (2), because density is relevant to refractive index, metallocene is that ethene-alpha-olefin copolymer (b) can be selected by density.
Therefore, metallocene is ethene-alpha-olefin copolymer (b), is preferably set to density at 898kg/m
3above, 913kg/m
3below.
In addition, metallocene is ethene-alpha-olefin copolymer (b), and MFR is less than the words that 0.5g/10 divides, be difficult to be dispersed in the molecule of matrix propylene resin (a), metallocene is that the dispersion footpath of ethene-alpha-olefin copolymer (b) becomes large, produces scattering of light, can be detrimental to the transparency.On the other hand, MFR is greater than 6.0g/10 and divides, and with the intermiscibility variation of matrix propylene resin (a), metallocene is that ethene-alpha-olefin copolymer (b) can't disperse, and becomes huge particle and exists.In this kind of state, metallocene is that the particle of ethene-alpha-olefin copolymer (b) can produce scattering of light, diminishes the transparency.
Various blend polymers are mixing during to poised state, and the Dispersed Phase Size D of blend can, as shown in the formula shown in (3), mean with the Wu formula.Herein, D is that Dispersed Phase Size, γ are interfacial tension, η
mfor viscosity, the G of matrix is shear rate, η
dfor dispersed phase viscosity.
[several 3]
Wherein,
Viscosities il due to matrix
m, shear rate G is certain, Dispersed Phase Size D is with dispersed phase viscosity η
dwith interfacial tension γ be parameter.Known as shown in above formula (3), the viscosity of matrix and decentralized photo more approaches 1, and Dispersed Phase Size D is less, and light scattering reduces, and the transparency promotes.In the present invention, shear rate 60sec
-1the time ratio of viscosities be 1.0～3.0, demonstrate the transparency good.That the MFR that is ethene-alpha-olefin copolymer (b) at the metallocene of above-mentioned range of viscosities is that 0.5g/10 divides is above, 6.0g/10 divides.
In addition, in the 2A of intermediate layer, more than preferably adding propylene resin (a) 80 quality %, below 99.5 quality %, metallocene is more than ethene-alpha-olefin copolymer (b) 0.5 quality %, below 20 quality %.
That is, metallocene is that the interpolation quantitative change of ethene-alpha-olefin copolymer (b) is many, and the rigidity of the former material 2 obtained may descend.On the other hand, metallocene is the words that the addition of ethene-alpha-olefin copolymer (b) tails off, metallocene is that ethene-alpha-olefin copolymer (b) can't fully disperse in propylene resin (a), and it is insufficient that the growth of spherocrystal suppresses, and is difficult to promote the transparency.
On the other hand, superficial layer 2B, by the melt index that compares to intermediate layer 2A (Melt Flow Rate: hereinafter referred to as MFR), large and short crystalline resin, for example polypropylene-based resin of relaxation time forms.Particularly, superficial layer 2B, preferably than the MFR of intermediate layer 2A more than 1.5 times.1.5 times of MFR less thaies, the transparency to improve effect little.In addition, the relaxation time is preferably below 80% of intermediate layer 2A.Relaxation time is greater than 80%, the transparency to improve effect little.
For the mensuration of MFR, according to JIS-K7210, to measure 230 ℃ of temperature, loading 2.16kg mensuration.
In addition, the relaxation time (τ) is in the rotary-type flow graph of manufacturing in レ オ メ ト リ Star Network ス society, tries to achieve cone-plate and is
cone angle is the angular frequency of the frequency dispersion under 175 ℃ of 0.1 radians (rad), temperature while the measuring=relaxation time of 0.01rad/ under second.Concrete, the complex modulus G measured for resin particle
*(i ω) is as shown in the formula (4), by stress σ
*with strain γ
*be defined as σ
*/ γ
*, relaxation time τ tries to achieve by following formula (5).
[formula (4)]
G
*(iω)＝σ
*/γ
*＝G’(ω)+IG″(ω)…(4)
[formula (5)]
τ(ω)＝G’(ω)/(ωG″(ω))…(5)
(in formula, G ' means storage modulus, G " the expression loss modulus.)
Describe the relaxation time (τ) in detail herein.
Apply external force to the substance system in poised state, after reaching new poised state or stable state, remove the words of external force, internal motion by this system, the phenomenon that system is returned to initial poised state is called relaxation phenomena, as the characteristic time constant of relaxation required time standard, is called the relaxation time.For example, in the situation of high molecular shaping processing (extrusion molding), make the macromolecule of melting flow, now strand is elongated, draws neat (orientation) to flow direction.In addition, flow after end, cooling beginning, put on the stress relieved of molecule, each strand setting in motion, soon towards any direction (relaxation that is called strand).
Relaxation time, when extrusion molding in, relevant to the reply easness of the strand that is orientated the direction of extrusion, the relaxation time more in short-term, means easily to reply.
In addition, in this example, though former material 2 is 3 layers, being not limited to this, can be also only at the single face of intermediate layer 2A, to form 2 layers of superficial layer 2B.In addition, former material 2, can be also to be provided with more than 3 layers of superficial layer 2B on the surface that 2A, intermediate layer, intermediate layer 2A at least simultaneously is set of substrate layer.
In addition, as resin raw material, be not limited to polypropylene-based resin.
[manufacture method of transparent resin laminate]
Then the operation of sheet transparency resin laminate 3 is manufactured in explanation by above-mentioned manufacturing installation 1.
At first, by temperature adjustment device, carry out temperature control, make the cooling outer peripheral face temperature with endless belt 115 and the 3rd chill roll 113 of the cooling pressurizing unit 110 of former material building mortion 10 remain on the dew point of molten resin 2C above, below 50 ℃.Herein, when temperature surpasses 50 ℃, in the good transparency that can't obtain former material 2, it is many that alpha-crystal becomes, and may be difficult to hot forming.Therefore, control is below 50 ℃, preferably below 30 ℃.In addition, during lower than dew point, surface meeting dewfall, the water droplet spot may appear in thin slice, is difficult to even masking, more than therefore being controlled at dew point.
In addition, by temperature adjustment device, carry out temperature control, make in the annealing device body 220 of annealing device 20, heating remains on the crystallization temperature of former material 2 by the outer peripheral face temperature of endless belt 227 or the 4th warm-up mill 224 more than, below fusing point.In addition, can carry out temperature control, make in the preheating device 210 of annealing device 20, preheating be the temperature cooling by the cooling pressurizing unit 110 of former material building mortion 10, more than 50 ℃, below crystallization temperature.
Under this state, T-shaped die head 102 from T-shaped die head pressurizing unit 100, the molten resin 2C of intermediate layer 2A and superficial layer 2B, with the extruding of the state of sheet lamination, is directed between the outer peripheral face of cooling the 3rd chill roll 113 with endless belt 115 and rotation in rotary moving of cooling pressurizing unit 110.
The molten resin 2C of the intermediate layer 2A of this importing and the sheet lamination of superficial layer 2B, in by planar crimping by chilling.
During chilling, be subject to the extruding force of 113 of the second chill roll 112 and the 3rd chill rolls, elastomeric material 111A strain is compressive state.In addition, molten resin 2C in center angle θ 1 part (with reference to Fig. 2) of the second chill roll 112 of elastomeric material 111A strain and the 3rd chill roll 113, is jammed with endless belt 115 with cooling simultaneously, be subject to the post-equalization power of elastomeric material 111A, by planar extruding.
In addition, face now press preferred 0.1MPa above, below 20.0MPa.Herein, face forces down in 0.1MPa, cooling with between endless belt 115, the 3rd chill roll 113 and molten resin 2C, having air to be involved in, and the thin slice outward appearance may be bad.On the other hand, face is pressed higher than 20.0MPa, and the angle based on the cooling life-span with endless belt 115 is unsatisfactory.Therefore, more than the face of planar extruding is installed with and fixes on 0.1MPa, below 20.0MPa.
Then, be sandwiched in the second chill roll 112 and cooling with intermediate layer 2A and superficial layer 2B between endless belt 115, at the nearly lower half of the second chill roll 112 in corresponding circular arc portion, by the second chill roll 112 and cooling with the planar crimping in endless belt 115.In addition, intermediate layer 2A and superficial layer 2B, go out cooling water 116A to cooling by the 115 back side, endless belt one side spray by cooling water nozzle 116, by further chilling.
In addition, face now press be preferably set to 0.01MPa above, below 0.5MPa.In addition, the temperature of cooling water 116A be preferably set to more than 0 ℃, below 30 ℃.In addition, the cooling water 116A of ejection is when being reclaimed by tank 117, and the water 117A of recovery is discharged from by discharge outlet 117B.
Herein, face forces down in 0.01MPa, and the cooling control of crawling with endless belt 115 becomes difficult, and possibly can't steady production.On the other hand, face is pressed higher than 0.5MPa, and be applied to the cooling tension force with endless belt 115 and uprise, the angle based on the life-span, unsatisfactory.Therefore, more than the face of planar extruding is pressed and is preferably set to 0.01MPa, below 0.5MPa.
So, the second chill roll 112 and cooling with between endless belt 115 to the words of intermediate layer 2A and the planar crimping of superficial layer 2B, after cooling, be attached to cooling with endless belt 115 intermediate layer 2A and superficial layer 2B, along with cooling, with endless belt 115 in rotary moving the time, on the 3rd chill roll 113, move.In addition, through intermediate layer 2A and the superficial layer 2B of stripper roll 119 guiding, be situated between cooling with endless belt 115, cooling by the 3rd chill roll 113.
In addition, be attached to the cooling water with 115 back sides, endless belt, be removed by being arranged at the suction roll 118 that the second chill roll 112 moves in way to the 3rd chill roll 113.
The intermediate layer 2A be cooled on the 3rd chill roll 113 and superficial layer 2B, peel off with endless belt 115 from cooling by stripper roll 119, is configured as former material 2.
The former material 2 that this obtains, internal haze is below 20%, and at least the surface roughness of single face is below Rmax=0.5 μ m.That is, in cooling pressurizing unit 110, preferably with can obtain internal haze below 20% and the condition of the former material 2 below at least unilateral surface roughness Rmax=0.5 μ m carry out chilling and planar crimping.
Herein, mist degree (Tan り degree) can be according to JIS-K-7105, the total light transmittance (Tt) of the light full dose seen through to former material 2 irradiation light by expression and the ratio of the diffusing light transmitance (Td) seen through spread through former material 2, try to achieve with following formula (6).In addition, total light transmittance (Tt) is the parallel rays transmitance (Tp) and diffusing light transmitance (Td) sum coaxially seen through with incident light.
[formula (6)]
Mist degree (H)=(Td/Tt) * 100... (6)
In addition, internal haze refers to, and measures the transparency of thin slice inside for the impact that is not subject to the sheet surface roughness, in the sheet surface silicon-coating, and the mist degree of mensuration.Herein, when the value of internal haze is greater than 20%, even implemented the heating of annealing device body 220 of back segment and the processing of planar extruding, internal haze also can uprise, and possibly can't obtain high transparent transparent resin laminate 3.
On the other hand, surface roughness is greater than Rmax=0.5 μ m, when the 4th warm-up mill 224 in the annealing device body 220 of back segment and heating are adhered to by endless belt 227 heat, may be involved in air, produces so-called bubble.Therefore, preferably former material 2 is configured as internal haze below 20%, surface roughness is below Rmax=0.5 μ m.
Then, the outer peripheral face that the former material 2 that cooling pressurizing unit 110 is shaped is set up in the first preheat roll 211, the second preheat roll 212 and the 3rd preheat roll 213 of preheating device 210 makes it mobile, carries out preheating.
In addition, the rubber rollers 225 and the heating that the former material of preheating device 210 preheatings 2 are imported to annealing device body 220 are used between the outer peripheral face of endless belt 227.The former material 2 of this importing,, adhered to by heat by the planar outer peripheral face of heating with endless belt 227 that be squeezed in by rubber rollers 225.Make the former material 2 that this heat is adhered to jointly move with endless belt 227 with heating in rotary moving, import between the outer peripheral face of heating with endless belt 227 and the 4th warm-up mill 224.The former material 2 of this importing, with the 4th warm-up mill 224 of the former material 2 that is being situated between, through the heating of the 4th warm-up mill 224 tension force effects with endless belt 227 by planar crimping.
Heating-up temperature in the heat treatment of this former material 2, more than the crystallization temperature of former material 2, below fusing point.For example, former material 2 is ethene-alpha-olefin copolymer (b) while forming by above-mentioned propylene resin (a) and metallocene, with the surface temperature of former material 2 more than 120 ℃, the condition heating of not enough fusing point.In addition, face during heat treatment is pressed, and can suitably set according to the shape be shaped.
Herein, under the lower temperature of the crystallization temperature lower than former material 2, former material 2 softening insufficient, can't form the shape of expectation.On the other hand, under the higher temperature of the fusing point higher than former material 2, the high-order that in cooling pressurizing unit 110, chilling obtains is destructurized, and the gonorrhoea that becomes can't obtain the transparency.
Afterwards, former material 2 is peeled off by the outer peripheral face from the 4th warm-up mill 224, is being attached to heating with being heated in movement under the state of endless belt 227.In addition, the former material 2 of heating, by the guiding of guide roller 226, is peeled off with endless belt 227 from heating, as the transparent resin laminate 3 of sheet, extracts out.
The transparent resin laminate 3 that this is obtained is set up in the first cooled guide roller 231 of cooling device 230 and the outer peripheral face of the second cooled guide roller 232, crawls mobile cooling, from 233 of a pair of guide rollers, sends.
In addition, the transparent resin laminate 3 as product be sent batches by for example not shown devices for taking-up.
More than the gross thickness of the transparent resin laminate 3 obtained by above manufacture method is preferably dimensioned to be 160 μ m, less than 500 μ m.
Herein, when the gross thickness size of transparent resin laminate 3 is thinner than 160 μ m, the chilling effect of each chill roll 111～114 of cooling pressurizing unit 110 is insufficient, can obtain not necessarily wanting the transparency of the degree of lamination.On the other hand, the gross thickness size of transparent resin laminate 3 when above, can't be expected heat conducting chilling effect at 500 μ m, and result is that the effect of lamination can't embody.
[action effect of embodiment]
In above-mentioned example, the formed superficial layer 2B of crystalline resin that at least one side is upper, large by the MFR that compares to the crystalline resin that forms intermediate layer 2A and the relaxation time is short that is formed with the intermediate layer 2A of crystalline resin and is formed at this intermediate layer 2A.In addition, at least any one party in intermediate layer 2A and superficial layer 2B, concrete is that the metallocene that intermediate layer 2A contains the manufacture of use metallocene catalyst is ethene-alpha-olefin copolymer.
Therefore, the stress while pushing as sheet, intermediate layer 2A applied, relaxed by superficial layer 2B, can reduce and cause the residual stress easily resulted from apart from the spherocrystal generation of surperficial certain depth position.In addition, containing metallocene by the depth location produced at spherocrystal is ethene-alpha-olefin copolymer, can suppress generation and the growth of spherocrystal, and in the amount that reduces spherocrystal, the size of spherocrystal also diminishes.Therefore, can reduce the scattering of light that spherocrystal causes, promote the transparency (reduction mist degree).
In addition, each crystalline resin of intermediate layer 2A and superficial layer 2B pushes in molten condition, cooling under platy layer cumuliformis state, forms former material 2, and this former material 2 is heat-treated with the temperature more than crystallization temperature, below fusing point.
Therefore, not there will be high-order in the good former material 2 of the cooling degree of crystallinity obtained destructurized, damage transparent problem, can form well sheet, obtain the sheet transparency resin laminate 3 of high transparent.
In addition, as intermediate layer 2A, by the isotactic pentad fraction more than 80 quality %, below 99.5 quality % more than 85%, below 99%, MFR divides above, 5.0g/10 to divide following propylene resin (a) at 0.5g/10, and the use metallocene catalyst that 0.5 quality % is above, 20 quality % are following manufacture, density is at 898kg/m
3above, 913kg/m
3below, at 0.5g/10, to divide above, 6.0g/10 to divide following metallocene be that ethene-alpha-olefin copolymer (b) forms to MFR.
Therefore, the propylene resin in the 2A of intermediate layer (a) with suppress metallocene that spherocrystal grows up be the refractive index of ethene-alpha-olefin copolymer (b) roughly in same degree, can promote the transparency.
In addition, due to propylene resin (a) and metallocene be the value of ratio of viscosities of ethene-alpha-olefin copolymer (b) 1.0 or more, below 3.0, therefore can be dispersed well, can prevent can't be dispersed and cause transparency decline.
In addition, the propylene resin of interpolation (a) is more than 80 quality %, below 99.5 quality %, and metallocene is that ethene-alpha-olefin copolymer (b) is more than 0.5 quality %, below 20 quality %.Therefore, can prevent that the metallocene that becomes impurity for propylene resin (a) from being the problem that ethene-alpha-olefin copolymer (b) too much causes rigidity to descend.On the other hand, also can prevent from suppressing the metallocene that spherocrystal grows up is that ethene-alpha-olefin copolymer (b) is very few, and propylene resin (a) integral body can't fully disperse, can't fully suppress spherocrystal and grow up, can't fully promote transparent possibility.
In addition, the crystalline resin as forming intermediate layer 2A and superficial layer 2B, preferably used propylene resin.
Therefore, by use be widely used, sheet-like formed and heat treatment etc. easily, propylene resin on human body without impact, transparent resin laminate 3 can be used in various fields, and transparent resin laminate 3 can be provided at an easy rate.
In addition, as metallocene, be ethene-alpha-olefin copolymer, use straight chain shape low density polyethylene (LDPE).
Therefore, roughly the same with the refractive index of propylene resin (a), and easily dispersed mixing, can easily promote the transparency.Therefore, can easily form the transparent resin laminate 3 of high transparent.
In addition, the former material 2 of formation is 2 kinds of 3 layers of structures that are provided with superficial layer 2B on 2A two sides, the intermediate layer of sheet.
Therefore, compare to the situation that is arranged on single face, the stress applied during intermediate layer 2A extruding can more relax, and can further reduce residual stress, further promotes the transparency.
In addition, can be also, on the two sides of the formed substrate layer of crystalline resin as base material, intermediate layer 2A is set, the surface of interbed 2A arranges 5 layers of structure of superficial layer 2B more in these.
Make 3 kinds of 5 layers of structures of this kind, even, at the low viscous propylene resin of superficial layer lamination (a), also can hinder the growth of residual spherocrystal, suppress to cause light scattering and make the transparency descend the generation of huge spherocrystal.In addition, by reduction, be added with the thickness that metallocene is the layer of ethene-alpha-olefin copolymer (b), the metallocene that can prevent different material is the refraction of the light that causes of ethene-alpha-olefin copolymer (b), therefore can further promote the transparency.
Particularly by using the crystalline resin of propylene resin as substrate layer, because the refractive index of substrate layer and intermediate layer 2A and superficial layer 2B is roughly the same, even 3 kinds of 5 layers of structures also can obtain the transparent resin laminate 3 of high transparent.
In addition, in the manufacturing installation 1 of present embodiment, with cooling pressurizing unit 110, manufacture former material 2, directly heat-treat by annealing device 20, manufacture continuously transparent resin laminate 3.
Therefore, can further manufacture efficiently the transparent resin laminate 3 of the high transparent of expectation.
[variation]
In addition, what sample state described above showed is a sample state of the present invention, and the present invention is not limited to above-mentioned example.Distortion and improvement in the purpose of inventing at attainable cost and the scope of effect also are contained in content of the present invention.
For example, also former material 2 can be batched after manufacture, to the annealing device 20 of split, supply with the former material 2 of having manufactured and heat-treat, manufacture transparent resin laminate 3, the formation of manufacturing installation 1 is not limited to above-mentioned embodiment.
In addition, as former material 2, be to be provided with the formation of superficial layer 2B on 2A two sides, intermediate layer, but can be also that 2 layers of formation of superficial layer 2B only are set at the single face of intermediate layer 2A.In addition, can be also that single face at substrate layer arranges intermediate layer 2A, 3 kinds of 3 layers of structures of superficial layer 2B are set on the surface of this intermediate layer 2A.In addition, can also be that only on the two sides of substrate layer, the surface of the side intermediate layer 2A in set intermediate layer 2A arranges the 3 kinds 4 layers structure etc. of superficial layer 2B.
In addition, propylene resin (a) and metallocene are the physical property of ethene-alpha-olefin copolymer (b) and addition etc., as long as the intermediate layer 2A for crystalline resin, the condition that the MFR of superficial layer 2B is large, the relaxation time is short gets final product, and can suitably set according to the transparent resin laminate 3 of expectation.In addition, being not limited to propylene resin (a) and metallocene is ethene-alpha-olefin copolymer (b).
[embodiment]
(embodiment 1～8, comparative example 1～5)
In above-mentioned embodiment, the actual conditions of manufacturing installation and manufacture method is as follows.In addition, the material resin in each embodiment and each comparative example forms as shown in table 2～4 as table 1, layer.
The mensuration of the melt index of material resin
Use the material resin shown in table 1, by the annealing device 20 of the above-mentioned manufacturing installation 1 of former material 2 use, manufacture container.This creates conditions as follows.
Extruder:
The first substrate layer is used; Diameter 90mm
The second substrate layer is used; Diameter 50mm
The width dimensions of rack type die: 900mm
(lamination of the molten resin 2C of feed sleeve pipe mode)
The surface roughness of chill roll: Rmax=0.1 μ m
The cooling endless belt of using:
Material; Separating out curing is stainless steel
Surface roughness; Rmax=0.1 μ m
Width dimensions; 900mm
Length dimension; 7700mm
Gauge; 0.8mm
The acquisition speed of former material 2: 10m/ divides
The width dimensions of former material 2: 780mm
Temperature when the container heating is shaped: 130 ℃ of the surface temperatures of former material 2
In addition, measure the internal haze of the former material 2 obtained and the mist degree of container.
Herein, internal haze is used mist degree to measure machine (NDH-300A, Japanese electric look Industrial Co., Ltd manufacture) to measure.The mensuration of internal haze, be after the two sided coatings silicone oil of thin slice, and the impact in the thin slice outside is removed on the two sides of clamping this thin slice with glass plate, with mist degree mensuration machine, measures.The mist degree of container, by representative to thin slice irradiate light, the total light transmittance (Tt) of the full dose of the light that sees through and ratio through thin slice diffusion, the diffusing light transmitance (Td) that sees through, with the formula (3) of above-mentioned embodiment, try to achieve.
In addition, the average thickness of container, used micrometer (ID-C112C, the ミ of Co., Ltd. Star ト ヨ manufacture) to measure.Cutting 5cm * 5cm，Yi center, hold the mean value of 3 points of total of 2 points from container top surface is 1 sample, the average thickness that the mean value of 5 samples of take is container.
The MFR and the density that as metallocene, are the straight chain shape low density polyethylene (LDPE) (LLDPE) of ethene-alpha-olefin copolymer are put down in writing as above-mentioned embodiment.
Measurement result is as shown in table 2～4.
[result]
From result shown in table 2～4, density has been added at 898kg/m in intermediate layer
3above, 913kg/m
3below, MFR divides above, 6.0g/10 to divide following metallocene at 0.5g/10 to be the thin slice of ethene-alpha-olefin copolymer (b), can to obtain the good transparency.By metallocene, be the interpolation of ethene-alpha-olefin copolymer (b), it is large that the transparency promotes effect.
The industry utilizability
The present invention can be used in such as the packing purposes of food, pharmaceuticals, change make-up product etc. and other and require transparent various uses.
Claims (10)
1. the manufacture method of a transparent resin laminate, described transparent resin laminate possesses the intermediate layer formed by crystalline resin and is arranged at least superficial layer formed by crystalline resin of one side in this intermediate layer, it is characterized in that,
The crystalline resin of described superficial layer is, compares to the crystalline resin that forms described intermediate layer, the resin that melt index is large, the relaxation time is short,
The crystalline resin that forms described intermediate layer and at least one party in the crystalline resin that forms described superficial layer contain that to use the metallocene of metallocene catalyst manufacture be ethene-alpha-olefin copolymer,
By forming the crystalline resin and the crystalline resin melting separately, the extruding that form described superficial layer in described intermediate layer, cooling with the state of sheet lamination, form the resin laminate,
This resin laminate is heat-treated with the temperature more than crystallization temperature, below fusing point.
2. the manufacture method of transparent resin laminate according to claim 1, is characterized in that,
The isotactic pentad fraction that described intermediate layer is above by: 80 quality %, 99.5 quality % are following more than 85%, below 99%, melt index divides above, 5.0g/10 to divide following propylene resin at 0.5g/10, and
0.5 that the use metallocene catalyst that quality % is above, 20 quality % are following is manufactured, density is at 898kg/m
3above, 913kg/m
3below, at 0.5g/10, to divide above, 6.0g/10 to divide following metallocene be that ethene-alpha-olefin copolymer forms to melt index.
3. according to the manufacture method of claim 1 or transparent resin laminate claimed in claim 2, it is characterized in that, the crystalline resin that forms described intermediate layer and described superficial layer is propylene resin.
4. the manufacture method of transparent resin laminate according to claim 3, is characterized in that, described metallocene is that ethene-alpha-olefin copolymer is straight chain shape low density polyethylene (LDPE).
5. according to the manufacture method of claim 1 ~ described transparent resin laminate of claim 4 any one, it is characterized in that, on the two sides of the substrate layer formed by crystalline resin, described intermediate layer be set,
On the surface in this intermediate layer, described superficial layer is set.
6. the manufacture method of transparent resin laminate according to claim 5, is characterized in that, the crystalline resin that forms described substrate layer is propylene resin.
7. a formed body, possess the intermediate layer formed by crystalline resin and at least superficial layer formed by crystalline resin of one side that is arranged at this intermediate layer, it is characterized in that,
The crystalline resin of described superficial layer is, compares to the crystalline resin that forms described intermediate layer, the resin that melt index is large, the relaxation time is short,
The crystalline resin that forms described intermediate layer and at least one party in the crystalline resin that forms described superficial layer contain that to use the metallocene of metallocene catalyst manufacture be ethene-alpha-olefin copolymer,
By forming the crystalline resin and the resin laminate that the crystalline resin sheet lamination, the chilling under molten condition that form described superficial layer obtain in described intermediate layer, with the temperature more than crystallization temperature, below fusing point, carry out hot forming.
8. formed body according to claim 7, is characterized in that, on the two sides of the substrate layer formed by crystalline resin, described intermediate layer is set,
On the two sides in this intermediate layer, described superficial layer is set.
9. a resin laminate, form transparent resin laminate by heat treatment, it is characterized in that,
Possess the intermediate layer formed by crystalline resin and at least superficial layer formed by crystalline resin of one side that is arranged at this intermediate layer,
The crystalline resin in described intermediate layer contains: the isotactic pentad fraction that 80 quality % are above, 99.5 quality % are following 85% or more, 99% below, melt index divides above, 5.0g/10 to divide following propylene resin at 0.5g/10, and 0.5 quality % is above, the manufacture of the use metallocene catalyst below 20 quality %, density is at 898kg/m
3above, 913kg/m
3below, at 0.5g/10, to divide above, 6.0g/10 to divide following metallocene be ethene-alpha-olefin copolymer to melt index,
The crystalline resin of described superficial layer compares to the crystalline resin that forms described intermediate layer, and melt index is large, the relaxation time is short.
10. resin laminate according to claim 9, is characterized in that, on the two sides of the substrate layer formed by crystalline resin, described intermediate layer is set,
On the two sides in this intermediate layer, described superficial layer is set.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010188696A JP5713604B2 (en) | 2010-08-25 | 2010-08-25 | Method for producing transparent resin laminate, molded article, and resin laminate |
| JP2010-188696 | 2010-08-25 | ||
| PCT/JP2011/069006 WO2012026478A1 (en) | 2010-08-25 | 2011-08-24 | Method for producing transparent resin laminate, molded body and resin laminate |
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| CN103097132A true CN103097132A (en) | 2013-05-08 |
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| CN2011800405290A Pending CN103097132A (en) | 2010-08-25 | 2011-08-24 | Method for producing transparent resin laminate, molded body and resin laminate |
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| Country | Link |
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| JP (1) | JP5713604B2 (en) |
| KR (1) | KR20130100985A (en) |
| CN (1) | CN103097132A (en) |
| TW (1) | TW201213127A (en) |
| WO (1) | WO2012026478A1 (en) |
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| JP5878695B2 (en) * | 2011-04-01 | 2016-03-08 | 出光ユニテック株式会社 | Transparent recycling sheet manufacturing method and transparent recycling sheet |
| WO2013161291A1 (en) * | 2012-04-26 | 2013-10-31 | 出光ユニテック株式会社 | Laminated body and method for constructing same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08112865A (en) * | 1994-10-17 | 1996-05-07 | Chisso Corp | Manufacture of multi-layered molded item |
| CN1198445A (en) * | 1997-03-26 | 1998-11-11 | 日本聚合化学株式会社 | Propylene resin sheet for thermoforming and process for preparing it |
| CN1938144A (en) * | 2004-03-26 | 2007-03-28 | 出光统一科技株式会社 | Method for producing transparent polypropylene based sheet and transparent polypropylene based sheet |
| JP2007091783A (en) * | 2005-09-27 | 2007-04-12 | Sumitomo Chemical Co Ltd | Film for retort packaging |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2680079B2 (en) * | 1988-11-22 | 1997-11-19 | チッソ株式会社 | Coextrusion laminated film |
| JP3751338B2 (en) * | 1995-07-21 | 2006-03-01 | 出光興産株式会社 | Method for producing impact-resistant plastic sheet |
| JP3416433B2 (en) * | 1996-12-25 | 2003-06-16 | 日本ポリケム株式会社 | Propylene polymer laminated sheet |
| JP5865577B2 (en) * | 2010-03-12 | 2016-02-17 | 出光ユニテック株式会社 | Method for producing transparent laminated sheet and transparent laminated sheet |
-
2010
- 2010-08-25 JP JP2010188696A patent/JP5713604B2/en active Active
-
2011
- 2011-08-24 WO PCT/JP2011/069006 patent/WO2012026478A1/en active Application Filing
- 2011-08-24 KR KR1020137003962A patent/KR20130100985A/en not_active Application Discontinuation
- 2011-08-24 CN CN2011800405290A patent/CN103097132A/en active Pending
- 2011-08-25 TW TW100130549A patent/TW201213127A/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08112865A (en) * | 1994-10-17 | 1996-05-07 | Chisso Corp | Manufacture of multi-layered molded item |
| CN1198445A (en) * | 1997-03-26 | 1998-11-11 | 日本聚合化学株式会社 | Propylene resin sheet for thermoforming and process for preparing it |
| CN1938144A (en) * | 2004-03-26 | 2007-03-28 | 出光统一科技株式会社 | Method for producing transparent polypropylene based sheet and transparent polypropylene based sheet |
| JP2007091783A (en) * | 2005-09-27 | 2007-04-12 | Sumitomo Chemical Co Ltd | Film for retort packaging |
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| Publication number | Publication date |
|---|---|
| JP5713604B2 (en) | 2015-05-07 |
| TW201213127A (en) | 2012-04-01 |
| JP2012045783A (en) | 2012-03-08 |
| WO2012026478A1 (en) | 2012-03-01 |
| KR20130100985A (en) | 2013-09-12 |
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