CN103038276A - Thermoplastic resin foam sheet, method for producing thin sheet of thermoplastic resin foam, and light-reflecting plate - Google Patents
Thermoplastic resin foam sheet, method for producing thin sheet of thermoplastic resin foam, and light-reflecting plate Download PDFInfo
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- CN103038276A CN103038276A CN2011800374945A CN201180037494A CN103038276A CN 103038276 A CN103038276 A CN 103038276A CN 2011800374945 A CN2011800374945 A CN 2011800374945A CN 201180037494 A CN201180037494 A CN 201180037494A CN 103038276 A CN103038276 A CN 103038276A
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
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- 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
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/3442—Mixing, kneading or conveying the foamable material
- B29C44/3446—Feeding the blowing agent
- B29C44/3453—Feeding the blowing agent to solid plastic material
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- 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
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/35—Component parts; Details or accessories
- B29C44/355—Characteristics of the foam, e.g. having particular surface properties or structure
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- 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
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/56—After-treatment of articles, e.g. for altering the shape
- B29C44/5627—After-treatment of articles, e.g. for altering the shape by mechanical deformation, e.g. crushing, embossing, stretching
- B29C44/5654—Subdividing foamed articles to obtain particular surface properties, e.g. on multiple modules
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- 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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
- G02B5/0236—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element
- G02B5/0247—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element by means of voids or pores
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0273—Diffusing elements; Afocal elements characterized by the use
- G02B5/0284—Diffusing elements; Afocal elements characterized by the use used in reflection
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/08—Mirrors
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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- C08J2201/00—Foams characterised by the foaming process
- C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
- C08J2201/032—Impregnation of a formed object with a gas
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- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/048—Bimodal pore distribution, e.g. micropores and nanopores coexisting in the same foam
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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Abstract
Provided is a thermoplastic resin foam sheet in which first bubbles and second bubbles are included in the thermoplastic resin sheet, and the second bubbles have a greater average diameter than that of the first bubbles and are distributed in the thickness-wise middle part of the thermoplastic resin sheet. Further provided is a production method, in which, during formation of a resin sheet (13) by extrusion molding of a thermoplastic resin in which a plasticizer is dispersed, extrusion is performed so that a shear force is applied to the extruded resin sheet (13), and the resin sheet (13) is impregnated with an inert gas, after which the resin sheet (13) is heated and caused to foam; first bubbles (11) are formed on both thickness-wise sides, and second bubbles (12) having a greater average diameter than that of the first bubbles (11) are formed at the thickness-wise center to form a thermoplastic resin foam sheet (10); and the region of the thermoplastic resin foam sheet (10) in which the second bubbles (12) are formed is sliced by a slicing blade (20) to divide the thermoplastic resin foam sheet (10) in the plane intersecting the thickness direction to form thin sheets (14, 15) of the thermoplastic resin foam.
Description
Technical field
The present invention relates to manufacture method and the reflector of the thin-film sheet of thermoplastic resin foam sheet material, thermoplastic resin foam.
Background technology
In the past, as being used for the backlight of lamp box billboard, lighting fixtures or indicating meter etc., the product (for example with reference to patent documentation 1) that obtains by catoptrical plastic sheet material being processed into three-dimensional shape had been proposed.As catoptrical plastic sheet material, the known sheet material (for example with reference to patent documentation 2) that has a kind of inside to have the thermoplastic resin foam of a large amount of micro bubbles.The mean diameter of the bubble that comprises in this sheet material is about 10 μ m, is fine that therefore there is a large amount of walls in the thickness direction at sheet material, and the result has realized high-reflectivity.
In recent years, the product that following formation occurred: the mean diameter of the bubble that these sheet materials that are used for the thermoplastic resin foam of reflector comprise by miniaturization to 2 μ m～3 μ m about, even this sheet film also can be kept reflectivity (for example with reference to patent documentation 3) to 0.5mm.When this reflector is used as the component parts of backlight or billboard, consist of further attenuation, the product that required thickness is thinner in order to make it.But there is restriction in the sheet material that is used for the thermoplastic resin foam of reflector in manufacturing process, and the product about thickness 1.0mm is the industrial the thinnest product that can produce.
For the further thin-walled property of the sheet thickness that makes thermoplastic resin foam, the technology (for example with reference to patent documentation 4) that the sheet material of thermoplastic resin foam is cut into slices is disclosed in recent years.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2002-122863 communique
Patent documentation 2:WO97/001117 brochure
Patent documentation 3:WO06/068009 brochure
Patent documentation 4: TOHKEMY 2009-244749 communique
Summary of the invention
The problem that invention will solve
But, as shown in Figure 3, use the structure of thermoplastic resin foam sheet material 110 for having uniform micro bubble 111 (for example mean diameter is the bubble about 1.0 μ m～1.6 μ m) in the microtomy, produce problems such as " lights (て か り) " on the slicing knife 120 generation chatters when therefore having slice processing or the section of thermoplastic resin foam sheet material 110.For example, if slicing knife 120 produces chatter, then slicing knife can't be at thickness direction incision thermoplastic resin foam sheet material 110.In the poorest situation, thermoplastic resin foam sheet material 110 breaks on the section way.In addition, if produce " light " at sliced surfaces 110S, then sliced surfaces 110S is formed in the situation of reflector as the back side, can see through and be not diffuse-reflectance on sliced surfaces 110S from the light of a surperficial side incident, therefore can cause reflectivity to reduce.Therefore, be the mode on coarse surface according to sliced surfaces 110S preferably, utilize 120 pairs of sheet materials of slicing knife to cut off.The coarse surface of indication refers to for example such lusterless condition of surface in mat glass surface herein.
In addition, in the production process of foam sheet, need this 2 procedure of gas impregnation operation and foamed process, for example in order to utilize method in the past to obtain 2 sheet materials, need to carry out these operations to each sheet material.Therefore, in order to obtain the foam sheet of regulation area, existing needs a large amount of such problems such as gas impregnation equipment.
Problem of the present invention is, intention solves following problems: on thickness direction the thermoplastic resin foam sheet material cut off and when making the slice processing of its attenuation, slicing knife produces the problem of chatter and produces the problem of " light " at the section of thermoplastic resin foam sheet material.
For the means of dealing with problems
The present invention is a kind of thermoplastic resin foam sheet material, it is for comprising the thermoplastic resin foam sheet material of the 1st bubble and the 2nd bubble in thermoplastic resin sheet, the mean diameter of described the 2nd bubble is greater than described the 1st bubble and be distributed in the thickness direction central part of described thermoplastic resin sheet.
In the thermoplastic resin foam sheet material of the present invention, disperse mean diameter to be arranged greater than the 2nd bubble of the 1st bubble at the thickness direction central part, therefore than other parts, be dispersed with a little less than the physical strength of part of the 2nd bubble.Therefore, in the situation that the face that the thickness direction with the thermoplastic resin foam sheet material intersects is cut into slices, the face of the thickness direction central part by being distributed with the 2nd bubble easily utilizes slicing knife to cut into slices.Thus, by cutting into slices at this face, when section, can not produce chatter, and on sliced surfaces, can not produce " light ".And then there is the 2nd bubble in sliced surfaces, thereby has formed coarse surface.
The present invention is a kind of manufacture method of thin-film sheet of thermoplastic resin foam, and it has following operation:
When forming resin sheet in the thermoplastic resin extrusion moulding that will be dispersed with softening agent, extrude according to the mode that makes this resin sheet that is extruded produce shear-stress, make the operation of this softening agent miniaturization in the sheet material of two face side that are scattered in this resin sheet;
Make described resin sheet contain the operation that is soaked with rare gas element;
Heat and make its foaming containing the described resin sheet that is soaked with rare gas element, make thickness direction two face side produce the 1st bubble, and make the thickness direction central part produce mean diameter greater than the 2nd bubble of the 1st bubble, thereby form the operation of thermoplastic resin foam sheet material;
Use slicing knife to have the zone of described the 2nd bubble to cut into slices to the generation of described thermoplastic resin foam sheet material, on the face that intersects with thickness direction, described thermoplastic resin foam sheet material is cut apart, thereby formed the operation of the thin-film sheet of thermoplastic resin foam.
In the manufacture method of the thin-film sheet of thermoplastic resin foam of the present invention, there is mean diameter to be present in the zone of the 2nd bubble of thickness direction central part greater than the 1st bubble and deflection for generation, than this regional periphery, this zone machines weak strength.Cut into slices in zone a little less than utilizing slicing knife to this physical strength, thereby slicing knife can not produce chatter, and on sliced surfaces, can not produce " light ", the thermoplastic resin foam sheet material is divided on the face that intersects with thickness direction, for example can form the thin-film sheet of 2 thermoplastic resin foams.
The reason that does not produce chatter as slicing knife herein, is considered as follows.The one of the main reasons that chatter occurs is that the friction of machined object and cutter is excessive.Act on the zone that is dispersed with the 2nd bubble of thermoplastic resin and the friction between the slicing knife by forming the 2nd bubble larger than the 1st bubble, can alleviating.Therefore, can not produce chatter, can utilize slicing knife successfully the plastic resin foam sheet to be cut into slices.
Then, the reason that does not produce " light " as sliced surfaces is presumed as follows.In manufacture method of the present invention, cut into slices in the zone that has the 2nd bubble a little less than the physical strength, thereby can successfully cut into slices, to occur forming sliced surfaces by the state of the male and fomale(M﹠F) of Bubble formation on the sliced surfaces.That is, can be not smooth because of the friction of slicing knife by the concavo-convex of Bubble formation, therefore on sliced surfaces, can not produce " light ".Thus, can be occurring forming sliced surfaces by the concavo-convex state of the 2nd Bubble formation on the sliced surfaces, so sliced surfaces forms the coarse face that is conducive to luminous reflectance.
The invention effect
Thermoplastic resin foam sheet material of the present invention can be brought into play the effect of following excellence: in the situation about thickness being cut apart cutting into slices, can not produce chatter when utilizing slicing knife to cut into slices, and can not produce " light " on sliced surfaces.
The manufacture method of the thin-film sheet of thermoplastic resin foam of the present invention can be brought into play following excellent effect: in the situation of cutting into slices in the mode that the thickness of thermoplastic resin foam sheet material is cut apart, when section, can not produce chatter, and on sliced surfaces, can not produce " light ".
Above-mentioned and other feature and advantage of the present invention can be suitably with reference to accompanying drawing and clearer by following record.
Description of drawings
Fig. 1 is the partial mode sectional view that shows a preferred exemplary of thermoplastic resin foam sheet material of the present invention.
Fig. 2 is the manufacturing procedure picture of a preferred exemplary in the manufacture method of thin-film sheet that shows thermoplastic resin foam of the present invention with the cross section pattern.
Fig. 3 is the partial mode sectional view of an example that shows the section of thermoplastic resin foam sheet material in the past.
Embodiment
[thermoplastic resin foam sheet material]
For one of thermoplastic resin foam sheet material of the present invention preferred embodiment, utilize the partial mode sectional view of Fig. 1 to describe.
As shown in Figure 1, for thermoplastic resin foam sheet material 10, its inside is dispersed with the 1st bubble 11 and mean diameter greater than the 2nd bubble 12 of the 1st bubble 11.The 2nd bubble 12 is distributed in the thickness direction central part of thermoplastic resin foam sheet material 10.Need to prove that in the scope that section described later is not impacted, the 1st bubble 11 also can be dispersed in the thickness direction central part as the distributed areas of the 2nd bubble 12.
Below, further describe with regard to thermoplastic resin foam sheet material of the present invention.
Use thermoplastic resin among the present invention, but be not particularly limited for its kind, can suitably select such as polyester, polymeric amide, the linear polyphenylene sulfide that is white in color, syndiotactic polystyrene, polyetherketone etc.Among these, preferred polyester.Need to prove, in the present invention, preferably use crystalline thermoplastic resin.Further, in the present invention, as thermoplastic resin, can use separately a kind, also can mix 2 kinds with on use.Herein, " crystallinity " of thermoplastic resin refers to can observe peak crystallization in the heat analysis of DSC etc. is measured.
Representational example as above-mentioned polyester, can enumerate polybutylene terephthalate, polyethylene terephthalate, PEN, PBN etc., in addition, can also enumerate such as polyethylene glycol isophthalate-polyethylene terephthalate, gather the copolyesters such as m-phthalic acid butanediol ester-polybutylene terephthalate, polyethylene terephthalate-PEN, polybutylene terephthalate-PBN etc.Wherein, from thermotolerance, shock-resistance equal angles, particularly preferably polyethylene terephthalate.
[mean diameter of bubble]
For above-mentioned the 1st bubble 11, it is more than the 0.5 μ m and below the 3 μ m that its mean diameter is preferably formed.In addition, for above-mentioned the 2nd bubble 12, it is that 50 μ m are following, more preferably 30 μ m are following and be more than 2 times of mean diameter of above-mentioned the 1st bubble that its mean diameter is preferably formed.
As mentioned above, making the mean diameter of the 1st bubble 11 is to be in order to obtain visible scattering of light/reflection more than the 0.5 μ m.If it is too high that the mean diameter of the 1st bubble 11, then is incident to the transmitance of visible light of thermoplastic resin foam sheet material 10 less than 0.5 μ m, thereby visible scattering of light/reflection is reduced.Need to prove that if consider the seeing through of light of whole visible region, then the mean diameter of the 1st bubble 11 is more preferably more than the 0.8 μ m.In addition, if consider the section of thermoplastic resin foam sheet material 10, then more preferably 0.5 μ m is above and 1.0 μ m following, more preferably 0.8 μ m is above and below the 1.0 μ m for the mean diameter of the 1st bubble 11.Need to prove that visible light wavelength is that 380nm is above and below the 780nm, still according to JIS Z8120, its short wavelength side is defined as 360nm～400nm, long wavelength side is defined as 760nm～800nm.
If making the mean diameter of the 1st bubble 11 is to be because mean diameter is excessive than this value below the 3 μ m, the bubble number of plies is reduced, cause reflectivity to reduce.
In addition, making the mean diameter of the 2nd bubble 12 is to be based on following reason below the 50 μ m.If the mean diameter of the 2nd bubble 12 surpasses 50 μ m, then incident light infiltrates into the inside of reflector or the irreflexive number of times minimizing on the bubble interface, so diffuse-reflection factor has the tendency of reduction.
Further, the mean diameter more than 2 times that makes the 2nd bubble 12 have the mean diameter of the 1st bubble 11 is because following reason.
According to from the thickness direction central part of thermoplastic resin foam sheet material 10 with thickness mode in two, separate when forming thin-film sheet thereby use slicing knife to cut off, require high foamability for sliced surfaces.If this is because expansion ratio is excessively low, then the resin ratio in the sliced surfaces uprises, the deterioration of section property.When in general wanting to obtain high foamability, the means that improve the available gas amount of each bubble are effective.Namely, directly be more than 2 times by the average bubble that makes the 2nd bubble 12, can obtain the expansion ratio higher than the layer of the 1st bubble 11.So, even if slicing knife is attempted to shake to surface one side or the back side one side of the sheet material that is dispersed with the 1st bubble 11 because of certain reason, also can make slicing knife get back to the zone that is dispersed with the 2nd bubble 12 of cutting into slices easily.That is to say, slicing knife physical strength than around always advance in the weak zone that is dispersed with the 2nd bubble 12, its result can prevent the generation of chatter.For slicing knife 20 can so be worked, preferred the 2nd bubble 12 has the mean diameter more than 2 times of the mean diameter of the 1st bubble 11.And, from the judgement of section property, the multiplying power of the mean diameter of bubble more preferably, the 2nd bubble 12 is more than 10 times and below 30 times of mean diameter of the 1st bubble 11.Need to prove that the bubble footpath is not only determined by expansion ratio.
[proportion]
If the proportion of thermoplastic resin foam sheet material 10 of the present invention increases, is that expansion ratio reduces that the result can cause reducing the reflectivity reduction, the formability that cause by bubble rate and reduce and the minimizing of lightweight effect.Therefore, use in the situation of polyester as crystalline thermoplastic resin, the proportion of thermoplastic resin foam sheet material 10 is preferably below 0.7.More preferably below 0.65, more preferably below 0.5.Lower value for this proportion is not particularly limited, and the viewpoint from practicality is generally more than 0.2.
In the thermoplastic resin foam sheet material 10 of the present invention, than the 1st bubble 11 to two surface arrangement in the outside, therefore the 2nd bubble 12 that mean diameter is larger is scattered in the thickness direction central part, than than other parts, is dispersed with a little less than the physical strength of part of the 2nd bubble 12.Therefore, in the situation that the face that the thickness direction with thermoplastic resin foam sheet material 10 intersects is cut into slices, the friction of the face of the thickness direction central part by being dispersed with the 2nd bubble 12 and slicing knife (not illustrating and shown in Figure 2 at Fig. 1) reduces, and cuts into slices easily.Thus, can bring into play the effect of following excellence by cutting into slices at this face: can not produce chatter during section, and on sliced surfaces, can not produce " light ".In addition, there is the 2nd bubble 12 in sliced surfaces, therefore also exists to have formed coarse surperficial such advantage.
Thickness for thermoplastic resin foam sheet material of the present invention is not particularly limited, and is generally 0.3mm～2.0mm, is preferably 0.5mm～1.2mm.
In addition, be not particularly limited for the thickness of the thin-film sheet of thermoplastic resin foam of the present invention, be generally 0.15mm～1.0mm, be preferably 0.25mm～0.6mm.
[manufacture method of the thin-film sheet of thermoplastic resin foam]
For a preferred implementation of the manufacture method of the thin-film sheet of thermoplastic resin foam of the present invention, utilize the partial mode sectional view of the expression manufacturing process of Fig. 2 to describe.
(resin sheet formation operation)
At first, thus will be dispersed with the thermoplastic resin extrusion moulding of softening agent form resin sheet.At this moment, the mode that puts on the resin sheet that is extruded according to shear-stress is extruded, and makes the softening agent miniaturization in the sheet material that is scattered in resin sheet two face side.
Above-mentioned thermoplastic resin can use the crystalline thermoplastic resin that has above illustrated.Wherein preferred above-mentioned polyester based resin particularly preferably is pet resin.This pet resin is advantageous particularly at aspects such as thermotolerance, shock-resistance.
Be not particularly limited for above-mentioned softening agent, can use polyoxyethylene glycol, polyester oligomer, unsaturated fatty acids etc.As unsaturated fatty acids, can enumerate palmitinic acid, Zoomeric acid, stearic acid, oleic acid, isooleic acid, linolic acid, (9,12,15)-linolic acid, (6,9,12)-linolic acid, eleostearic acid, eicosanoic acid, arachidonic acid, Selacholeic acid etc.Among these, consider the dispersiveness in the pet resin, particularly preferably use the mixture more than a kind or 2 kinds of unsaturated fatty acids.
With respect to above-mentioned thermoplastic resin 100 mass parts, the addition of above-mentioned softening agent is preferably more than 0.1 mass parts and below 5 mass parts.To narrate hereinafter about its reason.
For above-mentioned extrusion moulding, use the extruding forming method that has utilized the flat-die that is called as the T die head.During this extrusion moulding, in resin sheet, particularly produce stronger shear-stress in the top layer of its two face side, utilize this shear-stress that the softening agent in the top layer of two face side that are scattered in resin sheet is carried out miniaturization.
Usually, in the situation that the fluid of thermoplastic resin flows in the extrusion channel of extrusion shaping machine, the fluid of this thermoplastic resin is subject to the resistance from the extrusion channel wall.Because this resistance, the fluid of thermoplastic resin has produced current difference near the central part of extrusion channel and wall.Because of this current difference, produce shear-stress in the fluid of thermoplastic resin.And think, make its miniaturization and disperse thereby utilize this shear-stress that the softening agent piece that flows together in the fluid of thermoplastic resin is torn up.Above-mentioned current difference is more larger near flow path wall, thereby above-mentioned shear-stress is more larger near the extrusion channel wall.Therefore, the result is exactly that the both side surface of the resin sheet that more obtains near the moulding of thermoplastic resin fluid institute of softening agent just more can be disperseed with the state of miniaturization.
Above-mentioned softening agent in the fluid of thermoplastic resin is by miniaturization and be dispersed in the fluid of thermoplastic resin, till final until its cohesive force, surface tension (the less surface tension of softening agent piece is larger usually) etc. and shear-stress are the state of balance.
Perhaps can think, after the extrusion moulding, softening agent is from the volatilization of resin sheet surface, the concentration difference that has produced softening agent at surface and the central part of resin sheet, thereby softening agent more just more disperses with the state of miniaturization near the both side surface of the resin sheet of the fluid institute moulding of thermoplastic resin.The plasticizer molecule amount is lower and volatilization temperature is also low, and the heat in the time of therefore can be because of extrusion moulding is from the volatilization of resin sheet surface.Therefore, with respect to central core, the amount of the softening agent of resin sheet near surface reduces.Results presumption, the raw material zone (material De メ イ Application) of the softening agent that originally exists thus by miniaturization, since the movement of softening agent has formed the fine zone of softening agent or when extruding because near and the compound action of shear-stress etc. and sheet surface, formed fine nuclei of bubbles and produce fine foaming.
Overlapping and roll by above-mentioned resin sheet that moulding like this is obtained and dividing plate (セ パ レ ー タ), can form reel (ロ ー Le).As long as dividing plate as used herein has rare gas element and the space that can freely come in and go out of employed organic solvent and can ignore rare gas element soaking in himself as required, just can be any dividing plate.As dividing plate, particularly preferably resin non-woven fabrics or metal net.As the resin non-woven fabrics, be that resin consists of by polyolefin-based resins or nylon preferably.In addition, even the non-woven fabrics that the resin that is by polyester consists of, so long as the words of the non-woven fabrics that fiber is extensible and rare gas element is difficult to soak into also can preferably be used.As metal net, be preferably the use plain weave that is commonly referred to as wire cloth (ワ イ ヤ ー Network ロ ス), tiltedly knit, the weaving manner such as seat type plain weave, seat type are tiltedly knitted is woven into right angle orientation with ordinate and horizontal line and the net that obtains.Material can be suitable for iron, copper, aluminium, titanium or their alloy etc., but considers price, life-span, then more preferably stainless steel.On the other hand, resin sheet is preferably not extension.If this is because resin sheet extends, and then gas can't soak into to sheet material fully, therefore can't obtain the target foam sheet.
(organic solvent impregnation operation)
Need to prove, before the operation that makes resin sheet impregnation rare gas element of subsequent processing, can make resin sheet impregnation organic solvent.If make resin sheet contain organic solvent, be in the situation of for example thermoplastic polyester sheet material at resin sheet then, can make degree of crystallinity [representing take (degree of crystallinity)=(crystal region part)/(crystal region part and non-crystalline areas part sum) * 100 (%)] as more than 30%.Consequently, be difficult to remain on the sheet surface thereby the rigidity of resin sheet increases the vestige of dividing plate, can shorten the penetration period of rare gas element simultaneously.
As above-mentioned organic solvent, can enumerate benzene, toluene, methyl ethyl ketone, ethyl formate, acetone, acetic acid, dioxan, meta-cresol, aniline, vinyl cyanide, dimethyl phthalate, nitroethane, Nitromethane 99Min., phenylcarbinol etc.Among these, from the viewpoint of operability and economy, more preferably acetone.
Need to prove that the kind because of dividing plate also can make the vestige of dividing plate can not remain on the resin sheet surface sometimes, thereby to make the processing that resin sheet contains organic solvent be not to be necessary.But from shortening the viewpoint of gas penetration period, preferred enforcement makes resin sheet contain the processing of organic solvent.
As making above-mentioned reel contain the method for organic solvent, can use reel to be impregnated in the method in the organic solvent or reel is remained on method in the steam of organic solvent.The latter's method is compared with the former method, and following excellent aspect several: the usage quantity of organic solvent is to get final product on a small quantity, and has hardly and be added into resin sheet, the particularly stripping of the additive of thermoplastic polyester sheet material.
In the method that reel be impregnated in the organic solvent, treatment time at room temperature as long as be fully in several hours to tens hours, even if the process time longer than the above-mentioned time processes, the content of the organic solvent in the resin sheet can not increase accordingly yet.Thereby the treatment time that reel is remained in when making it contain organic solvent in the steam of organic solvent is different because of the difference of the thickness of the kind of the resin that foams, resin sheet.For example, under room temperature, normal atmosphere, the reel of pet resin sheet material is put into the encloses container of acetone saturated with vapor, thereby acetone is soaked into to situation wherein, if the thickness of resin sheet is 0.6mm, then the treatment time is more than 24 hours; If thickness is 0.9mm, then be more than 48 hours fully.By this processing, the content of the acetone in the resin sheet is 4 quality %～5 quality %.
Need to prove, thereby reel is contained in the situation of degree of crystallinity that organic solvent improves resin sheet, do not need to improve degree of crystallinity by containing a large amount of rare gas elementes, therefore can shorten the impregnation time of rare gas element.For example, with 60kg/cm
2Condition carbonic acid gas is soaked in the situation to the pet resin sheet material, if the thickness of resin sheet is 0.6mm, then penetration period is more than 1 hour; If 0.9mm then is more than 2 hours fully.
In addition, the sheet material of drum be impregnated in the situation of organic solvent, before subsequent processing, also resin sheet can be rolled again with the dividing plate of other preparation, thereby again be made reel.
(the impregnation operation of rare gas element)
Then, above-mentioned resin sheet is contained be soaked with rare gas element, make the thermoplastic resin crystallization.Be not particularly limited for this operation, if but consider production, then preferred following method: thereby being remained on, above-mentioned reel in the inert gas atmosphere of pressurization rare gas element is contained to be immersed in the resin sheet.Also can contain additive in this resin sheet.
In addition, thereby make the thermoplastic resin crystallization in order to soak into by rare gas element to thermoplastic resin, with respect to above-mentioned thermoplastic resin 100 mass parts, the addition that preferably makes above-mentioned softening agent is that 0.1 mass parts is above and below 5 mass parts, the addition that more preferably makes softening agent is more than 1 mass parts and below 3 mass parts.Owing to passed through this crystallization, can obtain good thermoplastic resin foam.On the other hand, if the addition of softening agent is very few, the bubble that then generates directly distributes excessive.In addition, if the addition of softening agent is too much, the towing (ド ロ ー イ Application グ when then resin sheet is extruded) fierce so that be difficult to obtain resin sheet, and the dispersion of softening agent directly becomes greatly, and bubble directly distributes and becomes excessive.Thereby preferably making softening agent is the addition of above-mentioned scope.
As above-mentioned rare gas element, can enumerate the gases such as helium, nitrogen, carbonic acid gas, argon.Rare gas element in the resin sheet of thermoplastic resin reaches capacity rare gas element penetration period and rare gas element amounts of saturation till the state because of the kind of the kind of the thermoplastic resin that foams, rare gas element, thickness etc. different of soaking into pressure and resin sheet.If consider the gas impregnability (such as wetting-out rate, solubleness etc.) in the thermoplastic resin, more preferably above-mentioned carbonic acid gas.
In addition, can contain a large amount of carbonic acid gas in thermoplastic polyester, from this aspect, also be preferred.The pressure that soaks into of rare gas element is preferably 30kg/cm
2～70kg/cm
2, 50kg/cm more preferably
2～70kg/cm
2The penetration period of rare gas element is more than 1 hour, more preferably soaks into gas until the state that reaches capacity.For example with 60kg/cm
2Carbonic acid gas is soaked into to the situation of polyethylene terephthalate sheet material, if the thickness of resin sheet is 0.6mm, then penetration period was preferably more than 24 hours; If 0.9mm then was preferably more than 96 hours.Under this condition, the carbon dioxide content in the resin sheet is 6 quality %～7 quality %.
(foamed process)
Then, shown in Fig. 2 (1), thereby heat and make its foaming containing the resin sheet 13 that is soaked with rare gas element, make the 1st bubble 11 result from thickness direction two face side, and produce mean diameter greater than the 2nd bubble 12 of the 1st bubble 11 in the position than the more close thickness direction central part in the position of the 1st bubble 11, thereby form thermoplastic resin foam sheet material 10.Before this foamed process, in advance dividing plate is removed.For example can only again form reel to contain the resin sheet 13 that is soaked with rare gas element.
Be not particularly limited for this foaming method, if but consider production, for example under normal pressure (for example normal atmosphere), thereby heat and make its foaming containing the resin sheet 13 that is soaked with rare gas element with the temperature more than the second-order transition temperature and below the fusing point, section forms the 1st bubble 11 and the 2nd bubble 12 within it.This foamed process for example carries out with the heated air circulation type foaming furnace of continuous supplying to hot blast.At this moment, after resin sheet 13 is taken out, to until the time till its foaming is adjusted, thereby can adjust the bulk specific gravity of resulting thermoplastic resin foam sheet material 10 from the inert gas atmosphere of high pressure.
In the above-mentioned foamed process, the softening agent that is disperseed by miniaturization in resin sheet 13 (not shown) is the caryogenic starting point of bubble, at the Surface Realize of two face side the 1st fine bubble 11 below the mean diameter 1 μ m for example, generate for example the 2nd thick bubble 12 more than the mean diameter 5 μ m at the thickness direction central part.Thereby the size of the bubble that generates is determined by the miniaturization state of softening agent.About the mean diameter of these bubbles, as mentioned above, preferably, the mean diameter of the 1st bubble forms more than the 0.5 μ m and below the 3 μ m, and the mean diameter of the 2nd bubble 12 forms below the 30 μ m and is more than 2 times of the 1st bubble 11.
(slicing process)
Then, shown in Fig. 2 (2), use the generation of 20 pairs of thermoplastic resin foam sheet materials 10 of slicing knife to have the zone of the 2nd bubble 12 to cut into slices, on the face that intersects with thickness direction, thermoplastic resin foam sheet material 10 is cut apart, thereby formed the thin-film sheet 14,15 of thermoplastic resin foam.
For this slicing process, for example can use the slicing experiment machine of ball Zhong ironworker manufacturing, cut-off velocity is set as 1.0m/min～20m/min, carry out thus slice processing.
In above-mentioned manufacture method, in the scope that the thin-film sheet 14 of thermoplastic resin foam, 15 characteristic are not exerted an influence, the various additives such as crystallization promoter, bubble nucleating agent, antioxidant, static inhibitor, anti UV agent, photostabilizer, white dyes, pigment, dyestuff, expanding material, lubricant, reinforcer, fire retardant, linking agent, crosslinking coagent, softening agent, tackifier, viscosity depressant are mixed in also can the thermoplastic resin before foaming.In addition, on resulting thermoplastic resin foam, the resin of above-mentioned additive can be lamination contained, also the coating that contains above-mentioned additive can be applied.
The manufacture method of the invention described above is applicable in the situation of production process of thin-film sheet of foam, and to compare productivity good with manufacture method in the past.Namely, can obtain simultaneously 2 as the thin-film sheet 14,15 of reflector by 1 thermoplastic resin foam sheet material 10, during the thin-film sheet of the area that therefore obtains stipulating, compare number of devices in the past, gas impregnation equipment etc. can be further cut down, the reduction of manufacturing cost can be realized.
Then, about reflector of the present invention, below 1 is preferred embodiment described.
Though do not show in the drawings, but reflector of the present invention is the reflector that the thin-film sheet by thermoplastic resin foam consists of, and the thin-film sheet of this thermoplastic resin foam is to utilize the manufacture method of the thin-film sheet of above-mentioned thermoplastic resin foam to make to obtain.The thin-film sheet of this thermoplastic resin foam within it section comprises the 1st bubble and the 2nd bubble.The 2nd bubble forms according to the mode of mean diameter greater than the 1st bubble.For example, for the 1st bubble, it is more than the 0.5 μ m and below the 3.0 μ m that its mean diameter is preferably formed, and more preferably forms more than the 0.5 μ m and below the 1.0 μ m, and further being preferably formed is more than the 0.8 μ m and below the 1.0 μ m.And for the 2nd bubble, being preferably formed is more than 2 times of mean diameter of the 1st bubble, more preferably forms more than 10 times and below 30 times; And it is below the 50 μ m that mean diameter is preferably formed, more preferably below the 30 μ m.And, as mentioned above, the single side surface of the thin-film sheet of thermoplastic resin foam is to use slicing knife the zone that is dispersed with the 2nd bubble (namely in the substantial middle section of the thickness direction of thermoplastic resin foam sheet material and be positioned at zone with the plane of this thickness direction approximate vertical) to be cut into slices and the face that obtains, has therefore formed to expose that the part that the 2nd bubble is arranged is cut off and the coarse surface of the recess that obtains.As reflector, the part of the 2nd bubble that exposes is scattered in the rear side as the thin-film sheet of the thermoplastic resin foam of the face opposite with the light incident side of light.
Thereby the thin-film sheet of above-mentioned thermoplastic resin foam is dispersed with the 1st fine bubble of reflect visible light in a side of light incident.In addition, its rear side is not to produce the face of " light " or level and smooth face, but for according to the coarse surface of exposing mode that a part that the 2nd bubble is arranged or the 2nd bubble be cut off the recess that produces and forming, even so back side of the thin-film sheet of thermoplastic resin foam, the light that sees through in the thin-film sheet also can be reflected, and therefore can access higher reflectivity.
In addition, the shape that is shaped to around a part of ambient light source and so on by the thin-film sheet with above-mentioned thermoplastic resin foam, for example have the shape of the plane of reflection of a plurality of of concavity or flexure plane, can obtain the reflector that lighting fixtures is used.As this forming method, for example can use following method: use the compression molding forming machine be equipped with the male and female mould, carrying out compression molding more than the second-order transition temperature of the thin-film sheet of thermoplastic resin foam and under the heating condition below the fusing point.The thin-film sheet of thermoplastic resin foam is in the situation of thermoplastic polyester foam sheet, for example can use more than 200 ℃ and the heating condition below 240 ℃.
The pattern of the reflector of using for lighting fixtures for example is installed on lamp the central part of the reflector of the plane of reflection with a plurality of of concavities, is surrounded by the plane of reflection of reflector around the lamp.
In this case, reflector doubles as basket.In addition, also can be further at the arranged outside basket of reflector.Need to prove that the plane of reflection of reflector also can form continuous flexure plane.
[embodiment]
Below, the present invention is described in more detail based on embodiment, but the present invention is not limited by these embodiment.
Utilize manufacture method described above to make the sample of embodiment 1～4.In addition, made comparative example 1～3, it uses in the past the thermoplastic resin foam sheet material of structure to cut into slices and obtains.
[embodiment 1]
As shown in Figure 2, carry out in accordance with the following methods the manufacturing of the thin-film sheet of thermoplastic resin foam.
The epoxidised soybean oil (E-2000H (trade(brand)name) that new Japanese physics and chemistry is made) that adds 0.5 quality % in pet resin (NEH2070 (trade(brand)name) that UNITIKA makes) uses the in the same way biaxial extruder (KZW15-30MG (trade(brand)name) that TECHNOVEL makes) that is set as 235 ℃～260 ℃ to carry out mixing.Then, while be that the T die head of 120mm is given shear-stress with the resin extruded one-tenth sheet after mixing by width, use the roller that is set as 70 ℃ to extract, having obtained as the thickness of motherboard is the resin sheet 13 of 0.5mm.Then, described motherboard being statically placed in the pressurized vessel, is under 17 ℃ the condition in temperature, is full of carbon dioxide with the pressure of 5.5Mpa in container, then places 48 hours.After storage period, motherboard is taken out from pressurized vessel, the gas amounts of saturation of motherboard is measured, the result is 7.9 quality %.Then, in being 220 ℃ thermostatic bath, Temperature Setting with motherboard heating 1 minute, makes its foaming.
The mean diameter of the 1st bubble 11 of skin section that is distributed in resulting thickness and is the thermoplastic resin foam sheet material 10 of 0.8mm is 1 μ m, the thickness in the zone of main existence the 1st bubble 11 is about 40 μ m, the mean diameter that is distributed in the 2nd bubble 12 of thickness direction central part is 10 μ m, expansion ratio is 5.0 times, and proportion is 0.2g/cm
3, reflectivity is 99.5%.
And thermoplastic resin foam sheet material 10 being cut into slices and obtain thickness at the sheet material central part is that the thin-film sheet 14,15 of 0.4mm has even and coarse surface property, and reflectivity is 98.5%.
Need to prove that in following each embodiment and comparative example, resin sheet 13, thermoplastic resin foam sheet material 10 and thin-film sheet 14,15 thickness are identical with above-described embodiment 1 respectively.
[embodiment 2]
As shown in Figure 2, carry out in accordance with the following methods the manufacturing of the thin-film sheet of thermoplastic resin foam.
The epoxidised soybean oil (E-2000H (trade(brand)name) that new Japanese physics and chemistry is made) that adds 2.0 quality % in pet resin (NEH2070 (trade(brand)name) that UNITIKA makes) uses the in the same way biaxial extruder (KZW15-30MG (trade(brand)name) that TECHNOVEL makes) that is set as 235 ℃～260 ℃ to carry out mixing.Then, while be that the T die head of 120mm is given shear-stress with the resin extruded one-tenth sheet after mixing by width, use the roller that is set as 70 ℃ to extract, obtained the resin sheet 13 as motherboard.Then, described motherboard being statically placed in the pressurized vessel, is under 17 ℃ the condition in temperature, is full of carbon dioxide with the pressure of 5.5Mpa in container, then places 48 hours.After the specified time, motherboard is taken out from pressurized vessel, the gas amounts of saturation of motherboard is measured, the result is 7.9 quality %.Then, in being 220 ℃ thermostatic bath, Temperature Setting with motherboard heating 1 minute, makes its foaming.
The mean diameter of the 1st bubble 11 that is distributed in the skin section of resulting thermoplastic resin foam sheet material 10 is 1 μ m, the thickness in the zone of main existence the 1st bubble 11 is about 100 μ m, the mean diameter that is distributed in the 2nd bubble 12 of thickness direction central part is 10 μ m, expansion ratio is 6.0 times, and proportion is 0.16g/cm
3, reflectivity is 100.1%.
And thermoplastic resin foam sheet material 10 being cut into slices and obtain thin-film sheet 14,15 at the sheet material central part has even and coarse surface property, and reflectivity is 100.1%.
[embodiment 3]
As shown in Figure 2, carry out in accordance with the following methods the manufacturing of the thin-film sheet of thermoplastic resin foam.
The epoxidised soybean oil (E-2000H (trade(brand)name) that new Japanese physics and chemistry is made) that adds 3.0 quality % in pet resin (NEH2070 (trade(brand)name) that UNITIKA makes) uses the in the same way biaxial extruder (KZW15-30MG (trade(brand)name) that TECHNOVEL makes) that is set as 235 ℃～260 ℃ to carry out mixing.Then, while be that the T die head of 120mm is given shear-stress with the resin extruded one-tenth sheet after mixing by width, use the roller that is set as 70 ℃ to extract, obtained the resin sheet 13 as motherboard.Then, described motherboard being statically placed in the pressurized vessel, is under 17 ℃ the condition in temperature, is full of carbon dioxide with the pressure of 5.5Mpa in container, then places 48 hours.After the specified time, motherboard is taken out from pressurized vessel, the gas amounts of saturation of motherboard is measured, the result is 7.9 quality %.Then in Temperature Setting is 220 ℃ thermostatic bath with motherboard heating 1 minute, make its foaming.
The mean diameter of the 1st bubble 11 that is distributed in the skin section of resulting thermoplastic resin foam sheet material 10 is 0.5 μ m, the thickness in the zone of main existence the 1st bubble 11 is about 150 μ m, the mean diameter that is distributed in the 2nd bubble 12 of thickness direction central part is 10 μ m, expansion ratio is 6.0 times, and proportion is 0.16g/cm
3, reflectivity is 100.1%.
And thermoplastic resin foam sheet material 10 being cut into slices and obtain thin-film sheet 14,15 at the sheet material central part has even and coarse surface property, and reflectivity is 100.1%.
[embodiment 4]
As shown in Figure 2, carry out in accordance with the following methods the manufacturing of the thin-film sheet of thermoplastic resin foam.
The 4-cyclohexenyl-1 that in pet resin (NEH2070 (trade(brand)name) that UNITIKA makes), adds 1.0 quality %, two (2-ethylhexyl) esters of 2-dioctyl phthalate (DOTP that new Japanese physics and chemistry is made) use the in the same way biaxial extruder (KZW15-30MG (trade(brand)name) that TECHNOVEL makes) that is set as 235 ℃～260 ℃ to carry out mixing.Then, while be that the T die head of 120mm is given shear-stress with the resin extruded one-tenth sheet after mixing by width, use the roller that is set as 70 ℃ to extract, obtained the resin sheet 13 as motherboard.Then, described motherboard being statically placed in the pressurized vessel, is under 17 ℃ the condition in temperature, is full of carbon dioxide with the pressure of 5.5Mpa in container, then places 48 hours.After the specified time, motherboard is taken out from pressurized vessel, the gas amounts of saturation of motherboard is measured, the result is 7.9 quality %.Then in Temperature Setting is 220 ℃ thermostatic bath with motherboard heating 1 minute, make its foaming.
The mean diameter of the 1st bubble 11 that is distributed in the skin section of resulting thermoplastic resin foam sheet material 10 is 0.5 μ m, the thickness in the zone of main existence the 2nd bubble 12 is about 100 μ m, the mean diameter that is distributed in the 2nd bubble 12 of thickness direction central part is 15 μ m, expansion ratio is 4.0 times, and proportion is 0.30g/cm
3, reflectivity is 99.4%.
And, thermoplastic resin foam sheet material 10 is cut into slices and to obtain the surface properties that thin-film sheet 14,15 has homogeneous and cushion at the sheet material central part, reflectivity is 99.4%.
[comparative example 1]
Carry out in accordance with the following methods the manufacturing of the thin-film sheet of the thermoplastic resin foam as shown in above-mentioned Fig. 3.
In pet resin (NEH2070 (trade(brand)name) that UNITIKA makes), add the styrene-ethylene/butylene-styrene (SEBS) (DYNARON8630 (trade(brand)name) that JSR makes) of 1.0 quality % as elastomerics, use the in the same way biaxial extruder (KZW15-30MG (trade(brand)name) that TECHNOVEL makes) that is set as 235 ℃～260 ℃ to carry out mixing.Then, by width be the T die head of 120mm with the resin extruded one-tenth sheet after mixing, use the roller that is set as 70 ℃ to extract, obtained the resin sheet as motherboard.Then, described motherboard being statically placed in the pressurized vessel, is under 17 ℃ the condition in temperature, is full of carbon dioxide with the pressure of 5.5Mpa in container, then places 48 hours.After the specified time, motherboard is taken out from pressurized vessel, the gas amounts of saturation of motherboard is measured, the result is 7.9 quality %.Then in Temperature Setting is 220 ℃ thermostatic bath with motherboard heating 1 minute, make its foaming.
The mean diameter of bubble that is distributed in the skin section of resulting thermoplastic resin foam sheet material is 1.6 μ m, and the mean diameter that is distributed in the bubble of thickness direction central part is 1.6 μ m too, and expansion ratio is 3.6 times, and proportion is 0.37g/cm
3, reflectivity is 100.1%.
Then, trial is cut into slices to the thermoplastic resin foam sheet material at the sheet material central part, and slicing knife 20 produces chatter as a result, can't carry out stable slice processing, the sheet surface mixing that section obtains has gloss section and semi-gloss section, can't obtain the same surface property.The reflectivity of the sheet material after the section is 98%.
[comparative example 2]
Carry out in accordance with the following methods the manufacturing of the thin-film sheet of the thermoplastic resin foam as shown in above-mentioned Fig. 3.
The polyester based thermoplastic elastomerics (Hytrel2551 (trade(brand)name) that TORAY makes) that adds 1.0 quality % in pet resin (NEH2070 (trade(brand)name) that UNITIKA makes) uses the in the same way biaxial extruder (KZW15-30MG (trade(brand)name) that TECHNOVEL makes) that is set as 235 ℃～260 ℃ to carry out mixing.Then, by width be the T die head of 120mm with the resin extruded one-tenth sheet after mixing, use the roller that is set as 70 ℃ to extract, obtained the resin sheet as motherboard.Then, described motherboard being statically placed in the pressurized vessel, is under 17 ℃ the condition in temperature, is full of carbon dioxide with the pressure of 5.5Mpa in container, then places 48 hours.After the specified time, will take out from the motherboard pressurized vessel, the gas amounts of saturation of motherboard is measured, the result is 7.9 quality %.Then, in being 220 ℃ thermostatic bath, Temperature Setting with motherboard heating 1 minute, makes its foaming.
The mean diameter of bubble that is distributed in the skin section of resulting thermoplastic resin foam sheet material is 1.0 μ m, and the mean diameter that is distributed in the bubble of thickness direction central part is 1.0 μ m too, and expansion ratio is 2.8 times, and proportion is 0.51g/cm
3, reflectivity is 100.8%.
Then, attempt at the sheet material central part thermoplastic resin foam sheet material being cut into slices, slicing knife 20 produces chatter, can't carry out slice processing.The part of thermoplastic resin foam sheet material exists by the position of section for the thickness of half, and the reflectivity at this position is 100.8%.
[comparative example 3]
Carry out in accordance with the following methods the manufacturing of the thin-film sheet of the thermoplastic resin foam as shown in above-mentioned Fig. 3.
The modified PE (modified poly ethylene that Mitsubishi's oiling is made) that adds 3.0 quality % in pet resin (NEH2070 (trade(brand)name) that UNITIKA makes) uses the in the same way biaxial extruder (KZW15-30MG (trade(brand)name) that TECHNOVEL makes) that is set as 235 ℃～260 ℃ to carry out mixing.Then, by width be the T die head of 120mm with the resin extruded one-tenth sheet after mixing, use the roller that is set as 70 ℃ to extract, obtained the resin sheet as motherboard.Then, described motherboard being statically placed in the pressurized vessel, is under 17 ℃ the condition in temperature, is full of carbon dioxide with the pressure of 5.5Mpa in container, then places 48 hours.After the specified time, motherboard is taken out from pressurized vessel, the gas amounts of saturation of motherboard is measured, the result is 7.9 quality %.Then, in being 220 ℃ thermostatic bath, Temperature Setting with motherboard heating 1 minute, makes its foaming.
The mean diameter of bubble that is distributed in the skin section of resulting thermoplastic resin foam sheet material is 3.0 μ m, and the mean diameter that is distributed in the bubble of thickness direction central part is 3.0 μ m too, and expansion ratio is 3.6 times, and proportion is 0.37g/cm
3, reflectivity is 99.5%.
Then, at the sheet material central part thermoplastic resin foam sheet material is cut into slices, obtain sheet material, produced " light " (position with high-luster) on the part of this sheet material, but most positions have even and coarse surface property, and reflectivity is 97%.
Table 1
Then, describe with regard to measuring method below.
(measuring method of the thickness of skin section)
The take pictures SEM photo in cross section of thermoplastic resin foam sheet material, thus the thickness of obtaining skin section measured at the SEM photo.
(bubble footpath ask method)
Obtain the bubble footpath according to ASTM D3576-77.That is, the SEM photo in the cross section of the sheet material of taking pictures in the scope of the regulation of SEM photo, draws straight line in the horizontal direction with on the vertical direction, averages for the length t of straight line crosscut bubble.Be M with the multiplier indicia of photo, bring the mean value d that obtains the bubble footpath in the following formula into.
d=t/(0.616×M)
(measuring method of proportion)
Be that quality status stamp is M (g) under m (g) and the atmosphere with quality status stamp in the water, utilize in the water substitution method to obtain proportion ρ by following formula.
ρ=M/(M-m)
(expansion ratio ask method)
So that the form of the ratio of the proportion (ρ s) of the proportion (ρ f) of the foam sheet that substitution method mensuration obtains in the water and the resin before the foaming is calculated expansion ratio.
(reflectivity ask method)
Mensuration of carrying out luminous reflectance factor as described below.The spectrophotometer U-4100 that uses Hitachi high-tech society to make is under the condition of 4nm at a minute optical slits, and the light splitting total reflectivity that sample carries out under the wavelength of light 550nm is measured.Reference uses aluminum oxide white plate (210-0740:(strain) Hitachi high-tech fielding to make), measured value is the relative value with respect to reference.Existing the measured value of reflectivity to surpass 100% situation is because the cause that represents with the relative value with respect to reference.
(metewand of section property)
Section property is to have or not the generation of chatter and the visual observation of sliced surfaces is judged by slicing knife.
◎ (excellent): slicing knife is without chatter.The sliced surfaces of thin-film sheet is even and coarse surface.
Zero (very): slicing knife is without chatter.The part of the sliced surfaces of thin-film sheet produces gloss section (light), is uniform uneven surface in most zones still.
△ (poor): slicing knife has chatter.The sliced surfaces of thin-film sheet is mixed and is had gloss section (light) and semi-gloss section, is inhomogeneous surface.
* (can not): slicing knife has chatter.Can't carry out slice processing.
Judge based on above determinating reference.
More than the present invention and its embodiment together are illustrated, but we think, as long as no specifying, then the present invention is not limited in any details of description, and should make wide in range explanation under the prerequisite of not violating the invention aim shown in the claims and scope.
The application requires based on the right of priority of on October 5th, 2010 at the patent application Japanese Patent Application 2010-225671 of Japan's submission, and the application charges to the application as the part of this specification sheets record with reference to the content of above-mentioned patent application and with its content.
[nomenclature]
10 thermoplastic resin foam sheet materials
11 the 1st bubbles
12 the 2nd bubbles
13 resin sheets
14, the thin-film sheet of 15 thermoplastic resin foams
Claims (6)
1. thermoplastic resin foam sheet material, it is for comprising the thermoplastic resin foam sheet material of the 1st bubble and the 2nd bubble in thermoplastic resin sheet, this thermoplastic resin foam sheet material is characterised in that, the mean diameter of described the 2nd bubble is greater than described the 1st bubble and be distributed in the thickness direction central part of described thermoplastic resin sheet.
2. thermoplastic resin foam sheet material as claimed in claim 1, it is characterized in that, the mean diameter of described the 1st bubble is that 0.5 μ m is above and below the 3 μ m, the mean diameter of described the 2nd bubble is below the 50 μ m and is more than 2 times of mean diameter of described the 1st bubble.
3. the manufacture method of the thin-film sheet of a thermoplastic resin foam is characterized in that, this manufacture method has following operation:
When forming resin sheet in the thermoplastic resin extrusion moulding that will be dispersed with softening agent, the operation of extruding according to the mode that makes this resin sheet that is extruded produce shear-stress;
Make described resin sheet contain the operation that is soaked with rare gas element;
Heat and make its foaming containing the described resin sheet that is soaked with rare gas element, make two face side of thickness direction produce the 1st bubble, and make the thickness direction central part produce mean diameter greater than the 2nd bubble of the 1st bubble, thereby form the operation of thermoplastic resin foam sheet material;
Use slicing knife to have the zone of described the 2nd bubble to cut into slices to the generation of described thermoplastic resin foam sheet material, on the face that intersects with thickness direction, described thermoplastic resin foam sheet material is cut apart, thereby formed the operation of the thin-film sheet of thermoplastic resin foam.
4. the manufacture method of the thin-film sheet of thermoplastic resin foam as claimed in claim 3 is characterized in that, with respect to described thermoplastic resin, adds being dispersed with the described softening agent that 0.1 quality % is above and 5 quality % are following.
5. such as the manufacture method of the thin-film sheet of claim 3 or thermoplastic resin foam claimed in claim 4, it is characterized in that, the mean diameter of described the 1st bubble is that 0.5 μ m is above and below the 3 μ m, the mean diameter of described the 2nd bubble is below the 50 μ m and is more than 2 times of mean diameter of described the 1st bubble.
6. reflector, it is the thin-film sheet of thermoplastic resin foam, this reflector is characterised in that, the thin-film sheet of described thermoplastic resin foam within it section comprises the 1st bubble and the 2nd bubble, the mean diameter of described the 2nd bubble is greater than described the 1st bubble, exposes a part that has because of described the 2nd bubble in the single side surface of the thin-film sheet of described thermoplastic resin foam and is cut off the recess that forms.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-225671 | 2010-10-05 | ||
| JP2010225671 | 2010-10-05 | ||
| PCT/JP2011/072893 WO2012046743A1 (en) | 2010-10-05 | 2011-10-04 | Thermoplastic resin foam sheet, method for producing thin sheet of thermoplastic resin foam, and light-reflecting plate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103038276A true CN103038276A (en) | 2013-04-10 |
Family
ID=45927738
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011800374945A Pending CN103038276A (en) | 2010-10-05 | 2011-10-04 | Thermoplastic resin foam sheet, method for producing thin sheet of thermoplastic resin foam, and light-reflecting plate |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPWO2012046743A1 (en) |
| KR (1) | KR20130116071A (en) |
| CN (1) | CN103038276A (en) |
| WO (1) | WO2012046743A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101706907B1 (en) * | 2015-11-12 | 2017-02-20 | 주식회사 휴비스 | Resin foamed article containing hollowness and method of preparing the same |
| KR101716193B1 (en) * | 2015-12-08 | 2017-03-28 | 주식회사 휴비스 | Core-Shell Structured Foam Comprising Hollowness |
| US11738492B2 (en) | 2016-03-31 | 2023-08-29 | Toray Plastics (America), Inc. | Methods of producing polyolefin foam sheets and articles made thereof |
| CN115960383B (en) * | 2021-08-05 | 2024-06-25 | 江苏大毛牛新材料有限公司 | Method for preparing physical foaming material |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4178567B2 (en) * | 1997-09-12 | 2008-11-12 | ヤマハ株式会社 | Production method of resin foam |
| JP2003039512A (en) * | 2001-08-01 | 2003-02-13 | Sumitomo Chem Co Ltd | Thermoplastic resin foamed molded object |
| EP2160290B1 (en) * | 2007-01-17 | 2011-12-14 | Microgreen Polymers, Inc. | Multi-layer foamed polymeric object |
-
2011
- 2011-10-04 JP JP2012537722A patent/JPWO2012046743A1/en active Pending
- 2011-10-04 WO PCT/JP2011/072893 patent/WO2012046743A1/en active Application Filing
- 2011-10-04 CN CN2011800374945A patent/CN103038276A/en active Pending
- 2011-10-04 KR KR1020137002546A patent/KR20130116071A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| KR20130116071A (en) | 2013-10-22 |
| JPWO2012046743A1 (en) | 2014-02-24 |
| WO2012046743A1 (en) | 2012-04-12 |
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Application publication date: 20130410 |