CN102033254A - Method for producing a laminated resin plate - Google Patents

Method for producing a laminated resin plate Download PDF

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Publication number
CN102033254A
CN102033254A CN2010105043503A CN201010504350A CN102033254A CN 102033254 A CN102033254 A CN 102033254A CN 2010105043503 A CN2010105043503 A CN 2010105043503A CN 201010504350 A CN201010504350 A CN 201010504350A CN 102033254 A CN102033254 A CN 102033254A
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China
Prior art keywords
transparent resin
resin
basic unit
end material
mentioned
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Chinese (zh)
Inventor
滨松丰博
坂本隆
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • 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
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/418—Refractive
    • 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
    • B32B2551/00—Optical elements
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Laminated Bodies (AREA)
  • Optical Elements Other Than Lenses (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides a method for producing a laminated resin plate, comprising the following steps: laminating a surface layer containing a transparent resin (B) on at least one surface of a base layer containing a transparent resin (A) to obtain a lamination plate, cutting at least part of the edge part of the lamination plate to obtain an end material; laminating the surface layer containing the transparent resin (B) on at least one surface of the base layer containing the end material or the mixture of the end material and the transparent resin (A) to form a laminated resin plate, wherein the Hansen solubility parameter of the transparent resin (A) and the transparent resin (B) is set as 'Delta delta' and the absolute value of the difference between the refractive index of the transparent resin (A) and the refractive index of the transparent resin (B) is set as 'Delta n', the relationship of the Delta delta x Delta n <=0.42 is established.

Description

The manufacture method of laminated resin plate
Technical field
The present invention relates to a kind of method of making laminated resin plate, its end material that will produce in the time will making (ear material) has suppressed painted when recycling fully.
Background technology
As liquid crystal indicator, for example be well known that in the rear side that possesses the liquid crystal panel of liquid crystal cells (image displaying part) as the device that disposes the formation of planar light source device backlight.As the planar light source device of above-mentioned usefulness backlight, known have a planar light source device that disposes a plurality of light sources and dispose the formation of light diffusing sheet in the front face side of these light sources in lamp box (framework).
As above-mentioned light diffusing sheet, be well known that the stacked multilayer light diffusing sheet (with reference to TOHKEMY 2008-292977 communique (patent documentation 1)) that contains the superficial layer of styrene-methylmethacrylate copolymer and ultraviolet light absorber in the basic unit that constitutes by polystyrene.By stacked this kind superficial layer, just can prevent the deterioration that causes by ultraviolet ray.Like this, because as light diffusing sheet, except the light diffusing energy, also require to possess various characteristics accordingly, therefore plywoods that form at the folded superficial layer that constitutes by the resin different of at least one surface layer of basic unit that use with the resin that constitutes basic unit with its purposes more.
But, in recent years, consider from the viewpoint of the environment of preserving our planet, begin requirement resin material is recycled.So the inventor visualizes following manufacture method in order to respond this viewpoint, that is, the end material (ear material) that produces during with the manufacturing light diffusing sheet utilizes as the part of the material that constitutes basic unit again.
But, under the situation that adopts above-mentioned stacked formation in the past, for example in basic unit, use polystyrene, in superficial layer, use styrene-methylmethacrylate copolymer (styrene units 40 quality %, methyl methacrylate units 60 quality %) under the situation, if this kind end material utilized as the part of basic unit again and make, then can become and in polystyrene, be mixed with styrene-methylmethacrylate copolymer (styrene units 40 quality % as basic unit, methyl methacrylate units 60 quality %) composition, form if this kind mixes, then exist light diffusing sheet to become the problem of slightly yellow tone.
Summary of the invention
The present invention finishes in view of this technical background, and purpose is, a kind of method of making laminated resin plate is provided, and it can be recycled the end material that produces during fabrication, and has suppressed painted fully.
In order to reach above-mentioned purpose, the invention provides following approach.
[1] a kind of manufacture method of laminated resin plate, it comprises:
One side at least in the basic unit of containing transparent resin (A), the stacked superficial layer that contains transparent resin (B) and after obtaining plywood, cut out the circumference that cuts this plywood at least a portion and as the end material that the end material is obtained obtain operation and
Containing the maybe one side at least of the basic unit of the potpourri of this end material and transparent resin (A) of above-mentioned end material, stackedly containing the superficial layer of transparent resin (B) and make the operation of laminated resin plate;
Be made as " Δ δ " in Hansen solubility parameter with above-mentioned transparent resin (A) and above-mentioned transparent resin (B), when the absolute value of the difference of the refractive index of the refractive index of above-mentioned transparent resin (A) and above-mentioned transparent resin (B) was made as " Δ n ", the relational expression of Δ δ * Δ n≤0.42 was set up.
[2] a kind of manufacture method of laminated resin plate, it comprises:
One side at least in the basic unit of containing transparent resin (A), the stacked superficial layer that contains transparent resin (B) and after obtaining the ground floor lamination is cut out at least a portion of the circumference that cuts this ground floor lamination and is obtained operation as the first end material that the first end material is obtained,
One side at least in the basic unit of the potpourri that contains the above-mentioned first end material or this first end material and transparent resin (A), the stacked superficial layer that contains transparent resin (B) and after obtaining second layer lamination, sanction cut this second layer lamination circumference at least a portion and as the second end material that the second end material is obtained obtain operation and
One side at least in the basic unit of the potpourri that contains the above-mentioned second end material or this second end material and transparent resin (A) stackedly contains the superficial layer of transparent resin (B) and makes the operation of laminated resin plate;
Be made as " Δ δ " in Hansen solubility parameter with above-mentioned transparent resin (A) and above-mentioned transparent resin (B), when the absolute value of the difference of the refractive index of the refractive index of above-mentioned transparent resin (A) and above-mentioned transparent resin (B) was made as " Δ n ", the relational expression of Δ δ * Δ n≤0.42 was set up.
[3] according to the method described in above-mentioned [1] or [2], wherein, the thickness of the basic unit in the above-mentioned plywood is 9 times～100 times of thickness of superficial layer, when above-mentioned transparent resin (A) is mixed with above-mentioned end material, the above-mentioned first end material or the above-mentioned second end material, being that 1 quality % is above and mix less than the mode of 100 quality % with respect to the above-mentioned transparent resin (A) and the containing ratio of the above-mentioned end material of the total amount of above-mentioned end material, the above-mentioned first end material or the above-mentioned second end material, the above-mentioned first end material or the above-mentioned second end material.
[4] according to any described method in above-mentioned [1]～[3], wherein, the relational expression of 0.03≤Δ n≤0.15 is set up.
[5] according to any described method in above-mentioned [1]～[4], wherein, above-mentioned transparent resin (A) is a phenylethylene resin series, and above-mentioned transparent resin (B) is phenylethylene resin series or acrylic resin.
[6] a kind of laminated resin plate, it possesses:
The basic unit of containing transparent resin (A) 100 mass parts and transparent resin (B) 0.01～20 mass parts,
Be laminated in above-mentioned basic unit one side at least, contain the superficial layer of transparent resin (B);
The thickness of above-mentioned basic unit is 9 times～100 times of thickness of above-mentioned superficial layer,
Be made as " Δ δ " in Hansen solubility parameter with above-mentioned transparent resin (A) and above-mentioned transparent resin (B), when the absolute value of the difference of the refractive index of the refractive index of above-mentioned transparent resin (A) and above-mentioned transparent resin (B) was made as " Δ n ", the relational expression of Δ δ * Δ n≤0.42 was set up.
[7] according to the laminated resin plate described in above-mentioned [6], wherein, above-mentioned transparent resin (A) 100 mass parts, above-mentioned transparent resin (B) 0.01～20 mass parts and light diffusion particle 0.01～10 mass parts are contained in above-mentioned basic unit.
[8] according to the laminated resin plate described in above-mentioned [6] or [7], wherein, above-mentioned transparent resin (A) is a phenylethylene resin series, and above-mentioned transparent resin (B) is phenylethylene resin series or acrylic resin.
[9] a kind of planar light source device, it possesses light diffusing sheet that is made of any described laminated resin plate in above-mentioned [6]～[8] and a plurality of light sources that are disposed at the rear side of this light diffusing sheet.
[10] a kind of liquid crystal indicator, a plurality of light sources of the rear side that it possesses the light diffusing sheet that is made of any described laminated resin plate in above-mentioned [6]～[8], be disposed at this light diffusing sheet and be disposed at the liquid crystal panel of the front face side of above-mentioned light diffusing sheet.
[1] or in the invention of [2] (manufacture method),, therefore can form the resources effective utilization, can the earth environment protection as social requirement be contributed because the end material that produces in the manufacturing process is utilized as the part of the constituent material of basic unit again.In addition, owing to be made as " Δ δ " in Hansen solubility parameter with above-mentioned transparent resin (A) and above-mentioned transparent resin (B), when the absolute value of the difference of the refractive index of the refractive index of transparent resin (A) and transparent resin (B) is made as " Δ n ", the relational expression of Δ δ * Δ n≤0.42 is set up, therefore will hold ratio that material utilizes as the part of the constituent material of basic unit again (promptly even increase, contain ratio even increase the recovery of end material), also can produce and suppress painted laminated resin plates such as yellow fully.
[3] in the invention, because the thickness of the basic unit in the plywood is 9 times～100 times of thickness of superficial layer, and in transparent resin (A), mix the end material and when obtaining basic unit and using material, it is above and mix less than the mode of 100 quality % to reach 1 quality % according to the containing ratio of end material with respect to the total amount of transparent resin (A) and end material, therefore can produce and suppress painted laminated resin plates such as yellow more fully.
[4] in the invention, it is the formation of the relational expression establishment of 0.03≤Δ n≤0.15, even the big formation of refringence of this kind transparent resin (A) and transparent resin (B), also be the formation of the relational expression establishment of Δ δ * Δ n≤0.42, therefore can produce and suppress painted laminated resin plates such as yellow fully.
[5] in the invention, because transparent resin (A) is a phenylethylene resin series, transparent resin (B) is phenylethylene resin series or acrylic resin, therefore can produce and suppress painted laminated resin plates such as yellow more fully.
[6] invention is the laminated resin plate of the formation that is fit in the middle of the laminated resin plate that is equivalent to utilize the manufacture method of [1]～[5] to obtain, it is the formation that transparent resin (A) 100 weight portions and transparent resin (B) 0.01～20 mass parts are contained in basic unit, at the folded superficial layer that contains transparent resin (B) of at least one surface layer of basic unit, the thickness of basic unit is set to 9～100 times scope of the thickness of superficial layer, be the formation of the relational expression establishment of Δ δ * Δ n≤0.42, therefore can provide and suppress painted laminated resin plates such as yellow fully.
[7] in the invention, be the formation that the light diffusion particle is also contained in basic unit, even this kind contains the formation of light diffusion particle, it is painted also can to suppress yellow etc. fully.In basic unit, exist under the situation of light diffusion particle, the optical path length that passes in the laminated resin plate is elongated, therefore as a rule, compare with the situation that does not have the light diffusion particle, painted be easy to eye-catching especially, even exist in basic unit under the situation of light diffusion particle, it is painted also can to suppress yellow etc. fully yet in the present invention.That is,, also can provide and suppress painted light diffusing laminated resin plates such as yellow fully although in basic unit, contain the light diffusion particle.
[8] in the invention, transparent resin (A) is a phenylethylene resin series, and transparent resin (B) is phenylethylene resin series or acrylic resin, therefore can provide and suppress painted laminated resin plates such as yellow more fully.
[9] in the invention, can penetrate the high diffusion light of whiteness that does not have yellow in fact.
[10] in the invention, can provide not have the liquid crystal indicator of realizing that yellowly nature, high-quality colour show.
Description of drawings
Fig. 1 is the sectional view of an embodiment of expression laminated resin plate of the present invention.
Fig. 2 is the process flow diagram of summary of an example of expression manufacture method of the present invention.
Wherein, 3... plywood, 8... basic unit, 9... superficial layer, the thickness of R... basic unit, the thickness of T... superficial layer
Embodiment
In reference Fig. 1 and 2, the manufacture method of laminated resin plate of the present invention is described.And, in the following description and Fig. 2, " step " brief note is " S ".
At first, the one side at least in the basic unit of containing transparent resin (A) (8) stackedly contains the superficial layer (9) of transparent resin (B) and obtains ground floor lamination (3) (S1).In the present embodiment, obtain ground floor lamination (3) (with reference to Fig. 1) at the two sides of basic unit (8) laminate surface layer (9) (9).
Here, as above-mentioned transparent resin (A), transparent resin (B), use the material of setting up in following formula (1) each other.Promptly, use is in the transparent resin (A) and the transparent resin (B) of following relation, be made as " Δ δ " in Hansen solubility parameter with above-mentioned transparent resin (A) and above-mentioned transparent resin (B), when the absolute value of the difference of the refractive index of the refractive index of above-mentioned transparent resin (A) and above-mentioned transparent resin (B) was made as " Δ n ", following formula (1) was set up.
Δδ×Δn≤0.42...(1)
Then, cut out at least a portion of the circumference of the ground floor lamination cut gained, the size product that obtains stipulating (first cascade resin plate), and the part that sanction is cut out obtained (S2) as the first end material.The first end material is obtained operation and is made of S1 and S2.
The first cascade resin plate that so obtains is the stacked formation that contains the superficial layer (9) (9) of transparent resin (B) on the two sides of the basic unit of containing transparent resin (A) (8).
Then, by the above-mentioned first end material is mixed the basic unit that preparation makes new advances resin (S3) with transparent resin (A).At this moment, be that 1 quality % is above and mix less than the mode of 100 quality % and to prepare the composition of basic unit with resin preferably according to making containing ratio with respect to the first end material of the total amount of the transparent resin (A) and the first end material.
Afterwards, the one side at least in the basic unit that is made of with resin above-mentioned basic unit (8) stackedly contains the superficial layer (9) of transparent resin (B) and obtains second layer lamination (S4).
Then, cut out at least a portion of the circumference of the second layer lamination cut gained, the size product that obtains stipulating (second laminated resin plate), and the part that sanction is cut out obtained (S5) as the second end material.The second end material is obtained operation and is made of S3, S4 and S5.
Second laminated resin plate that so obtains is the stacked formation that contains the superficial layer (9) (9) of transparent resin (B) on the two sides of the basic unit (8) of containing transparent resin (A) and transparent resin (B), yet because the relational expression of Δ δ * Δ n≤0.42 is set up between transparent resin (A) and transparent resin (B), although therefore the first end material is utilized as the part of the constituent material of basic unit (8) again, also can produce and suppress the second painted laminated resin plates such as yellow fully.In addition, even increase the ratio (that is, containing ratio even increase the recovery of end material) that the first end material is utilized as the part of the constituent material of basic unit (8) again, it is painted also can to suppress yellow etc. fully.
Above-mentioned second laminated resin plate that obtains through S3 and S4 is the end material to be used for utilizing for 1 time again and the material (with reference to Fig. 2) that produces like this, and in manufacture method of the present invention, also can further implement following operation and carries out the manufacturing of laminated resin plate.
That is, mix with transparent resin (A), and then prepare the basic unit's resin (S6) that makes new advances by cutting the above-mentioned second end material that produces in the operation in the sanction of S5.At this moment, same as described above, be to mix more than the 1 quality % and less than the mode of 100 quality % to prepare the composition of basic unit preferably with resin according to making with respect to the transparent resin (A) and the containing ratio of the second end material of the total amount of the second end material.
Afterwards, the one side at least in the basic unit that is made of with resin above-mentioned basic unit (8) stackedly contains the superficial layer (9) of transparent resin (B) and obtains the 3rd plywood (S7).
Then, cut out at least a portion of the circumference of the 3rd plywood cut gained, the size product that obtains stipulating (the 3rd laminated resin plate), and the part that sanction is cut out obtained (S8) as the 3rd end material.The 3rd end material is obtained operation and is made of S6, S7 and S8.
The 3rd laminated resin plate that so obtains is the stacked formation that contains the superficial layer (9) (9) of transparent resin (B) on the two sides of the basic unit (8) of containing transparent resin (A) and transparent resin (B).Here, the second end material that is reused in S6 is the material that is mixed with the first end material that is reused in its basic unit in above-mentioned S3, can be described as to be used to secondary utilization again.So the basic unit that obtains in S6 compares increase with the basic unit that obtains among the containing ratio of the above-mentioned transparent resin (B) in the composition of resin and in front the S3 with the containing ratio of the above-mentioned transparent resin (B) in the composition of resin, yet, therefore still can have been suppressed painted laminated resin plate fully owing to be the formation of the relational expression establishment of Δ δ * Δ n≤0.42 between transparent resin (A) and transparent resin (B).
Then, by above-mentioned the 3rd end material is mixed with transparent resin (A), and the basic unit that makes new advances of preparation is with resin (S9).Same as described above, be to mix more than the 1 quality % and less than the mode of 100 quality % to prepare the composition of basic unit preferably with resin according to making with respect to the transparent resin (A) and the containing ratio of the 3rd end material of the total amount of the 3rd end material.
Below, by similarly carrying out S7～S9 successively repeatedly, just can when utilize again, the end material that will produce in manufacture process produce and suppress painted laminated resin plates (the 4th laminated resin plate, the folded resin plate of layer 5, the folded resin plate of layer 6 ...) such as yellow fully.Promptly, though because of holding material to be used for 2 times, utilization again more than 3 times or 4 times, and containing ratio, the recovery that makes the end material in the laminated resin plate of gained little by little increases, yet as mentioned above because the formation that adopts the relational expression of Δ δ * Δ n≤0.42 between transparent resin (A) and transparent resin (B) to set up, even therefore will hold material repeatedly to be used for utilizing again, also can have been suppressed painted laminated resin plates such as yellow fully.Like this, in this manufacture method, it is painted not only certainly to suppress yellow etc. under the situation that will hold material to be used for utilizing again for 1 time, and under the situation that will hold material repeatedly to be used for utilizing again, it is painted also can to suppress yellow etc., so this manufacture method is suitable for commercial production.
And, as with above-mentioned basic unit (8) and the stacked method of above-mentioned superficial layer (9), be not particularly limited, for example can enumerate methods such as coextrusion shaping method, applying method, thermal bonding, solvent welding method, polymerization bonding method, cast polymerization, surface coated method.Wherein, preferred operation easily and make the efficient height, do not need to use other the coextrusion shaping method of material such as bonding agent.
In addition, also can be with owing to having damage, dirt, breaking etc. and can't be mixed together in the transparent resin (A) as the quality that product provides bad laminated resin plate and above-mentioned end material.
In addition, though in the above-described embodiment, use in the resins operation (S3, S6, S9) in basic unit, transparent resin (A) is mixed and prepares basic unit's resin with the end material, yet be not particularly limited in this, also above-mentioned base material can be used (not mixed transparent resin (A)) as basic unit with resin.
Among the present invention, as above-mentioned transparent resin (A) and above-mentioned transparent resin (B), so long as following transparent resin, promptly, be made as " Δ δ " in Hansen solubility parameter with above-mentioned transparent resin (A) and above-mentioned transparent resin (B), when the absolute value of the difference of the refractive index of the refractive index of transparent resin (A) and transparent resin (B) was made as " Δ n ", the relational expression of Δ δ * Δ n≤0.42 was set up each other, no matter is which kind of resin can use then.Following table 1 is a table of the numerical value of " Δ δ * Δ n " in the combination of 2 kinds of resins being made the form record, a side who for example can be in this kind combination with Δ δ * Δ n be the resin of the combination below 0.42 uses as transparent resin (A), and the opposing party is used as transparent resin (B).And in the table 1, Δ δ * Δ n surpasses 0.42 in the combination that has " * ".
Table 1
Figure BSA00000302454100091
And the value representation of " Δ δ " on the basis of calculating of " Δ δ * Δ n " that will become table 1 is in table 2, and the value representation of " Δ n " on the basis of calculating of " Δ δ * Δ n " that will become table 1 is in table 3.In addition, will become δ d, δ p and the δ h of each resin on the basis of calculating of " Δ δ " and the value representation of refractive index n of each resin on the basis of calculating that becomes " Δ n " in table 4.
Table 2
Figure BSA00000302454100111
Table 3
Figure BSA00000302454100121
Table 4
Figure BSA00000302454100131
Here, above-mentioned refractive index is to use the value (definition) that the refractometer " multi-wavelength Abbe refractometer DR-M4 " of the ATAGO of Co., Ltd. system determines according to JIS K7142-1996.
But, for calculating and the refractive index n of each resin of table 4 of the Δ n of table 3, convenient for the purpose of, use the refractive index of this resin of record in the following document 1, for the resin that not have in the document 1 to put down in writing, use the refractive index of this resin of following document 2.And, do not have in these documents 1,2 under the situation of record of refractive index of multipolymer, utilizing the molar ratio refractive index that calculate, that be multipolymer of the composition of the refractive index of known resin and each unit cell is by the refractive index of each unit cell and the product addition of each composition molar ratio are calculated.These aspects also are identical in embodiment described later.
Document 1: " POLYMER HANDBOOK (THIRD EDITION) ", author: J.BRANDRUP and E.H.IMMERGUT, distribution unit: AWILEY-INTERSCIENCE PUBLICATION, publication in 1989, p.VI/453～VI/461
Document 2: " the transparent resin in generation light time ", chief editor: well goes out Wen Xiong, distribution unit: CMC publication, distribution on June 30 in 2004, first published, the 10th chapter, p.128～137.
In addition, the above-mentioned Δ δ solubility parameter that is Hansen (method of utilizing Hansen is calculated and the solubility parameter obtained).According to Hansen, δ is to use the parameter of the three-dimensional of (δ d, δ p, δ h), utilizes following formula (2) to define.And, this thinking methods (theory) that Hansen advocated be recorded in " PROPERTIES OF POLYMERS " (author: D.W.VAN KREVENLEN, the distribution unit: ELSEVIER SCIENTIFICPUBLISHING COMPANY, 1989 the distribution, the 5th edition) in.
δ 2＝(δd) 2+(δp) 2+(δh) 2...(2)
δ d:London dispersancy item
δ p: molecular polarization item
δ h: hydrogen bond item
Among the present invention, " Δ δ " defines with following formula (3).
(Δδ) 2＝(δd 1-δd 2) 2+(δp 1-δp 2) 2+(δh 1-δh 2) 2...(3)
δ d 1: the London dispersancy item of transparent resin (A)
δ d 2: the London dispersancy item of transparent resin (B)
δ p 1: the molecular polarization item of transparent resin (A)
δ p 2: the molecular polarization item of transparent resin (B)
δ h 1: the hydrogen bond item of transparent resin (A)
δ h 2: the hydrogen bond item of transparent resin (B)
Among the present invention, Hansen solubility parameter (Δ δ) can be obtained specifically as followsly.
1) utilizes " the CHAPTER7 COHESIVEPROPERTIES AND SOLUBILITY " specified particular of (129～158 pages), the group mole that gimmick is calculated each functional group traction constant (グ Le one プ モ Le Pull draws fixed number) (Fdi, Fpi, Ehi) and the molar volume (Vi) of " PROPERTIES OF POLYMERS " (author: D.W.VANKREVENLEN, distribution unit: ELSEVIER SCIENTIFIC PUBLISHINGCOMPANY, distribution in 1989, the 5th edition).
2) the unit group mole of polymkeric substance (resin) traction constant is according to above-mentioned 1) in the group mole traction constant (Fdi, Fpi, Ehi) and the molar volume (Vi) of each functional group of obtaining, utilize following formula (4), formula (5), formula (6) to calculate respectively.
δd＝∑Fdi/∑Vi...(4)
δp＝(∑(Fpi) 2) 1/2/∑Vi...(5)
δh＝(∑Ehi/∑Vi) 1/2...(6)
3), multiply by there is molar ratio of each unit cell and calculate for the polymkeric substance that contains a plurality of monomeric units (multipolymer).
As above-mentioned transparent resin (A) and above-mentioned transparent resin (B), the transparent resin that preferably uses the relational expression of Δ δ * Δ n≤0.30 each other to set up, the especially preferably transparent resin set up of the relational expression of Δ δ * Δ n≤0.20 each other.Under the littler situation of the value of " Δ δ * Δ n ",, also can produce and suppress painted laminated resin plates (light diffusing sheet etc.) such as yellow fully like this even will hold material to use more as the part of the constituent material of basic unit.
In addition, the absolute value (Δ n) of the difference of the refractive index of the refractive index of transparent resin (A) and transparent resin (B) is preferably 0.03～0.15, and more preferably 0.032～0.13.
Above-mentioned transparent resin (A) is preferably 0.0～12.0 with the Hansen solubility parameter (Δ δ) of above-mentioned transparent resin (B), even the further increase ratio that will hold material to utilize again as the part of the constituent material of basic unit in this case, it is painted also can to suppress yellow etc. fully.Wherein, more preferably Δ δ is 0.0～10.0.
And the combination of transparent resin shown in the table 1 (A) and transparent resin (B) is an example only, is not particularly limited in these illustrative situations.That is,,, for example can from following transparent resin, be used in combination as long as the relational expression of Δ δ * Δ n≤0.42 is set up each other as above-mentioned transparent resin (A), above-mentioned transparent resin (B).For example, can enumerate methacrylic resin, MS resin (styrene-methylmethacrylate copolymer), ABS resin (acrylonitrile-butadiene-styrene copolymer), polystyrene, AS resin (acrylonitritrile-styrene resin), tygon, polypropylene, cyclic olefin resin etc.
In the middle of them, preferably use phenylethylene resin series, use phenylethylene resin series or acrylic resin as above-mentioned transparent resin (B) as above-mentioned transparent resin (A).Certainly, in this case, set up as the phenylethylene resin series of transparent resin (A) with as the relational expression that the phenylethylene resin series or the acrylic resin of transparent resin (B) also must be Δ δ * Δ n≤0.42 each other.
The containing ratio that above-mentioned so-called phenylethylene resin series is the styrenic monomers unit is the resin of 50～100 quality %.As above-mentioned styrenic monomers, except styrene, for example also can use substituted phenylethylene class etc.As above-mentioned substituted phenylethylene class, be not particularly limited, for example can enumerate ring-alkylated styrenes classes such as halogenated styrenes class, vinyltoluene, α-Jia Jibenyixi such as chlorostyrene, bromostyrene etc.Above-mentioned styrenic monomers both may be used singly or in combination of two or more.
For in above-mentioned phenylethylene resin series, can be used as the styrenic monomers monomer in addition that monomeric unit contains, be not particularly limited, for example can enumerate methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, cyclohexyl methacrylate, the methacrylic acid stearyl, phenyl methacrylate, benzyl methacrylate, methacrylic acid 2-Octyl Nitrite, 2-hydroxyethyl methacrylate, methacrylic acid diamantane ester, methacrylic acid three ring esters in the last of the ten Heavenly stems, methacrylic acid turnip ester, methacrylic acid norborneol ester, methyl acrylic esters such as methacrylic acid norborny methyl esters, methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-EHA, acrylic acid 2-hydroxy methacrylate, esters of acrylic acids such as acrylic acid three ring esters in the last of the ten Heavenly stems, methacrylic acid, unsaturated acids such as acrylic acid, vinyl cyanide, methacrylonitrile, maleic anhydride, phenyl maleimide, the cyclohexyl maleimide, glutaric anhydride, glutarimide etc., also can contain they more than 2 kinds.
Above-mentioned so-called acrylic resin is the resin that contains the above methyl methacrylate of 50 quality % as monomeric unit, both can come down to single polymers of methyl methacrylate, also can be with methyl methacrylate more than the 50 quality % and the copolymerization with it below the 50 quality % other monomer copolymerization and multipolymer.
For being to can be used as monomer beyond the methyl methacrylate that monomeric unit contains (can with other monomer of methyl methacrylate copolymer) in the resin in aforesaid propylene acid, be not particularly limited, for example can enumerate Jia Jibingxisuanyizhi, butyl methacrylate, cyclohexyl methacrylate, the methacrylic acid stearyl, phenyl methacrylate, benzyl methacrylate, methacrylic acid 2-Octyl Nitrite, 2-hydroxyethyl methacrylate, methacrylic acid diamantane ester, methacrylic acid three ring esters in the last of the ten Heavenly stems, methacrylic acid turnip ester, methacrylic acid norborneol ester, methyl acrylic esters such as methacrylic acid norborny methyl esters, methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-EHA, acrylic acid 2-hydroxy methacrylate, esters of acrylic acids such as acrylic acid three ring esters in the last of the ten Heavenly stems, methacrylic acid, unsaturated acids such as acrylic acid, vinyl cyanide, methacrylonitrile, maleic anhydride, phenyl maleimide, the cyclohexyl maleimide, glutaric anhydride, glutarimide, styrenic monomers etc., also can contain they more than 2 kinds.As above-mentioned styrenic monomers, except styrene, also can use above-mentioned substituted phenylethylene class.In addition, be in the resin in aforesaid propylene acid, also can contain glutaric anhydride unit or glutarimide unit.
In above-mentioned basic unit (8), also can contain the light diffusion particle.Under this situation, can form suitable light diffusing sheet as light diffusing sheet.As above-mentioned smooth diffusion particle, so long as with the resin or the different particle of hybrid resin refractive index that constitute above-mentioned basic unit (8), and be just to be not particularly limited seeing through the particle of the light diffusion of laminated resin plate (light diffusing sheet) by containing this particle dispersedly.For example both can be inorganic particulates such as glass particle, glass fibre, silicon dioxide granule, aluminum hydroxide particles, calcium carbonate particle, barium sulphate particle, Titanium particles, talcum, also can be organic fillers such as styrenic particle, acrylic acid series polymeric compounds particle, cyclohexane based polymer particle.
In addition, in above-mentioned basic unit (8), in the scope that hinders effect of the present invention, also can contain adjuvants such as ultraviolet light absorber, thermal stabilizer, antioxidant, weather resisting agent, light stabilizer, fluorescer, processing stabilizers, nucleator not obviously.
Similarly, in the scope that hinders effect of the present invention not obviously, in above-mentioned superficial layer (9), also can contain adjuvants such as ultraviolet light absorber, thermal stabilizer, antioxidant, weather resisting agent, light stabilizer, fluorescer, processing stabilizers, nucleator.
The thickness (R) of above-mentioned basic unit (8) as a rule is 50～2990 μ m.By being made as more than the 50 μ m, just can guarantee enough intensity, and, just can suppress cost and increase by being made as below the 2990 μ m.Wherein, the thickness (R) of above-mentioned basic unit (8) is preferably more than the 100 μ m, is preferably in addition below the 2980 μ m, more preferably below the 2500 μ m.
In addition, the thickness (T) of above-mentioned superficial layer (9) as a rule is 10 μ m～300 μ m.By being made as more than the 10 μ m, just can obtain the superficial layer of stable thickness, and, just can suppress cost and increase by being made as below the 300 μ m.Wherein, the thickness (T) of above-mentioned superficial layer (9) is preferably 20 μ m～200 μ m.
The thickness of above-mentioned basic unit is preferably 9 times～100 times of thickness (simultaneously) of above-mentioned superficial layer.By being made as more than 9 times, just can suppressing cost and increase, and, just can obtain the superficial layer of stable thickness by being made as below 100 times.Wherein, the thickness of above-mentioned basic unit 10 times～80 times of thickness of above-mentioned superficial layer more preferably.And the thickness of above-mentioned laminated resin plate is 0.05mm～5mm as a rule, is preferably 0.07mm～4mm, and more preferably 0.1mm～3.5mm is preferably 0.2mm～3mm especially.
And, though in the above-described embodiment, employing is at the two sides of basic unit (8) laminate surface layer (9) (9) and incorporate formation (with reference to Fig. 1), yet is not particularly limited in this kind formation, also can adopt the formation at the one side laminate surface layer (9) of basic unit (8).But, consider from the aspect that can prevent warpage more fully, preferably as above-mentioned embodiment in the formation of the two sides of basic unit (8) laminate surface layer (9) (9).
In addition, even surface can be made in the surface of laminated resin plate, also can make uneven surface (マ ッ ト) shape, lens shape etc., is not particularly limited.
Be suitable for as the formation of the laminated resin plate that utilizes manufacture method of the present invention to obtain be, possess the basic unit (8) of containing transparent resin (A) 100 mass parts and transparent resin (B) 0.01～20 mass parts and be laminated in the one side at least of above-mentioned basic unit and contain the superficial layer (9) of transparent resin (B), the thickness of basic unit is 9 times～100 times of the thickness of superficial layer (simultaneously).The laminated resin plate of this kind formation can suppress painted fully.
And the manufacture method of laminated resin plate of the present invention is not particularly limited the method in above-mentioned illustrative embodiment, so long as in the scope of asking for protection, so long as do not break away from the method for its spirit, also allow the change of any design.
Embodiment
Below, specific embodiment of the present invention is described, yet the present invention is not particularly limited in these embodiment.
＜embodiment 1 〉
By with the styrene-methylmethacrylate copolymer (containing ratio of styrene units: about 80 quality %, the containing ratio of methyl methacrylate units: (chemical company of Nippon Steel system " MS200 ") 90.90 mass parts about 20 quality %), acrylic acid series polymeric compounds particle (cross-linking polymer particle) (sumitomo chemical company system " Sumipex XC1A ", the about 25 μ m of volume average particle size) 8.00 mass parts, (benzotriazole is a ultraviolet light absorber to Adekastab LA31, the ADEKA corporate system) 1.00 mass parts, Sumilizer GP (processing stabilizers, sumitomo chemical company system) after 0.10 mass parts is carried out the dry type mixing, extruder to screw diameter 40mm is supplied with and the fusion mixing, obtains superficial layer formation resin combination B1.
By with polystyrene resin (Japan's styrene corporate system " HRM40 ") 84.45 mass parts, acrylic acid series polymeric compounds particle (cross-linking polymer particle) (Rohm ﹠amp; Hass corporate system " Paraloid EXL5766 ", the about 0.8 μ m of volume average particle size) 14.00 mass parts, Sumisorb200 (benzotriazole is ultraviolet light absorber, sumitomo chemical company system) 1.00 mass parts, Sumilizer GP (processing stabilizers, sumitomo chemical company system) 0.50 mass parts, White Flow PSN (fluorescer, Sumika Color corporate system) 0.05 mass parts carry out dry type and mix, and obtain master batch resin composition A1.
With the above-mentioned superficial layer of the polystyrene resin (Japan's styrene corporate system " HRM40 ") of 100 mass parts, 4.63 mass parts form mix with the above-mentioned master batch resin composition A1 dry type of resin combination B1,11.00 mass parts after, supply with and, supply with to first extruder of screw diameter 40mm to many manifold dies at 250 ℃ of following fusion mixings.
On the other hand, above-mentioned superficial layer is formed with resin combination B1 to second extruder supply of screw diameter 20mm and at 250 ℃ of following fusion mixings, to many manifold dies supplies.
According to making the resin combination of supplying with to many manifold dies from above-mentioned first extruder become basic unit (8), become the mode of superficial layer (9) (9) to the resin combination of many manifold dies supplies from above-mentioned second extruder, under 245～250 ℃ of temperature, carry out coextrusion and be shaped, produce the light diffusing sheet that 3 folded layer by layer resin plates by thick 2.0mm (1.9mm of basic unit, superficial layer 0.05mm * 2) as shown in Figure 1 constitute.
And, because (containing ratio of styrene units: the containing ratio of about 80 quality %, methyl methacrylate units: about 20 quality %) the Δ δ * Δ n between (transparent resin (B)) was 0.093 (with reference to table 1), and therefore the relational expression of Δ δ * Δ n≤0.42 is set up between these two kinds of resins for above-mentioned polystyrene resin (transparent resin (A)) and above-mentioned styrene-methylmethacrylate copolymer.
The laminated resin plate that obtains among this embodiment 1 is equivalent to the laminated resin plate of following manufacturing, promptly, the thickness that sanction is cut the basic unit of transparent resin (A) system be the thickness of the superficial layer of 1.9mm, transparent resin (B) system be 0.05mm (both sides add up to 0.10mm) plywood circumference and obtain as the end material, by holding material 92 mass parts and transparent resin (A) 8 mass parts to mix the two sides of basic unit of the thick 1.9mm that constitutes of resin combination, the superficial layer of the thick 0.05mm of stacked transparent resin (B) system and making respectively.
＜embodiment 2 〉
Except will being set at the condition shown in the table 5 respectively, produce 3 layers laminated resin plate in the same manner with embodiment 1 to the thickness that contains proportional and each layer of each composition of resin combination that first extruder is supplied with (basic unit with).
The laminated resin plate that obtains among this embodiment 2 is equivalent to the laminated resin plate of following manufacturing, promptly, the thickness that sanction is cut the basic unit of transparent resin (A) system be the thickness of the superficial layer of 1.6mm, transparent resin (B) system be 0.2mm (both sides add up to 0.4mm) plywood circumference and obtain as the end material, by holding material 49 mass parts and transparent resin (A) 51 mass parts to mix the two sides of basic unit of the thick 1.9mm that constitutes of resin combination, the superficial layer of the thick 0.05mm of stacked transparent resin (B) system and making respectively.
＜reference example 1 〉
Above-mentioned superficial layer is formed with resin combination B1 to second extruder supply of screw diameter 20mm and at 250 ℃ of following fusion mixings, to many manifold dies supplies.
After the above-mentioned master batch resin composition A1 dry type of the polystyrene resin (Japan's styrene corporate system " HRM40 ") of 100.0 mass parts, 11.00 mass parts mixed, supply with and, supply with to first extruder of screw diameter 40mm to many manifold dies at 250 ℃ of following fusion mixings.
According to making the resin combination of supplying with to many manifold dies from above-mentioned first extruder become basic unit (8), become the mode of superficial layer (9) (9) to the resin combination of many manifold dies supplies from above-mentioned second extruder, under 245～250 ℃ of temperature, carry out coextrusion and be shaped, produce the 3 folded layer by layer resin plates of thick 2.0mm (1.9mm of basic unit, superficial layer 0.05mm * 2) as shown in Figure 1.
This reference example 1 is equivalent to not use fully as the constituent material of basic unit the situation of the end material of plywood.
＜embodiment 3 〉
By with the styrene-methylmethacrylate copolymer (containing ratio of styrene units: about 80 quality %, the containing ratio of methyl methacrylate units: (chemical company of Nippon Steel system " MS200 ") 78.55 mass parts about 20 quality %), acrylic acid series polymeric compounds particle (cross-linking polymer particle) (sumitomo chemical company system " Sumipex XC1A ", the about 25 μ m of volume average particle size) 20.00 mass parts, (benzotriazole is a ultraviolet light absorber to Adekastab LA31, the ADEKA corporate system) 1.00 mass parts, Sumilizer GP (processing stabilizers, sumitomo chemical company system) 0.20 mass parts, バ Le one HSP 311 (release agents, ball water chestnut oiling corporate system) after 0.25 mass parts is carried out the dry type mixing, extruder to screw diameter 40mm is supplied with and the fusion mixing, obtains superficial layer formation resin combination B2.
Above-mentioned superficial layer is formed with resin combination B2 to second extruder supply of screw diameter 20mm and at 250 ℃ of following fusion mixings, to many manifold dies supplies.
On the other hand, with styrene-methacrylic acid copolymer (containing ratio of styrene units: about 90.5 quality %, the containing ratio of methacrylic acid unit: (Japan's styrene corporate system " T080 ") 96.70 mass parts about 9.5 quality %), silicone rubber particle (Toray Dowcorning corporate system " DY33-719 ") 0.10 mass parts, (ponding changes into product industrial group system " MBX2H " to acrylic acid series polymeric compounds particle (cross-linking polymer particle), the about 3 μ m of volume average particle size) 0.50 mass parts, (benzotriazole is a ultraviolet light absorber to Sumisorb200, sumitomo chemical company system) 0.10 mass parts, Sumilizer GP (processing stabilizers, sumitomo chemical company system) 0.10 mass parts, after above-mentioned superficial layer forms the 2.50 mass parts dry types mixing of using resin combination B2, supply with and, supply with to first extruder of screw diameter 40mm to many manifold dies at 250 ℃ of following fusion mixings.
According to making the resin combination of supplying with to many manifold dies from above-mentioned first extruder become basic unit (8), become the mode of superficial layer (9) (9) to the resin combination of many manifold dies supplies from above-mentioned second extruder, under 245～250 ℃ of temperature, carry out coextrusion and be shaped, produce the 3 folded layer by layer resin plates of thick 2.0mm (1.9mm of basic unit, superficial layer 0.05mm * 2) as shown in Figure 1.
And, because (containing ratio of styrene units: the containing ratio of about 90.5 quality %, methacrylic acid unit: about 9.5 quality %) (containing ratio of styrene units: the containing ratio of about 80 quality %, methyl methacrylate units: about 20 quality %) the Δ δ * Δ n between (transparent resin (B)) was 0.088 (with reference to table 1) to above-mentioned polystyrene-methacrylic acid copolymer, and therefore the relational expression of Δ δ * Δ n≤0.42 is set up between these two kinds of resins for (transparent resin (A)) and above-mentioned styrene-methylmethacrylate copolymer.
The laminated resin plate that obtains among this embodiment 3 is equivalent to the laminated resin plate of following manufacturing, promptly, the thickness that sanction is cut the basic unit of transparent resin (A) system be the thickness of the superficial layer of 1.9mm, transparent resin (B) system be 0.05mm (both sides add up to 0.10mm) plywood circumference and obtain as the end material, by holding material 50 mass parts and transparent resin (A) 50 mass parts to mix the two sides of basic unit of the thick 1.9mm that constitutes of resin combination, the superficial layer of the thick 0.05mm of stacked transparent resin (B) system and making respectively.
＜reference example 2 〉
Above-mentioned superficial layer is formed with resin combination B1 to second extruder supply of screw diameter 20mm and at 250 ℃ of following fusion mixings, to many manifold dies supplies.
With styrene-methacrylic acid copolymer (containing ratio of styrene units: about 90.5 quality %, the containing ratio of methacrylic acid unit: (Japan's styrene corporate system " T080 ") 99.20 mass parts about 9.5 quality %), silicone rubber particle (Toray Dowcorning corporate system " DY33-719 ") 0.10 mass parts, (ponding changes into product industrial group system " MBX2H " to acrylic acid series polymeric compounds particle (cross-linking polymer particle), the about 3 μ m of volume average particle size) 0.50 mass parts, (benzotriazole is a ultraviolet light absorber to Sumisorb200, sumitomo chemical company system) 0.10 mass parts, Sumilizer GP (processing stabilizers, sumitomo chemical company system) after 0.10 mass parts dry type is mixed, supply with and, supply with to first extruder of screw diameter 40mm to many manifold dies at 250 ℃ of following fusion mixings.
According to making the resin combination of supplying with to many manifold dies from above-mentioned first extruder become basic unit (8), become the mode of superficial layer (9) (9) to the resin combination of many manifold dies supplies from above-mentioned second extruder, under 245～250 ℃ of temperature, carry out coextrusion and be shaped, produce the 3 folded layer by layer resin plates of thick 2.0mm (1.9mm of basic unit, superficial layer 0.05mm * 2) as shown in Figure 1.
This reference example 2 is equivalent to not use fully as the constituent material of basic unit the situation of the end material of plywood.
＜embodiment 4 〉
By with the styrene-methylmethacrylate copolymer (containing ratio of styrene units: about 40 quality %, the containing ratio of methyl methacrylate units: (chemical company of Nippon Steel system " MS600 ") 78.55 mass parts about 60 quality %), acrylic acid series polymeric compounds particle (cross-linking polymer particle) (sumitomo chemical company system " Sumipex XC1A ", the about 25 μ m of volume average particle size) 20.00 mass parts, (benzotriazole is a ultraviolet light absorber to Adekastab LA31, the ADEKA corporate system) 1.00 mass parts, Sumilizer GP (processing stabilizers, sumitomo chemical company system) 0.20 mass parts, バ Le one HSP 311 (release agents, ball water chestnut oiling corporate system) after 0.25 mass parts is carried out the dry type mixing, extruder to screw diameter 40mm is supplied with and the fusion mixing, obtains superficial layer formation resin combination B3.
Above-mentioned superficial layer is formed with resin combination B3 to second extruder supply of screw diameter 20mm and at 250 ℃ of following fusion mixings, to many manifold dies supplies.
On the other hand, with styrene-methacrylic acid copolymer (containing ratio of styrene units: about 90.5 quality %, the containing ratio of methacrylic acid unit: (Japan's styrene corporate system " T080 ") 96.70 mass parts about 9.5 quality %), silicone rubber particle (Toray Dowcorning corporate system " DY33-719 ") 0.10 mass parts, (ponding changes into product industrial group system " MBX2H " to acrylic acid series polymeric compounds particle (cross-linking polymer particle), the about 3 μ m of volume average particle size) 0.50 mass parts, (benzotriazole is a ultraviolet light absorber to Sumisorb200, sumitomo chemical company system) 0.10 mass parts, Sumilizer GP (processing stabilizers, sumitomo chemical company system) 0.10 mass parts, after above-mentioned superficial layer forms the 2.50 mass parts dry types mixing of using resin combination B3, supply with and, supply with to first extruder of screw diameter 40mm to many manifold dies at 250 ℃ of following fusion mixings.
According to making the resin combination of supplying with to many manifold dies from above-mentioned first extruder become basic unit (8), become the mode of superficial layer (9) (9) to the resin combination of many manifold dies supplies from above-mentioned second extruder, under 245～250 ℃ of temperature, carry out coextrusion and be shaped, produce the 3 folded layer by layer resin plates of thick 2.0mm (1.9mm of basic unit, superficial layer 0.05mm * 2) as shown in Figure 1.
And, because (containing ratio of styrene units: the containing ratio of about 90.5 quality %, methacrylic acid unit: about 9.5 quality %) (containing ratio of styrene units: the containing ratio of about 80 quality %, methyl methacrylate units: about 20 quality %) the Δ δ * Δ n between (transparent resin (B)) was 0.271 (with reference to table 1) to above-mentioned polystyrene-methacrylic acid copolymer, and therefore the relational expression of Δ δ * Δ n≤0.42 is set up between these two kinds of resins for (transparent resin (A)) and above-mentioned styrene-methylmethacrylate copolymer.
The laminated resin plate that obtains among this embodiment 4 is equivalent to the laminated resin plate of following manufacturing, promptly, the thickness that sanction is cut the basic unit of transparent resin (A) system be the thickness of the superficial layer of 1.9mm, transparent resin (B) system be 0.05mm (both sides add up to 0.10mm) plywood circumference and obtain as the end material, by holding material 50 mass parts and transparent resin (A) 50 mass parts to mix the two sides of basic unit of the thick 1.9mm that constitutes of resin combination, the superficial layer of the thick 0.05mm of stacked transparent resin (B) system and making respectively.
＜reference example 3 〉
Above-mentioned superficial layer is formed with resin combination B3 to second extruder supply of screw diameter 20mm and at 250 ℃ of following fusion mixings, to many manifold dies supplies.
On the other hand, with styrene-methacrylic acid copolymer (containing ratio of styrene units: about 90.5 quality %, the containing ratio of methacrylic acid unit: (Japan's styrene corporate system " T080 ") 99.20 mass parts about 9.5 quality %), silicone rubber particle (Toray Dowcorning corporate system " DY33-719 ") 0.10 mass parts, (ponding changes into product industrial group system " MBX2H " to acrylic acid series polymeric compounds particle (cross-linking polymer particle), the about 3 μ m of volume average particle size) 0.50 mass parts, (benzotriazole is a ultraviolet light absorber to Sumisorb200, sumitomo chemical company system) 0.10 mass parts, Sumilizer GP (processing stabilizers, sumitomo chemical company system) after 0.10 mass parts dry type is mixed, supply with and, supply with to first extruder of screw diameter 40mm to many manifold dies at 250 ℃ of following fusion mixings.
According to making the resin combination of supplying with to many manifold dies from above-mentioned first extruder become basic unit (8), become the mode of superficial layer (9) (9) to the resin combination of many manifold dies supplies from above-mentioned second extruder, under 245～250 ℃ of temperature, carry out coextrusion and be shaped, produce the 3 folded layer by layer resin plates of thick 2.0mm (1.9mm of basic unit, superficial layer 0.05mm * 2) as shown in Figure 1.
This reference example 3 is equivalent to not use fully as the constituent material of basic unit the situation of the end material of plywood.
Table 5
Figure BSA00000302454100251
＜comparative example 1 〉
By with the styrene-methylmethacrylate copolymer (containing ratio of styrene units: about 40 quality %, the containing ratio of methyl methacrylate units: (chemical company of Nippon Steel system " MS600 ") 90.90 mass parts about 60 quality %), acrylic acid series polymeric compounds particle (cross-linking polymer particle) (sumitomo chemical company system " Sumipex XC1A ", the about 25 μ m of volume average particle size) 8.00 mass parts, (benzotriazole is a ultraviolet light absorber to Adekastab LA31, the ADEKA corporate system) 1.00 mass parts, Sumilizer GP (processing stabilizers, sumitomo chemical company system) after 0.10 mass parts dry type is mixed, extruder to screw diameter 40mm is supplied with and the fusion mixing, obtains superficial layer formation resin combination B4.
Above-mentioned superficial layer is formed with resin combination B4 to second extruder supply of screw diameter 20mm and at 250 ℃ of following fusion mixings, to many manifold dies supplies.
On the other hand, with the above-mentioned superficial layer of the polystyrene resin (Japan's styrene corporate system " HRM40 ") of 100 mass parts, 2.20 mass parts form mix with the above-mentioned master batch resin composition A1 dry type of resin combination B4,11.00 mass parts after, supply with and, supply with to first extruder of screw diameter 40mm to many manifold dies at 250 ℃ of following fusion mixings.
According to making the resin combination of supplying with to many manifold dies from above-mentioned first extruder become basic unit (8), become the mode of superficial layer (9) (9) to the resin combination of many manifold dies supplies from above-mentioned second extruder, under 245～250 ℃ of temperature, carry out coextrusion and be shaped, produce the 3 folded layer by layer resin plates of thick 2.0mm (1.9mm of basic unit, superficial layer 0.05mm * 2) as shown in Figure 1.
And, because (containing ratio of styrene units: the containing ratio of about 40 quality %, methyl methacrylate units: about 60 quality %) the Δ δ * Δ n between (transparent resin (B)) was 0.495 (with reference to table 1), and therefore the relational expression of Δ δ * Δ n≤0.42 is false between these two kinds of resins for above-mentioned polystyrene resin (transparent resin (A)) and above-mentioned styrene-methylmethacrylate copolymer.
The laminated resin plate that obtains in this comparative example 1 is equivalent to the laminated resin plate of following manufacturing, promptly, the thickness that sanction is cut the basic unit of transparent resin (A) system be the thickness of the superficial layer of 1.9mm, transparent resin (B) system be 0.05mm (both sides add up to 0.10mm) plywood circumference and obtain as the end material, by holding material 44 mass parts and transparent resin (A) 56 mass parts to mix the two sides of basic unit of the thick 1.9mm that constitutes of resin combination, the superficial layer of the thick 0.05mm of stacked transparent resin (B) system and making respectively.
＜reference example 4 〉
Above-mentioned superficial layer is formed with resin combination B4 to second extruder supply of screw diameter 20mm and at 250 ℃ of following fusion mixings, to many manifold dies supplies.
On the other hand, after the above-mentioned master batch resin composition A1 dry type of the polystyrene resin (Japan's styrene corporate system " HRM40 ") of 100 mass parts, 11.0 mass parts mixed, supply with and, supply with to first extruder of screw diameter 40mm to many manifold dies at 250 ℃ of following fusion mixings.
According to making the resin combination of supplying with to many manifold dies from above-mentioned first extruder become basic unit (8), become the mode of superficial layer (9) (9) to the resin combination of many manifold dies supplies from above-mentioned second extruder, under 245～250 ℃ of temperature, carry out coextrusion and be shaped, produce the 3 folded layer by layer resin plates of thick 2.0mm (1.9mm of basic unit, superficial layer 0.05mm * 2) as shown in Figure 1.
This reference example 4 is equivalent to not use fully as the constituent material of basic unit the situation of the end material of plywood.
Table 6
(the unit that forms the numerical value on hurdle: mass parts)
Figure BSA00000302454100271
Each laminated resin plate that obtains is as described above estimated according to following evaluation method.Evaluation result is shown in the table 5,6.
＜total light transmittance determination method 〉
Determine total light transmittance (%) of laminated resin plate according to JIS K7361-1997.
＜diffusion light transmittance determination method 〉
Determine the diffusion light transmittance (%) of laminated resin plate according to JIS K7136-2000.
＜mist pH-value determination pH method 〉
Determine the mist value (%) of laminated resin plate according to JIS K7136-2000.
＜utilize the determination method of the yellow chromaticity YI that spectral transmission measures 〉
Use possesses the self-recording spectrophotometer (Hitachi's system " UV-4000 ") of integrating sphere, and the spectral transmission of the wavelength coverage of 380～780nm of mensuration laminated resin plate is calculated yellow chromaticity YI based on it.
The determination method of＜diffusivity 〉
Use automatic goniophotometer (Murakami K. K.'s look material technical research made " GP-1R "), measure respectively with respect to laminated resin plate and inject from normal direction in the middle of the transmitted light of light time towards the intensity I of transmitted light that with respect to normal direction is 5 ° angle 5, towards the intensity I of transmitted light that with respect to normal direction is 20 ° angle 20, towards the intensity I of transmitted light that with respect to normal direction is 70 ° angle 70, utilize following formula to obtain diffusivity D (%).
D＝100×(I 20+I 70)/(2×I 5)
Can be clear that from table 5 and 6, utilize the yellow chromaticity YI of light diffusing sheet of the embodiment 1～4 that manufacture method of the present invention makes little, paintedly be suppressed fully.Promptly, for example can be clear that with the contrast of the YI value of embodiment 4 with contrast, the reference example 3 of the YI value of embodiment 3 from contrast, the reference example 2 of reference example 1 with the YI value of embodiment 1,2, even it is big (promptly that the superficial layer in the basic unit forms with the mixture ratio of resin combination, even it is big that the recovery of end material contains ratio), yellow chromaticity YI also is suppressed very for a short time.Promptly, the YI value of having carried out the embodiment 1,2 that utilizes again of end material is equal with the YI value of the reference example 1 of utilization again of holding material, the YI value of YI value and the reference example of utilizing again 2 of holding material of having carried out the embodiment 3 that utilizes again of end material is equal, carried out the end material the embodiment 4 that utilizes again the YI value and to hold the YI value of the reference example 3 of utilization again of material be equal.
In addition, in the light diffusing sheet of these embodiment 1～4, even the superficial layer in the basic unit forms the mixture ratio big (that is, big even the recovery of end material contains ratio) with resin combination, total light transmittance and diffusion light transmittance all do not change basically yet, are roughly certain levels.
In manufacture method of the present invention, will hold under the situation that material repeatedly is used for utilizing again, when repeating to hold the utilizing again of material at every turn, the recovery of the end material in the laminated resin plate contains ratio and little by little increases, even yet in such cases, also can suppress yellow chromaticity YI very little, total light transmittance and diffusion light transmittance all do not change basically, if so adopt manufacture method of the present invention, just can when will holding material to utilize again, make the laminated resin plate that possesses stable quality.
Relative with it, in the laminated resin plate of the comparative example 1 of the invalid formation of relational expression that belongs to Δ δ * Δ n≤0.42, utilize again because of holding material, and make yellow chromaticity YI bigger, have slightly yellow paintedly, diffusivity reduces.
The industrial possibility of utilizing
Utilize the laminated resin plate of manufacture method manufacturing of the present invention for example to be suitable for use as light diffusing sheet, wherein be particularly suitable for the light diffusing sheet used as the planar light source device of the use such as backlight that is used as that liquid crystal indicator uses, yet be not limited thereto kind of a purposes.

Claims (10)

1. the manufacture method of a laminated resin plate, it comprises:
One side at least in the basic unit of containing transparent resin A, the stacked superficial layer that contains transparent resin B and after obtaining plywood, cut out the circumference that cuts this plywood at least a portion and as the end material that the end material is obtained obtain operation and
Containing the maybe one side at least of the basic unit of the potpourri of this end material and transparent resin A of described end material, stackedly containing the superficial layer of transparent resin B and make the operation of laminated resin plate;
Be made as " Δ δ " in Hansen solubility parameter with described transparent resin A and described transparent resin B, when the absolute value of the difference of the refractive index of the refractive index of described transparent resin A and described transparent resin B was made as " Δ n ", the relational expression of Δ δ * Δ n≤0.42 was set up.
2. the manufacture method of a laminated resin plate, it comprises:
One side at least in the basic unit of containing transparent resin A, the stacked superficial layer that contains transparent resin B and after obtaining the ground floor lamination is cut out at least a portion of the circumference that cuts this ground floor lamination and is obtained operation as the first end material that the first end material is obtained,
One side at least in the basic unit of the potpourri that contains the described first end material or this first end material and transparent resin A, the stacked superficial layer that contains transparent resin B and after obtaining second layer lamination, sanction cut this second layer lamination circumference at least a portion and as the second end material that the second end material is obtained obtain operation and
One side at least in the basic unit of the potpourri that contains the described second end material or this second end material and transparent resin A stackedly contains the superficial layer of transparent resin B and makes the operation of laminated resin plate;
Be made as " Δ δ " in Hansen solubility parameter with described transparent resin A and described transparent resin B, when the absolute value of the difference of the refractive index of the refractive index of described transparent resin A and described transparent resin B was made as " Δ n ", the relational expression of Δ δ * Δ n≤0.42 was set up.
3. method according to claim 1 and 2, wherein, the thickness of the basic unit in the described plywood is 9 times～100 times of thickness of superficial layer, when described transparent resin A is mixed with described end material, being to mix more than the 1 quality % and less than the mode of 100 quality % with the containing ratio of the described end material of the total amount of described end material with respect to described transparent resin A.
4. according to any described method in the claim 1～3, wherein, the relational expression of 0.03≤Δ n≤0.15 is set up.
5. according to any described method in the claim 1～4, wherein, described transparent resin A is a phenylethylene resin series, and described transparent resin B is phenylethylene resin series or acrylic resin.
6. laminated resin plate, it possesses:
Contain transparent resin A100 mass parts and transparent resin B0.01～20 mass parts basic unit and
Be laminated in the one side at least of described basic unit, contain the superficial layer of transparent resin B;
The thickness of described basic unit is 9 times～100 times of thickness of described superficial layer,
Be made as " Δ δ " in Hansen solubility parameter with described transparent resin A and described transparent resin B, when the absolute value of the difference of the refractive index of the refractive index of described transparent resin A and described transparent resin B was made as " Δ n ", the relational expression of Δ δ * Δ n≤0.42 was set up.
7. laminated resin plate according to claim 6, wherein, described transparent resin A100 mass parts, described transparent resin B0.01～20 mass parts and light diffusion particle 0.01～10 mass parts are contained in described basic unit.
8. according to claim 6 or 7 described laminated resin plates, wherein, described transparent resin A is a phenylethylene resin series, and described transparent resin B is phenylethylene resin series or acrylic resin.
9. planar light source device, it possesses a plurality of light sources of light diffusing sheet that is made of any described laminated resin plate in the claim 6～8 and the rear side that is disposed at this light diffusing sheet.
10. liquid crystal indicator, a plurality of light sources of the rear side that it possesses the light diffusing sheet that is made of any described laminated resin plate in the claim 6～8, be disposed at this light diffusing sheet and be disposed at the liquid crystal panel of the front face side of described light diffusing sheet.
CN2010105043503A 2009-10-05 2010-10-08 Method for producing a laminated resin plate Pending CN102033254A (en)

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