JP2006083309A - Light diffusing thermoplastic resin composition and light diffusing plate composed of the light diffusing thermoplastic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a light diffusing resin composition with improved light diffusing property and luminance by blending a light diffusing agent and a fluorescent brightener, if desired, to a polycaprolactone and the other transparent thermoplastic resin, and a light diffusing plate prepared from the composition. <P>SOLUTION: The light diffusing thermoplastic resin composition at 100 pts.wt. is composed of 0.1-15 wt.% of the polycaprolactone (A) and 85-99.9 wt.% of the other transparent thermoplastic resin (B), and 0.1-10 pts.wt. of the light diffusing agent (C) and 0-0.1 pt.wt. of the fluorescent brightener (D), and the light diffusing plate prepared from the composition. The light diffusing plate prepared by molding the light diffusing thermoplastic resin composition of the present invention is favorably used for an epicentral back light unit of a liquid crystal television receiver, a diffusing plate of an edge light type unit, a glove box of lighting apparatus, switches of various devices and those requiring the light diffusing property and has optical properties of more advanced light diffusing property and luminance. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention provides a light diffusing resin composition having improved light diffusibility and brightness by blending a light diffusing agent and, optionally, a fluorescent whitening agent, with polycaprolactone and other transparent thermoplastic resin, And a light diffusing plate comprising the same. Specifically, for members that cover the light source, for example, light diffusing plates of direct-type backlight units and edge light type units of liquid crystal televisions, glove boxes of lighting fixtures, switches of various devices, and general applications that require light diffusibility The present invention provides a light diffusing thermoplastic resin composition suitably used and a light diffusing plate formed by molding the same.

  Transparent thermoplastic resins are widely used in the fields of electricity, electronics, OA, automobiles, etc. because of their light transmission properties. In each field, resins that satisfy the required performance are selected and used separately. ing. In particular, in applications such as liquid crystal television direct type and edge light type units, lighting fixture covers and various device switches, the use of a transparent thermoplastic resin allows light to pass through because it transmits light. There is a demand for a material imparted with light diffusibility without recognizing the shape of the light source (lamp) behind the resin molded product and without impairing the luminance of the light source as much as possible.

For the purpose of imparting light diffusibility to a transparent thermoplastic resin, in the prior art, there is a method in which a polymer phase or inorganic particle having a different refractive index is blended as a dispersed phase with a thermoplastic resin that forms a continuous phase. It has been adopted. In addition, a method for expressing desired light diffusibility by adjusting the range of the difference in refractive index between the dispersed phase and the continuous phase and the size of the particles in the dispersed phase has been proposed.
JP-A-60-184559 Japanese Patent Laid-Open No. 3-143950

  However, there is a demand for imparting a high level of light diffusibility and brightness over the prior art, and various improvements have been studied in terms of the composition, refractive index, particle shape, particle diameter, etc. of the light diffusing agent. However, the optical performance to be expressed is determined by the light diffusing agent to be blended, and it is difficult to achieve the optical performance required by the modification of the light diffusing agent.

  As a result of intensive investigations in view of such problems, the present inventors have found that by blending a transparent thermoplastic resin with polycaprolactone and a light diffusing agent, and optionally with a fluorescent brightening agent, an even more advanced optical The inventors have found a light diffusing thermoplastic resin composition capable of obtaining a light diffusing plate having performance, and completed the present invention.

  That is, the present invention relates to 100 parts by weight of a resin component comprising 0.1 to 15% by weight of polycaprolactone (A) and 85 to 99.9% by weight of other transparent thermoplastic resin (B), a light diffusing agent (C A light diffusing thermoplastic resin composition comprising 0.1 to 10 parts by weight and a fluorescent brightening agent (D) 0 to 0.1 parts by weight, and a light diffusing plate formed by molding the light diffusing thermoplastic resin composition It is to provide.

A light diffusing plate obtained by molding the light diffusing thermoplastic resin composition of the present invention is a member that covers a light source, that is, a diffusing plate for a direct backlight unit and an edge light type unit of a liquid crystal television, and a glove box for a lighting fixture. It is preferably used for switches of various devices and general applications requiring light diffusibility, and has optical performances of higher light diffusibility and brightness.

The polycaprolactone (A) used in the present invention is a polymer produced by ring-opening polymerization of ε-caprolactone in the presence of a catalyst, and in particular, a homopolymer of 2-oxepanone is preferably used. The polymer is easily available as a commercial product, and a tone polymer manufactured by Dow Chemical Company, CAPA manufactured by Solvay Company, and the like are used. The viscosity average molecular weight of the polycaprolactone (A) is preferably 10,000 to 100,000, more preferably 40,000 to 90,000.

  In addition, polycaprolactone (A) includes a modified polycaprolactone in which ε-caprolactone is modified by ring-opening polymerization in the presence of 1,4-butanediol or the like, or a molecular end substituted with an ether or ester group. Is also included.

The composition ratio of the polycaprolactone (A) is 0.1 to 15% by weight based on the resin components (A) and (B) made of the other transparent thermoplastic resin (B). When the composition ratio is less than 0.1% by weight, the light diffusion effect cannot be obtained and sufficient luminance cannot be obtained, which is not preferable. On the other hand, if it exceeds 15% by weight, an extreme decrease in heat resistance occurs, and the pellets are fixed in the preliminary drying step before the molding process, and blocking is not preferable. A more preferable composition ratio is 0.3 to 10% by weight.

  Examples of the transparent thermoplastic resin (B) used in the present invention include polycarbonate resin, polymethyl methacrylate, polystyrene, acrylonitrile / styrene copolymer, methacrylate / styrene copolymer, acrylonitrile / butadiene / styrene copolymer, and the like. Examples thereof include styrene-based copolymers, polyesters, polyetherimides, polyimides, polyamides, modified polyphenylene ethers, polyarylate, cycloolefin polymers, and polymer alloys obtained by blending polycarbonate and polyester. In particular, polycarbonate resin, polymethyl methacrylate, methyl methacrylate / styrene copolymer, polyarylate, styrene copolymer resin, or cycloolefin polymer is preferably used. The degree of transparency of the thermoplastic resin (B) is such that the observer recognizes the object when light is transmitted and the molded article of the resin is interposed between the observer and the object such as a light source. The performance that can be done.

The polycarbonate resin used in the present invention is a polymer obtained by a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted, or a transesterification method in which a dihydroxydiaryl compound and a carbonate such as diphenyl carbonate are reacted. A typical example is polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).

  Examples of the dihydroxydiaryl compound include bisphenol 4-, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2, 2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3) -Tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis ( Bis (hydroxyaryl) alkanes such as 4-hydroxy-3,5-dichlorophenyl) propane, 1,1- (4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3 Dihydroxy diaryl ethers such as 3,3'-dimethyldiphenyl ether, dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3 ' Dihydroxy diaryl sulfoxides such as dimethyldiphenyl sulfoxide, dihydroxy diary such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone Sulfone, and the like. These are used individually or in mixture of 2 or more types. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, and the like may be mixed and used.

  Furthermore, the above dihydroxyaryl compound and a trivalent or higher phenol compound as shown below may be used in combination. Trihydric or higher phenols include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6-dimethyl-2,4,6-tri- (4 -Hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis- [4 4- (4,4'-dihydroxydiphenyl) -cyclohexyl] -propane and the like.

  The viscosity average molecular weight of the polycarbonate resin is usually 10,000 to 100,000, preferably 15,000 to 35,000, and more preferably 17,000 to 28,000. In producing such a polycarbonate resin, a molecular weight regulator, a catalyst and the like can be used as necessary.

  The light diffusing agent (C) used in the present invention is not particularly limited in terms of chemical composition such as polymer and inorganic, but the light diffusing agent is used for the resin component (A) and / or (B) of the present invention. When (C) is added and dispersed by a known method such as melt mixing with an extruder, it is necessary that it is not compatible with the matrix phase or is present as particles that are hardly compatible.

Specific examples of the light diffusing agent (C) include calcium carbonate, silica, silicone, zinc sulfide, zinc oxide, titanium oxide, titanium phosphate, magnesium titanate, magnesium titanate, mica, glass filler, barium sulfate, clay, Inorganic diffusing agents such as talc, silicone rubber elastic, polymethylsilsesoxane, acrylic, styrene, polyester, polyolefin, urethane, nylon, methacrylate-styrene, fluorine, norbornene, etc. And organic diffusing agents.

  Furthermore, the particle size of the light diffusing agent (C) is not particularly limited as long as the desired light diffusibility can be obtained by adding the diffusing agent, but the average particle size is about 1 to 30 μm. Is preferred. If the thickness is less than 1 μm, it is not preferable because only the light is transmitted and it becomes difficult to obtain the light diffusion effect. On the other hand, if it is larger than 30 μm, a sufficient light diffusion effect cannot be obtained and visibility is inferior. The particle size distribution is not particularly limited, but is about 0.1 to 100 μm, preferably 0.1 to 25 μm. Further, two or more kinds of light diffusing agents having different average particle sizes, particle size distributions, and types may be used in combination, and the particle size distribution is not uniform, and those having two or more particle size distributions are used alone or It can also be used in combination.

  As a compounding quantity of a light-diffusion agent (C), it is 0.1-10 weight part per 100 weight part of resin components which consist of (A) and (B) of this invention. If the blending amount is less than 0.1 parts by weight, it is difficult to obtain a sufficient light diffusion effect, which is not preferable. On the other hand, if the amount exceeds 10 parts by weight, the light transmission property is impaired, and sufficient light diffusion performance cannot be obtained. More preferably, it is the range of 0.2-6 weight part.

  Further, in the light diffusing thermoplastic resin composition comprising (A), (B) and (C) of the present invention, the fluorescent whitening agent (D) is added to (A) and (B) in order to make the color tone vivid. You may add up to 0.1 parts by weight per 100 parts by weight of the resin component. If the added amount exceeds 0.1 parts by weight, the thermal stability is deteriorated, which is not preferable. More preferably, it is up to 0.03 parts by weight. Depending on the type of thermoplastic resin, it has the property of absorbing some of the blue light and has a slightly yellowish color. Therefore, a compound (fluorescent whitening agent) that emits blue or purple fluorescence corresponding to this yellow complementary color is used. When added, the fluorescence cancels the yellowish color and a vivid color tone can be obtained. A fluorescent whitening agent absorbs energy in the ultraviolet region and emits a wavelength range from blue to violet in the visible region. By using this in combination, the light diffusing performance is maintained and a more vivid color tone is achieved. Obtainable.

  In the light diffusable thermoplastic resin composition of the present invention, various known additives, polymers, and the like can be added as necessary depending on the performance required in addition to light diffusivity. For example, in order to suppress discoloration of resin molded products when exposed to light for a long period of time, a hindered amine light-resistant stabilizer, a benzotriazole-based, benzophenone-based, triazine-based, and malonate-based UV absorber and a combination thereof are used. May be added.

When flame retardancy is required, various known flame retardants, for example, brominated flame retardants such as tetrabromobisphenol A oligomers, monophosphate esters such as triphenyl phosphate and tricresyl phosphate, bisphenol A diesters, etc. In order to further improve the flame retardancy, phosphorous flame retardants such as phosphate-type condensed phosphates such as phosphate, resorcin diphosphate, tetraxylenyl resorcin diphosphate, ammonium polyphosphate and red phosphorus, various silicone flame retardants And metal salts of aromatic sulfonic acid and perfluoroalkanesulfonic acid, preferably 4-methyl-N- (4-methylphenyl) sulfonyl-benzenesulfonamide potassium salt, diphenylsulfone- 3- potassium sulfonate, Potassium phenyl sulfonic -3-3'- disulfonic acid, sodium para-toluene sulfonic acid, also organic metal salts such as potassium perfluorobutane sulfonate and the like may be added. Among these flame retardants, phosphorus-based flame retardants can be suitably used because they can improve not only flame retardancy but also fluidity.

In the light diffusing thermoplastic resin composition of the present invention, known additives other than those described above, such as phenol-based or phosphorus-based heat stabilizers [2,6-di-t-butyl-4-methylphenol, 2- ( 1-methylcyclohexyl) -4,6-dimethylphenol, 4,4'-thiobis- (6-tert-butyl-3-methylphenol), 2,2-methylenebis- (4-ethyl-6-tert-methylphenol) ), N-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, tris (2,4-di-t-butylphenyl) phosphite, 4,4'-biphenylenediphosphinic acid Tetrakis- (2,4-di-t-butylphenyl), etc.], lubricant [paraffin wax, n-butyl stearate, synthetic beeswax, natural beeswax, glycerin monoester, Tanic acid wax, polyethylene wax, pentaerythritol tetrastearate, etc.], colorant [eg titanium oxide, carbon black, dye], filler [calcium carbonate, clay, silica, glass fiber, glass sphere, glass flake, carbon fiber, Talc, mica, various whiskers, etc.], fluidity improvers, spreading agents [epoxidized soybean oil, liquid paraffin, etc.], other thermoplastic resins and various impact resistance improvers (polybutadiene, polyacrylate, A rubber reinforced resin obtained by graft polymerization of a compound such as methacrylic acid ester, styrene, acrylonitrile, etc. to a rubber such as an ethylene / propylene rubber may be added as necessary.

  There is no restriction | limiting in the embodiment and order in this invention. For example, polycaprolactone (A), a transparent thermoplastic resin (B), a light diffusing agent (C), and optionally a fluorescent brightening agent (D) are weighed in arbitrary amounts, and are tumbler, riboblender, high speed mixer After batch mixing by, etc., the mixture is melt-kneaded using a normal single-screw or twin-screw extruder and pelletized, or each component is partially or all weighed separately, and from multiple supply devices A method of charging into an extruder and melt-mixing, and further blending (A) and / or (C) and / or (D) at a high concentration, once melt-mixing and pelletizing to make a master batch, The masterbatch and the transparent thermoplastic resin (B) can be mixed at a desired ratio. Then, when these components are melt-mixed, arbitrary conditions such as the position at which the extruder is introduced, the extrusion temperature, the screw rotation speed, the supply amount, and the like can be selected and pelletized. Further, the master batch and the transparent thermoplastic resin (B) can be dry-mixed at a desired ratio and then directly fed into an injection molding apparatus or a sheet extruder apparatus to form a molded product.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples, unless the summary is exceeded. Unless otherwise specified, “%” and “part” in the examples are based on weight standards.

In addition, the various compounding components used are as follows.
Polycaprolactone:
CAPA6800 manufactured by Solvay
(Viscosity average molecular weight: 80000, hereinafter abbreviated as PCL-1)
CAPA6500C made by Solvay
(Viscosity average molecular weight: 50000, hereinafter abbreviated as PCL-2)
Tone polymer P-787 manufactured by Dow Chemical Company
(Viscosity average molecular weight: 80000, hereinafter abbreviated as PCL-3)
Polycarbonate resin:
Sumitomo Dow Caliber 200-30
(Viscosity average molecular weight: 17200, hereinafter abbreviated as PC-1)
Caliber 200-3 manufactured by Sumitomo Dow
(Viscosity average molecular weight: 28000, hereinafter abbreviated as PC-2)
Light diffusing agent:
MSP-S020 made by Nikko Rica
(Polymethylsilsesoxane-based diffusing agent, hereinafter abbreviated as LD-1)
GM-0449S manufactured by Gantz Kasei
(Acrylic diffusing agent, hereinafter abbreviated as LD-2)
Fluorescent whitening agent: HOSTARUX KSN manufactured by Clariant Japan

A method for measuring various evaluation items in the present invention will be described.
(Evaluation of formability)
When preparing a flat test piece using an injection molding machine, in the pellets to be molded, the state of the pellets after preliminary drying is visually confirmed, and those that are difficult to mold with the pellets fixed to each other are rejected. Pass (x), what can be molded without problems was determined to be acceptable (O).

(Measurement of shielding rate)
The shielding factor in the present invention represents the amount of light that does not transmit at 380 to 720 nm, which is the visible light wavelength region, and is calculated by the following general formula and measured with an ultraviolet-visible spectrophotometer (V-570 manufactured by JASCO Corporation). Is done.
Shielding rate (%) = {1− (transmitted light amount / 34,000)} × 100
When the shielding rate calculated by the measurement method was in the range of 60 to 85%, it was determined to be acceptable (◯), and other cases were determined to be unacceptable (x). Exceeding this range is not preferable because the inter-lamp luminance decreases and sufficient luminance cannot be obtained.

(Measurement of brightness)
Two cold-cathode tubes were placed on the back side of the flat test piece, and the luminance and chromaticity y on the surface of the test piece in the vertical direction between the lamps were measured. The luminance means the ratio of the luminous intensity directed in a certain direction per unit area in a plane perpendicular to the direction, and generally represents the degree of brightness of the light emitting surface [unit: (cd / m ² ). ]. In addition, the chromaticity y is evaluated as a criterion for evaluation when the measured value of the luminance between lamps is 2500 cd / m ² or more, (◯), and when it is less than 2500 cd / m ^2, it is rejected (×). . An outline of the measurement method is shown in FIG.

(Measurement of blueness)
B * was measured with a spectrophotometer CMS-35SP manufactured by Murakami Color Research Co., Ltd. using a flat plate test piece prepared by an injection molding machine. b * represents the degree from yellow to blue, and the smaller b *, the less yellow and the stronger blue.

(Comprehensive judgment)
In the evaluation of the shielding rate, luminance, and moldability, a sample satisfying all of them was evaluated as acceptable (◯), and a sample not satisfied was evaluated as unacceptable (x).

(Example 1 to Example 6)
Polycaprolactone (PCL-1), polycarbonate resin (PC-1), and light diffusing agent (LD-1) were dry-mixed by a super floater manufactured by Kawata at a mixing ratio shown in Table 1. Next, the resultant pellets were melt-kneaded at a temperature of 250 to 290 ° C. by a twin screw extruder KTX-37 (shaft diameter = 37 mmφ, L / D = 30, A in FIG. 1) manufactured by Kobe Steel. A flat test piece having a length of 90 mm, a width of 50 mm, and a thickness of 2 mm was prepared using a J100E2P injection molding machine manufactured by Nippon Steel. The pellets did not stick to each other after the preliminary drying, and the moldability was good. Further, the shielding rate and inter-lamp brightness were also good results. The results are shown in Table 1.

(Example 7 to Example 8)
Except changing the kind of polycaprolactone to PCL-2 or PCL-3, the same operation as Example 2 was performed and the flat test piece was created. The pellets did not stick to each other after the preliminary drying, and the moldability was good. The shielding rate and inter-lamp brightness were also good results. The results are shown in Table 2.

Example 9
Except changing the kind of polycarbonate resin to PC-2, operation similar to Example 2 was performed and the flat test piece was created. The pellets did not stick to each other after the preliminary drying, and the moldability was good. The shielding rate and inter-lamp brightness were also good results. The results are shown in Table 2.

(Example 10 to Example 11)
The same operation as in Example 2 was performed except that the type of the light diffusing agent was changed to LD-1 and the addition amount thereof was changed to 1.5 parts in Example 10 and 6 parts in Example 11. A test piece was prepared. The pellets did not stick to each other after the preliminary drying, and the moldability was good. The shielding rate and inter-lamp brightness were also good results. The results are shown in Table 2.

(Example 12)
A plate test piece was prepared in the same manner as in Example 2 except that 0.01 part of the optical brightener was added to Example 2. The pellets did not stick to each other after the preliminary drying, and the moldability was good. The shielding rate and inter-lamp brightness were also good results. In addition, the color tone showed a decrease in chromaticity y value in comparison with Example 2, and exhibited a vivid blue tint even visually. The results are shown in Table 3.

(Comparative Examples 1 to 3)
The compounding amount of the light diffusing agent (LD-1) is fixed at 0.3 part, and in Comparative Example 1, 100% of the polycarbonate resin (PC-1) is added without adding polycaprolactone (PCL-1). Then, the same procedure as in Example 2 was performed, except that the composition ratio of polycaprolactone (PCL-1) was changed to 0.05%, and in Comparative Example 3, the composition ratio of polycaprolactone (PCL-1) was changed to 20%. A flat plate test piece was prepared. The evaluation results are shown in Table 4.
In Comparative Example 1, no polycaprolactone was blended, and in Comparative Example 2, the composition ratio of polycaprolactone was less than the constituent requirements of the present invention, and both had inferior lamp brightness.
Comparative Example 3 was a case where the composition ratio of polycaprolactone was larger than the constituent requirements of the present invention, and the inter-lamp luminance was good, but the moldability was poor.

(Comparative Example 4 to Comparative Example 5)
The composition ratio of polycaprolactone (PCL-1) was fixed at 3%, and the blending amount was 0.05 parts LD-1 as a light diffusing agent in Comparative Example 4, and LD-2 as a light diffusing agent in Comparative Example 5. A flat plate test piece was prepared by performing the same operation as in Example 2 except that was changed to 15 parts. The evaluation results are shown in Table 4.
Comparative Example 4 is an example where the blending amount of the light diffusing agent is less than the constituent requirement of the present invention, and Comparative Example 5 is an example where the blending amount of the light diffusing agent is greater than the constituent requirement of the present invention. It was inferior in the shielding rate and the brightness between lamps.

It is a figure which shows the measuring method of the brightness | luminance between lamps of this invention.

Explanation of symbols

A: Luminance meter B: Lamp (cold cathode tube)
C: Inter-lamp luminance measurement site D: Sample

Claims (7)

  100 parts by weight of a resin component comprising 0.1 to 15% by weight of polycaprolactone (A) and 85 to 99.9% by weight of the other transparent thermoplastic resin (B), and 0.1 to 10 of a light diffusing agent (C) A light-diffusing thermoplastic resin composition comprising 0 parts by weight and 0 to 0.1 parts by weight of a brightening agent (D).   The composition ratio of polycaprolactone (A) is 0.3 to 10% by weight, and the light diffusable thermoplastic resin composition according to claim 1.   The compounding amount of the light diffusing agent (C) is 0.2 to 6 parts by weight per 100 parts by weight of the resin component composed of the polycaprolactone (A) and the other transparent thermoplastic resin (B). Item 3. The light diffusing thermoplastic resin composition according to Item 1 or Item 2.   The viscosity-average molecular weight of polycaprolactone (A) is 40,000 to 90,000, and the light diffusable thermoplastic resin composition according to any one of claims 1 to 3.   The transparent thermoplastic resin (B) is one or more selected from polycarbonate resin, polymethyl methacrylate, methyl methacrylate / styrene copolymer, polyarylate, styrene copolymer resin or cycloolefin polymer. The light-diffusing thermoplastic resin composition according to any one of claims 1 to 3, wherein the light-diffusing thermoplastic resin composition is characterized. The light diffusing plate formed by shape | molding the light diffusable thermoplastic resin composition as described in any one of Claims 1-5. The light diffusing plate according to claim 6, which is used for a direct type backlight for a liquid crystal display.

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