JPH03231954A - Acrylic resin composition for molded body, molded product and production thereof - Google Patents
Acrylic resin composition for molded body, molded product and production thereofInfo
- Publication number
- JPH03231954A JPH03231954A JP2907890A JP2907890A JPH03231954A JP H03231954 A JPH03231954 A JP H03231954A JP 2907890 A JP2907890 A JP 2907890A JP 2907890 A JP2907890 A JP 2907890A JP H03231954 A JPH03231954 A JP H03231954A
- Authority
- JP
- Japan
- Prior art keywords
- acrylic resin
- weight
- fine particles
- resin composition
- particle size
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 40
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 40
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000002245 particle Substances 0.000 claims abstract description 46
- 239000010419 fine particle Substances 0.000 claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 17
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920006037 cross link polymer Polymers 0.000 claims abstract description 16
- 238000009826 distribution Methods 0.000 claims abstract description 9
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 7
- 230000003287 optical effect Effects 0.000 claims abstract description 6
- 238000001746 injection moulding Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 239000011342 resin composition Substances 0.000 claims 1
- 238000009792 diffusion process Methods 0.000 abstract description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 12
- 238000002156 mixing Methods 0.000 abstract description 10
- 238000004132 cross linking Methods 0.000 abstract description 5
- 238000000465 moulding Methods 0.000 abstract description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 abstract description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 abstract 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 238000002834 transmittance Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- -1 divinylbenzene Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Optical Elements Other Than Lenses (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は成形体用アクリル樹脂組成物、成形品およびそ
の製造法に関し、より詳しくは、光拡散性及び艶消し性
に優れた成形体用アクリル樹脂組成物、該組成物を射出
成形あるいは押出成形してなる高い光拡散性と良好な艶
消し性とを有するアクリル樹脂成形品およびその製造方
法に関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to an acrylic resin composition for molded articles, a molded article, and a method for producing the same, and more specifically, an acrylic resin composition for molded articles having excellent light diffusing properties and matte properties. The present invention relates to an acrylic resin composition, an acrylic resin molded article having high light diffusivity and good matting properties obtained by injection molding or extrusion molding of the composition, and a method for producing the same.
アクリル樹脂は照明カバー、デイスプレィ、看板等の光
拡散性を必要とする種々の用途に用゛いられており、こ
のような光拡散性アクリル樹脂としては従来（ａ）平均
粒径１０μｍ以下の硫酸バリウム、炭酸カルシウム、酸
化チタン等の無機微粉末をアクリル樹脂中に含有せしめ
たもの（特開昭６０−１３９７５８号公報）、（ｂ）４
〜５０μｍのシリカ、ガラス、水酸化アルミニウム等の
透明微粒子をアクリル樹脂中に分散せしめたもの（特開
昭６０−１８４５５９号公報、特開昭６１−４７６２号
公報）および（Ｃ）スチレン系樹脂又は粒子径３０〜５
００μｍの架橋したスチレン−アルキルアクリレート系
ポリマーをアクリル樹脂中に混合分散せしめたもの（特
開昭５６＝３６５３５号公報、特開昭６１−１５９４４
０号公報）などが知られている。Acrylic resins are used in a variety of applications that require light diffusing properties, such as lighting covers, displays, and signboards. Conventionally, such light-diffusing acrylic resins include (a) sulfuric acid with an average particle size of 10 μm or less; Inorganic fine powder such as barium, calcium carbonate, titanium oxide, etc. contained in acrylic resin (Japanese Unexamined Patent Publication No. 139758/1983), (b) 4
~50 μm transparent fine particles of silica, glass, aluminum hydroxide, etc. dispersed in acrylic resin (JP-A-60-184559, JP-A-61-4762) and (C) styrene resin or Particle size 30-5
00 μm cross-linked styrene-alkyl acrylate polymer mixed and dispersed in acrylic resin (JP-A-56-36535, JP-A-61-15944)
Publication No. 0) and the like are known.
しかしながら、前記（ａ）、 （ｂ）の方法の如く無機
微粒子を含有するアクリル樹脂の場合には十分に光拡散
性を高めようとすると光線透過率が低下してしまうとい
う欠点を有しており、また前記（Ｃ）の方法のようにス
チレン系樹脂、粒子径３０〜５００μｍの架橋したスチ
レン−アルキルアクリレート系ポリマーを含有するアク
リル樹脂の場合には光拡散効果は発現するものの完全拡
散に近づけるにはやはり光線透過率が低下してしまった
り、分散不良や流れ模様などの成形品外観の欠点が発生
したり、あるいは表面の艶消し状態が十分でなかったり
するなどの問題点を有しており、高い光線透過率と高い
光拡散効果とを求める市場の要請に十分底えられないの
が実情であった。特に近年普及がめざましいＯＡ機器、
液晶デイスプレィ、バックライトパネル等の光学機器用
光拡散板においてはその光線透過率、光拡散性の改善要
望が強い。However, in the case of acrylic resin containing inorganic fine particles as in the methods (a) and (b) above, there is a drawback that the light transmittance decreases when trying to sufficiently increase light diffusivity. In addition, as in method (C) above, in the case of a styrene resin or an acrylic resin containing a crosslinked styrene-alkyl acrylate polymer with a particle size of 30 to 500 μm, although a light diffusion effect is produced, it is difficult to achieve close to complete diffusion. However, they still have problems such as reduced light transmittance, defects in the appearance of molded products such as poor dispersion and flow patterns, and insufficient matte surfaces. The reality is that the market demand for high light transmittance and high light diffusion effect cannot be fully met. In particular, OA equipment, which has become rapidly popular in recent years,
There is a strong desire to improve the light transmittance and light diffusivity of light diffusing plates for optical devices such as liquid crystal displays and backlight panels.
したがって、本発明は、上記問題点を解決して完全拡散
に近い高度の光拡散性を有する艶消性アクリル樹脂成形
品を提供することを目的とする。Therefore, an object of the present invention is to solve the above-mentioned problems and provide a matte acrylic resin molded product having a high degree of light diffusivity close to perfect diffusion.
本発明者等は、前記課題を解決すべく光拡散剤の種類に
ついて鋭意研究を進めた結果、特定粒子径を有する架橋
ポリスチレン重合体微粒子をメタクリル酸メチル系重合
体に配合するのが有効であることを見出し、本発明を完
成した。The present inventors have carried out intensive research on the types of light diffusing agents to solve the above problems, and have found that it is effective to blend crosslinked polystyrene polymer fine particles having a specific particle size with a methyl methacrylate polymer. They discovered this and completed the present invention.
すなわち、本発明によれば」二足目的は、メタクリル酸
メチル系重合体１００重量部に対して、芳香族ビニルモ
ノマー５０〜９９重量％および架橋性モノマー１〜５０
重量％からなる平均粒子径１〜１５μｍの架橋ポリマー
微粒子を１〜２０重量部含有してなる成形体用アクリル
樹脂組成物、および該組成物よりなるアクリル樹脂成形
品によって達成される。That is, according to the present invention, the "two-legged object" is based on 100 parts by weight of the methyl methacrylate polymer, and 50 to 99% by weight of the aromatic vinyl monomer and 1 to 50% by weight of the crosslinking monomer.
This is achieved by an acrylic resin composition for a molded article containing 1 to 20 parts by weight of crosslinked polymer fine particles having an average particle diameter of 1 to 15 μm, and an acrylic resin molded article made of the composition.
また、上記目的は、アクリル樹脂材料を射出成形してア
クリル樹脂成形品を得るに際し、上記アクリル樹脂組成
物を艶消し加工の施こされていない成形型キャビティ内
に射出成形することによって達成される。Further, the above object is achieved by injection molding the acrylic resin composition into a mold cavity that is not subjected to matte processing when injection molding an acrylic resin material to obtain an acrylic resin molded product. .
以下本発明の詳細な説明する。The present invention will be explained in detail below.
本発明でいうメタクリル酸メチル系重合体とは、メタク
リル酸メチルホモポリマーまたはメタクリル酸メチルを
８０％以上含むコポリマーをいい、紫外線吸収剤、熱安
定剤、着色剤、無機微粉末等の微量添加剤は目的範囲内
で含んでいることは、なんら差し支えない。また、その
分子量は、特に本発明において制限されるものではない
が、射出成形および押出成形時などの混純のしやすさあ
るいは物性面等から一般に５万乃至５０万、好ましくは
、７万乃至３０万である。The methyl methacrylate-based polymer used in the present invention refers to a methyl methacrylate homopolymer or a copolymer containing 80% or more of methyl methacrylate, and includes trace additives such as ultraviolet absorbers, heat stabilizers, colorants, and inorganic fine powders. There is no problem in including it within the scope of the purpose. The molecular weight is not particularly limited in the present invention, but is generally 50,000 to 500,000, preferably 70,000 to 500,000, in view of ease of mixing during injection molding and extrusion molding, and physical properties. It is 300,000.
本発明の架橋ポリマー微粒子は芳香族ビニル千ツマ−お
よび架橋性モノマーを重合することによって得られる微
粒子であるが、本発明の目的に支障を与えない範囲で他
の共重合性モノマーを加えることもできる。The crosslinked polymer fine particles of the present invention are fine particles obtained by polymerizing an aromatic vinyl polymer and a crosslinkable monomer, but other copolymerizable monomers may be added as long as they do not impede the purpose of the present invention. can.
芳香族ビニルモノマーとしてはスチレン、αメチルスチ
レン、ビニルトルエン、ハロゲン化スチレン等を用いる
ことが可能であるが、スチレンが特に好ましい。該芳香
族ビニルモノマーの使用量は５０〜９９重量％、好まし
くは８０〜９５重量％の範囲である。As the aromatic vinyl monomer, styrene, α-methylstyrene, vinyltoluene, halogenated styrene, etc. can be used, but styrene is particularly preferred. The amount of the aromatic vinyl monomer used is in the range of 50 to 99% by weight, preferably 80 to 95% by weight.
架橋性モノマーとしては分子内に２個以上の不飽和結合
をもつ化合物が用いられ、その具体例としてはエチレン
グリコールジメククリレート、ポリエチレングリコール
ジメタクリレート、１，４ブタンジオールジメタクリレ
ート、ネオペンチルグリコールなどの二官能性ジメタク
リレートやジビニルベンゼン等の多価ビニルベンゼン等
ヲ好マしく挙げることができ、ジビニルベンゼンが特に
好ましい。該架橋性モノマーの使用量は前モノマ−に対
し１〜５０重量％、好ましくは５〜２０重量％の範囲で
ある。As the crosslinking monomer, a compound having two or more unsaturated bonds in the molecule is used, and specific examples thereof include ethylene glycol dimecrylate, polyethylene glycol dimethacrylate, 1,4 butanediol dimethacrylate, neopentyl glycol, etc. Preferred examples include bifunctional dimethacrylates and polyvalent vinylbenzenes such as divinylbenzene, with divinylbenzene being particularly preferred. The amount of the crosslinking monomer used is in the range of 1 to 50% by weight, preferably 5 to 20% by weight, based on the previous monomer.
本発明に用いられる前記微粒子の粒径は１〜４０μｍ、
好ましくは１〜２５μｍ、最も好ましくは１〜１０μｍ
であり、また平均粒子径は１〜１５μｍ、好ましくは５
〜９μｍの範囲であり、更に好ましい微粒子の態様とし
ては、ポリマー微粒子粒径別含量の変動に対する光拡散
性、艶消し表面外観への影響の観点から前記範囲におい
て粒径１０μｍ未満の粒子が重量分布で６０％以上、好
ましくは９０％以上を占めるものである。ここでいう平
均粒子径とは、各粒径を重量積算し全重量の５０％にあ
たる粒径を意味し、たとえば重力沈降法により透過式粒
度分布測定器（（株）セイシン企業製： ＳＫＡ ５０
００）等により測定できる。光拡散状態の均−性及び風
合いの点から懸濁重合による球状微粒子が好ましく使用
され、粒径分布の狭い方が均一な光拡散性が得られるの
でより好ましく使用される。これらの懸濁重合による微
粒子としては特開昭６４−２６６１７号公報、特開平１
−１４６９１０号公報、特開平１−１７２４１２号公報
等で示された処方及び懸濁方法によって製造されたもの
、あるいは市販のものとして積水化成品工業株式会社製
：テクポリマー５ＢＸ−４、５ＢＸ−６、５ＢＸ−８、
ＳＢχ−１２（架橋ポリスチレン微小球状微粒子）など
が使用できる。ポリマー微粒子の粒径が１μｍ未満の場
合には透過光により赤っぽく見える傾向があり好ましく
なく、一方４０μｍを超える場合又は平均粒子径が１５
μｍを超える場合には完全拡散に近い高度の光拡散性を
得ることができず好ましくない。The particle size of the fine particles used in the present invention is 1 to 40 μm,
Preferably 1-25 μm, most preferably 1-10 μm
and the average particle diameter is 1 to 15 μm, preferably 5
The particle size is in the range of ~9 μm, and a more preferable embodiment of the fine particles is that particles with a particle size of less than 10 μm in the above range have a weight distribution from the viewpoint of light diffusivity and influence on matte surface appearance with respect to variations in the content of fine polymer particles depending on particle size. occupies 60% or more, preferably 90% or more. The average particle size here refers to the particle size that corresponds to 50% of the total weight by adding up each particle size by weight.
00) etc. Spherical fine particles produced by suspension polymerization are preferably used from the viewpoint of uniformity of light diffusion state and texture, and narrower particle size distribution is more preferably used because uniform light diffusivity can be obtained. These fine particles produced by suspension polymerization are disclosed in JP-A-64-26617 and JP-A-1
Techpolymer 5BX-4, 5BX-6 manufactured by Sekisui Plastics Co., Ltd. manufactured by the formulation and suspension method shown in JP-A-146910, JP-A-1-172412, etc., or commercially available products. , 5BX-8,
SBχ-12 (crosslinked polystyrene microspherical particles), etc. can be used. If the particle size of the polymer fine particles is less than 1 μm, it tends to look reddish when exposed to transmitted light, which is undesirable. On the other hand, if it exceeds 40 μm or the average particle size is 15
If it exceeds μm, it is not preferable because a high degree of light diffusivity close to perfect diffusion cannot be obtained.
また該微粒子の配合量は、メタクリル酸メチル系重合体
１００重量部あたり１〜２０重量部、好ましくは３〜１
０重量部である。その配合量が１重量部未満の場合には
透けやすくなると共に十分な光拡散性を得ることができ
ずまた表面の艶消し状態も十分でなく、一方２０重量部
を超える場合には光線透過率が低下し、またこれ以上添
加しても艶消し状態や光拡散性などが更に向上する効果
は見られないので好ましくない。The blending amount of the fine particles is 1 to 20 parts by weight, preferably 3 to 1 parts by weight, per 100 parts by weight of the methyl methacrylate polymer.
It is 0 parts by weight. If the amount is less than 1 part by weight, it will become transparent, it will not be possible to obtain sufficient light diffusivity, and the surface will not be sufficiently matte, while if it exceeds 20 parts by weight, the light transmittance will be insufficient. It is not preferable because the effect of further improving the matte state and light diffusivity is not seen even if it is added in excess of this amount.
このようにして得られた架橋ポリマー微粒子は、十分な
光拡散性を得る目的からゲル含有量の値が９５％以上で
かつ膨潤度が２以下であることが好ましい。ゲル含有量
が９５％未満の場合、又は膨潤度が２を超える場合には
混練時粒子の粒径が変化し完全拡散に近い拡散性を得る
ことができないばかりか艶消し外観も均一にきめ細いも
のとならず好ましくない。The thus obtained crosslinked polymer fine particles preferably have a gel content of 95% or more and a swelling degree of 2 or less for the purpose of obtaining sufficient light diffusivity. If the gel content is less than 95% or the degree of swelling is more than 2, the particle size of the particles changes during kneading, making it impossible to obtain near-perfect dispersion, and the matte appearance will also be uniform and fine-grained. It is undesirable and undesirable.
架橋ポリマーのゲル含有量、膨潤度の調整は架橋性モノ
マーの種類、量の調整および連鎖移動剤の使用により行
うことができるが、前記通常行われる懸濁重合によりゲ
ル含有量９５％以上、膨潤度２以下の架橋ポリマー微粒
子を得ることができる。The gel content and degree of swelling of the crosslinked polymer can be adjusted by adjusting the type and amount of the crosslinking monomer and by using a chain transfer agent. Crosslinked polymer fine particles having a degree of 2 or less can be obtained.
本発明における光拡散性及び艶消し性にすぐれた成形体
用アクリル樹脂組成物とは、メタクリル酸メチル系重合
体１００重量部に対して前記架橋ポリマー微粒子を１〜
２０重量部含有するものであり、たとえばメタクリル酸
メチル重合体および前記微粒子をヘンシェルミキサーな
どで攪拌混合したものあるいは混合後押出機にかけてペ
レット状にしたものなどをいう。該組成物は安定に保存
するためあるいは成形機への喰い込みを良くするためベ
レット状にしたものが好ましく用いられる。In the present invention, the acrylic resin composition for molded objects having excellent light diffusivity and matting properties is defined as a mixture of 1 to 100 parts by weight of the crosslinked polymer fine particles per 100 parts by weight of the methyl methacrylate polymer.
For example, the methyl methacrylate polymer and the fine particles may be stirred and mixed using a Henschel mixer or the like, or may be pelletized using an extruder after mixing. The composition is preferably used in the form of a pellet in order to store it stably or to improve its penetration into a molding machine.
このような成形体用アクリル樹脂組成物は押出成形ある
いは射出成形などの成形体用材料として使用されるが、
押出成形では樹脂を押出した後の成形ロールとの接触状
態により艶消し状態が左右されやすいため、このような
問題のない射出成形に好適であり、射出成形に適し光拡
散性及び艶消性に優れた成形体用アクリル樹脂組成物と
して好ましく使用される。Such acrylic resin compositions for molded bodies are used as materials for molded bodies in extrusion molding, injection molding, etc.
In extrusion molding, the matte state tends to be affected by the contact state with the molding roll after extruding the resin, so it is suitable for injection molding that does not have such problems, and is suitable for injection molding with good light diffusion and matte properties. It is preferably used as an excellent acrylic resin composition for molded objects.
本発明における射出成形条件は本発明の本質的な構成要
件ではなく、通常の射出成形機を用い通常の射出条件下
で前記アクリル樹脂組成物を艶消し加工の施こされてい
ない成形型キャビティに射出成形することにより、光拡
散性及び艶消し性にすぐれたアクリル樹脂成形品を製造
することができる。たとえば、前記メタクリル酸メチル
重合体及び前記微粒子をヘンシルミキサーなどで攪拌混
合したものあるいは混合後押出成形機にかけてぺ０
レッド状にしたものを射出成形機で鏡面金型キャビティ
内に射出成形することにより、従来のものでは決して得
ることのできなかった。完全拡散に近い拡散性と均一で
美麗な艶消し表面を有するアクリル樹脂成形品を得るこ
とができる。The injection molding conditions in the present invention are not essential components of the present invention, and the acrylic resin composition is injected into a mold cavity without matte processing under normal injection conditions using a normal injection molding machine. By injection molding, it is possible to produce an acrylic resin molded product with excellent light diffusion and matte properties. For example, the above-mentioned methyl methacrylate polymer and the above-mentioned fine particles may be stirred and mixed using a Henshil mixer or the like, or after mixing, an extruder may be used to form a powder into a red shape, and the mixture may be injection molded into a mirror-finished mold cavity using an injection molding machine. This could never be achieved with conventional methods. It is possible to obtain an acrylic resin molded product having near perfect diffusion and a uniform and beautiful matte surface.
（実施例） 以下、実施例により本発明をさらに具体的に説明する。(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.
なお、実施例、比較例における「％」および［部Ｊはす
べて「重量％」および「重量部」をそれぞれ表わし、ま
た実施例および比較例により得られたアクリル樹脂成形
品の性能および架橋ポリマー微粒子のゲル含有量、膨潤
度は以下の方法により測定、評価した。In addition, "%" and "part J" in Examples and Comparative Examples all represent "% by weight" and "Part by weight", respectively, and the performance of acrylic resin molded products and crosslinked polymer fine particles obtained in Examples and Comparative Examples The gel content and degree of swelling were measured and evaluated by the following method.
ｌ碌透過事潰よブｃＡｉｉ
ＪＩＳ Ｋ７１０５に準拠して積分球式光線透過率測定
装置（（株）村上色彩研究所型：ＲＭ−１５）により測
定し、全光線透過率、ヘイズ値を算出した。The total light transmittance and haze value were calculated using an integrating sphere type light transmittance measuring device (Murakami Color Research Institute model: RM-15) in accordance with JIS K7105. .
１
を用い下記の光学条件によりＯｏ、５°、１０゜２０’
、３０°、４０°、５０°、６０°、７０゜８０°、９
０°の各角度について透過率を測定した。1 and the following optical conditions: Oo, 5°, 10°20'
, 30°, 40°, 50°, 60°, 70°80°, 9
Transmittance was measured for each angle of 0°.
光束：１２φｍ／ｍ 。Luminous flux: 12φm/m.
平行度：±０．５以下、
集光レンズ：有効口径１６ｍ／ｍφ、
受光視野角： ０．８６゜
受光スリット径：３ｍ／ｍφ
分光条件：Ｃ光に対するＣＩＥ比視感度に近似表皿状皿
室内において螢光灯を試料表面に反射させて目視観察し
、試料の艶消し状態を次の記号で表わした。Parallelism: ±0.5 or less, Condensing lens: Effective aperture 16 m/mφ, Receiving viewing angle: 0.86° Receiving slit diameter: 3 m/mφ Spectral conditions: Disc-shaped dish approximating CIE relative luminous efficiency for C light A fluorescent lamp was reflected on the sample surface indoors for visual observation, and the matte state of the sample was expressed by the following symbol.
◎・・・螢光灯の輪郭は全く見えず均一美麗な艶消し表
面である。◎...The outline of the fluorescent lamp is not visible at all, and the surface is uniform and beautiful.
○・・・螢光灯の輪郭が認められないかほとんど認めら
れない。○...The outline of the fluorescent lamp is not recognized or is hardly recognized.
△・・・螢光灯の輪郭は認められるが不明瞭であり、表
面の凹凸がある。△: The outline of the fluorescent lamp is recognized, but it is unclear, and the surface is uneven.
２
×・・・蛍光灯の輪郭が明瞭に認められ、表面の凹凸が
ほとんどない。2×: The outline of the fluorescent lamp is clearly recognized, and there are almost no irregularities on the surface.
××・・・表面が荒れており、均一な艶消し状になって
いない。XX: The surface is rough and does not have a uniform matte finish.
透Ｍ−状旦
１５Ｗの直管蛍光灯（ナシゴナル製：バルック）前方８
Ｃ１ｍの位置に試料片を平行に置き、更に該試料片から
５０ｃｍ離れた位置で試料片を通して光源の輪郭が見え
るかどうか目視観察し、次の記号で表わした。Transparent M-shaped 15W straight tube fluorescent light (manufactured by Nasigonal: Bulk) Front 8
A sample piece was placed in parallel at a position of C1m, and visually observed at a position 50 cm away from the sample piece to see if the outline of the light source could be seen through the sample piece, and was expressed by the following symbol.
○・・・蛍光灯の輪郭は認められない。○...The outline of the fluorescent lamp is not recognized.
△・・・蛍光灯の輪郭がかすかに認められる。△...The outline of the fluorescent lamp is faintly recognized.
×・・・蛍光灯の輪郭が明瞭に認められる。×: The outline of the fluorescent lamp is clearly recognized.
Ｙ土含有量二１１渡７
所定量の架橋ポリマー微粒子を秤量ビンに秤量し、約１
００倍量のメチルエチルケトン（ＭＥＫ）中に４８時間
浸漬する。浸漬後余分のＦ’ｌＥＫをデカンテーシジン
により十分に除去しＭＥＫで膨潤状態にある試料の重量
を求める。ついで減圧乾燥によりＭＥＫを乾燥し、試料
の絶乾重量を求める。これに３
より次式から算出する。Y Soil content 211W 7 Weigh a predetermined amount of crosslinked polymer fine particles into a weighing bottle, and weigh approximately 1
Soak in 00 times the volume of methyl ethyl ketone (MEK) for 48 hours. After immersion, excess F'lEK is thoroughly removed with decantation, and the weight of the sample swollen with MEK is determined. The MEK is then dried under reduced pressure and the absolute dry weight of the sample is determined. Based on this, it is calculated from the following formula.
ゲル含有量（重量％）
実施例１
５１のセパラブルフラスコに、懸濁分散剤としてポリビ
ニルアルコール（（株）クラレ製ＰＴ＾４２０） １８
．３７ｇを２６２５１１１ｉ！の蒸留水に溶解させ、モ
ノマー系としてスチレン５４０戚、ジビニルベンゼン６
０威、トルエン４００ｄ、ラウロイルパーオキサイド１
２００ｇの溶液を加えた。この混合液をラボディスパー
ザ−（三田村理研（株）製Ｘ−１０２０型）を用い、顕
微鏡で観察した粒径が最大のもので２５μｍになるまで
分散させた。フラスコに温度計、攪拌装置、冷却管をと
りつけ、窒素気流下８０°Ｃで６時間重合反応を行なっ
た。得られたスラリーを吸引濾過し、濾別した微粒子を
再び蒸留水に分散させて付着しているポリビニルアルコ
−４
ルを洗浄し濾過した。これを１００°Ｃで２日間真空乾
燥して希釈剤のトルエンを蒸発させた後、粒径を透過式
粒度分布測定器（（株）セイシン企業製： ５ＫＡ５０
００）で測定したところ粒径が２〜２５μｍ、平均粒子
径８μｍ（１０μｍ未満の粒子は重量分布で６５％）の
架橋ポリマー微粒子を得た。Gel content (wt%) Example 1 Polyvinyl alcohol (PT^420 manufactured by Kuraray Co., Ltd.) was added as a suspending and dispersing agent to a 51 separable flask.
．． 37g is 2625111i! of styrene 540 and divinylbenzene 6 as monomers.
0 weight, toluene 400d, lauroyl peroxide 1
200g of solution was added. This mixed solution was dispersed using a lab body spazer (Model X-1020, manufactured by Mitamura Riken Co., Ltd.) until the maximum particle size as observed under a microscope was 25 μm. A thermometer, a stirring device, and a cooling tube were attached to the flask, and a polymerization reaction was carried out at 80° C. for 6 hours under a nitrogen stream. The resulting slurry was suction filtered, and the filtered fine particles were again dispersed in distilled water to wash off the adhering polyvinyl alcohol and filtered. After vacuum drying this at 100°C for 2 days to evaporate the toluene diluent, the particle size was measured using a transmission particle size distribution analyzer (manufactured by Seishin Enterprise Co., Ltd.: 5KA50).
Crosslinked polymer fine particles having a particle size of 2 to 25 μm and an average particle size of 8 μm (particles smaller than 10 μm account for 65% of the weight distribution) were obtained as measured by 00).
この微粒子のゲル含有量は９８％、膨潤度は１以下であ
った。得られた微粒子をアクリル酸メチル５％を含有す
るメタクリル酸メチル重合体（（株）クラレ製：バラビ
ーズ）１００部に対して５部添加し、ヘンシェルミキサ
ーで混合攪拌の後、押出機（中央機械製作所製： ＶＳ
Ｋ−４０）で押出してペレット化し、このペレットを射
出成形機（東芝機械（株）製： ｌＳ−２５Ｚｐ）によ
り成形温度２００〜２４０°Ｃ１金型温度５０℃の条件
で鏡面キャビティー内に射出成形し、厚さ２ｒｒｃｌの
平板成形品を得た。The gel content of these fine particles was 98%, and the degree of swelling was 1 or less. 5 parts of the obtained fine particles were added to 100 parts of methyl methacrylate polymer containing 5% methyl acrylate (manufactured by Kuraray Co., Ltd.: Barabeads), and after mixing and stirring with a Henschel mixer, an extruder (Chuo Machinery Co., Ltd.) was added. Manufactured by: VS
K-40) to pelletize, and the pellets were injected into a mirror cavity using an injection molding machine (Toshiba Machine Co., Ltd.: lS-25Zp) at a molding temperature of 200 to 240°C and a mold temperature of 50°C. A flat plate molded product with a thickness of 2rrcl was obtained.
この成形品の性能評価の結果を第１表に示すが高光拡散
性の良好な艶消し表面を有するアクリル樹脂成形品が得
られた。The results of the performance evaluation of this molded article are shown in Table 1, and an acrylic resin molded article having a good matte surface with high light diffusivity was obtained.
実施例２〜４
５
下記組成及び粒径の架橋ポリマー微粒子を各種添加量で
添加する以外は実施例１と同様にしてペレット化及び射
出成形し厚さ２［ｌｌｆｆ１の平板成形品を得た。これ
らの成形品の性能評価の結果を第１表に示す。Examples 2 to 4 5 Pelletization and injection molding were carried out in the same manner as in Example 1 except that crosslinked polymer fine particles having the following composition and particle size were added in various amounts to obtain a flat plate molded product having a thickness of 2 [llff1]. Table 1 shows the results of performance evaluation of these molded products.
比較例１．２
下記組成及び粒径の架橋ポリマー微粒子を各種添加量で
添加する以外は実施例１と同様にしてペレット化及び射
出成形し厚さ２■の平板成形品を得た。これらの成形品
の性能評価結果を第１表に示す。Comparative Example 1.2 Pelletization and injection molding were carried out in the same manner as in Example 1, except that crosslinked polymer fine particles having the composition and particle size shown below were added in various amounts to obtain flat molded products with a thickness of 2 cm. Table 1 shows the performance evaluation results of these molded products.
６
平均粒子径５０μｍのものは、樹脂の充填速度が速い場
合大きい粒子による流れ模様が出やすい傾向が見られる
ほか、成形品表面が均一の艶消し状とならず、また光拡
散性も劣っていた。6.For those with an average particle diameter of 50 μm, when the resin filling speed is high, flow patterns due to large particles tend to appear, the surface of the molded product does not have a uniform matte finish, and the light diffusivity is poor. Ta.
比較例３
アクリル酸メチル５％を含有するメタクリル酸メチル重
合体１００部に対して、１．０〜２０μｍの粒度分布を
有し平均粒子径６μｍ（１０μｍ未満の粒子は重量分布
で９０％）のポリスチレン微粒子を１部、３部、５部、
１０部それぞれ添加しヘンシェルミキサーで混合攪拌の
後、実施例１と同様に厚さ２胴の平板成形品を得た。こ
れらの性能評価結果を第１表に示すが、高拡散で高光線
透過率の成形品は得られず、又添加量が少くない時７
は成形品に分散不良があり、添加量が多いと貝から模様
が発生した。Comparative Example 3 For 100 parts of methyl methacrylate polymer containing 5% methyl acrylate, a polymer with a particle size distribution of 1.0 to 20 μm and an average particle diameter of 6 μm (particles less than 10 μm are 90% in weight distribution) 1 part, 3 parts, 5 parts of polystyrene fine particles,
After adding 10 parts each and mixing and stirring using a Henschel mixer, a flat plate molded product with a thickness of 2 cylinders was obtained in the same manner as in Example 1. The results of these performance evaluations are shown in Table 1. Molded products with high diffusion and high light transmittance cannot be obtained, and when the amount added is not small, the molded product has poor dispersion, and when the amount added is large A pattern emerged from the shell.
比較例４
比較例３で用いたメタクリル酸メチル重合体１００部に
対して、３〜３０μｍの粒度分布を有し平均粒子径１０
μｍのポリスチレン微粒子（積木化成品工業（株）製：
テクボリマー５Ｂ−１０）を０．５部、１部、５部、１
０部それぞれ添加しヘンシェルミキサーで混合攪拌の後
、実施例１と同様にして厚さ２ＩＩＩＩ１１の平板成形
品を得た。これらは高拡散で高光線透過率の成形品は得
られず、比較８
〔発明の効果〕
本発明は以上説明したように、メタクリル酸メチル系重
合体１００重量部に対して、芳香族ビニルモノマー５０
〜９９重量％および架橋性モノマー１〜５０重量％から
なる平均粒子径１〜１５μｍの架橋ポリマー微粒子を１
部〜２０重量部含有してなる光拡散性及び艶消性にすぐ
れた成形体用アクリル樹脂組成物であるから、配合する
ポリマー微粒子の粒径および添加量により光拡散性およ
び艶消し状態を変化させることができるので、簡便に種
々の光拡散性、艶消し性を有する成形体用の組成物を提
供することができ、特に量産性にすぐれた射出成形材料
として有用である。Comparative Example 4 With respect to 100 parts of the methyl methacrylate polymer used in Comparative Example 3, it had a particle size distribution of 3 to 30 μm and an average particle size of 10
μm polystyrene fine particles (manufactured by Tsukiki Kaseihin Kogyo Co., Ltd.:
Techvolimer 5B-10) 0.5 parts, 1 part, 5 parts, 1
After adding 0 parts of each and mixing and stirring using a Henschel mixer, a flat plate molded product having a thickness of 2III11 was obtained in the same manner as in Example 1. Comparison 8 [Effects of the Invention] As explained above, the present invention uses an aromatic vinyl monomer based on 100 parts by weight of a methyl methacrylate polymer. 50
1 to 99% by weight of crosslinked polymer fine particles with an average particle diameter of 1 to 15 μm consisting of 1 to 50% by weight of a crosslinkable monomer.
Since this is an acrylic resin composition for molded objects with excellent light diffusivity and matte property, the light diffusivity and matte state can be changed depending on the particle size and addition amount of the fine polymer particles to be blended. Therefore, it is possible to easily provide compositions for molded articles having various light-diffusing properties and matte properties, and is particularly useful as an injection molding material with excellent mass productivity.
また、上記成形体用アクリル樹脂組成物を押出成形又は
射出成形してなる光拡散性及び艶消し性に優れたアクリ
ル樹脂成型品であるから、大量に安価に供給できると共
に種々の光拡散性及び艶消し性を有する照明カバー、デ
イスプレー、グレージング、計器カバー等として有用で
あり、特に近年普及がめざましいＯＡ機器、液晶デイス
プレィ、０
バックライトパネル等の光学機器用光拡散板として好適
である。In addition, since it is an acrylic resin molded product with excellent light diffusivity and matte property obtained by extrusion molding or injection molding of the above-mentioned acrylic resin composition for molded objects, it can be supplied in large quantities at low cost and has various light diffusivity and matte properties. It is useful as a matte lighting cover, display, glazing, instrument cover, etc., and is particularly suitable as a light diffusion plate for optical equipment such as office automation equipment, liquid crystal displays, and backlight panels, which have become rapidly popular in recent years.
更に本発明は、上記アクリル樹脂組成物を成形型キャビ
ティ内に射出成形する光拡散性及び艶消し性に優れたア
クリル樹脂成形品の製造方法であるから、キャビテイ面
を微細に加工するとか、十分に鏡面に研磨する必要がな
く安価に金型を製作することができ、また１つの型で成
型材料を変えることにより種々の光拡散性及び艶消し性
に優れた成形品を製造することができ、分散不良や貝か
ら模様の発生が皆無であるので、安価、簡便に光拡散性
及び艶消し性に優れたアクリル樹脂成型品を提供するこ
とができ有利である。Furthermore, since the present invention is a method for producing an acrylic resin molded product with excellent light diffusion and matte properties by injection molding the above acrylic resin composition into a mold cavity, the cavity surface may be finely processed or It is possible to manufacture molds at low cost because there is no need to polish them to a mirror surface, and by changing the molding material in one mold, it is possible to manufacture various molded products with excellent light diffusion and matte properties. Since there is no poor dispersion or pattern formation from shells, it is advantageous to be able to provide an acrylic resin molded product with excellent light diffusivity and matteness at low cost and easily.
第１図は、実施例１（Ａ）、実施例２の微粒子配合量３
部（Ｂ）、実施例３の微粒子配合量３部（Ｃ）、実施例
４の微粒子配合量５部（Ｄ）、比較例１の微粒子配合量
５部（Ｅ）および比較例２の微粒子配合量１０部（Ｆ）
の透過特性をそれぞれ表わした図である。
１Figure 1 shows the fine particle blending amount 3 of Example 1 (A) and Example 2.
Part (B), 3 parts of fine particles in Example 3 (C), 5 parts in Example 4 (D), 5 parts of fine particles in Comparative Example 1 (E), and 5 parts of fine particles in Comparative Example 2 Amount: 10 parts (F)
FIG. 1
Claims (5)
て、芳香族ビニルモノマー５０〜９９重量％および架橋
性モノマー１〜５０重量％からなる平均粒子径１〜１５
μｍの架橋ポリマー微粒子を１〜２０重量部含有してな
る成形体用アクリル樹脂組成物。(1) An average particle diameter of 1 to 15% consisting of 50 to 99% by weight of an aromatic vinyl monomer and 1 to 50% by weight of a crosslinkable monomer based on 100 parts by weight of the methyl methacrylate polymer.
An acrylic resin composition for a molded article containing 1 to 20 parts by weight of crosslinked polymer fine particles of μm size.
重量分布で６０％以上含有する平均粒子径５〜９μｍの
微粒子である請求項１記載の樹脂組成物。(2) The resin composition according to claim 1, wherein the crosslinked polymer fine particles have an average particle size of 5 to 9 μm and contain 60% or more of particles with a particle size of less than 10 μm in weight distribution.
るアクリル樹脂成形品。(3) An acrylic resin molded article comprising the acrylic resin composition according to claim 1 or 2.
。(4) A diffuser plate for optical equipment comprising the molded article according to claim 3.
消し性を有するアクリル樹脂成形品を得る方法において
、請求項１又は２記載のアクリル樹脂組成物を艶消し加
工の施こされていない成形型キャビティ内に射出成形す
ることを特徴とするアクリル樹脂成形品の製造方法。(5) In a method of injection molding an acrylic resin material to obtain an acrylic resin molded article having light diffusing properties and matte properties, the acrylic resin composition according to claim 1 or 2 is not subjected to matte processing. A method for producing an acrylic resin molded product, characterized by injection molding inside a mold cavity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2907890A JPH03231954A (en) | 1990-02-07 | 1990-02-07 | Acrylic resin composition for molded body, molded product and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2907890A JPH03231954A (en) | 1990-02-07 | 1990-02-07 | Acrylic resin composition for molded body, molded product and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03231954A true JPH03231954A (en) | 1991-10-15 |
Family
ID=12266312
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2907890A Pending JPH03231954A (en) | 1990-02-07 | 1990-02-07 | Acrylic resin composition for molded body, molded product and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03231954A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07318708A (en) * | 1994-03-29 | 1995-12-08 | Toray Ind Inc | Light transmission type light diffusion sheet and image display device as well as its production |
-
1990
- 1990-02-07 JP JP2907890A patent/JPH03231954A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07318708A (en) * | 1994-03-29 | 1995-12-08 | Toray Ind Inc | Light transmission type light diffusion sheet and image display device as well as its production |
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