JP2994687B2 - Acrylic resin multilayer board - Google Patents
Acrylic resin multilayer boardInfo
- Publication number
- JP2994687B2 JP2994687B2 JP2121906A JP12190690A JP2994687B2 JP 2994687 B2 JP2994687 B2 JP 2994687B2 JP 2121906 A JP2121906 A JP 2121906A JP 12190690 A JP12190690 A JP 12190690A JP 2994687 B2 JP2994687 B2 JP 2994687B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- resin layer
- multilayer board
- acrylic resin
- 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.)
- Expired - Fee Related
Links
Landscapes
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、アクリル樹脂多層板に関し、より詳しく
は、照明カバー,照明看板,液晶バックライパネル用光
拡散板等に好適な耐候性及び光拡散性に優れたアクリル
樹脂多層板に関するものである。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an acrylic resin multilayer board, and more particularly, to weather resistance and light diffusion suitable for a lighting cover, a lighting signboard, a light diffusing plate for a liquid crystal backlight panel, and the like. The present invention relates to an acrylic resin multilayer board having excellent properties.
照明器具のカバー,各種ディスプレイ,看板用等の光
拡散性を必要とする種々の用途にアクリル樹脂は用いら
れている。上記のような用途では高い光拡散性を有する
と共に、電力エネルギーの効率的使用の点からも高い光
線透過性を兼ね備えるということが望まれており、従来
このような光拡散性アクリル樹脂としては、(a)平均
粒径10μm以下の硫酸バリウム,炭酸カルシウム等の無
機微粉末を透明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)などが挙げられる。Acrylic resins are used in various applications that require light diffusion, such as covers for lighting fixtures, various displays, and signs. In the applications as described above, it is desired to have high light diffusivity and also have high light transmittance from the viewpoint of efficient use of power energy.Conventionally, as such a light diffusing acrylic resin, (A) An inorganic fine powder having an average particle size of 10 μm or less, such as barium sulfate or calcium carbonate, contained in a transparent resin (Japanese Unexamined Patent Publication No.
139758), (b) silica and glass of 4 to 50 μm,
What disperses transparent fine particles such as aluminum hydroxide in an acrylic resin (JP-A-60-184559, JP-A-60-184559)
-4762) and the like.
しかしながら、前記(a),(b)の光拡散性アクリ
ル樹脂では、光拡散性粉末として無機物質粉末を主に添
加含有せしめるため、全光線透過率を高くする目的でそ
の粉末の添加量を減ずると光拡散性が劣り、一方、充分
な光拡散性を得る目的でその粉末の添加量を高めると全
光線透過率が低下してしまうという問題点を有してい
た。さらにこれらは光拡散性粉末として堅い無機物質粉
末を使用するため、成形機のスクリュー、シリンダー、
ノズル、ダイ、金型等の摩耗、損傷が発生しやすく、特
に押出成形法によりアクリル樹脂板を製造する場合にお
いては、粉末粒子の粒径が大きいか又は粒径が小さくて
も添加量が大きい為、これに起因するダイライン等の欠
点が発生し、事実上、長時間の連続運転が困難であると
いう問題点があった。このため更に高い光拡散性と高光
線透過率を有する光拡散性樹脂の出現を切望する市場の
要請に十分対応できていないのが実情である。However, in the light-diffusing acrylic resin of (a) and (b), since an inorganic substance powder is mainly added and contained as a light-diffusing powder, the added amount of the powder is reduced for the purpose of increasing the total light transmittance. On the other hand, when the amount of the powder added is increased for the purpose of obtaining a sufficient light diffusing property, the total light transmittance is lowered. Furthermore, since these use hard inorganic substance powder as light diffusing powder, the screw, cylinder,
Abrasion and damage of nozzles, dies, molds, etc. are liable to occur, especially in the case of manufacturing an acrylic resin plate by an extrusion molding method, the amount of addition is large even if the particle size of the powder particles is large or small. For this reason, a defect such as a die line occurs due to this, and there has been a problem that it is practically difficult to continuously operate for a long time. For this reason, it is a fact that it has not been possible to sufficiently respond to the demands of the market for the desire for the emergence of a light diffusing resin having higher light diffusivity and higher light transmittance.
また、前記無機物質粉末に対し、例えば、(c)平均
直径0.5〜5μmのスチレン系架橋重合体微粒子を含有
せしめたもの(特公昭39−10515号公報)、(d)スチ
レン系樹脂又は粒子径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アクリル樹脂に混
合分散せしめたもの(特開昭56−36535号公報、特開昭6
1−159440号公報)などが知られている。しかし、スチ
レン系のポリマーはアクリル樹脂に比較し耐候性に劣る
という問題があり、特に屋外用に供されるアクリル樹脂
板の中に混合分散して使用することは敬遠され実用化さ
れないで今日に至っているのが実情である。Further, for example, (c) a styrene-based crosslinked polymer fine particle having an average diameter of 0.5 to 5 μm is added to the inorganic substance powder (Japanese Patent Publication No. 39-10515); 30-500 μm crosslinked styrene-alkyl acrylate polymer mixed and dispersed in an acrylic resin (JP-A-56-36535, JP-A-56-36535)
Publication No. 1-159440) is known. However, styrene-based polymers have a problem that they are inferior to acrylic resins in terms of weather resistance, and in particular, mixing and dispersing them in acrylic resin plates used for outdoor use has been shunned and not practically used today. That is the fact.
したがって、本発明は、量産性に適し、耐候性及び光
拡散性に優れたアクリル樹脂板を提供することを目的と
する。Therefore, an object of the present invention is to provide an acrylic resin plate which is suitable for mass production and is excellent in weather resistance and light diffusion.
本発明者らは、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、スチレン系架橋ビーズ
を含む光拡散性アクリル樹脂層の表面に紫外線吸収剤を
含有する樹脂層を設けることにより、これ迄にない高い
光拡散性と高光線透過率を有し、且つ耐候性に優れたア
クリル樹脂板が得られることを見出し、本発明を完成し
た。The present inventors have conducted intensive research on the type of light diffusing agent in order to solve the above problems, and as a result, provide a resin layer containing an ultraviolet absorber on the surface of a light diffusing acrylic resin layer containing styrene-based crosslinked beads. As a result, they have found that an acrylic resin plate having an unprecedentedly high light diffusion property and a high light transmittance and having excellent weather resistance can be obtained, and the present invention has been completed.
すなわち、本発明の要旨とするところは、 (1) メタクリル酸メチル系重合体100重量部に対し
て平均粒子径1〜30μmの架橋スチレン系ポリマーを1
〜20重量部含有する樹脂層(A)及びメタクリル酸メチ
ル系重合体100重量部に対して紫外線吸収剤を0.005〜2
重量部含有する樹脂層(B)からなり、樹脂層(A)の
少なくとも一つの表面に樹脂層(B)を設けたアクリル
樹脂多層板、および (2) メタクリル酸メチル系重合体100重量部に対し
て平均粒子径1〜30μmの架橋スチレン系ポリマーを1
〜20重量部含有する樹脂層(A)及びメタクリル酸メチ
ル系重合体100重量部に対して紫外線吸収剤0.005〜2重
量部と粒子径1〜50μmの架橋メタクリル酸エステル重
合体微粒子および/または高重合度メタクリル酸エステ
ル重合体微粒子0.5〜15重量部とを含有する樹脂層
(B)からなり、樹脂層(A)の少なくとも一つの表面
に樹脂層(B)を設けたアクリル樹脂多層板である。That is, the gist of the present invention is as follows: (1) A crosslinked styrene-based polymer having an average particle diameter of 1 to 30 μm is added to 100 parts by weight of a methyl methacrylate-based polymer.
0.005 to 2 parts by weight of the ultraviolet absorbent per 100 parts by weight of the resin layer (A) and 100 parts by weight of the methyl methacrylate-based polymer.
(2) 100 parts by weight of an acrylic resin multilayer board comprising a resin layer (B) containing at least one resin layer (B) on at least one surface of the resin layer (A) and (2) a methyl methacrylate polymer. On the other hand, a crosslinked styrene polymer having an average particle diameter of 1 to 30 μm
0.005 to 2 parts by weight of an ultraviolet absorber and a crosslinked methacrylic acid ester polymer fine particle having a particle diameter of 1 to 50 μm based on 100 parts by weight of the resin layer (A) and 100 parts by weight of a methyl methacrylate polymer containing An acrylic resin multilayer board comprising a resin layer (B) containing 0.5 to 15 parts by weight of a methacrylate polymer fine particle having a degree of polymerization, wherein at least one surface of the resin layer (A) is provided with the resin layer (B). .
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明に用いられるメタクリル酸メチル系重合体と
は、メタクリル酸メチル(以下MMAと称す)を60重量%
以上、好ましくは80重量%以上含むモノマーを公知の懸
濁重合、塊状重合等で重合することにより得られるメタ
クリル酸メチルホモポリマーまたはそのコポリマーをい
う。MMAが60%未満となると耐候性が低下し黄変し易く
なる傾向があり好ましくない。MMA以外の共重合成分と
しては特に限定はないが、アクリル酸メチル、アクリル
酸ブチル、スチレン等が挙げられる。該重合体の重合度
は、押出機で混練押出することから2500以下であり、好
ましくは2200以下のものが用いられる。また、重合度の
下限界は特に明確ではないが、樹脂の強度の点等から80
0以上が好ましい。The methyl methacrylate polymer used in the present invention refers to methyl methacrylate (hereinafter referred to as MMA) at 60% by weight.
As described above, it refers to a methyl methacrylate homopolymer or a copolymer thereof obtained by polymerizing a monomer containing preferably 80% by weight or more by known suspension polymerization, bulk polymerization, or the like. If the MMA is less than 60%, the weather resistance tends to decrease and yellowing tends to occur, which is not preferred. The copolymerization component other than MMA is not particularly limited, and examples thereof include methyl acrylate, butyl acrylate, and styrene. The degree of polymerization of the polymer is 2500 or less, and preferably 2200 or less, since it is kneaded and extruded by an extruder. Further, although the lower limit of the degree of polymerization is not particularly clear, it is 80% from the viewpoint of the strength of the resin and the like.
0 or more is preferable.
本発明に用いられるスチレン系ポリマーはスチレン系
モノマーおよび架橋性モノマーを懸濁重合することによ
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。このようにして得られる架橋スチレン系ポリマー微
粒子はメタクリル酸メチル系重合体と混合し混練押出し
てもほとんど溶融することなく、原形の球状を保持して
いることが好ましい。また、架橋スチレン系ポリマーの
耐候性を改善する目的でベンゾトリアゾール系などの紫
外線吸収剤やヒンダードアミン系の光安定剤等を含むこ
とができる。The styrenic polymer used in the present invention is fine particles obtained by suspension polymerization of a styrenic monomer and a crosslinkable monomer, but other copolymerizable monomers may be added as long as the object of the present invention is not hindered. Can also. It is preferable that the thus obtained crosslinked styrene-based polymer fine particles hardly melt even when they are mixed with a methyl methacrylate-based polymer, kneaded and extruded, and retain the original spherical shape. Further, for the purpose of improving the weather resistance of the crosslinked styrene-based polymer, a benzotriazole-based ultraviolet absorber or a hindered amine-based light stabilizer may be included.
スチレン系モノマーとしてはスチレン、α−メチルス
チレン、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。該スチレン系モノマー
の使用量は50〜99重量%、好ましくは80〜95重量%の範
囲である。Styrene, α-methylstyrene, halogenated styrene and the like can be used as the styrene monomer, but styrene is particularly preferred. The amount of the styrenic 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
ングリコールジメタクリレート、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
等を好ましく挙げることができる。該架橋性モノマーの
使用量は前モノマーに対し1〜50重量%、好ましくは5
〜20重量%の範囲である。As the crosslinkable monomer, a compound having two or more unsaturated bonds in a molecule is used. Specific examples thereof include ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, and neopentyl glycol. And polyfunctional vinyl benzenes such as difunctional methacrylate and divinyl benzene. The amount of the crosslinking monomer used is 1 to 50% by weight, preferably 5
It is in the range of ~ 20% by weight.
本発明に用いられる前記微粒子の平均粒子径は1〜30
μm、好ましくは3〜20μm、最も好ましくは5〜9μ
m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、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:SKA5000)等により測定できる。光拡散状態の
均一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、粒径分譜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SBX−4,SBX−6,SBX−8,SBX−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15μm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。
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3〜10重量
部であり、全光線透過率、拡散光線透過率等要求される
光学的な性能に応じて調整することができる。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、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
光拡散性が更に向上する効果は見られないので好ましく
ない。The average particle diameter of the fine particles used in the present invention is 1 to 30
μm, preferably 3-20 μm, most preferably 5-9 μm
m, as a more preferred embodiment of the fine particles, the light diffusibility to the variation of the content of the polymer fine particles by particle size, from the viewpoint of the effect on the surface appearance, particles having a particle size of less than 10 μm in the above range 60% or more by weight distribution, Preferably, it accounts for 90% or more. The average particle size here means a particle size equivalent to 50% of the total weight by integrating the respective particle sizes by weight. For example, a transmission type particle size distribution measuring device by gravity sedimentation method (manufactured by Seishin Enterprise Co., Ltd .: SKA5000), etc. Can be measured. Spherical fine particles obtained by suspension polymerization are preferably used from the viewpoint of uniformity of light diffusion state and feeling, and a narrower particle diameter is more preferably used because uniform light diffusion can be obtained. As fine particles by these suspension polymerization, JP-A-64-26617, JP-A-1-146910, those manufactured by the formulation and suspension method shown in JP-A-1-172412, etc., or Sekisui Plastics Co., Ltd .: Techpolymer SBX-4, SBX-6, SBX-8, SBX-12 (crosslinked polystyrene fine spherical fine particles) and the like can be used as commercial products. When the particle size of the polymer particles is less than 1 μm, it tends to look reddish by transmitted light, which is not preferable. On the other hand, when the particle size exceeds 40 μm or when the average particle size exceeds 15 μm, high light diffusivity close to perfect diffusion is obtained. Cannot be obtained, which is not preferable.
Further, the compounding amount of the fine particles is a methyl methacrylate polymer.
It is 1 to 20 parts by weight, preferably 3 to 10 parts by weight per 100 parts by weight, and can be adjusted according to the required optical performance such as the total light transmittance and the diffused light transmittance. If the compounding amount is less than 1 part by weight, it becomes easy to be transparent and sufficient light diffusibility cannot be obtained. On the other hand, if it exceeds 20 parts by weight, the light transmittance decreases, This is not preferable because the effect of further improving the light diffusivity is not seen.
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表面外観も均一にきめ細いものと
ならず好ましくない。The crosslinked polymer fine particles thus obtained 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. When the gel content is less than 95%, or when the degree of swelling exceeds 2, the particle size of the particles changes during kneading, and it is not possible to obtain diffusivity close to perfect diffusion, and the surface appearance is uniformly fine. This is not preferred.
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 the degree of swelling of the crosslinked polymer can be adjusted by adjusting the type and amount of the crosslinkable monomer and by using a chain transfer agent. Crosslinked polymer fine particles having a degree of 2 or less can be obtained.
本発明で用いられる紫外線吸収剤としては特に限定さ
れるものではないが、耐候性を改良する目的からベンゾ
フェノン系、ベンゾトリアゾール系、サリチル酸フェニ
ル系、または安息香酸フェニル系などから誘導される化
合物で、その最大吸収波長が240〜380nmの範囲にある化
合物が好ましい。これらの紫外線吸収剤は単独で用いて
も良いし、2種以上を併用してもよい。The ultraviolet absorber used in the present invention is not particularly limited, but a compound derived from a benzophenone-based, benzotriazole-based, phenyl salicylate-based, or phenyl benzoate-based compound for the purpose of improving weather resistance, Compounds having a maximum absorption wavelength in the range of 240 to 380 nm are preferred. These ultraviolet absorbers may be used alone or in combination of two or more.
この紫外線吸収剤の配合割合は、メタクリル酸メチル
系重合体100重量部に対して0.005〜2重量部、好ましく
は0.1〜0.5重量部である。その配合割合が0.05重量部未
満では耐候性の向上が十分でなく、一方2重量部を超え
る場合には押出成形時ポリシングロール表面を汚すため
クモリ、汚れが発生しやすく、またスリップなど運転上
のトラブルが起りやすくなり好ましくない。The compounding ratio of the ultraviolet absorber is 0.005 to 2 parts by weight, preferably 0.1 to 0.5 part by weight, per 100 parts by weight of the methyl methacrylate polymer. If the compounding ratio is less than 0.05 part by weight, the weather resistance is not sufficiently improved, while if it exceeds 2 parts by weight, the polishing roll surface is soiled at the time of extrusion molding, so that clouding and dirt are likely to occur, and slipping and other operational problems. Trouble is likely to occur, which is not preferable.
本発明のアクリル樹脂多層板は、メタクリル酸メチル
系重合体100重量部に対して前記平均粒子径1〜30μの
架橋スチレン系ポリマーを1〜20重量部含有する樹脂層
(A)及びメタクリル酸メチル系重合体100重量部に対
して前記紫外線吸収剤を0.005〜2重量部含有する樹脂
層(B)からなり、樹脂層(A)の少なくとも一つの表
面に樹脂層(B)を設けたものであり、樹脂層(B)/
樹脂層(A)、樹脂層(B)/樹脂層(A)/樹脂層
(B)などの2層構造、3層構造の多層板が具体例とし
て挙げられる。The acrylic resin multilayer board of the present invention comprises a resin layer (A) containing 1 to 20 parts by weight of a crosslinked styrene-based polymer having an average particle diameter of 1 to 30 μm per 100 parts by weight of a methyl methacrylate-based polymer, and methyl methacrylate. A resin layer (B) containing 0.005 to 2 parts by weight of the ultraviolet absorber with respect to 100 parts by weight of the base polymer, wherein the resin layer (B) is provided on at least one surface of the resin layer (A). Yes, resin layer (B) /
Specific examples include a multilayer board having a two-layer structure and a three-layer structure such as a resin layer (A), a resin layer (B) / a resin layer (A) / a resin layer (B).
本発明でいう多層板とは、共押出成形法で得られるシ
ート、基材樹脂板にフィルムをラミネートして得られる
シート等をいい、板厚として特に制限はないが、通常0.
5〜15mm、好ましくは1〜10mmのものが用いられる。樹
脂層(B)の厚味は得に制限されないが、通常30〜500
μm、好ましくは50〜300μmのものが用いられる。The multilayer board referred to in the present invention refers to a sheet obtained by a coextrusion molding method, a sheet obtained by laminating a film on a base resin board, and the like, and there is no particular limitation as to the thickness of the board, but it is usually 0.
Those having a size of 5 to 15 mm, preferably 1 to 10 mm are used. The thickness of the resin layer (B) is not particularly limited, but is usually 30 to 500.
μm, preferably 50-300 μm.
本発明のアクリル樹脂多層板における樹脂層(B)に
は、さらに粒子径1〜50μmの架橋メタクリル酸エステ
ル重合体微粒子および/または高重合度メタクリル酸エ
ステル重合体微粒子を0.5〜15重量部含有することがで
き、これにより多層板の片面又は両面に微細でかつ均一
な凹凸を持つエンボウ面を設けることができる。ここ
で、架橋メタクリル酸エステル重合体微粒子および/ま
たは高重合度メタクリル酸エステル重合体微粒子とは、
メタクリル酸エステルまたはメタクリル酸エステルを主
単量体成分とするメタクリル酸エステルと共重合可能な
単量体混合物と架橋剤とを塊状重合、鋳込重合したもの
を機械粉砕した微粉体あるいは懸濁重合して得られる微
粒子、メタクリル酸エステルまたはメタクリル酸エステ
ルを主単量体成分とするメタクリル酸エステルと共重合
可能な単量体混合物を重合度5000以上、好ましくは8000
以上に塊状重合、鋳込重合したものを機械粉砕した微粉
体あるいは懸濁重合して得られる微粒子、またはこれら
を混合した微粒子をいう。The resin layer (B) in the acrylic resin multilayer board of the present invention further contains 0.5 to 15 parts by weight of crosslinked methacrylate polymer fine particles and / or high polymerization degree methacrylate polymer fine particles having a particle diameter of 1 to 50 μm. Accordingly, an embossed surface having fine and uniform unevenness can be provided on one or both surfaces of the multilayer board. Here, the crosslinked methacrylate polymer fine particles and / or the high polymerization degree methacrylate polymer fine particles are:
Fine powder or suspension polymerization obtained by mechanically pulverizing a methacrylic acid ester or a monomer mixture copolymerizable with a methacrylic acid ester containing a methacrylic acid ester as a main monomer component and a crosslinker, and then mechanically pulverizing the crosslinked polymer. Fine particles obtained by, a methacrylic acid ester or a monomer mixture copolymerizable with a methacrylic acid ester having a methacrylic acid ester as a main monomer component a polymerization degree of 5000 or more, preferably 8000
A fine powder obtained by mechanically pulverizing a product obtained by bulk polymerization or cast polymerization, a fine particle obtained by suspension polymerization, or a fine particle obtained by mixing these materials.
これらの微粒子の製造に使用されるメタクリル酸エス
テルとしては、メタクリル酸メチル、メタクリル酸オク
チル、メタクリル酸ステアリルなどの直鎖脂肪族エステ
ル、メタクリル酸tert−ブチル、メタクリル酸2−エチ
ルヘキシルなどの分岐脂肪族エステル、メタクリル酸ア
リルなどの不飽和エステルなどであり、メタクリル酸メ
チル、メタクリル酸ステアリルなどの直鎖脂肪族エステ
ルが好ましく、メタクリル酸メチルが最も好ましい。メ
タクリル酸エステルと共重合可能な単量体の例として
は、たとえば主成分とするメタクリル酸エステル以外の
(メタ)アクリル酸アルキルエステル((メタ)アクリ
ル酸アルキルエステルとはアクリル酸アルキルエステ
ル、およびメタクリル酸アルキルエステルをいう。以下
同じ。)、(メタ)アクリル酸ヒドロキシアルキルエス
テル、(メタ)アクリル酸、(メタ)アクリルニトリ
ル、無水マレイン酸等がある。また架橋剤としては特に
限定されないが、2個以上の不飽和基を有する架橋剤を
用いるのが好ましく、たとえばエチレングリコールジメ
タクリレート、ポリエチレングリコールジメタクリレー
ト、ネオペンチルグリコールジメタクリレートなどの二
官能性のジメタクリレートや、ジビニルベンゼン等が好
ましく使用でき、全モノマーに対し1〜50重量%、好ま
しくは5〜50重量%の範囲で用いられる。これらの懸濁
重合による微粒子としては、特開昭48−49838号公報、
特願昭62−307238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松
本油脂製薬株式会社製:マツモトマイクロスフェアーM3
05(架橋ポリメチルメタクリレート球状微粒子)、積水
化成品工業株式会社製:テクポリマーMB(ポリメチルメ
タクリレート微小球状微粒子:高重合度タイプ)、同MB
X(架橋ポリメチルメタクリレート微小球状微粒子)な
どが使用できる。本発明に用いられる前記微粒子の粒径
は1〜50μm、好ましくは1〜30μmであり、平均粒子
径は3〜25μm、好ましくは4〜15μmであり、更に好
ましい微粒子の態様としては、重合体微粒子含量変動に
対する艶消し外観の安定性および艶消し表面の均一制の
観点から粒径が1〜30μm、好ましくは1〜20μmの範
囲でかつ粒径10μm未満の粒子が重量分布で70%以上、
好ましくは90%以上を占めるものである。重合体微粒子
の平均粒径が50μmを超える場合又は平均粒子径が25μ
mを超える場合には表面が細かく均一な艶消し状態とな
らず好ましくない。またその配合量は、目的とする用途
によって異なるが、良好な防眩性を得るためには0.5〜1
5重量部、好ましくは2〜10重量部をメタクリル酸メチ
ル系重合体100重量部あたり配合することが必要であ
る。0.5重量部未満の場合には表面の艶消し状態が十分
にならず光沢度が上昇し美麗さが失なわれ、一方15部を
超える場合には表面の艶消し状態は均一であるが、とく
に性能上好ましい影響を及ぼさない。また上記微粒子が
架橋系でなく重合度が5000未満の場合には、押出成形の
混練時微粒子が基材樹脂に溶解し艶消状態が発現しなか
ったり、極めて不充分であったりして好ましくない。Examples of the methacrylate used in the production of these fine particles include methyl methacrylate, octyl methacrylate, linear aliphatic esters such as stearyl methacrylate, tert-butyl methacrylate, and branched aliphatics such as tert-butyl methacrylate 2-ethylhexyl methacrylate. Esters, unsaturated esters such as allyl methacrylate, etc., straight-chain aliphatic esters such as methyl methacrylate and stearyl methacrylate are preferred, and methyl methacrylate is most preferred. Examples of monomers copolymerizable with methacrylic acid esters include, for example, alkyl (meth) acrylates other than methacrylic acid ester as the main component (alkyl (meth) acrylates are alkyl acrylates, and methacrylic acid). Acid alkyl ester, the same applies hereinafter), (meth) acrylic acid hydroxyalkyl ester, (meth) acrylic acid, (meth) acrylonitrile, maleic anhydride and the like. The crosslinking agent is not particularly limited, but it is preferable to use a crosslinking agent having two or more unsaturated groups, for example, a bifunctional difunctional compound such as ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, or neopentyl glycol dimethacrylate. Methacrylate, divinylbenzene, or the like can be preferably used, and is used in an amount of 1 to 50% by weight, preferably 5 to 50% by weight based on all monomers. As fine particles by these suspension polymerization, JP-A-48-49838,
Matsumoto Microsphere M3 manufactured by Matsumoto Yushi-Seiyaku Co., Ltd., manufactured by the formulation and suspension method disclosed in Japanese Patent Application No. 62-307238, or as a commercially available product.
05 (cross-linked polymethyl methacrylate spherical fine particles), manufactured by Sekisui Plastics Co., Ltd .: Techpolymer MB (polymethyl methacrylate fine spherical fine particles: high polymerization type), MB
X (crosslinked polymethyl methacrylate fine spherical fine particles) and the like can be used. The particle diameter of the fine particles used in the present invention is 1 to 50 μm, preferably 1 to 30 μm, and the average particle diameter is 3 to 25 μm, preferably 4 to 15 μm. From the viewpoint of the stability of the matte appearance with respect to the content variation and the uniformity of the matte surface, the particle size is in the range of 1 to 30 μm, preferably 1 to 20 μm, and the particles having a particle size of less than 10 μm are 70% or more in weight distribution,
Preferably, it accounts for 90% or more. If the average particle size of the polymer fine particles exceeds 50μm or the average particle size is 25μ
If it exceeds m, the surface is not fine and uniform and the matte state is not preferable. The compounding amount varies depending on the intended use, but in order to obtain a good antiglare property, 0.5 to 1
It is necessary to mix 5 parts by weight, preferably 2 to 10 parts by weight, per 100 parts by weight of the methyl methacrylate polymer. If the amount is less than 0.5 parts by weight, the matte state of the surface will not be sufficient and the glossiness will increase and the beauty will be lost, while if it exceeds 15 parts, the matte state of the surface will be uniform, but especially Does not have a favorable effect on performance. In addition, when the fine particles are not a crosslinked system and the degree of polymerization is less than 5,000, the fine particles dissolve in the base resin during kneading of the extrusion molding and the matte state is not expressed, or it is extremely insufficient, which is not preferable. .
本発明のアクリル樹脂多層板は、(イ)紫外線吸収剤
あるいは紫外線吸収剤と架橋メタクリル酸エステル重合
体微粒子および/または高重合度メタクリル酸エステル
重合体微粒子を含むアクリルフィルムを前記架橋スチレ
ン系ポリマーの光拡散剤を含むアクリル樹脂板にラミネ
ートする方法、(ロ)フィードブロック及びマルチマニ
ホールドダイを用い、複数の押出機により紫外線吸収剤
あるいは紫外線吸収剤と前記重合体微粒子を含むアクリ
ル樹脂と光拡散剤を含むアクリル樹脂とを押し出す共押
出法によって製造することができ、量産性の点で後者の
(ロ)の方法が好ましい。The acrylic resin multilayer board of the present invention comprises (a) an acrylic film containing an ultraviolet absorber or an ultraviolet absorber and crosslinked methacrylate polymer fine particles and / or high polymerization degree methacrylate polymer fine particles. A method of laminating on an acrylic resin plate containing a light diffusing agent, (b) an ultraviolet absorbent or an acrylic resin containing an ultraviolet absorbent and the polymer fine particles and a light diffusing agent by a plurality of extruders using a feed block and a multi-manifold die. Can be produced by a co-extrusion method of extruding with an acrylic resin containing, and the latter method (b) is preferable in terms of mass productivity.
以下の実施例等における評価からも明らかなように、
本発明のアクリル樹脂多層板は耐候性及び光拡散性の優
れたものであって、光学機器用光拡散板として好適であ
る。As is clear from the evaluation in the following examples,
The acrylic resin multilayer board of the present invention has excellent weather resistance and light diffusion properties, and is suitable as a light diffusion plate for optical equipment.
以下、実施例により本発明をさらに具体的に説明する
が、本発明はこれらに何ら限定されるものではない。Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto.
なお、実施例、比較例における「%」および「部」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板
の性能は以下の方法により測定、評価した。In Examples and Comparative Examples, “%” and “parts” all represent “% by weight” and “parts by weight”, respectively.
The performance of the acrylic resin plates obtained in the examples and comparative examples was measured and evaluated by the following methods.
光線透過率およびヘイズ値 JIS K7105に準拠して積分球式光線透過率測定装置
((株)村上色彩研究所製:RM−15)により測定し、全
光線透過率、ヘイズ値を算出した。Light Transmittance and Haze Value Total light transmittance and haze value were calculated with an integrating sphere light transmittance measurement device (manufactured by Murakami Color Research Laboratory: RM-15) in accordance with JIS K7105.
透過特性 変角光度計((株)村上色彩研究所製:GP−1R)を用
い下記の光学条件により0゜,5゜,10゜,20゜,30゜,40
゜,50゜,60゜,70゜,80゜,90゜の各角度について透過率
を測定した。Transmission characteristics Using a goniophotometer (GP-1R, manufactured by Murakami Color Research Laboratory Co., Ltd.) under the following optical conditions: 0 ゜, 5 ゜, 10 ゜, 20 ゜, 30 ゜, 40
The transmittance was measured at angles of ゜, 50 ゜, 60 ゜, 70 ゜, 80 ゜, and 90 ゜.
光 束: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 表面状態 室内において蛍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。Beam: 12φm / m, Parallelism: ± 0.5 or less, Condensing lens: Effective aperture: 16m / mφ, Receiving viewing angle: 0.86 ゜, Receiving slit diameter: 3m / mφ, Spectral condition: CIE relative visibility to C light Approximate surface state The fluorescent lamp was reflected on the sample surface in the room and visually observed, and the matte state of the sample was represented by the following symbols.
◎…蛍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 surface of the fluorescent lamp is not visible at all and has a beautiful matte surface.
○…蛍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 hardly recognized.
△…蛍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。Δ: The outline of the fluorescent lamp is recognized but unclear, and the surface has irregularities.
×…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。×: The outline of the fluorescent lamp is clearly recognized, and there is almost no unevenness 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 form a uniform mat.
透け状態 15Wの直管蛍光灯(ナショナル製:パルック)前方8cm
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 15W straight tube fluorescent lamp (National: Parook) 8cm in front
The sample was placed in parallel at the position of, and visually observed through the sample at a position 50 cm away from the sample to see if the outline of the light source was visible, and represented by the following symbols.
○…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。 Δ: The outline of the fluorescent lamp is slightly 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.
実施例1 アクリル酸メチル6%を含有する重合度1600のメタク
リル酸メチル共重合体ビーズ100部に対して平均粒子径
8μmの架橋スチレン系ポリマー(積水化成品工業
(株)製:SBX−8,10μm未満の粒子70%)4部を攪拌混
合の後第1の押出機から溶融押出し、別に調整した上記
共重合体100部に対して紫外線吸収剤である2−(5−
メチル−2−ヒドロキシフェニル)ベンゾトリアゾール
0.01部を添加混合した樹脂を第2の押出機から溶融押出
し、押出機とダイスの間に設けられたアダプター内で両
者を合流させT型ダイから押出・冷却して、紫外線吸収
剤を含有した150〜170μm厚の樹脂層を両表面に有した
2mm厚のアクリル樹脂多層板を得た。得られた多層板の
性能を測定・評価し、その結果を第1表に示す。また、
この多層板をサンシャインウェザーメーターで促進暴露
試験を行ない、測色測定によりΔE値を求めた結果を第
2表に示す。Example 1 A crosslinked styrene-based polymer having an average particle size of 8 μm (SBX-8, manufactured by Sekisui Plastics Co., Ltd.) was used for 100 parts of methyl methacrylate copolymer beads containing 6% of methyl acrylate and having a polymerization degree of 1600. After stirring and mixing 4 parts of particles having a particle size of less than 10 μm (70%), the mixture was melt-extruded from the first extruder and 100 parts of the above-prepared copolymer was used as an ultraviolet absorber 2- (5-).
Methyl-2-hydroxyphenyl) benzotriazole
The resin to which 0.01 part was added and mixed was melt-extruded from the second extruder, the two were combined in an adapter provided between the extruder and the die, extruded and cooled from a T-die, and contained an ultraviolet absorber. 150-170μm thick resin layer on both surfaces
An acrylic resin multilayer board having a thickness of 2 mm was obtained. The performance of the obtained multilayer board was measured and evaluated, and the results are shown in Table 1. Also,
The multilayer board was subjected to an accelerated exposure test with a sunshine weather meter, and the ΔE value was determined by colorimetric measurement. Table 2 shows the results.
実施例2 架橋スチレンポリマー5部とする他は実施例1と同様
にして多層板を得、その評価結果を第1表に示す。Example 2 A multilayer board was obtained in the same manner as in Example 1 except that the crosslinked styrene polymer was 5 parts, and the evaluation results are shown in Table 1.
実施例3 架橋スチレン系ポリマーを平均粒子径6μmのもの
(SBX−6,10μm未満の粒子91%)とする他は実施例1
と同様にして多層板を得た。得られた多層板の性能を測
定・評価し、その結果を第1表に示す。Example 3 Example 1 except that the crosslinked styrenic polymer had an average particle size of 6 μm (SBX-6, 91% of particles smaller than 10 μm).
A multilayer board was obtained in the same manner as described above. The performance of the obtained multilayer board was measured and evaluated, and the results are shown in Table 1.
実施例4 紫外線吸収剤を含む層に、更に平均粒子径8μmの架
橋メタクリル酸メチル重合体微粒子(MBX−8)を10部
含有させる他は実施例1と同様にして両面エンボス状の
アクリル樹脂多層板を得た。得られた多層板の評価結果
を実施例1と同様に第1表及び第2表に示す。Example 4 A double-sided embossed acrylic resin multilayer was prepared in the same manner as in Example 1, except that the layer containing an ultraviolet absorber further contained 10 parts of crosslinked methyl methacrylate polymer fine particles (MBX-8) having an average particle diameter of 8 μm. I got a board. The evaluation results of the obtained multilayer board are shown in Tables 1 and 2 in the same manner as in Example 1.
実施例5,6 紫外線吸収剤を0.2部とする他は実施例1又は実施例
4と同様にして多層板を得た。得られた多層板の促進暴
露試験結果を第2表に示す。Examples 5 and 6 A multilayer board was obtained in the same manner as in Example 1 or Example 4 except that the ultraviolet absorber was used in an amount of 0.2 part. Table 2 shows the results of the accelerated exposure test of the obtained multilayer board.
比較例1 実施例1のメタクリル酸メチル共重合体ビーズ100
部、架橋スチレン系ポリマー4部及び紫外線吸収剤0.01
部を攪拌混合の後押出し、単層で2mm厚のアクリル樹脂
板を得た。得られた樹脂板を実施例1と同様に評価し、
その結果を第1表及び第2表に合せて示す。耐候性が実
施例1に比べて劣っていることがわかる。Comparative Example 1 Methyl methacrylate copolymer beads 100 of Example 1
Parts, 4 parts of cross-linked styrene polymer and 0.01 parts of ultraviolet absorber
The portion was stirred and mixed and then extruded to obtain a single-layer acrylic resin plate having a thickness of 2 mm. The obtained resin plate was evaluated in the same manner as in Example 1,
The results are shown in Tables 1 and 2. It can be seen that the weather resistance is inferior to Example 1.
比較例2 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5部添加しヘンシェルミキサー
で混合攪拌の後、比較例1と同様に厚さ2mmのアクリル
樹脂板を得た。こ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
くない時あるいは多い時には板に流れ模様などが発生し
やすい傾向が見られた。Comparative Example 2 An average particle size of 6 μm having a particle size distribution of 1.0 to 20 μm with respect to 100 parts of a methyl methacrylate polymer containing 5% of methyl acrylate (particles smaller than 10 μm are 90% by weight distribution).
5 parts of polystyrene fine particles were added and mixed and stirred with a Henschel mixer. As in Comparative Example 1, an acrylic resin plate having a thickness of 2 mm was obtained. The performance evaluation results are shown in Table 1. As a result, a molded article having a high diffusion and a high light transmittance could not be obtained, and when the addition amount was small or large, a flow pattern or the like tended to be generated on the plate. Was.
参考例1〜5 下記組成及び粒径の架橋スチレン系ポリマー微粒子を
各種添加量で添加する以外は比較例1と同様にして押出
成形し厚さ2mmのアクリル樹脂板を得た。これらの成形
板の性能評価の結果を第3表に示す。Reference Examples 1 to 5 Extrusion molding was performed in the same manner as in Comparative Example 1 except that crosslinked styrene-based polymer fine particles having the following composition and particle diameter were added in various amounts to obtain an acrylic resin plate having a thickness of 2 mm. Table 3 shows the results of the performance evaluation of these molded plates.
参考例6〜10 下記組成及び粒径の架橋メタクリル酸エステル重合体
微粒子または高重合度メタクリル酸エステル重合体微粒
子を各種添加量で添加する以外は比較例1と同様にして
押出成形し、厚さ2mmのアクリル樹脂板を得た。これら
の成形板の性能評価の結果を第4表に示す。 Reference Examples 6 to 10 Extrusion molding was performed in the same manner as in Comparative Example 1 except that crosslinked methacrylate polymer fine particles or high polymerization degree methacrylate polymer fine particles having the following composition and particle size were added in various amounts, and the thickness was extruded. A 2 mm acrylic resin plate was obtained. Table 4 shows the results of the performance evaluation of these molded plates.
〔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重量部に対して平均粒子径1〜30μmの架橋
スチレン系ポリマーを1〜20重量部含有する樹脂層
(A)及びメタクリル酸メチル系重合体100重量部に対
して紫外線吸収剤を0.005〜2重量部含有する樹脂層
(B)からなり、樹脂層(A)の少なくとも一つの表面
に樹脂(B)を設けたアクリル樹脂多層板であるから、
量産性に適すると共に耐候性及び光拡散性に優れている
ので、大量に安価に供給できると共に種々の光拡散性を
有する照明カバー、ディスプレイ、グレージング等とし
て有用であり、特に近年普及がめざましいOA機器、液晶
ディスプレイ、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。また本発明のアクリル樹脂多層
板の樹脂層(B)に更に架橋メタクリル酸エステル重合
体微粒子および/または高重合度メタクリル酸エステル
重合体微粒子を含有させた多層板であるから、簡便に種
々の光拡散性、艶消し性を調節できるので、上記用途に
好ましく用いることができる。 [Effect of the Invention] As described above, the present invention provides a resin layer (A) containing 1 to 20 parts by weight of a crosslinked styrene-based polymer having an average particle diameter of 1 to 30 µm based on 100 parts by weight of a methyl methacrylate-based polymer. And a resin layer (B) containing 0.005 to 2 parts by weight of an ultraviolet absorber with respect to 100 parts by weight of a methyl methacrylate polymer, and the resin (B) is provided on at least one surface of the resin layer (A). Because it is an acrylic resin multilayer board,
It is suitable for mass production and has excellent weather resistance and light diffusivity, so it can be supplied in large quantities at low cost and is useful as a lighting cover, display, glazing, etc. with various light diffusivities. It is suitable as a light diffusion plate for optical equipment such as a liquid crystal display and a backlight panel. Since the resin layer (B) of the acrylic resin multilayer board of the present invention further contains crosslinked methacrylic acid ester polymer fine particles and / or high polymerization degree methacrylic acid ester polymer fine particles, various types of light can be easily prepared. Since the diffusivity and the matting property can be adjusted, it can be preferably used for the above-mentioned applications.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 萩原 正明 新潟県北蒲原郡中条町倉敷町2番28号 株式会社クラレ内 審査官 芦原 ゆりか (56)参考文献 特開 昭57−8154(JP,A) 特公 昭39−10515(JP,B1) (58)調査した分野(Int.Cl.6,DB名) B32B 1/00 - 35/00 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masaaki Hagiwara 2-28 Kurashiki-cho, Nakajo-cho, Kitakanbara-gun, Niigata Examiner at Kuraray Co., Ltd. Yurika Ashihara (56) References JP-A-57-8154 (JP, A) JP-B-39-10515 (JP, B1) (58) Fields investigated (Int. Cl. 6 , DB name) B32B 1/00-35/00
Claims (3)
対して平均粒子径1〜30μmの架橋スチレン系ポリマー
を1〜20重量部含有する樹脂層(A)及びメタクリル酸
メチル系重合体100重量部に対して紫外線吸収剤を0.005
〜2重量部含有する樹脂層(B)からなり、樹脂層
(A)の少なくとも一つの表面に樹脂層(B)を設ける
ことを特徴とするアクリル樹脂多層板。1. A resin layer (A) containing 1 to 20 parts by weight of a crosslinked styrene-based polymer having an average particle diameter of 1 to 30 μm based on 100 parts by weight of a methyl methacrylate-based polymer and 100 parts by weight of a methyl methacrylate-based polymer 0.005 UV absorber per part
An acrylic resin multilayer board comprising a resin layer (B) containing at least one resin layer (B) on at least one surface of the resin layer (A).
架橋メタクリル酸エステル重合体微粒子および/または
高重合度メタクリル酸エステル重合体微粒子を0.5〜15
重量部含有することを特徴とする請求項1記載の多層
板。2. The resin layer (B) further comprises a crosslinked methacrylate polymer fine particle having a particle diameter of 1 to 50 μm and / or a high polymerization degree methacrylate polymer fine particle of 0.5 to 15 μm.
The multilayer board according to claim 1, wherein the multilayer board is contained in parts by weight.
機器用光拡散板。3. A light diffusing plate for an optical device comprising the multilayer plate according to claim 1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2121906A JP2994687B2 (en) | 1990-05-11 | 1990-05-11 | Acrylic resin multilayer board |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2121906A JP2994687B2 (en) | 1990-05-11 | 1990-05-11 | Acrylic resin multilayer board |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0418346A JPH0418346A (en) | 1992-01-22 |
JP2994687B2 true JP2994687B2 (en) | 1999-12-27 |
Family
ID=14822838
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2121906A Expired - Fee Related JP2994687B2 (en) | 1990-05-11 | 1990-05-11 | Acrylic resin multilayer board |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2994687B2 (en) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3516976B2 (en) * | 1994-02-04 | 2004-04-05 | 株式会社きもと | Surface light source |
JP3989983B2 (en) * | 1995-09-18 | 2007-10-10 | 旭化成ケミカルズ株式会社 | Color tone retention sheet for light source protection cover |
TW454028B (en) | 1997-10-02 | 2001-09-11 | Sumitomo Chemical Co | Laminated extruded resin sheet |
KR100818176B1 (en) * | 2002-12-30 | 2008-03-31 | 주식회사 코오롱 | Light diffusable acrylic resin composite |
DE10320318A1 (en) | 2003-05-06 | 2004-12-02 | Röhm GmbH & Co. KG | Process for the preparation of light-scattering molded parts with excellent optical properties |
JP2006106185A (en) * | 2004-10-01 | 2006-04-20 | Kuraray Co Ltd | Light diffusion multilayer plate |
WO2006057355A1 (en) * | 2004-11-26 | 2006-06-01 | Denki Kagaku Kogyo Kabushiki Kaisha | Multilayer sheet and light diffusion sheet |
TWI434073B (en) * | 2006-01-06 | 2014-04-11 | Sumitomo Chemical Co | Multilayered light diffuser plate |
DE102006011436A1 (en) | 2006-03-07 | 2007-09-13 | Sibylle Wagner-Quinte | Plastic composite |
JP2009211055A (en) * | 2008-02-06 | 2009-09-17 | Sumitomo Chemical Co Ltd | Light-diffusing layered resin film, method of forming the same, antiglare film, antiglare polarizing plate, and image display |
JP4832496B2 (en) * | 2008-11-18 | 2011-12-07 | タキロン株式会社 | Backlight unit |
DE102012216081A1 (en) | 2012-09-11 | 2013-03-14 | Evonik Industries Ag | Manufacturing light diffusing molded part useful e.g. in a light-emitting diodes-lighting control system, comprises injecting a molding composition comprising a polymethyl methacrylate matrix and spherical plastic particles, into a tool |
-
1990
- 1990-05-11 JP JP2121906A patent/JP2994687B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JPH0418346A (en) | 1992-01-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5607764A (en) | Optical diffuser | |
JP2994687B2 (en) | Acrylic resin multilayer board | |
EP1703305A2 (en) | Anisotropic scattering sheet | |
JP4695071B2 (en) | Light control sheet and surface light source using the same | |
WO2016104055A1 (en) | Transparent film, transparent screen provided with same, and image projection device provided with same | |
JP3040705B2 (en) | Resin fine particles for light diffusion sheet and light diffusion sheet | |
EP1950605A1 (en) | Light diffusion plate for liquid crystal display | |
JP3684587B2 (en) | Light-diffusing methacrylic resin plate | |
EP1995627A1 (en) | Voided optical diffuser film with beads on a surface | |
WO2003072645A2 (en) | Transparent thermoplastic composition comprising hollow glass beads | |
JP3352832B2 (en) | Light diffusion plate | |
JPWO2009051256A1 (en) | Light diffusing agent | |
JPH1160966A (en) | Light diffusing resin composition | |
JP2000169722A (en) | Light-diffusing thermoplastic resin composition and its molded article | |
JPH1044285A (en) | Light diffusible resin laminated plate for illumination equipment cover and the illumination equipment cover | |
JP3374316B2 (en) | Light diffusing laminated resin plate | |
JPH05179054A (en) | Light-diffusing agent and resin composition containing light-diffusing agent | |
JPH0632973A (en) | Light-scattering polycarbonate resin composition | |
JP2006243084A (en) | Light diffusion plate | |
JP5341053B2 (en) | Light diffusing laminated resin plate and manufacturing method thereof | |
JPH1067829A (en) | Microparticle suitable for light-diffusing plastic | |
JP4970451B2 (en) | Light diffusion resin composition and light diffusion plate | |
KR100804062B1 (en) | Light diffusion film for LCD back-light unit | |
JP2002249525A (en) | Resin particle for preparing light diffusion sheet, resin composition, and light diffusion sheet | |
JPH11227115A (en) | Resin laminate with ground glass tone surface |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20071022 Year of fee payment: 8 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081022 Year of fee payment: 9 |
|
LAPS | Cancellation because of no payment of annual fees |