JP4743493B2 - Shock absorbing resin composition for liquid crystal display, shock absorbing material for liquid crystal display using the same, optical filter for liquid crystal display using the same, and liquid crystal display - Google Patents

Description

  The present invention relates to a shock absorbing resin composition for liquid crystal displays useful for preventing cracking of liquid crystal display panels and relaxing stress and shock, a shock absorbing material for liquid crystal displays using the same, an optical filter for liquid crystal displays using the same, and It relates to a liquid crystal display.

  The current large-sized liquid crystal display generally has an anti-glare (AG) treatment on the front polarizing plate surface of the liquid crystal panel to reduce reflection. In the case of this configuration, no special measures are taken with respect to shock absorption, and the entire panel and the structure as a set are provided with impact resistance. The problem with this configuration is that the image looks blurred due to AG processing, the panel is bent when touching the surface, the image is distorted, and it is difficult to remove dirt due to AG processing, and it is easy to get scratched. As the size of the panel increases, the impact resistance of the panel may decrease, and a problem may occur in the impact resistance.

  In view of this, it is conceivable that a front plate subjected to anti-reflection (AR) processing is placed in front of the liquid crystal panel to eliminate the disadvantages derived from AG processing. However, when the space between the front plate and the liquid crystal panel is air, the transmittance may be lowered, the image quality may be lowered due to double projection, and it has been proposed to fill the space with a resin or the like (Patent Document 1, Patent Document 1). 2, 3, 4).

JP 05-011239 A Japanese Patent Laid-Open No. 03-204616 Japanese Patent Laid-Open No. 06-59253 JP 2004-125868 A

However, the oil used in Patent Document 1 is difficult to seal to prevent leakage, may damage the material used in the liquid crystal panel, and the oil leaks when the front plate is cracked. There is a problem. Further, the unsaturated polyester of Patent Document 2 tends to be colored yellow, and application to a display device is not desirable. The silicone of Patent Document 3 has a low adhesive force and requires a separate pressure-sensitive adhesive for fixing, and the process becomes complicated. Further, since the adhesive force with the pressure-sensitive adhesive is not so large, it peels off when an impact is applied, and bubbles are generated. There is a problem of entering. The polymer of the acrylic monomer of Patent Document 4 has a low adhesive force and does not require a separate adhesive for small devices, but requires a separate adhesive to support the front plate of a large display, and the process is complicated. become. In addition, since the raw material is composed only of a monomer, the viscosity is low, and the curing shrinkage is large, so that it is difficult to uniformly produce a film having a large area.
Therefore, the present invention provides a shock-absorbing resin composition for a liquid crystal display, which is transparent, has an appropriate adhesive strength and shock absorption necessary for the protection of a liquid crystal display, and does not attack the constituent materials of the liquid crystal panel. It is an object of the present invention to provide a shock absorber for liquid crystal display used, an optical filter for liquid crystal display using the same, and a liquid crystal display.
In addition, the front panel is attached to the front surface of the liquid crystal panel via the shock absorbing resin composition for liquid crystal display and the shock absorbing material for liquid crystal display using the same. An object is to provide a liquid crystal display that is not disturbed.

The present invention relates to the following .
1 . 15 to 60 parts by weight of copolymer 39 to 84 parts by weight of monomer having one acryloyl group 0.5 to 10 parts by weight of monomer having two or more acryloyl groups and 0.3 to 3 parts by weight of a photopolymerization initiator,
The above copolymer is an alkyl acrylate having 4 to 18 carbon atoms in an alkyl group (hereinafter referred to as AA monomer) of 50 to 87% by weight and the following general formula (I)

（ただし、式中、ｍは２、３又は４、ｎは１〜１０の整数をしめす。）
で表されるヒドロキシル基含有アクリレート（以下、ＨＡモノマーという。）１３〜５０重量％を重合させて得られるものであり、
上記のアクリロイル基を１個有するモノマーとして、ＡＡモノマーを５０〜８７重量％及びＨＡモノマーを１３〜５０重量％の割合になるように使用し、
上記コポリマー中のＨＡモノマーの割合（Ｐ重量％）と、アクリロイル基を１個有するモノマーにおけるＨＡモノマーの割合（Ｍ重量％）との間に、

(In the formula, m represents 2, 3 or 4, and n represents an integer of 1 to 10.)
It is obtained by polymerizing 13 to 50% by weight of a hydroxyl group-containing acrylate represented by the following (hereinafter referred to as HA monomer),
As a monomer having one acryloyl group as described above, an AA monomer is used in a proportion of 50 to 87% by weight and an HA monomer in a proportion of 13 to 50% by weight,
Between the proportion of HA monomer in the copolymer (P wt%) and the proportion of HA monomer in the monomer having one acryloyl group (M wt%),

の関係があるように配合されてなる液晶ディスプレイ向け衝撃吸収用樹脂組成物。
２． 光重合開始剤がα−ヒドロキシアルキルフェノン系化合物あるいはアシルフォスフィンオキサイド系化合物あるいはオリゴ（２−ヒドロキシ−２−メチル−１−（４−（１−メチルビニル）フェニル）プロパノン）である項１記載の液晶ディスプレイ向け衝撃吸収用樹脂組成物。
３． ＡＡモノマーが２−エチルヘキシルアクリレートまたはイソオクチルアクリレートまたはｎ−オクチルアクリレートであり、ＨＡモノマーが２−ヒドロキシエチルアクリレートまたは１−ヒドロキシエチルアクリレートまたは２−ヒドロキシプロピルアクリレートまたは３−ヒドロキシプロピルアクリレートまたは１−ヒドロキシプロピルアクリレートまたは４−ヒドロキシブチルアクリレートまたは３−ヒドロキシブチルアクリレートまたは２−ヒドロキシブチルアクリレートまたは１−ヒドロキシブチルアクリレートである項１又は２記載の液晶ディスプレイ向け衝撃吸収用樹脂組成物。
４． コポリマーの重量平均分子量が１００，０００〜６００，０００である項１〜３のいずれかに記載の液晶ディスプレイ向け衝撃吸収用樹脂組成物。
５． コポリマー ４０〜６０重量部、
アクリロイル基を１個有するモノマー ３９〜５９重量部、
アクリロイル基を２個以上有するモノマー １〜５重量部、
及び
光重合開始剤 ０．５〜２．０重量部
を含有する項１〜４のいずれかに記載の液晶ディスプレイ向け衝撃吸収用樹脂組成物。
６． 項１〜５のいずれかに記載の液晶ディスプレイ向け衝撃吸収用樹脂組成物を硬化反応させてなる液晶ディスプレイ用衝撃吸収材。
７． 形状がシート状又はフィルム状である項６記載の液晶ディスプレイ用衝撃吸収材。
８． 項１〜５のいずれかに記載の液晶ディスプレイ向け衝撃吸収用樹脂組成物又は項６若しくは７に記載の液晶ディスプレイ用衝撃吸収材を使用して得られる液晶ディスプレイパネル用衝撃吸収層を備えた液晶ディスプレイ用光学フィルタ。
９． 項１〜５のいずれかに記載の液晶ディスプレイ向け衝撃吸収用樹脂組成物又は項６若しくは７に記載の液晶ディスプレイ用衝撃吸収材を使用して得られる液晶ディスプレイ。

Liquid crystal display for shock absorbing resin composition ing been formulated to have a relationship.
2 . Claim 1, wherein the photopolymerization initiator α- hydroxyalkyl phenone compound or an acylphosphine oxide-based compound or oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) Shock absorbing resin composition for liquid crystal displays.
3 . AA monomer is 2-ethylhexyl acrylate or isooctyl acrylate or n-octyl acrylate, and HA monomer is 2-hydroxyethyl acrylate or 1-hydroxyethyl acrylate or 2-hydroxypropyl acrylate or 3-hydroxypropyl acrylate or 1-hydroxypropyl Item 3. The resin composition for impact absorption for a liquid crystal display according to Item 1 or 2, which is acrylate, 4-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 2-hydroxybutyl acrylate, or 1-hydroxybutyl acrylate.
4 . Item 4. The resin composition for impact absorption for liquid crystal displays according to any one of Items 1 to 3 , wherein the copolymer has a weight average molecular weight of 100,000 to 600,000 .
5 . Copolymer over 40 to 60 parts by weight,
39 to 59 parts by weight of a monomer having one acryloyl group,
1 to 5 parts by weight of a monomer having two or more acryloyl groups,
Item 5. The impact-absorbing resin composition for liquid crystal displays according to any one of Items 1 to 4 , comprising 0.5 to 2.0 parts by weight of a photopolymerization initiator.
6 . Item 6. A shock absorber for liquid crystal display, which is obtained by curing reaction of the resin composition for shock absorption for liquid crystal display according to any one of items 1 to 5 .
7 . Item 7. The shock absorbing material for liquid crystal display according to Item 6 , wherein the shape is a sheet or film.
8 . Item 6. A liquid crystal comprising a shock absorbing layer for a liquid crystal display panel obtained by using the shock absorbing resin composition for a liquid crystal display according to any one of Items 1 to 5 or the shock absorbing material for a liquid crystal display according to Item 6 or 7. Optical filter for display.
9 . Item 8. A liquid crystal display obtained by using the shock absorbing resin composition for liquid crystal display according to any one of Items 1 to 5 or the shock absorbing material for liquid crystal display according to Item 6 or 7 .

The impact-absorbing resin composition for liquid crystal displays according to the present invention has excellent impact-absorbing properties and excellent transparency by causing a curing reaction thereof.
In addition, the resin composition for shock absorption for liquid crystal displays according to the present invention can increase the solubility of the polymer by making the composition of the polymer and the monomer substantially the same, and is transparent even when a high molecular weight polymer is used. Resin compositions and cured products can be produced. Furthermore, since it is diluted with a monomer, it can be molded without a solvent, and a thick film or sheet without bubbles can be produced.
In addition, since the high molecular weight polymer is contained at a relatively high concentration, the shock absorption is excellent even at a thin film thickness. Moreover, it has hardness and can suppress a decrease in scratch resistance. Due to this hardness, the composition is hardly deformed, and more excellent shock absorption can be exhibited with a thick film thickness. Furthermore, since it has high cohesive force and is stretchable, it is less likely to crack or streak when the film is bent or wound around a roll.
Further, the impact-absorbing resin composition for liquid crystal displays according to the present invention generally does not attack materials used for liquid crystal displays.
The shock absorbing material for liquid crystal display according to the present invention can be obtained by curing reaction of the shock absorbing resin composition for liquid crystal display, but the shape can be easily made into a sheet. In addition, since the impact absorbing material for liquid crystal display is given tackiness, it can be bonded to glass, other base materials and the like without using an adhesive or an adhesive.
The optical filter for liquid crystal display and the liquid crystal display provided with the shock absorbing layer obtained by using the above-mentioned shock absorbing resin composition for liquid crystal display or the shock absorbing material for liquid crystal display are the same as the shock absorbing material for liquid crystal display described above. Inherits the effects.

A acrylic acid derivative polymer are those obtained by polymerizing a monomer having one in the molecule a polymerizable unsaturated bond in the acrylic acid derivative monomer having two or more polymerizable unsaturated bonds in the molecule May be used in combination. The weight average molecular weight (measured using a standard polystyrene calibration curve by gel permeation chromatography) is preferably 100,000 to 700,000, more preferably 150,000 to 400,000, 200, 000-350,000 is more preferable.
The acrylic acid derivative polymer may be a polymer obtained by polymerization using a monomer other than the acrylic acid derivative.

Examples of the acrylic acid derivatives include acrylic acid or methacrylic acid, and derivatives thereof. Specifically, monomers having one polymerizable unsaturated bond in the molecule include methyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, 2-ethylhexyl methacrylate, isononyl methacrylate, n-octyl methacrylate, and lauryl methacrylate. , Alkyl methacrylates such as stearyl methacrylate, methyl acrylate, n-butyl acrylate, i-butyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, n-octyl acrylate and other alkyl acrylates, benzyl methacrylate and other aralkyl methacrylates, benzyl acrylate and the like Alkoxyalkyl methacrylates such as aralkyl acrylate and butoxyethyl methacrylate, butoxyethyl acrylate Alkoxyalkyl acrylate such as N, N-dimethylaminoethyl methacrylate, aminoalkyl methacrylate such as N, N-dimethylaminoethyl acrylate, aminoalkyl acrylate such as N, N-dimethylaminoethyl acrylate, methacrylic acid ester of diethylene glycol ethyl ether, methacrylic acid of triethylene glycol butyl ether esters, methacrylic acid esters of polyalkylene glycol alkyl ethers such as methacrylic acid esters of dipropylene glycol methyl ether, acrylic acid esters of diethylene glycol ethyl ether, acrylic acid esters of triethylene glycol butyl ether, dipropylene glycol acrylate methyl ether Acrylic acid ester of polyalkylene glycol alkyl ether such as Methacrylic acid esters of polyalkylene glycol aryl ethers, such as methacrylic acid esters of hexaethylene glycol phenyl-ether, acrylic acid esters of polyalkylene glycol aryl ethers such as acrylic acid ester of hexaethylene glycol phenyl-ether, cyclohexyl methacrylate, cyclohexyl acrylate, Methacrylic acid ester or acrylic acid ester having an alicyclic group such as dicyclopentanyl methacrylate, dicyclopentanyl acrylate, isobornyl methacrylate, methoxylated cyclodecatriene methacrylate, isobornyl acrylate, methoxylated cyclodecatriene acrylate , Fluorinated alkyl methacrylates such as heptadecafluorodecyl methacrylate, heptadecaf Fluorinated alkyl acrylates such as lorodecyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, glycerol methacrylate, glycerol Methacrylic acid ester or acrylic acid ester having a hydroxyl group such as acrylate, methacrylic acid ester or acrylic acid ester having a carboxyl group such as acrylic acid or methacrylic acid, methacrylic acid ester or acrylic acid having a glycidyl group such as glycidyl methacrylate or glycidyl acrylate Examples include esters and acrylamides. These can be used alone or in combination of two or more.

  These monomers having one polymerizable unsaturated bond in the molecule can be used alone or in combination of two or more.

A monomer having two or more polymerizable unsaturated bonds in the molecule can be used together with the monomer having one polymerizable unsaturated bond in the molecule. Such monomers include bisphenol A dimethacrylate 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol. Dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, tris (methacryloxyethyl) isocyanurate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pen Tame Acrylate, bisphenol A diacrylate, 1,4-butanediol di Accession relays preparative, 1,3-butylene glycol diacrylate, diethylene glycol diacrylate, glycerol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol di Acrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tris (acryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate Etc.

  Examples of the monomer having two or more polymerizable unsaturated bonds in the molecule further include the general formula (a)

（ただし、式中、Ｒはエチレン基又はプロピレン基を示し、ｍ及びｎはそれぞれ独立に、１〜２０の整数を示す）で示されるビスフェノールＡのアルキレンオキシド付加物のジアクリレート、一般式（ｂ）

(Wherein, R represents an ethylene group or a propylene group, and m and n each independently represents an integer of 1 to 20), a diacrylate of an alkylene oxide adduct of bisphenol A, represented by the general formula (b )

（ただし、式中、ｍ及びｎはそれぞれ独立に、１〜１０の整数を示す）で示されるビスフェノールＡのエピクロルヒドリン変性物とアクリル酸の付加エステル化物、ビスフェノールＡジメタクリレート、１，４−ブタンジオールジアクリレート、１，３−ブチレングリコールジアクリレート、ジエチレングリコールジメタクリレート、グリセロールジメタクリレート、ネオペンチルグリコールジアクリレート、一般式（ｃ）

(Wherein m and n each independently represents an integer of 1 to 10), an epichlorohydrin modified product of bisphenol A and an addition esterified product of acrylic acid, bisphenol A dimethacrylate, 1,4-butanediol Diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol diacrylate, general formula (c)

（ただし、式中、Ｒはエチレン基又はプロピレン基を示し、ｍ及びｎはそれぞれ独立に、１〜２０の整数を示す）で示されるリン酸のアルキレンオキシド付加物のジアクリレート、一般式（ｄ）

(Wherein, R represents an ethylene group or a propylene group, and m and n each independently represents an integer of 1 to 20) diacrylate of an alkylene oxide adduct of phosphoric acid represented by the general formula (d )

（ただし、式中、ｍ及びｎはそれぞれ独立に、１〜１０の整数を示す）で示されるフタル酸のエピクロリン変性物とアクリル酸の付加エステル化物、ポリエチレングリコールのジアクリレート、ポリプロピレングリコールのジメタクリレート、テトラエチレングリコールジアクリレート、一般式（ｅ）

(Wherein m and n each independently represents an integer of 1 to 10), an epichlorine modified product of phthalic acid and an addition ester of acrylic acid, diacrylate of polyethylene glycol, dimethacrylate of polypropylene glycol , Tetraethylene glycol diacrylate, general formula (e)

（ただし、式中、ｍ及びｎはそれぞれ独立に、１〜２０の整数を示す）で示される１，６−ヘキサンジオールのエピクロリン変性物とアクリル酸の付加エステル化物（アクリル基を一分子中に２個有するもの）、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、一般式（ｆ）

(Wherein in, m and n are each independently 1 to 20 represent an integer of) Epikurorin modified product of 1,6-hexanediol represented by the additional ester of acrylic acid (A chestnut Le based on one molecule 2), trimethylolpropane triacrylate, pentaerythritol triacrylate, general formula (f)

（ただし、式中、Ｒはエチレン基又はプロピレン基を示し、３個のｍはそれぞれ独立に、１〜２０の整数を示す）で示されるリン酸のアルキンオキシド付加物のトリアクリレート、一般式（ｇ）

(Wherein R represents an ethylene group or a propylene group, and three m's each independently represents an integer of 1 to 20), a triacrylate of an alkyne oxide adduct of phosphoric acid represented by the general formula ( g)

（ただし、式中、Ｒはエチレン基又はプロピレン基を示し、ｍ、ｍ′及びｍ″はそれぞれ独立に、１〜２０の整数を示す）で示されるトリメチロールプロパンのアルキレンオキシド付加物のトリアクリレート、トリス（メタクリロキシエチル）イソシアヌレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールテトラアクリレート、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールペンタアクリレートなどが挙げられる。これらのモノマーは、単独で又は２種以上を組み合わせて用いることができる。

(Wherein R represents an ethylene group or a propylene group, and m, m ′, and m ″ each independently represents an integer of 1 to 20), a triacrylate of an alkylene oxide adduct of trimethylolpropane. , Tris (methacryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, etc. These monomers may be used alone or in combination of two or more. Can be used.

In addition to the above acrylic acid derivatives, monomers having one polymerizable unsaturated bond in the molecule such as acrylonitrile, styrene, vinyl acetate, ethylene, propylene can be used. In addition, monomers other than the acrylic acid derivatives described above and having two or more polymerizable unsaturated bonds in the molecule (such as divinylbenzene) can also be used.
In the above, in order to obtain the effect, of the total amount of the monomers used, the amount of the monomer other than acrylic acid derivative is preferably 90 wt% or less, more preferably 50 wt% or less, in particular, 20 wt% The following is preferred.
The amount of the monomer having two or more polymerizable unsaturated bonds in the molecule is preferably 10% by weight or less, more preferably 5% by weight or less, based on the total amount of the monomers used. If it is used in an amount of 10% by weight or more, the impact absorbing layer tends to tear due to impact.

  15 to 89.9 parts by weight of acrylic acid derivative is used for 10 to 80 parts by weight of the acrylic acid derivative polymer, and the polymerization initiator is used in an amount of 0.1 to 5 parts by weight and 100 parts by weight as a whole. It is preferred that The blend is used so that 15 to 60 parts by weight of acrylic acid derivative polymer, 35 to 84.9 parts by weight of acrylic acid derivative, 0.1 to 5 parts by weight of the polymerization initiator, and 100 parts by weight as a whole. It is more preferable.

  As a polymerization method of the above-mentioned monomer, known polymerization methods such as solution polymerization, emulsion polymerization and bulk polymerization can be used. These methods can also be used for the synthesis of the acrylic acid derivative polymer.

As the polymerization initiator, a photopolymerization initiator can be used, and it can be selected from known materials such as benzophenone, anthraquinone, benzoin, sulfonium salt, diazonium salt, onium salt and the like.
More specifically, as a photopolymerization initiator, benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy -4'-dimethylaminobenzophenone, α-hydroxyisobutylphenone, 2-ethylanthraquinone, t-butylanthraquinone, 1,4-dimethylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methyl Anthraquinone, 1,2-benzoanthraquinone, 2-phenylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy- , 2-diphenylethane-1-one, aromatic ketone compounds such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzoin compounds such as benzoin, methylbenzoin, ethylbenzoin, benzoin methyl ether, benzoin Benzoin ether compounds such as ethyl ether, benzoin isobutyl ether, benzoin phenyl ether, benzyl, 2,2-diethoxyacetophenone, benzyldimethyl ketal, β- (acridin-9-yl) acrylic acid diester compound, 9-phenylacridine, Acridine compounds such as 9-pyridylacridine, 1,7-diacridinoheptane, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di ( m-methoxy Phenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p- Methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) 5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole Dimer, 2,4,5-triarylimidazole dimer such as 2- (p-methylmercaptophenyl) -4,5-diphenylimidazole dimer, 2-benzyl-2-dimethylamino-1- ( 4 molar Horinofeniru) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propane, bis (2,4 6- trimethyl benzoyl) - phenyl phosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), and the like. In particular, those that do not color the resin composition include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy)- Α-hydroxyalkylphenone compounds such as phenyl] -2-hydroxy-2-methyl-1-propan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6 -Acylphosphine oxide compounds such as -dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, oligo (2-hydroxy-2-methyl- 1- (4- (1-methylvinyl) phenyl) propanone) and A combination of these is preferred. In order to produce particularly thick sheets, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine A photopolymerization initiator containing an acyl phosphine oxide compound such as oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide is preferable. In order to reduce the odor of the sheet, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) is preferable. These photopolymerization initiators may be used in combination.

  A thermal polymerization initiator may be used as the polymerization initiator. The thermal polymerization initiator is an initiator that generates radicals by heat, and specifically includes benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl. Peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, t-butylperoxyneodecanoate, t-butylperoxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl Examples thereof include organic peroxides such as peroxide and diacetyl peroxide. In addition, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonyl), 2,2′-azobis ( 2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate), 4,4′- Azos such as azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) propane] System compounds.

The resin material used in the present invention preferably has a glass transition temperature (Tg) of 0 ° C. or lower. When the glass transition temperature exceeds 0 ° C., the impact absorbing layer becomes hard and is easily broken by impact. Tg is more preferably -20 to -60 ° C.
For the purpose of increasing the adhesiveness, it is preferable to add a polar group to the polymer molecule used as the resin material used in the present invention. There are polar groups such as hydroxyl group, carboxyl group, cyano group, glycidyl group, etc., as polar groups that increase the adhesion to glass. These groups are introduced by copolymerizing monomers having such groups. can do.
The shock absorbing resin composition for liquid crystal display and the shock absorbing material for liquid crystal display using the same in the present invention are also used for the display device, and the shock absorbing resin composition for liquid crystal display and the same are used. The visible light transmittance of the impact absorbing material for liquid crystal display is preferably 80% or more.

As a resin composition for shock absorption for liquid crystal display in the present invention,
15 to 60 parts by weight of copolymer 39 to 84 parts by weight of monomer having one acryloyl group 0.5 to 10 parts by weight of monomer having two or more acryloyl groups and 0.3 to 3 parts by weight of a photopolymerization initiator,
The above copolymer is an alkyl acrylate having 4 to 18 carbon atoms in an alkyl group (hereinafter referred to as AA monomer) of 50 to 87% by weight and the following general formula (I)

（ただし、式中、ｍは２、３又は４、ｎは１〜１０の整数をしめす。）
で表されるヒドロキシル基含有アクリレート（以下、ＨＡモノマーという。）１３〜５０重量％を重合させて得られるものであり、
上記のアクリロイル基を１個有するモノマーとして、ＡＡモノマーを５０〜８７重量％及びＨＡモノマーを１３〜５０重量％の割合になるように使用し、
上記コポリマー中のＨＡモノマーの割合（Ｐ重量％）と、アクリロイル基を１個有するモノマーにおけるＨＡモノマーの割合（Ｍ重量％）との間に、

(In the formula, m represents 2, 3 or 4, and n represents an integer of 1 to 10.)
It is obtained by polymerizing 13 to 50% by weight of a hydroxyl group-containing acrylate represented by the following (hereinafter referred to as HA monomer),
As a monomer having one acryloyl group as described above, an AA monomer is used in a proportion of 50 to 87% by weight and an HA monomer in a proportion of 13 to 50% by weight,
Between the proportion of HA monomer in the copolymer (P wt%) and the proportion of HA monomer in the monomer having one acryloyl group (M wt%),

の関係があるように配合されてなるものが、特に好ましい。
ここで、光重合開始剤としては、前記したものが使用できる。

Those blended so as to have the following relationship are particularly preferred.
Here, as the photopolymerization initiator, those described above can be used.

  Examples of the AA monomer include n-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-octyl acrylate, isooctyl acrylate, 2 ethylhexyl acrylate, dodecyl acrylate, stearyl acrylate, and the like. Isooctyl acrylate, 2 ethylhexyl acrylate, and n-octyl acrylate are preferable, and ethylhexyl acrylate is particularly preferable. These acrylates may be used in combination of two or more.

  Examples of the HA monomer include 2-hydroxyethyl acrylate, 1-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 1-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 2 -Hydroxyl-containing acrylates such as hydroxybutyl acrylate and 1-hydroxybutyl acrylate, polyethylene glycol monoacrylates such as diethylene glycol and triethylene glycol, polypropylene glycol monoacrylates such as dipropylene glycol and tripropylene glycol, dibutylene glycol and tributylene glycol Of polybutylene glycol monoacrylate and the like. Ethyl acrylate, 1-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 1-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 2-hydroxybutyl acrylate, 1-hydroxybutyl acrylate Is preferred, and 2-hydroxyethyl acrylate is particularly preferred. These acrylates may be used in combination of two or more.

Copolymer obtained by polymerizing AA monomer with HA monomer definitive to the present invention is a weight average molecular weight (measured using a calibration curve of standard polystyrene by gel permeation chromatography, hereinafter the same) is 100,000～600 , 000 is preferable, 150,000 to 400,000 is more preferable, and 200,000 to 350,000 is more preferable.
As a method for synthesizing the copolymer, known polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization and bulk polymerization can be used, but solution polymerization or bulk polymerization is preferable. As the polymerization initiator, a compound capable of generating radicals by heat can be used. Specifically, benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n- Propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, t-butylperoxyneodecanoate, t-butylperoxybivalate, (3,5,5-trimethylhexanoyl) peroxide, di Organic peroxides such as propionyl peroxide, diacetyl peroxide, didodecyl peroxide, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1, 1'-azobis (cyclohexane-1-carbonyl), 2,2'-azobis (2 4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate), 4,4′-azobis ( Azo compounds such as 4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) propane] Is mentioned.

  In the present invention, monomers having two or more acryloyl groups include bisphenol A diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1, 3-butylene glycol diacrylate, diethylene glycol diacrylate, tripropylene glycol diacrylate, glycerol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, polybutylene glycol diacrylate, trimethylolpropane triacrylate, penta Erythritol triacrylate, tris (acryloxyethyl) isocyanurate, pentaerythritol tetraacryl Acrylate monomers such as acrylate monomers, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and acrylic oligomers such as epoxy acrylate, polyester acrylate, urethane acrylate, and acrylic acrylate. Diacrylates such as diol diacrylate, 1,9-nonanediol diacrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate, and polypropylene glycol diacrylate are preferred. In addition, monomers having two or more acryloyl groups can be appropriately selected from monomers having two or more polymerizable unsaturated bonds in the molecule.

The resin composition for shock absorption for a liquid crystal display of the present invention,
15-60 parts by weight copolymer, preferably, 30 to 60 by weight part, more preferably 39 to 84 parts by weight monomers having one 40-60 parts by acryloyl groups, preferably, 39 to 69 parts by weight, more preferably 39 to 59 parts by weight,
Monomer having 2 or more acryloyl groups 0.5 to 10 parts by weight, preferably 1 to 10 parts by weight,
And a photoinitiator 0.3-3 weight part, Preferably, it contains 0.5-2 weight part.
If the amount of the copolymer is too small, there will be a problem in mechanical properties, and the impact absorbability will be lowered when used in a shock absorbing layer for liquid crystal displays. Further, curing shrinkage becomes large, and a problem is likely to occur in the flatness of the film. On the other hand, if the amount is too large, the viscosity of the composition becomes too high, making it difficult to produce a sheet.
When the amount of the monomer having one acryloyl group is too small, the viscosity of the composition becomes too high, making it difficult to produce a sheet. When the amount is too large, there is a problem in mechanical properties.
If the amount of the monomer having two or more acryloyl groups is too small, it is difficult to maintain the shape of the cured product of the resin composition. Conversely, if the amount of the monomer is too large, the cured product of the resin composition becomes brittle and causes problems in mechanical properties. .
When the amount of the photopolymerization initiator is too small, the reaction does not proceed sufficiently. On the other hand, when the amount is too large, a large amount of the photopolymerization initiator remains, resulting in problems in optical properties and mechanical properties. In addition, when hardening said impact-absorbing material for liquid crystal displays by irradiation of an electron beam, it is not necessary to use a photoinitiator.

The copolymer is obtained by polymerizing 50 to 87% by weight of AA monomer, preferably 60 to 70% by weight, and 13 to 50% by weight, preferably 30 to 40% by weight of HA monomer.
As the monomer having one acryloyl group, AA monomer is 50 to 87% by weight, preferably 60 to 70% by weight, and HA monomer is 13 to 50% by weight, preferably 30 to 40% by weight. is there.
In these, if there are too many AA monomers, therefore, if there are too few HA monomers, the cured | curing material of the impact-absorbing material which concerns on this invention will become easily cloudy at the time of moisture absorption, conversely, if there are too many HA monomers, therefore, AA monomer When there is too little, the hardened | cured material of the shock absorber which concerns on this invention will deform | transform easily at the time of moisture absorption.

  In the present invention, between the ratio of HA monomer in the copolymer (P wt%) and the ratio of HA monomer in the monomer having one acryloyl group (M wt%),

の関係があるようにそれぞれの配合が調整される。（Ｐ−Ｍ）が上記の式を満足しない場合、硬化時に本発明に係る衝撃吸収材が白濁しやすくなる。前記コポリマー及びアクリロイル基を１個有するモノマーにおいて、ＡＡモノマー（及びＨＡモノマー）が、前記した好ましい割合にあるときは、常にこの条件を満足する。

Each formulation is adjusted so that When (PM) does not satisfy the above formula, the shock absorber according to the present invention tends to become cloudy at the time of curing. In the copolymer and the monomer having one acryloyl group, this condition is always satisfied when the AA monomer (and the HA monomer) are in the preferred ratio as described above.

The impact-absorbing resin composition for liquid crystal displays in the present invention is preferably formed or laminated on the display surface so that the film thickness is 0.1 mm to 3 mm. When not used in combination with a transparent protective plate, a thickness of 0.2 mm or more is more preferable in consideration of shock absorption. In particular, when it is desired to increase shock absorption, the thickness is preferably 1.3 mm or more. On the other hand, when using together with a transparent protective plate, it is preferable that it is 0.5 mm or less, and it is especially preferable that it is 0.2 mm or less. After coating on the display surface or the substrate of the optical filter to form a film, the film is cured by irradiation with light such as ultraviolet rays or radiation such as an electron beam. When producing an optical filter, after forming the resin composition for shock absorption for liquid crystal displays in the present invention on the base material or functional layer of the optical filter, the base material, functional layer or protective layer of the optical filter is further formed. After laminating, it may be cured by irradiation with radiation.
The impact-absorbing material for liquid crystal displays in the present invention can be obtained by curing reaction of the above-mentioned impact-absorbing resin composition for liquid crystal displays. When the shape is a sheet or film, the film thickness is preferably 0.1 mm to 3 mm. When not used in combination with a transparent protective plate, a thickness of 0.2 mm or more is more preferable in consideration of shock absorption. In particular, when it is desired to increase shock absorption, the thickness is preferably 1.3 mm or more. On the other hand, when using together with a transparent protective plate, it is preferable that it is 0.5 mm or less, and it is especially preferable that it is 0.2 mm or less. This mixture of the polymerization initiator and the monomers material can be produced by casting. Moreover, it can manufacture by apply | coating desired thickness using a general purpose coating machine, and irradiating radiation, such as light rays, such as an ultraviolet-ray, and an electron beam.

When the impact absorbing resin composition for liquid crystal display in the present invention is polymerized by irradiating with ultraviolet rays or the like, if the polymerization is inhibited when oxygen is present, the transparent film or transparent glass for blocking oxygen from the resin surface It is preferable to cover with. As the ultraviolet irradiation device, a single-wafer type or conveyor type ultraviolet irradiation device can be used. Moreover, as a light source for ultraviolet irradiation, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, an LED lamp or the like can be used, but a high pressure mercury lamp or a metal halide lamp is preferable.
Even if the impact-absorbing resin composition of the present invention is formed into a thick film or the impact-absorbing material of the present invention is thick, it contains a high molecular weight copolymer. The composition is hardly deformed in response to an impact, and therefore it is easy to improve the shock absorption by increasing the thickness.

The impact-absorbing resin composition of the present invention or the impact-absorbing material is formed by forming a functional layer such as an antireflection layer, an antifouling layer, a pigment layer, or a hard coat layer on a substrate film such as a polyethylene film or the like. Combined with laminated multilayer products, or plates made of glass, acrylic, polycarbonate, etc., or with multilayers obtained by forming or laminating functional layers on these plates, and as optical filters comprising such multilayer products. Can be used.
The antireflection layer may be any layer having antireflection properties such that the visible light reflectance is 5% or less, and a layer treated with a known antireflection method on a transparent substrate such as a transparent plastic film. Can be used.
The antifouling layer is for preventing the surface from getting dirty, and a fluorine resin layer, a silicon resin layer or the like is used to lower the surface tension. These known layers can be used.
The dye layer is used to increase the color purity, and is used to reduce unnecessary light when the color purity of light emitted from the liquid crystal display cell is low. A dye that absorbs light in unnecessary portions is dissolved in a resin, and formed or laminated on a base film such as a polyethylene film, or mixed with an adhesive.
The hard coat layer is used to increase the surface hardness. As a hard-coat layer, what formed or laminated | stacked acrylic resins, such as urethane acrylate and an epoxy acrylate, an epoxy resin, etc. on base films, such as a polyethylene film, can be used. Similarly, in order to increase the surface hardness, a plate made of glass, acrylic, polycarbonate or the like, or a hard coat layer formed or laminated on these plates can be used.
The impact-absorbing resin composition or the impact-absorbing material in the present invention can be used by laminating a functional layer such as an antireflection layer and a necessary one as appropriate. In this case, the functional layer may be laminated on one side of the transparent substrate, layers having different functions are separately provided on both sides of the transparent substrate, and layers having the same function are laminated on both sides thereof. May be. The order of stacking the functional layers is arbitrary.
When combined with these functional layers, the shock absorbing resin composition of the present invention or the shock absorbing material is preferably used on the liquid crystal panel side of these layers.
Moreover, it can also be laminated | stacked and used for a polarizing plate. In this case, it can also be used on the viewing surface side of the polarizing plate, and can also be used between the polarizing plate and the liquid crystal cell. When used on the viewing surface side of the polarizing plate, it is possible to laminate an antireflection layer, an antifouling layer, and a hard coat layer on the further viewing surface side of the shock absorbing resin composition of the present invention or the above shock absorber, When used between the polarizing plate and the liquid crystal cell, a functional layer can be laminated on the viewing surface side of the polarizing plate.

The impact-absorbing resin composition or the impact-absorbing material in the present invention can be used by laminating a functional layer such as an antireflection layer and a necessary one as appropriate. In this case, the functional layer may be laminated on one side of the transparent substrate, or layers having different functions may be separately provided on both sides of the transparent substrate, and layers having the same function may be laminated on both sides. good. The order of stacking the functional layers is arbitrary.
In the case of such a multilayer product, it is preferable that the shock absorbing resin composition for liquid crystal displays or the shock absorbing material for liquid crystal displays in the present invention be the outermost layer.
If necessary, these layers can be laminated by a roll laminating or a sheet laminating machine through an adhesive layer between each layer. Furthermore, the multilayer material laminated | stacked with the roll lamination and the sheet | seat bonding machine can be bonded to the liquid crystal display front surface or the front plate for liquid crystal displays using a roll laminator or a sheet bonding machine.

The impact-absorbing resin composition for liquid crystal displays or the impact-absorbing material for liquid crystal displays in the present invention is disposed at an appropriate position on the viewing side from the liquid crystal display cell of the liquid crystal display. It is particularly preferable to be applied between the liquid crystal display cell and the transparent protective substrate.
As the transparent protective plate in the present invention, a general optical transparent substrate can be used. Specific examples include a glass plate, an acrylic plate, a polycarbonate plate, and a thick polyester sheet. When high surface hardness is required, a plate such as glass or acrylic is preferable, and a glass plate is more preferable. The surface of these transparent protective plates may be subjected to treatments such as antireflection, antifouling, and hard coating. These surface treatments may be performed on one side or both sides of the transparent protective plate. These transparent protective plates can also be used in combination.
A general polarizing plate can be used for the polarizing plate in the present invention. The surface of these polarizing plates may be subjected to treatments such as antireflection, antifouling, and hard coating. These surface treatments may be performed on one side of the polarizing plate or on both sides.
As the liquid crystal display cell in the present invention, a general liquid crystal display cell can be used. The liquid crystal display cell is divided into TN, STN, VA, IPS and the like depending on the liquid crystal control method, but any liquid crystal display cell using any control method can be used.
This will be described with reference to the drawings. 1 and 2 are cross-sectional schematic views showing a conventional liquid crystal display, and FIGS. 3, 4, 5, and 6 are cross-sectional schematic views showing a liquid crystal display of the present invention.
As shown in FIG. 1 as an example, the structure of a conventional liquid crystal display includes a liquid crystal display cell 1, a polarizing plate 2 attached to both surfaces thereof, and a transparent protective plate 5 provided with a gap 3 provided on the front surface. Consists of The liquid crystal display cell 1 is a structure in which liquid crystal is sealed in two transparent glasses, and polarizing plates 2 and the like are attached to both sides of the outside of the glass. The lower part 4 of the liquid crystal display cell 1 is a reflector or a backlight system. In this case, an antireflection layer, an antifouling layer, a hard coat layer and the like are appropriately laminated on the front surface of the transparent protective plate 5. FIG. 2 shows another conventional liquid crystal display, which includes a liquid crystal display cell 1, a polarizing plate 2 attached to both surfaces thereof, and a reflector or a backlight unit 4. In this case, an antireflection layer, an antifouling layer, a hard coat layer and the like are appropriately laminated on the front surface of the polarizing plate 2. On the other hand, as a liquid crystal display in the present invention, FIG. 3 shows an example of a liquid crystal display configured through a transparent shock absorber. A polarizing plate 2 is laminated on both surfaces of the liquid crystal display cell 1, a sheet (impact absorber for liquid crystal display) 3 ′ is laminated on the polarizing plate 2, and a transparent protective plate 5 is laminated thereon to constitute a viewing side. On the other hand, a reflecting plate or a backlight system 4 is disposed on the polarizing plate 2.
Moreover, you may replace the order of the shock absorbing material 3 'for liquid crystal displays and the polarizing plate 2 by the side of visual recognition by the structure in FIG. 3 like FIG. In this case, an adhesive or the like may be used to attach the transparent protective plate 5 and the polarizing plate 2. When the transparent protective plate 5 is used as shown in FIGS. 3 and 4, an antireflection layer, an antifouling layer, a hard coat layer, or the like may be appropriately laminated on the surface of the transparent protective plate 5. Further, an antireflection layer, an antifouling layer, a hard coat layer, or the like may be laminated on the surface of the polarizing plate 2, but there may be no layer having these functionalities.
Further, in correspondence with the configuration of the liquid crystal display in FIGS. 3 and 4, there is a configuration in which the transparent protective plate 5 is not disposed as in FIGS. 5 and 6. However, in FIG. 6, the order of the liquid crystal display shock absorber 3 ′ and the polarizing plate 2 is further switched. When the polarizing plate 2 is at the forefront as shown in FIG. 5, an antireflection layer, an antifouling layer, a hard coat layer, or the like may be laminated on the surface of the polarizing plate 2. As shown in FIG. 6, when the shock absorber 3 ′ for liquid crystal display is at the forefront, an antireflection layer, antifouling layer, hard coat layer, etc. are laminated on the front surface of the shock absorber 3 ′ for liquid crystal display. It is particularly preferable that at least a hard coat layer is laminated.

Into a reaction vessel equipped with a condenser, thermometer, stirrer, dropping funnel and nitrogen injection tube, 84.0 g of 2-ethylhexyl acrylate, 36.0 g of 2-hydroxyethyl acrylate and 150.0 g of methyl isobutyl ketone are taken as initial monomers. While substituting with nitrogen at an air volume of 100 ml / min, the mixture was heated from room temperature to 70 ° C. for 15 minutes. Then, while maintaining this temperature, an additional monomer, 2-ethylhexyl acrylate using 21.0g of 2-hydroxyethyl acrylate 9.0 g, prepared them to a solution of laureate peroxide 0.6 g, this The solution was added dropwise over 60 minutes and allowed to react for an additional 2 hours after completion of the addition. Subsequently, methyl isobutyl ketone was distilled off to obtain a copolymer of 2-ethylhexyl acrylate and 2-hydroxyethyl acrylate (weight average molecular weight 250,000).
Next, 44.50 g of this copolymer,
38.25 g of 2-ethylhexyl acrylate,
16.25 g of 2-hydroxyethyl acrylate,
1.00 g of 1,6-hexanediol diacrylate,
1-hydroxy-cyclohexyl-phenyl-ketone 0.50 g
Is added and stirred and mixed to prepare an impact absorbing resin composition for a liquid crystal display, and then poured into a frame having a width of 100 mm, a depth of 100 mm, and a depth of 0.5 mm. A transparent sheet was obtained when 2,000 mJ was irradiated with ultraviolet rays using an irradiation apparatus. Next, when this sheet was bonded to a 2.8 mm thick float glass for a front glass, and further bonded to a 0.7 mm thick glass, an impact resistance test was conducted. Without breaking, it was damaged at 0.75J.
In addition, the sample was poured into a frame having a width of 40 mm, a depth of 40 mm, and a depth of 10 mm, and the sample was measured for rubber hardness measurement by irradiating 9,000 mJ of ultraviolet rays using an ultraviolet irradiation device with the upper part covered with ultraviolet transmissive glass. When the hardness was measured, the rubber hardness was 2.

42.75 g of the copolymer of Example 1
36.58 g of 2-ethylhexyl acrylate,
15.67 g of 2-hydroxyethyl acrylate,
5.00 g of 1,6-hexanediol diacrylate,
1-hydroxy-cyclohexyl-phenyl-ketone 0.50 g
After stirring and mixing, the mixture was poured into a frame having a width of 100 mm, a depth of 100 mm, and a depth of 0.5 mm, and the upper part was covered with an ultraviolet transmissive glass and irradiated with 2,000 mJ of ultraviolet rays using a UV irradiation device to be transparent. A good sheet was obtained. Next, when this sheet was bonded to a 2.8 mm thick float glass for a front glass and further bonded to a 0.7 mm thick glass, an impact resistance test was conducted. Without breaking, it was damaged at 1.25J.
In addition, the sample was poured into a frame having a width of 40 mm, a depth of 40 mm, and a depth of 10 mm, and the sample was measured for rubber hardness measurement by irradiating 9,000 mJ of ultraviolet rays using an ultraviolet irradiation device with the upper part covered with ultraviolet transmissive glass. When the hardness was measured, the rubber hardness was 22.

40.5 g of copolymer of Example 1
34.65 g of 2-ethylhexyl acrylate,
14.85 g of 2-hydroxyethyl acrylate,
10.00 g of 1,6-hexanediol diacrylate,
1-hydroxy-cyclohexyl-phenyl-ketone 0.50 g
After stirring and mixing, the mixture was poured into a frame having a width of 100 mm, a depth of 100 mm, and a depth of 0.5 mm, and the upper part was covered with an ultraviolet transmissive glass and irradiated with 2,000 mJ of ultraviolet rays using a UV irradiation device to be transparent. A good sheet was obtained. Next, when this sheet was bonded to a 2.8 mm thick float glass for a front glass and further bonded to a 0.7 mm thick glass, an impact resistance test was conducted. Without breaking, it was damaged at 0.75J.
In addition, the sample was poured into a frame having a width of 40 mm, a depth of 40 mm, and a depth of 10 mm, and the sample was measured for rubber hardness measurement by irradiating 9,000 mJ of ultraviolet rays using an ultraviolet irradiation device with the upper part covered with ultraviolet transmissive glass. When the hardness was measured, the rubber hardness was 38.

  When the resin of Example 1 was poured into a frame having a width of 100 mm, a depth of 100 mm, and a depth of 0.15 mm, and the upper part was covered with an ultraviolet transmissive glass, ultraviolet rays were irradiated to 2,000 mJ using an ultraviolet irradiation device, and a transparent sheet was obtained. Got. Next, when this sheet was bonded to a 2.8 mm thick float glass for a front glass and further bonded to a 0.7 mm thick glass, an impact resistance test was conducted. At 0.75 J, the front glass was damaged. Without breaking, it was damaged at 1.0J.

  When the sheet produced in the same manner as in Example 1 was bonded to a 6.0 mm thick float glass for a front glass and further bonded to a 0.7 mm thick glass, an impact resistance test was performed. Then, the front glass was not damaged, and it was damaged at 3.0J.

  When the sheet produced in the same manner as in Example 1 was bonded to a 1.3 mm thick float glass for a front glass and further bonded to a 0.7 mm thick glass, an impact resistance test was performed. Then, the front glass was not damaged, and was damaged at 0.5 J.

  A strip with a thickness of 0.5 mm and a width of 5 mm was attached to four sides of an AG-treated polarizing plate attached to the surface of a liquid crystal display cell having a diagonal size of 32 inches to form a formwork. The same shock absorbing resin composition for a liquid crystal display as in Example 1 was poured into the soda glass having a diagonal size of 32 inches and a thickness of 2.8 mm so as to prevent bubbles from entering. Covered. Next, using a conveyor type ultraviolet irradiation device using a metal halide lamp, exposure was performed with an integrated exposure amount of 2,000 mJ, and the resin was cured to obtain a liquid crystal display cell having a shock absorber for liquid crystal display and a transparent protective plate. This liquid crystal display cell was set in a casing having a backlight unit and a drive circuit to obtain a liquid crystal display. In this liquid crystal display, there was no change in color due to the coloring of the resin material inside, and peeling or floating at the interface between the shock absorber for liquid crystal display and the transparent protective plate was not seen. Further, there was no image deterioration due to double projection, and even when the surface was touched, there was no deterioration in image quality due to panel deflection.

Comparative Example 1
31.5 g of the copolymer of Example 1
26.95 g of 2-ethylhexyl acrylate,
11.55 g of 2-hydroxyethyl acrylate,
1,6-hexanediol diacrylate 30.00 g,
1-hydroxy-cyclohexyl-phenyl-ketone 0.50 g
After stirring and mixing, the mixture was poured into a frame having a width of 100 mm, a depth of 100 mm, and a depth of 0.5 mm, and the upper part was covered with an ultraviolet transmissive glass and irradiated with 2,000 mJ of ultraviolet rays using a UV irradiation device to be transparent. A good sheet was obtained. Next, when this sheet was bonded to a 2.8 mm thick float glass for a front glass, and further bonded to a 0.7 mm thick glass for an impact resistance test, the front glass was damaged at 0.25 J. did.
In addition, the sample was poured into a frame having a width of 40 mm, a depth of 40 mm, and a depth of 10 mm, and the sample was measured for rubber hardness measurement by irradiating 9,000 mJ of ultraviolet rays using an ultraviolet irradiation device with the upper part covered with ultraviolet transmissive glass. When the hardness was measured, the rubber hardness was 75.

Reference Example The resin of Example 1 was poured into a frame having a width of 100 mm, a depth of 100 mm, and a depth of 1.0 mm, and the upper part was covered with an ultraviolet transmissive glass. A good sheet was obtained. Next, when this sheet was bonded to a 2.8 mm thick float glass for a front glass and further bonded to a 0.7 mm thick glass, an impact resistance test was conducted. At 0.25 J, the front glass was damaged. Without breaking, it was damaged at 0.4J.

Comparative Example 3
When the impact resistance test was performed using only 0.7 mm glass, the glass was broken at 0.25 J.

Test methods in Examples and Comparative Examples are shown below.
(Weight average molecular weight measurement)
The weight average molecular weight was measured using gel permeation chromatography using THF as a solvent, and the weight average molecular weight was determined using a standard polystyrene calibration curve.
(Impact resistance test)
In the impact resistance test, the resin sheet bonded to the front glass was further bonded to the same glass used in a 0.7 mm thick liquid crystal panel, and 510 g of steel on the front glass side. The ball was dropped and evaluated. 5 cm, 8 cm, 10 cm, 12 cm, 15 cm, and thereafter, the steel ball was dropped by changing the center height of the steel ball in 5 cm increments, and a determination was made as to whether the front glass was broken. The impact strength was calculated from the following formula.
Impact strength = steel ball weight (Kg) × height (m) × 9.8 (m / s ² )
For example, when the height is 5 cm, 0.51 × 0.05 × 9.8 = 0.25J.
(Rubber hardness measurement)
Using a sample having a width of 40 mm, a depth of 40 mm, and a depth of 10 mm, the rubber hardness was measured with a spring type hardness meter (model: WR-104A) manufactured by Nishitokyo Seimitsu Co., Ltd. The measurement was performed at 5 points, and the average value of the 5 points was defined as the rubber hardness.

The cross-sectional schematic diagram which shows the conventional liquid crystal display. Sectional schematic diagram which shows the other example of the conventional liquid crystal display. The cross-sectional schematic diagram which shows the liquid crystal display of this invention. The cross-sectional schematic diagram which shows the other example of the liquid crystal display of this invention. The cross-sectional schematic diagram which shows the other example of the liquid crystal display of this invention. The cross-sectional schematic diagram which shows the other example of the liquid crystal display of this invention.

Explanation of symbols

1 Liquid crystal display cell 2 Polarizing plate 3 Air gap (air layer)
3 'Shock absorber for liquid crystal display 4 Backlight system 5 Transparent protective plate

Claims (9)

15 to 60 parts by weight of copolymer 39 to 84 parts by weight of monomer having one acryloyl group 0.5 to 10 parts by weight of monomer having two or more acryloyl groups and 0.3 to 3 parts by weight of a photopolymerization initiator,
The above copolymer is an alkyl acrylate having 4 to 18 carbon atoms in an alkyl group (hereinafter referred to as AA monomer) of 50 to 87% by weight and the following general formula (I)

(In the formula, m represents 2, 3 or 4, and n represents an integer of 1 to 10.)
It is obtained by polymerizing 13 to 50% by weight of a hydroxyl group-containing acrylate represented by the following (hereinafter referred to as HA monomer),
As a monomer having one acryloyl group as described above, an AA monomer is used in a proportion of 50 to 87% by weight and an HA monomer in a proportion of 13 to 50% by weight,
Between the proportion of HA monomer in the copolymer (P wt%) and the proportion of HA monomer in the monomer having one acryloyl group (M wt%),

Liquid crystal display for shock absorbing resin composition ing been formulated to have a relationship. Claim photopolymerization initiator is α- hydroxyalkyl phenone compound or an acylphosphine oxide-based compound or oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) 1 The resin composition for shock absorption for liquid crystal displays as described. AA monomer is 2-ethylhexyl acrylate or isooctyl acrylate or n-octyl acrylate, and HA monomer is 2-hydroxyethyl acrylate or 1-hydroxyethyl acrylate or 2-hydroxypropyl acrylate or 3-hydroxypropyl acrylate or 1-hydroxypropyl or acrylate or 4-hydroxybutyl acrylate 3 - hydroxybutyl acrylate, or 2-hydroxybutyl acrylate or 1-hydroxybutyl acrylate and which claim 2, a liquid crystal display for shock absorbing resin composition. The impact-absorbing resin composition for a liquid crystal display according to any one of claims 1 to 3 , wherein the copolymer has a weight average molecular weight of 100,000 to 600,000 . Copolymer over 40 to 60 parts by weight,
39 to 59 parts by weight of a monomer having one acryloyl group,
1 to 5 parts by weight of a monomer having two or more acryloyl groups,
And a liquid crystal display for shock absorbing resin composition according to any one of claims 1 to 4, which contains a photopolymerization initiator 0.5 to 2.0 parts by weight. LCD for shock absorber the liquid crystal display for shock absorbing resin composition obtained by curing reaction of any of claims 1-5. The impact absorbing material for a liquid crystal display according to claim 6 , wherein the shape is a sheet or film. A shock absorbing layer for a liquid crystal display panel obtained using the shock absorbing resin composition for a liquid crystal display according to any one of claims 1 to 5 or the shock absorbing material for a liquid crystal display according to claim 6 or 7. Optical filter for liquid crystal display. The liquid crystal display obtained using the impact-absorbing resin composition for liquid crystal displays in any one of Claims 1-5 , or the impact-absorbing material for liquid crystal displays of Claim 6 or 7 .

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