KR20150007695A - Photocurable resin compositions for non yellowing and flat panel display using the compositions - Google Patents

Abstract

The present invention relates to a photocurable resin composition with non-yellowing properties which includes: (A) (meta) acrylic-modified urethane resin obtained by copolymerizing a mixture including a diol compound having (a1) the number average molecular weight of 1,000-4,000; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; and (D) a functional additive. The photocurable resin composition with non-yellowing properties has excellent optical properties and does not cause yellowing which is a change from a transparent color to a yellow color. Therefore, the photocurable resin composition with non-yellowing properties not only maintains excellent expression of optical properties but also can contribute to maintaining high quality of a flat panel display. Moreover, the photocurable resin composition with non-yellowing properties can attach an image displaying part to a large area of a protection part of the flat panel display to be in the minimized thickness. Therefore, the photocurable resin composition with non-yellowing properties can contribute to making the flat panel display be light.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable resin composition for non-yellowing and flat panel display using the same,

The present invention relates to a photocurable non-yellowing resin composition and a flat panel display using the same. More particularly, the present invention relates to a photocurable non-yellowing resin composition and a flat panel display using the same, To a photo-curing optical non-yellowing resin composition which can be applied to fields requiring excellent optical characteristics and reliability such as flat panel display panels and touch panels.

Recently, flat panel displays have been getting higher quality each year, and as the size of the flat display increases, it is required to reduce the volume and thickness. In addition, the optical characteristics of panels and optical materials of flat panel displays are becoming more important, and thinner thicknesses are also required.

As a result, optical materials are becoming more excellent in optical properties, and hybrid optical materials capable of digesting various functions are applied to minimize the volume and thickness. In addition, adhesive sheets and adhesives for bonding various optical materials are used The thickness of the flat panel display panel is being reduced.

Japanese Patent Application Laid-Open No. 2009-263502 discloses an adhesive sheet capable of bonding a display panel and a protective plate to each other without causing bubbles or peeling at the interface between the display panel and the protective plate. This has the advantage of reducing the thickness by bonding the display portion and the protective portion of the flat panel display using the adhesive sheet. However, when the adhesive sheet is manufactured through the manufacturing process of such an optical tape, there is a limit to increase in size, It is troublesome that the defoaming process should be added in order to remove it.

For this reason, a photocurable composition suitable for a flat panel display panel or a touch panel to replace the adhesive sheet is required. The reason why the technique of bonding the display portion and the protective portion of the flat panel display panel or the like by applying the resin composition as described above is necessary because the thickness can be adjusted and the defoaming process is not additionally required so that the flat panel display can be made thinner and productivity can be improved .

In this regard, Japanese Patent Laid-Open No. 2009-186963 discloses a resin composition having a light transmittance and excellent adhesiveness between an image display portion of a liquid crystal display and a transparent protective portion via a resin curing composition and an image display device , The resin composition exhibits poor light resistance and heat resistance, and there is a possibility that the reliability of the optical properties is deteriorated.

In order to solve these problems, a photocurable non-yellowing resin composition excellent in optical characteristics and long-term reliability thereof is desperately needed.

1: JP-A-2009-263502 2: JP-A No. 2009-186963

Accordingly, the present inventors synthesized a (meth) acrylic-modified urethane resin usable as a photo-curing optical non-yellowing resin composition, and found that the resulting (meth) acrylic modified urethane resin, a photopolymerizable monomer, a photopolymerization initiator and a functional additive, It has been found that the use of the non-yellowing resin composition for photo-curable optical compositions obtained by mixing at an appropriate mixing ratio can be applied to fields requiring excellent optical characteristics and reliability thereof, and thus the present invention has been completed

Accordingly, an object of the present invention is to provide a photo-curing optical non-yellowing resin composition having excellent optical properties and stably maintaining optical properties even when exposed to an external environment for a long time.

Another object of the present invention is to provide a photocurable non-yellowing adhesive having optical properties suitable for bonding an image display portion such as a flat panel display panel or a touch panel to a protective portion.

It is still another object of the present invention to provide a flat panel display manufactured using the photocurable non-yellowing adhesive.

(A) a (meth) acryl-modified urethane resin obtained by copolymerizing (a1) a mixture comprising a diol compound having a number average molecular weight of 1,000 to 4,000; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; And (D) a functional additive. There is provided a photocurable non-yellowing resin composition.

The present invention provides a photocurable non-yellowing adhesive comprising the photocurable non-yellowing resin composition.

The present invention also provides a flat panel display manufactured using the photocurable non-yellowing adhesive.

The photocurable non-yellowing resin composition according to the present invention has excellent optical properties and does not cause yellowing that discolors transparent colors even when exposed to an external environment for a long time.

Accordingly, the present invention can not only maintain the excellent optical characteristic development of the flat panel display, but also contribute to the maintenance of high image quality of the flat panel display, and it is possible to bond a large area of the display portion and the protective portion of the flat panel display panel with a minimum thickness, Thereby contributing to weight reduction of the display.

The photocurable non-yellowing resin composition according to the present invention can be widely applied to fields requiring excellent optical characteristics and reliability such as flat panel display panels and touch panels.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view showing an arrangement state of an image display portion, a protective portion, and a resin composition in a flat panel display panel bonded using the photo-curable non-yellowing resin composition according to the present invention.

Hereinafter, the present invention will be described in more detail as an embodiment.

(A) a (meth) acrylic modified urethane resin obtained by copolymerizing (a1) a mixture comprising a diol compound having a number average molecular weight of 1,000 to 4,000; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; And (D) a functional additive.

The (A) (meth) acrylic modified urethane resin may be prepared by using (A-1) a monofunctional (meth) acrylic modified urethane resin, (A-2) a polyfunctional (meth) acrylic modified urethane resin, desirable.

In order to produce the monofunctional (meth) acrylic-modified urethane resin component (A-1) in the photocurable non-yellowing resin composition, the first reaction step is preferably carried out by adding (i) (a2) a diisocyanate compound having two isocyanate groups And (a4) an isocyanate compound having one isocyanate and one (meth) acrylate by reacting a (meth) acrylate monomer having a number average molecular weight of 300 or less and having one functional group selected from a hydroxyl group, .

Next, (ii) an isocyanate compound having one isocyanate and one (meth) acrylate prepared in the step (i) is reacted with (a3) a photopolymerizable monofunctional diluent as a solvent (a1) 4,000 diol compounds to obtain a monofunctional (meth) acrylic modified urethane resin.

On the other hand, the polyfunctional (meth) acryl-modified urethane resin (A-2) is a first reaction step in which (i) (a3) a photopolymerizable monofunctional diluent is used as a solvent to (a1) have an ethylenically unsaturated double bond A diol compound having a molecular weight of 1,000 to 4,000 and (a2) an excessive diisocyanate compound having two isocyanate groups in one molecule are reacted to prepare a urethane compound.

(A) a (meth) acrylate monomer having one functional group selected from a hydroxyl group, an amine group or a carboxyl group in one molecule and (a5) a carboxyl group having two functional groups selected from the group consisting of two (Meth) acryl-modified urethane compound can be prepared by mixing and reacting an ethylenically unsaturated compound having two or more ethylenically unsaturated groups.

The (B) photopolymerizable monomer (B1) a monofunctional acrylate having a polar hydroxy group; (b2) monofunctional acrylate having no polar functional group; (b3) a photopolymerizable monomer having an ethylenically unsaturated double bond and a cyclic aliphatic group; And (b4) at least one polyfunctional acrylate having two or more acrylic functional groups. The photocurable non-yellowing resin composition according to the present invention comprises (C) a photopolymerization initiator and (D) a functional additive component.

(A) 10 to 90 parts by weight of a (meth) acrylic modified urethane resin (A) when the sum of the (A) the (meth) acrylic modified urethane resin and the photopolymerizable monomer (B) is 100 parts by weight; (B) a photopolymerizable monomer 10 to 90 parts by weight; (C) 0.3 to 10 parts by weight of a photopolymerization initiator; And (D) 0 to 7 parts by weight of a functional additive.

The (meth) acryl-modified urethane resin (A) may be prepared by reacting 0 to 90 parts by weight of a monofunctional (meth) acrylic modified urethane resin (A-1) And 0 to 90 parts by weight of a polyfunctional (meth) acrylic modified urethane resin (A-2), and the total content is preferably 10 to 90 parts by weight.

Hereinafter, each component will be described in detail.

[Component (A)]: (meth) acryl-modified urethane resin

( a1 ) ingredient : Number average  Having a molecular weight of 1,000 to 4,000 Polyolefin Dior  compound

 (a1) A commercially available polyolefin diol compound can be used as the diol compound having a number average molecular weight of 1,000 to 4,000 (hereinafter referred to as a component (a1)). Specifically, the diol compound may be a polyethylene diol, a polypropylene diol, a polyisoprene diol , Hydrogenated polybutadiene diol, poly (ethylene-co-butylene) diol, and polybutene diol.

In the production of the (meth) acrylic modified urethane resin according to the present invention, it is preferable to use a diol compound having a number average molecular weight of 1,000 to 4,000.

In the case of using a diol compound having a number average molecular weight of less than 1,000, the proportion of the urethane component in the produced (meth) acrylic modified urethane resin is increased, which may cause a problem that the hardness is increased when cured. In the case of using a diol compound having a number average molecular weight of more than 4,000 It is preferable to use a diol compound having the number average molecular weight because the viscosity of the produced (meth) acrylic modified urethane resin may become too high.

The amount of the component (a1) used in the production of the (A-1) monofunctional (meth) acrylic-modified urethane resin is preferably such that (a4) (A1) is used in a proportion of 2 equivalents when the amount of the isocyanate compound having one isocyanate group and one acrylate group produced by reacting the (meth) acrylate monomer and (a2) diisocyanate group is 1 equivalent, desirable. When the hydroxyl group equivalent is less than 2 equivalents, the ratio of the isocyanate group relative to the hydroxyl group equivalent increases, and when the hydroxyl group is reacted with the hydroxyl group, a polyfunctional (meth) acrylic modified urethane resin may be produced. Since there is an excessive amount of the hydroxyl group, reliability problems may occur when applied as an optical adhesive.

The amount of the component (a1) used when preparing the polyfunctional (meth) acryl-modified urethane resin (A-2) is preferably from 0.1 to 0.5 equivalent weight of the hydroxyl group of the component (a1) when the (a2) diisocyanate group is 1 equivalent, Is preferably used. If the hydroxyl group equivalent is less than 0.1, excess unreacted isocyanate groups may be present in the resulting (meth) acrylic modified urethane resin, and if the hydroxyl group equivalent is more than 0.5, excess hydroxy groups may be present as optical adhesives This is because reliability problems may occur.

( a2 ) ingredient : One molecule  , Two isocyanate groups Diisocyanate  compound

(a2) A diisocyanate compound having two isocyanate groups in one molecule [hereinafter referred to as a 'component (a2)'), toluene-2,4-diisocyanate, 1,6-hexamethylene diisocyanate, xylene diisocyanate, Diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, and hydrogenated products thereof. [0035] The term "

In the production of the (A-1) monofunctional (meth) acrylic modified urethane resin, the amount of the component (a2) used is preferably 0.1 to 0.5 equivalents of the isocyanate group of the component (a2) relative to the hydroxyl group equivalent of the component (a1). (A2) is added in an amount of 0.1 to 1.0 equivalent equivalent to the isocyanate group equivalent of the component (a2) relative to the total hydroxyl equivalent weight of the component (a1) in the production of the polyfunctional (meth) acryl- It is good to use it. When the equivalent of the diisocyanate group is less than 0.1, an unreacted hydroxyl group is excessively present, which may cause reliability problems when applied as an optical adhesive, and when the equivalent of the diisocyanate group exceeds 1.0, unreacted isocyanate groups are excessively present Meth) acryl-modified urethane resin may cause a problem in storage stability.

( a3 ) ingredient : Light curing  possible Single sensory  diluent

(a3) The photopolymerizable monofunctional diluent [hereinafter referred to as the component (a3)] has a structure of the following formula (1) without having a polar functional group of a hydroxyl group, an amine group, a phosphoric acid group or a carboxyl group and has an ethylenically unsaturated double bond (Meth) acrylate compounds each having a straight-chain or cyclic aliphatic structure may be used alone or in combination of two or more.

[Chemical Formula 1]

H ₂ C = CHR ₁ -COO-R ₂

Wherein R ₁ is hydrogen or CH ₃ ; R ₂ is an alkyl structure having a straight chain or cyclic aliphatic structure consisting of only 1 to 12 carbon atoms and hydrogen.

Specific examples of the compound of formula (1) include methyl (meth) acrylate, lauryl (meth) acrylate, isononyl acrylate, cyclohexyl (meth) acrylate, isobonyl (meth) acrylate, dicyclopentenyl (Meth) acrylate, and dicyclopentanyloxyethyl (meth) acrylate. These may be used alone or in combination of two or more.

( a4 ) ingredient : One molecule  Lt; / RTI > Amine group  Or a carboxyl group, Number average  Having a molecular weight of 300 or less Meta ) Acrylate Monomer

(a4) a (meth) acrylate monomer having a number average molecular weight of 300 or less having one functional group selected from a hydroxyl group, an amine group or a carboxyl group in one molecule [hereinafter referred to as a 'component (a4) Acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate or 2-hydroxy-3-phenoxypropyl Methacrylate. Examples of the amine group-containing (meth) acrylate monomer include diethylaminoethyl (meth) acrylate or dimethylaminomethyl (meth) acrylate. (Meth) acrylate monomers containing carboxyl groups include (meth) acrylic acid, 2-acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl succinate, 2- acryloyloxyethyl phthalic acid, 2- (Meth) acryloyloxyethylphthalic acid, 2-acryloyloxyethylhexahydrophthalic acid and 2- (meth) acryloyloxyethylhexahydrophthalic acid.

The (meth) acrylate monomer containing a hydroxy group is preferably selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate, and 3-phenoxypropyl (meth) acrylate.

The amine group-containing (meth) acrylate monomer may include one or more selected from the group consisting of diethylaminoethyl (meth) acrylate and dimethylaminomethyl (meth) acrylate.

The (meth) acrylate monomer containing a carboxyl group may be selected from the group consisting of (meth) acrylic acid, 2-acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl succinate, 2- acryloyloxyethyl phthalic acid, 2- (Meth) acryloyloxyethylphthalic acid, 2-acryloyloxyethylhexahydrophthalic acid, and 2- (meth) acryloyloxyethylhexahydrophthalic acid.

The above-mentioned (meth) acrylate monomer compounds having a hydroxyl group, an amine group and a carboxyl group may be used alone or in combination of two or more.

( a5 ) ingredient : One molecule  Having two carboxyl groups Ethylenic  Unsaturated compound

(a5) An ethylenically unsaturated compound having two carboxyl groups in one molecule [hereinafter referred to as "component (a5)") may include at least one member selected from the group consisting of itaconic acid and fumaric acid.

 The amount of the compound having components (a2) and (a4) used in the step (i) in the production of the (A-1) monofunctional (meth) acrylic modified urethane resin is such that the amount of the Isocyanate compound is obtained by using the diisocyanate group of the component (a2) in an amount of 1 to 2 equivalents to obtain an isocyanate compound, and using the component (a3) as a solvent, isocyanate 0.1 To about 0.5 equivalent to obtain a monofunctional polymer.

(A1) is used in an amount of 0.6 to 0.9 equivalent of the hydroxyl group of the component (a1) relative to 1 equivalent of the isocyanate group of the component (a2) in the production of the polyfunctional (meth) acryl- The diisocyanate group of the component (a2) may be added in an amount of 0.1 to 0.4 equivalents relative to the equivalent of the hydroxyl group to give a polyfunctional polymer.

In the present invention, the urethane reaction can be completed by reacting at 75 to 95 ° C within 90 minutes.

(A4) is added to the isocyanate group remaining after completion of the urethane reaction in the step (a4) in the production of the polyfunctional (meth) acryl-modified urethane resin (A-2) (Meth) acrylic monomer having a functional group (s) and (a5) a compound having an ethylenically unsaturated double bond, wherein the (meth) acrylic monomer is a compound represented by the formula (A4) is used in an amount of 0.45 to 1.3 equivalents, and the component (a5) is used in a proportion of 0.05 to 0.2 equivalents, so that the sum of the hydroxyl group, amine group or carboxyl group equivalent of the components (a4) and .

The addition reaction of the components (a4) and (a5) of the present invention can be completed by reacting at 75 to 95 ° C within 90 minutes as in the urethane reaction.

The number average molecular weight of the (meth) acrylic modified urethane compound (A) is 5,000 to 50,000, and when the total amount of the ultraviolet (UV) curable monomer compound (B) is 100 parts by weight, 10 to 90 parts by weight . When the (meth) acrylic-modified urethane resin is less than 10 parts by weight, the physical properties such as hardness, tensile strength and elongation tend to decrease. When the (meth) acrylic-modified urethane resin is more than 90 parts by weight, The workability is lowered as well as the hardness is increased and the surface tackiness is lowered.

[Component (B)]: The photopolymerizable monomer

(B) 0.1 to 10 parts by weight of monofunctional acrylate (b1) having a polar hydroxyl group, based on 100 parts by weight of the sum of the components (A) and (B) (b2) 9 to 60 parts by weight of a linear monofunctional acrylate having no polar functional group; (b3) 0.9 to 15 parts by weight of a photopolymerizable monomer having an ethylenically unsaturated double bond and a cyclic aliphatic group; And (b4) 0 to 5 parts by weight of a polyfunctional acrylate having two or more acrylic functional groups.

 ( b1 ) Component: Having a polar hydroxy group Single sensory Acrylate Monomer

(meth) acrylate, 2-hydroxypropyl (meth) acrylate and 4-hydroxypropyl (meth) acrylate having a hydroxyl group of the following formula (b1) Hydroxybutyl acrylate, and hydroxybutyl acrylate.

( b2 ) Ingredients: have no polarity Single sensory Acrylate Monomer

(meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, (Meth) acrylate, n-hexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, isononyl acrylate and tridecyl One or two or more.

(B3) component: a photopolymerization monomer having an ethylenically unsaturated double bond and a cyclic aliphatic group

(b3) a photopolymerizable monomer having an ethylenically unsaturated double bond and a cyclic aliphatic group (hereinafter referred to as a 'component (b3)') is a copolymer of a cyclohexyl (meth) acrylate, a norbomyl (meth) acrylate, (Meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentanyl Acrylic vinyl norbornyl, and vinyl norbornyl stearate.

(B4) component: a multi-functional acrylate having two or more functional Acrylate Monomer

(b4) A multifunctional acrylate monomer having two or three acrylic functional groups (hereinafter referred to as a 'component (b4)') may be a monofunctional acrylate monomer having at least one functional group selected from the group consisting of 1,6-hexanediol diacrylate, 1,3-butanediol dimethacrylate, Tricyclodecane dimethanoldiacrylate, trimethylolpropane triacrylate, tricyclodecane dimethanoldiacrylate, and trimethylolpropane triacrylate.

The component (B) is preferably blended in an amount of 10 to 90 parts by weight based on 100 parts by weight of the total of the components (A) and (B). When the amount of the photopolymerizable monomer (B) is less than 10 parts by weight, the viscosity of the photopolymerizable monomer (B) is less than 10 parts by weight. When the amount of the photopolymerizable monomer (B) exceeds 90 parts by weight, the viscosity and curing rate become too low. A problem that the physical properties of the substrate is deteriorated occurs.

[Component (C)] [

The photopolymerization initiator (C) (hereinafter, referred to as component (C)) may include a carbonyl photopolymerization initiator, a sulfide photopolymerization initiator, a quinone photopolymerization initiator, an azo photopolymerization initiator and a peroxide photopolymerization initiator . The photopolymerization initiator may include one or more initiators selected from the above. Specifically, (C) the photopolymerization initiator is at least one selected from the group consisting of benzophenone, benzyl, benzoin, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, p- -Dimethylaminopropiophenone, p, p'-bisdiethylaminobenzophenone, benzoin methyl ether, benzoin isobutyl ether, benzoin-n-butyl ether, 1-hydroxycyclohexyl phenyl ketone, 2- Methyl-1-phenyl-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2,2-diethoxyacetophenone, N, N'-dimethylacetophenone, benzoquinone, anthraquinone, diphenyldisulfide, dibenzyl disulfide, tetraethylthiuram disulfide, tetramethylammonium monosulfide, azobisisobutyronitrile, 2,2 '-Azobispropane, hydrazine, thioxanthone, 2-methylthioxanthone benzoyl peroxide, di-t-butyl peroxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, - Propion-1-one and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl- propionyl) -benzyl] -Phenyl} -2-methyl-propan-1-one, which may be used alone or in combination of two or more.

In the present invention, the component (C) is preferably used in an amount of 0.3 to 10 parts by weight based on 100 parts by weight of the total of the components (A) and (B). If the amount is less than 0.3 part by weight, the resin composition will not be cured sufficiently, and if it is more than 10 parts by weight, the molecular weight of the resin after curing will be small and physical properties may be deteriorated.

[Component (D)] [

(D) a functional additive component [hereinafter referred to as a 'component (D)') may be one or two selected from the group consisting of a polymerization inhibitor, a silane coupling agent, an antioxidant, a heat stabilizer, a UV stabilizer, a plasticizer and a filler The above additives may be further used.

Specifically, the silane coupling agent is at least one member selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, trimethoxysilanyl (meth) acrylate, and vinyltriethoxysilanyl (meth) acrylate, Two or more species may be included.

The antioxidant may be a primary antioxidant selected from the group consisting of phenol type and aromatic amine type, and may be used alone or as a mixture of two or more selected from the group consisting of phosphite type and sulfur ester type. The primary antioxidant and the secondary antioxidant may be mixed together and used.

The thermal stabilizer may include one or more selected from the group consisting of lead, calcium, organic compounds, epoxy compounds and organic phosphorous acid esters.

The ultraviolet stabilizer is selected from the group consisting of hydroxybenzophenone, hydroxyphenylbenzotriazole, UV absorbers, aryl esters, phenol and amine-based primary antioxidants, benzoates and Hindered Amine Light Stabilizer (HALS) And at least one selected from the group consisting of

The plasticizer may include one or more selected from the group consisting of a phthalate ester, a tri-merate ester, an aliphatic dibasic acid ester, an epoxy, a phosphoric ester, a chlorine, and a polyester.

The filler may be at least one selected from the group consisting of silica, alumina, ceria and titania.

In the present invention, the component (D) is preferably used in an amount of 0 to 7 parts by weight based on 100 parts by weight of the total of the components (A) and (B). When the amount of the component (D) exceeds 7 parts by weight, the curing rate is slowed, and optical characteristics and reliability are lowered.

 [Photo-curable optical adhesive]

The present invention includes a photocurable non-yellowing adhesive containing the photocurable non-yellowing resin composition of the present invention described above. The above-described photocurable non-yellowing resin composition according to the present invention can be used as an optical adhesive for bonding a display portion and a protective portion of a flat panel display. In this case, if necessary, the resin composition for photocurable optical A modifying agent, a defoaming agent, and the like may be optionally added.

As the modifier, a leveling agent or the like may be used to improve the leveling property. Specific examples thereof include a polyether-modified dimethylpolysiloxane copolymer, a polyester-modified dimethylpolysiloxane copolymer, and a polyether-modified dimethylalkylpolysiloxane copolymer. And 0.01 to 10 parts by weight based on 100 parts by weight of the photo-curable optical adhesive.

As the antifoaming agent, known antifoaming agents such as a silicone oil, a fluorine oil, and a polycarboxylic acid polymer may be used, and they may be added in an amount of 0.01 to 50 parts by weight based on 100 parts by weight of the adhesive for photocurable optical.

[Flat Panel Display with Display and Protective Part Bonded]

In the present invention, the flat panel display is manufactured using the above-described non-yellowing resin composition for photo-curable optics. Such a flat panel display includes a liquid crystal display, a plasma display, and an organic light emitting diode display.

[Method for bonding the display portion and the protective portion of the flat panel display]

FIG. 1 shows a display unit and a protection unit of a flat panel display using the optical non-yellowing resin composition according to the present invention. In the present invention, the image display unit 1 and the protection unit 2 of the flat panel display panel are photo- Can be bonded by using the optical non-yellowing resin composition layer (3).

As a method for manufacturing the resin composition, a specific pattern is drawn on the backside of the protective part by using a dispensing method, and then the position and the interval are adjusted so that the display part and the resin composition come into contact with each other, At this time, the interval is kept constant so as to be 50 to 300 μm.

When the resin composition is applied uniformly over the entire area according to the pattern, ultraviolet rays are irradiated using a high-pressure mercury lamp, a metal halide lamp, an LED lamp, or the like as a light source, and the resin composition is cured to obtain a flat panel display in which a display portion and a protective portion are cemented.

Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

Manufacturing example  One : Single sensory  ( Meta ) Acrylic modified urethane production

20 parts by weight of isophorone diisocyanate and 13 parts by weight of 4-hydroxybutyl acrylate were added to a cleaned 4 L glass reactor equipped with a stirrer, a thermometer and a cooling jacket, stirred well, and the reactor temperature was raised to 85 캜. And 0.006 parts by weight of Laurate were added thereto, and the mixture was reacted for 1 hour and 30 minutes.

220 parts by weight of poly (ethylene-co-butylene) diol (trade name: GI-2000, manufactured by Nippon Procurement Co., Ltd., molecular weight: about 2,500) was added while maintaining the temperature at 85 占 폚 and dibutyltin dilaurate 0.014 And 0.06 parts by weight of itaconic acid were added, and the mixture was further reacted for 1 hour. The reactant was measured by an infrared spectrophotometer (FT-IR) to confirm that the isocyanate group had disappeared, and the reaction was terminated to obtain a urethane compound (HS-1) having an ethylenically unsaturated double bond.

Manufacturing example  2 : Single sensory  ( Meta ) Acrylic modified urethane production

20 parts by weight of isophorone diisocyanate and 13 parts by weight of 4-hydroxybutyl acrylate were added to a cleaned 4 L glass reactor equipped with a stirrer, a thermometer and a cooling jacket, stirred well, and the reactor temperature was raised to 85 캜. And 0.006 parts by weight of Laurate were added thereto, and the mixture was reacted for 1 hour and 30 minutes.

Thereto was added 308 parts by weight of poly (ethylene-co-butylene) diol (trade name: GI-3000, molecular weight: about 3,500, manufactured by Nippon Seishin KK) while keeping the temperature at 85 캜, and dibutyltin dilaurate 0.014 And 0.06 parts by weight of itaconic acid were added, and the mixture was further reacted for 1 hour. The reaction product was measured with an infrared spectrophotometer (FT-IR) to confirm disappearance of the isocyanate group, and the reaction was terminated to obtain a urethane compound (HS-2) having an ethylenically unsaturated double bond.

Manufacturing example  3: Multifunctional  ( Meta ) Acrylic modified urethane production

220 parts by weight of poly (ethylene-co-butylene) diol (trade name: GI-2000, trade name: GI-2000, molecular weight about 2,500) was added to a cleaned 4L glass reactor equipped with a stirrer, a thermometer and a cooling jacket, 45 parts by weight of butyl acrylate and 25 parts by weight of isophorone diisocyanate were added and stirred. After the temperature of the reactor was elevated to 85 ° C, 0.02 part by weight of dibutyltin dilaurate was added and reacted for 1 hour and 30 minutes.

Thereto, 10 parts by weight of 2-hydroxyethyl (meth) acrylate and 0.2 part by weight of itaconic acid were added while keeping the temperature at 85 占 폚, and the mixture was further reacted for 1 hour. The reaction product was measured by infrared spectroscopy (IR) to confirm disappearance of the isocyanate group, and the reaction was terminated to obtain a urethane compound (HS-3) having an ethylenically unsaturated double bond.

Manufacturing example  4 : Multifunctional  ( Meta ) Acrylic modified urethane production

308 parts by weight of poly (ethylene-co-butylene) diol (trade name: GI-3000, trade name: GI-3000, molecular weight: about 3,500) was added to a cleaned 4L glass reactor equipped with a stirrer, a thermometer and a cooling jacket, 45 parts by weight of isobornyl acrylate and 25 parts by weight of isophorone diisocyanate were added and stirred. After the temperature of the reactor was elevated to 85 캜, 0.02 part by weight of dibutyltin dilaurate was added and reacted for 1 hour and 30 minutes.

Thereto, 10 parts by weight of 2-hydroxyethyl (meth) acrylate and 0.2 part by weight of itaconic acid were added while maintaining the temperature at 85 占 폚 and further reacted for 1 hour. The reaction product was measured by infrared spectroscopy (IR) to confirm disappearance of the isocyanate group, and the reaction was terminated to obtain a urethane compound (HS-4) having an ethylenically unsaturated double bond.

Manufacturing example  5: Multifunctional  ( Meta ) Acrylic modified urethane production

A clean 4 L glass reactor equipped with a stirrer, a thermometer and a cooling jacket was charged with 10 parts by weight (molecular weight less than 1,000) of 2-butyl-2-ethyl-1,3-propanediol, poly (ethylene-co-butylene) 45 parts by weight of isobornyl acrylate as a diluent and 25 parts by weight of isophorone diisocyanate were added and stirred, and the temperature of the reactor was elevated to 85 ° C. (manufactured by Nippon Paper Industries Co., Ltd., trade name: GI-2000, molecular weight about 2,500) , 0.02 part by weight of dibutyltin dilaurate was added, and the mixture was reacted for 1 hour and 30 minutes.

Thereto, 10 parts by weight of 2-hydroxyethyl (meth) acrylate and 0.2 part by weight of itaconic acid were added while keeping the temperature at 85 占 폚, and the mixture was further reacted for 1 hour. The reaction product was determined by infrared spectroscopy (IR) to confirm disappearance of the isocyanate group, and the reaction was terminated to obtain a urethane compound (HS-5) having an ethylenically unsaturated double bond.

Example  One

, 59 parts by weight of the monofunctional (meth) acrylic modified urethane resin (HS-1) obtained in Preparation Example 1, 20 parts by weight of isobornyl acrylate, 17 parts by weight of octyldecyl acrylate, 2 parts by weight of tricyclodecane dimethanol diacrylate , 1 part by weight of trimethylolpropane triacrylate, 1 part by weight of vinyltrimethoxysilane, 0.8 parts by weight of 1-hydroxy-cyclohexyl-phenol-ketone (trade name IGACURE 184: Ciba Specialty Chemicals) 0.7 part by weight of 4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: IGACURE 819: Ciba Specialty Chemicals) were mixed to obtain a light (ultraviolet) curable resin composition.

Example  2

Except that 59 parts by weight of the monofunctional (meth) acrylic modified urethane resin (HS-2) obtained in Preparation Example 2 was used in place of the monofunctional (meth) acrylic modified urethane resin (HS-2).

Example  3

Except that 59 parts by weight of the polyfunctional (meth) acrylic modified urethane resin (HS-3) obtained in Preparation Example 3 was used in place of the polyfunctional (meth) acrylic modified urethane resin (HS-3).

Example  4

49 parts by weight of the monofunctional (meth) acrylic modified urethane resin (HS-1) obtained in Preparation Example 1, 10 parts by weight of the polyfunctional (meth) acrylic modified urethane resin (HS-3) obtained in Preparation Example 3, 20 parts by weight of octyldecyl acrylate, 17 parts by weight of octyldecyl acrylate, 2 parts by weight of tricyclodecane dimethanol diacrylate, 1 part by weight of trimethylolpropane triacrylate, 1 part by weight of vinyltrimethoxysilane, 0.8 part by weight of hexyl-phenyl-ketone (trade name: IGACURE 184: CIBA SPECIALTY CHEMICAL) and 0.7 part by weight of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name IGACURE 819: Ciba Specialty Chemicals) (Ultraviolet ray) curable resin composition was obtained.

Example  5

Except that 39 parts by weight of the monofunctional (meth) acrylic modified urethane resin (HS-1) obtained in Preparation Example 1 and 20 parts by weight of the polyfunctional (meth) acrylic modified urethane resin (HS-3) obtained in Preparation Example 3 were used (Ultraviolet ray) curable resin composition was obtained in the same manner as in Example 5 and in the same manner.

Example  6

Except that 49 parts by weight of the monofunctional (meth) acrylic modified urethane resin (HS-1) obtained in Preparation Example 1 and 10 parts by weight of the polyfunctional (meth) acrylic modified urethane resin (HS-4) obtained in Production Example 4 were used (Ultraviolet ray) curable resin composition was obtained in the same manner as in Example 5 and in the same manner.

Example  7

39 parts by weight of the monofunctional (meth) acrylic modified urethane resin (HS-1) obtained in Preparation Example 1, 10 parts by weight of the polyfunctional (meth) acrylic modified urethane resin (HS-3) obtained in Production Example 3, 10 parts by weight of a polyfunctional (meth) acrylic modified urethane resin (HS-4) obtained in Example 1, 20 parts by weight of isobornyl acrylate, 17 parts by weight of octyldecyl acrylate, 2 parts by weight of tricyclodecane dimethanol diacrylate, 1 part by weight of propane triacrylate, 1 part by weight of vinyltrimethoxysilane, 0.8 parts by weight of 1-hydroxy-cyclohexyl-petroleum-ketone (trade name IGACURE 184: Ciba Specialty Chemicals) Trimethylbenzoyl) -phenylphosphine oxide (trade name: IGACURE 819: Ciba Specialty Chemicals) were mixed to obtain an optical (ultraviolet) curable resin composition.

Comparative Example  One

Except for using 49 parts by weight of the monofunctional (meth) acrylic modified urethane resin (HS-1) obtained in Preparation Example 1 and 10 parts by weight of the monofunctional (meth) acrylic modified urethane resin (HS-5) obtained in Production Example 5 Were mixed at the same mixing ratio as in Example 3 to obtain a light (ultraviolet) curable resin composition.

Comparative Example  2

49 parts by weight of the monofunctional (meth) acrylic modified urethane resin (HS-1) obtained in Preparation Example 1, 30 parts by weight of a non-yellowing type urethane acrylate resin commercially available from Nippon Gosei Co., Ltd. (trade name: UVX-3000B, ) Were mixed at the same mixing ratios as in Example 3 to obtain a light (ultraviolet) curable resin composition.

Comparative Example  3

49 parts by weight of the monofunctional (meth) acrylic modified urethane resin (HS-1) obtained in Preparation Example 1 and 10 parts by weight of commercially available urethane acrylate resin (Miwon Specialty Chemicals, trade name: PU2300C, molecular weight: about 16,000) Were mixed at the same blending ratio as in Example 3 to obtain a light (ultraviolet) curable resin composition.

Comparative Example  4

(Ultraviolet ray) curable resin composition (trade name: SVR1320, Sony Chemical & Information Device Corporation) commercially available in the market was selected.

The results of molecular weight measurements of the urethane compounds of Production Examples 1 to 5 are shown in Table 1.

Molecular weight measurement result of urethane compound HS-1 HS-2 HS-3 HS-4 HS-5 M.W 16,800 21,200 8,000 21,700 7,600 PDI 3.01 2.40 3.74 3.29 3.25

The compounding characteristics of Examples 1 to 7 and Comparative Examples 1 to 4 are shown in Table 2.

In order to measure the optical characteristics and reliability of the resin composition, that is, the degree of yellowing, the following methods were used.

Experimental Example  : Of the Psalms Optical property  And reliability measurement

In order to measure the optical characteristics and reliability of the resin composition, that is, the degree of yellowing, first, the following specimens were prepared.

<Psalter Production>

A predetermined amount of the resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 was dropped on a glass substrate (80 mm × 30 mm × 10 mm) with a guide line of 300 μm height, and the resin composition dropped using an applicator was thinned . The applied resin composition is cured under a curing condition of a metal halide lamp and a light quantity of 3,000 mJ / cm2.

A colorimeter was used to determine the optical characteristics and reliability of the resin composition specimens of Examples 1 to 7 and Comparative Examples 1 to 4 obtained in the above manner, that is, the degree of yellowing, and more specifically, the following methods were used.

1) Initial b * measurement

The photo-curable urethane acrylate resin composition is susceptible to yellowing, in which the initial transparent color gradually changes to yellow due to the influence of the external environment (ultraviolet ray, temperature, moisture, etc.) for a long period of time after curing. In order to be applied as an optical adhesive, since the optical characteristics should be maintained and reliability must be ensured so as not to cause yellowing, the change amount is measured by measuring the b * value for a long period under conditions compatible with the external environment.

It is an object of the present invention to provide a non-yellowing resin composition for a photocurable optical element for bonding a display portion and a protective portion of a display. Therefore, in order to evaluate the level of yellowing, * &Lt; / RTI &gt;

These b * values are measured using a colorimeter.

The L * a * b * color coordinates are the result of studying to approach human emotions rather than the Yxy color coordinates, based on the color contrast between yellow, blue, green and red, in which humans perceive color. Here, L * denotes brightness, a * denotes a color range from red to green, b * denotes a range of colors ranging from yellow to blue, and a * denotes a red range in a positive range and a yellow range in a positive range in a b * , The initial color of the resin cured layer can be obtained by measuring the b * value.

2) b * remeasurement under the reliability evaluation condition

The reliability of the optical properties allows the specimen to be exposed for a long period of time under conditions compatible with the external environment. The measurement conditions were set at a high temperature of 80 占 폚 for 1,000 hours, a high temperature and a high humidity of 85 占 폚 of 85% RH, a thermal shock of 1,000 hours, a temperature of -40 to 85 占 폚 for 100 cycles and an ultraviolet of 30,000 mJ / cm2, Is exposed to each condition. At the end of the test time, the b * value of the specimen is remeasured to calculate the amount of change.

Blend characteristics and experimental results (units: parts by weight) of Examples 1 to 7 and Comparative Examples 1 to 3 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 HS-1 59 - - 49 39 49 39 49 49 49 - HS-2 - 59 - - - - - - - - - HS-3 - - 59 10 20 - 10 - - - - HS-4 - - - - - 10 10 - - - - HS-5 10 UVX-3000B - - - - - - - - 10 - - PU2300C - - - - - - - - - 10 - Isobornyl acrylate 20 20 20 20 20 20 20 20 20 20 - Butyl acrylate - - - - - - - - - - - Octyldecyl acrylate 17 17 17 17 17 17 17 17 17 17 - Tricyclodecane dimethanol diacrylate 2 2 2 2 2 2 2 2 2 2 - Trimethylolpropane triacrylate One One One One One One One One One One - Vinyltrimethoxysilane One One One One One One One One One One - Iga Cure 184 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 - Iga Cure 819 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 - Metal halide,
3,000 mJ / cm &lt;
After curing b * 0.30 0.31 0.32 0.33 0.35 0.36 0.39 0.33 0.36 0.33 0.32 Metal halide,
30,000 mJ / cm2,
After further investigation b * 0.31 0.34 0.59 0.38 0.38 0.40 0.41 0.60 0.70 0.95 0.35 ? B * 0.01 0.03 0.27 0.05 0.03 0.04 0.02 0.27 0.34 0.62 0.03 85 ?,
After 1000 hours b * 0.33 0.34 0.83 0.38 0.38 0.39 0.41 0.85 1.56 1.71 1.48 ? B * 0.03 0.03 0.51 0.05 0.03 0.03 0.02 0.52 1.20 1.38 1.16 85? 85%
After 1000 hours b * 1.32 1.29 2.09 1.08 1.25 1.22 1.10 2.12 2.52 2.96 2.26 ? B * 1.02 0.98 1.77 1.05 0.90 0.86 0.71 1.76 2.16 2.63 1.94 -40? ~ 85 ?,
After 100 cycles b * 0.42 0.41 0.7 0.46 0.49 0.49 0.49 0.71 1.10 1.38 0.67 ? B * 0.12 0.10 0.38 0.13 0.14 0.13 0.10 0.35 0.74 1.05 0.35

As shown in Table 2, after curing, the b * value was 0.3 colorless and transparent, but the reliability was slightly different.

As a result of evaluating the reliability of the optical characteristics, it was found that the change of the b * value was reduced as the monofunctional (meth) acrylic modified urethane resin prepared by the same method was applied using the diol compound having a large molecular weight in the results of Examples 1 and 2 And the result was favorable to yellowing. Also, the results of Examples 3 to 7 show that when the monofunctional (meth) acrylic modified urethane resin is mixed with the monofunctional (meth) acrylic modified urethane resin, the change of the b * value is decreased, As the molecular weight of the mixed polyfunctional (meth) acrylic modified urethane resin increased, the change of b * value decreased and it was found to be favorable to yellowing as the mixing ratio of urethane resin increased.

As in Comparative Example 4, the change in b * value was smaller in all reliability evaluation conditions than in the case of a product commercially available as a photo-curable optical adhesive in the market, indicating excellent reliability of optical characteristics. As in Comparative Example 1, when the diol compound having a molecular weight of less than 1,000 was mixed, the b * value was changed to be disadvantageous to yellowing. As in Comparative Examples 2 and 3, the commercially available polyfunctional urethane acrylate The reliability of the optical characteristics was also poor.

As a result, the photocurable resin composition according to the present invention maintains the long-term optical characteristics of the flat panel display and does not affect the color change of the image quality. Therefore, it can be said to have excellent optical characteristics and reliability have.

INDUSTRIAL APPLICABILITY The present invention can be suitably used as an optical adhesive for bonding a display portion and a protective portion of a flat panel display panel, such as a liquid crystal display, a plasma display, and an organic light emitting diode.

Description of the Related Art
1: image display unit of the panel
2: Protection unit
3: Photocurable non-yellowing resin composition layer

Claims (28)

(A) a (meth) acrylic-modified urethane resin obtained by copolymerizing (a1) a mixture comprising a diol compound having a number average molecular weight of 1,000 to 4,000;
(B) a photopolymerizable monomer;
(C) a photopolymerization initiator; And
(D) a functional additive;
Made up Photocurable non - yellowing resin composition.
The positive photosensitive composition as claimed in claim 1, wherein the total amount of the (A) (meth) acrylic modified urethane resin and the (B) photopolymerizable monomer is 100 parts by weight,
(A) 10 to 90 parts by weight of a (meth) acrylic-modified urethane resin;
(B) a photopolymerizable monomer 10 To 90 parts by weight;
(C) 0.3 to 10 parts by weight of a photopolymerization initiator; And
(D) 0 to 7 parts by weight of a functional additive;
Wherein the photo-curable non-yellowing resin composition comprises:
The thermoplastic resin composition according to claim 2, wherein the (meth) acryl-modified urethane resin (A) comprises 0 to 90 parts by weight of a monofunctional (meth) And 0 to 90 parts by weight of a polyfunctional (meth) acrylic modified urethane resin (A-2), wherein the total content is 10 to 90 parts by weight.
The polyurethane resin composition according to claim 3, wherein the (A-1) monofunctional (meth) acrylic-
(I) preparing an isocyanate compound having one isocyanate and one (meth) acrylate by reacting (a2) a diisocyanate compound and (a4) a (meth) acrylate monomer; And
(Ii) The diisocyanate compound prepared in step (i) is copolymerized with (a3) a diol compound having a number average molecular weight of 1,000 to 4,000 by using (a1) a photopolymerizable monofunctional diluent as a solvent, Urethane resin;
(Meth) acryl-modified urethane resin, which is produced through the reaction of the photo-curable non-yellowing resin composition.
The polyurethane resin composition according to claim 3, wherein the (A-2) polyfunctional (meth) acrylic modified urethane resin
(A) preparing a urethane compound by reacting (a1) a diol compound and (a2) a diisocyanate compound using (a3) a photopolymerizable monofunctional diluent as a solvent; And
(Ii) mixing (a4) a (meth) acrylate monomer and (a5) an ethylenically unsaturated compound with the urethane compound prepared in step (i) to obtain a polyfunctional (meth) acrylic modified urethane resin;
(Meth) acryl-modified urethane resin prepared by reacting a polyfunctional (meth) acryl-modified urethane resin.
6. The polyurethane foam according to claim 4 or 5, wherein the component (a1) is at least one member selected from the group consisting of polyethylene diol, polypropylene diol, polyisoprene diol, hydrogenated polybutadiene diol, poly (ethylene-co-butylene) Wherein the photo-curable, non-yellowing resin composition contains at least one member selected from the group consisting of a fluorine-containing resin and a fluorine-containing resin.
5. The photocurable non-yellowing resin composition according to claim 4, wherein the amount of the component (a1) used is 2 equivalents of the hydroxyl group of the component (a1) relative to 1 equivalent of the diisocyanate group of the component (a2).
6. The photosensitive resin composition according to claim 5, wherein the amount of the component (a1) used is 0.1 to 0.5 equivalents of a hydroxyl group of the component (a1) per 1 equivalent of the diisocyanate group of the component (a2) Composition.
6. The method according to claim 4 or 5, wherein the component (a2) is at least one selected from the group consisting of toluene-2,4-diisocyanate, 1,6-hexamethylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, tetramethylxylene diisocyanate , Isophorone diisocyanate, trimethylhexamethylene diisocyanate, and hydrogenated products thereof. The photocurable non-yellowing resin composition according to claim 1,
5. The photocurable non-yellowing resin composition according to claim 4, wherein the amount of the component (a2) used is 0.1 to 0.5 equivalent of an isocyanate group of the component (a2) relative to the hydroxyl group equivalent of the component (a1).
6. The photocurable non-yellowing resin composition according to claim 5, wherein the amount of the component (a2) to be used is 0.1 to 1.0 equivalent of an isocyanate group of the component (a2) relative to the hydroxyl group equivalent of the component (a1) .
[5] The method according to claim 4 or 5, wherein the component (a3) is a (meth) acrylate compound having a structure of the following formula (1) and having a straight chain or cyclic aliphatic structure having an ethylenically unsaturated double bond By weight based on the total weight of the resin composition.
[Chemical Formula 1]
H ₂ C = CHR ₁ -COO-R ₂
Wherein R ₁ is hydrogen or CH ₃ , and R ₂ is an alkyl structure having a straight-chain or cyclic aliphatic structure consisting of only 1 to 12 carbon atoms and hydrogen, provided that the formula is a hydroxyl group, an amine group, a phosphoric acid group or a carboxyl group It does not have a polar functional group.)
The positive resist composition according to claim 4 or 5, wherein the component (a4) is at least one compound selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2- (Meth) acrylate, 2-methacryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylsuccinic acid, and 2- (meth) acryloyloxyethyl methacrylate. (Meth) acryloyloxyethylmaleic acid, and (meth) acryloyloxyethylmaleic acid.
The photocurable non-yellowing resin composition according to claim 5, wherein the component (a5) comprises at least one member selected from the group consisting of itaconic acid and fumaric acid.
The composition according to claim 5, wherein the mixing amount of (a4) and (a5) is from 0.45 to 1.3 equivalents of the component (a4) and from 0.05 to 0.2 equivalents of the component (a5) based on 1 equivalent of the isocyanate of the component (a2) (A4) and (a5) so that the sum of the hydroxyl group, amine group or carboxyl group equivalent of the component (a5) is 0.5 to 1.5 equivalents.
6. The photocurable non-yellowing resin composition according to claim 4 or 5, wherein the (meth) acrylic-modified urethane resin has a number average molecular weight of 5,000 to 50,000.
The photopolymerizable composition according to claim 2, wherein the photopolymerizable monomer (B) based on the total amount of 100 parts by weight of the component (A) and the component (B)
(b1) 0.1-10 parts by weight of monofunctional acrylate having a polar hydroxyl group;
(b2) 9 to 60 parts by weight of a linear monofunctional acrylate having no polar group;
(b3) 0.9 to 15 parts by weight of a photopolymerizable monomer having an ethylenically unsaturated double bond and a cyclic aliphatic group; And
(b4) 0 to 5 parts by weight of a polyfunctional acrylate having two or more acrylic functional groups;
Wherein the photo-curable non-yellowing resin composition comprises:
The photopolymerization initiator of (1) or (2) above, wherein the photopolymerization initiator (C) is selected from the group consisting of a carbonyl photopolymerization initiator, a sulfide photopolymerization initiator, a quinone photopolymerization initiator, an azo photopolymerization initiator and a peroxide photopolymerization initiator Or a mixture of two or more of them.
The method according to claim 1 or 2, wherein the functional additive (D) is one or more additives selected from the group consisting of a polymerization inhibitor, a silane coupling agent, an antioxidant, a heat stabilizer, a UV stabilizer, a plasticizer and a filler By weight based on the total weight of the photocurable non-yellowing resin composition.
20. The method of claim 19 wherein the silane coupling agent is selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, trimethoxysilanyl (meth) acrylate, and vinyltriethoxysilanyl (meth) acrylate. Wherein the photo-curable non-yellowing resin composition comprises one or more of the following.
The antioxidant according to claim 19, wherein the antioxidant is a primary antioxidant selected from the group consisting of phenolic and aromatic amines, or mixtures thereof;
Wherein the second antioxidant is selected from the group consisting of phosphites and sulfur esters, or a mixture thereof.
20. The photocurable non-yellowing resin composition according to claim 19, wherein the heat stabilizer comprises at least one member selected from the group consisting of lead, calcium, organic compounds, epoxy compounds and organic phosphorous acid esters.
The ultraviolet light stabilizer according to claim 19, wherein the ultraviolet light stabilizer is selected from the group consisting of hydroxybenzophenone, hydroxyphenylbenzotriazole, aryl ester, phenol and amine primary antioxidant, benzoate and Hindered Amine Light Stabilizer (HALS) Or a mixture of two or more of the above-mentioned resins.
The plasticizer according to claim 19, wherein the plasticizer is one or more selected from the group consisting of a phthalate ester, a tri-merate ester, an aliphatic dibasic acid ester, an epoxy, a phosphoric acid ester, By weight based on the total weight of the photocurable non-yellowing resin composition.
The photocurable non-yellowing resin composition according to claim 19, wherein the filler is at least one selected from the group consisting of silica, alumina, ceria and titania.
A non-yellowing resin according to any one of claims 1 to 5, 7, 8, 10, 11, 14, 15, 17 and 20 to 25, (85 ° C, 85% RH, 1000 hours), thermal shock (-), and the like, when the thickness of the non-yellowing resin composition layer is 50 to 300 μm, 40 ~ 85 ℃, 100 cycles) or UV irradiation (30,000 under the condition of long-term reliability evaluation mJ / cm ^2), light-curable non-yellowing specimen, characterized in that the change in the b * value of 1.5 or less.
A non-yellowing resin according to any one of claims 1 to 5, 7, 8, 10, 11, 14, 15, 17 and 20 to 25, A photocurable non-yellowing adhesive comprising a composition.
27. A flat panel display according to claim 27, wherein the image display unit and the protection unit are bonded with the photo-curing non-yellowing adhesive and cured by ultraviolet rays, and the image display unit and the protection unit are cemented.

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