KR20120131420A - Composition for resin type light guide panel, backlight unit manufactured by the composition and liquid crystal display including the backlight unit - Google Patents

Abstract

PURPOSE: A resin type composition for a light guide plate is provided to have an extremely low contraction ratio, good transparency, low viscosity, and excellent mechanical properties, and to have a low haze value due to having excellent compatibility with other components. CONSTITUTION: A resin type composition for a light guide plate comprises asymmetrical urethane (meth)acrylate(A) indicated in chemical formula 1. The asymmetrical urethane (meth)acrylate is prepared by reacting a compound, which is obtained by reacting divalent polyol and divalent isocyanate, with alcohol and a hydroxy group-containing (meth)acrylate monomer. A backlight unit comprises a light emitting diode formed on a reflector, and a light guide plate which is formed to cover a light emitting diode by using the composition.

Description

Composition for resin type light guide panel, backlight unit manufactured by the composition and liquid crystal display including the backlight unit}

The present invention relates to a resin light guide plate composition, a backlight unit including a light guide plate formed using the same, and a liquid crystal display device including the backlight unit.

Liquid crystal display devices are used in various fields such as TVs and outdoor billboards as well as notebook PCs and monitors due to their small size, light weight, and low power consumption. The backlight unit used in the liquid crystal display device is classified into an edge type and a direct type according to the shape of the light source. The light sources include EL (Electro Luminescence) and CCFL (Cold Cathode Fluorescent Lamp). , Hot Cathode Fluorescent Lamp (HCFL), Light Emitting Diode (LED) and the like are used. Among them, light emitting diode packages using light emitting diodes as light sources have low power consumption and excellent luminous efficiency.

1 is a view showing the structure of a backlight unit of an edge type light emitting diode. As shown in the figure, when the LED is applied in an edge type, the LED package 30 is mounted on the printed circuit board 10 and fixed to the side of the light guide plate 40 -A. The light guide plate 40 -A spreads the light incident from the plurality of light emitting diode packages 30 evenly to a large area of the light guide plate 40 -A while traveling in the light guide plate 40 -A by a plurality of total reflections. Provide a surface light source. The reflector 20 is positioned on the rear surface of the light guide plate 40 -A, and reflects light passing through the rear surface of the light guide plate 40 -A toward the liquid crystal panel to improve the brightness of the light. However, such an edge type is difficult to apply local dimming, that is, partly turn off the lamp of the unnecessary part.

2 is a diagram illustrating a structure of a backlight unit of a direct type light emitting diode. As shown in FIG. 2, when the light emitting diode is applied in a direct type, the light emitting diode package 30 may be configured on the front surface of the printed circuit board 10 and the reflecting plate 20 to partially turn on / off the light emitting diode. Local dimming is possible. However, it is difficult to effectively apply the effect of reducing the power consumption of local dimming to increase the number of light emitting diodes 30 for the uniformity of brightness.

In order to solve the above problems, a modular backlight structure having a mixture of an edge type and a direct type has been proposed. The modular backlight unit has an edge type structure, but like the direct type structure, the LED package 30 is regularly formed on the front surface of the printed circuit board 10 and the reflecting plate 20 to reduce the number of light emitting diodes and maintain the effect of local dimming. It is possible to implement. However, although a light guide plate is required to evenly distribute the light generated from the light emitting diodes to the side, there is a problem that the light guide plate cannot be mounted on the entire printed circuit board.

In order to solve the above problems, the present applicant has the following formula prepared by reacting a compound prepared by reacting a divalent polyol with a divalent isocyanate with a (meth) acrylate monomer containing a hydroxy group in Korean Patent No. 10-1007769. The technique about the resin-type light-guide plate composition containing the urethane (meth) acrylate oligomer represented by 1 was disclosed.

≪ Formula 5 >

,

,

,

또는

이며, n 은 1 내지 10 의 정수이고, 상기 R₄는 수소 또는 메틸기이다.)(In Formula 5, R ₁ represents a residual structure excluding a terminal hydroxyl group in the divalent polyol, wherein R ₂ means a residual structure excluding the terminal isocyanate group from the divalent isocyanate, wherein R ₃ is

,

,

,

or

N is an integer of 1 to 10, and R ₄ is hydrogen or a methyl group.)

In the case of the resin light guide plate composition including the urethane (meth) acrylate oligomer represented by Chemical Formula 5, it has an advantage in that the resin light guide plate can be usefully used in the preparation of the resin light guide plate because it exhibits excellent adhesion to the substrate and little shrinkage. . However, the resin type light guide plate composition including the urethane (meth) acrylate oligomer represented by Chemical Formula 5 has a disadvantage in that the viscosity is high and the compatibility is low, so that the haze after curing is rather high.

Accordingly, the present invention can improve productivity due to low viscosity, and also have high compatibility with other components, so that no haze occurs after curing, and thus a resin-type light guide plate having high transmittance can be manufactured, and the adhesiveness with the substrate can be excellent. The purpose is to provide a composition for a topographic light guide plate.

Another object of the present invention is to provide a backlight unit including a light guide plate having a high transmittance, which is formed using the resin-type light guide plate composition.

Another object of the present invention is to provide a high quality liquid crystal display device including the backlight unit.

In order to achieve the above object, the present invention is prepared by reacting a compound prepared by reacting a divalent polyol with a divalent isocyanate with a (meth) acrylate monomer containing an alcohol and a hydroxy group. It provides the resin-type light guide plate composition containing urethane (meth) acrylate (A).

≪ Formula 1 >

,

,

,

또는

이며, n 은 1 내지 10 의 정수이고, 상기 R₄는 수소 또는 메틸기이며, R₅는 헤테로 원자를 포함해도 좋은 탄소수 1 내지 50의 말단 히드록시기를 갖는 알코올에서 말단의 히드록시기를 제외한 잔여 구조를 나타낸다.)(In Formula 1, R ₁ represents a residual structure excluding a terminal hydroxyl group in the divalent polyol, wherein R ₂ means a residual structure excluding the terminal isocyanate group from the divalent isocyanate, wherein R ₃ is

,

,

,

or

And n is an integer of 1 to 10, R ₄ is hydrogen or a methyl group, and R ₅ represents a residual structure excluding terminal hydroxy groups from an alcohol having a C 1 to C 50 terminal hydroxy group which may contain a hetero atom. )

It is preferable that the number average molecular weight of the asymmetric urethane (meth) acrylate (A) represented by the said Formula (1) is 2,000-10,000.

The asymmetric urethane (meth) acrylate (A) represented by the formula (1) is preferably contained 10 to 70 parts by weight based on 100 parts by weight of the total composition.

 A hydrogen bondable (meth) acrylate (B) in which the composition for resin light guide plate comprises a hydroxyl group or a carboxyl group; (Meth) acrylate monomer (C) having a maximum shrinkage ratio of 15% or less; And photoinitiators (D).

&Quot; (1) "

Maximum shrinkage percentage (%) = -2.58 + 3000 × [the molecular weight of the (meth) acrylic functional group number / (meth) acrylic monomer (C) of the (meth) acrylic monomer (C)]

The hydrogen bondable (meth) acrylate (B) may include at least one selected from the group consisting of compounds represented by the following Chemical Formulas 2 and 3.

<Formula 2>

In Formula 2, R ₁ Is a single bond or alkylene or heteroalkylene having 1 to 10 carbon atoms, cycloalkylene having 3 to 8 carbon atoms, phenylene, alkylphenylene having 1 to 10 carbon atoms, phosphorus, alkoxyphosphonoyl group having 1 to 10 carbon atoms or phosph; blood and Nikko group, R ₂ is H when R ₁ is a single bond, R ₁ is a hydroxy group or a carboxyl group is not a single bond R ₃ is hydrogen or a methyl group. )

<Formula 3>

In Formula 3, R ₁ Is an alkyl or heteroalkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group, an alkylphenyl group having 1 to 10 carbon atoms, and R ₃ is hydrogen or a methyl group.)

It is preferable that the said hydrogen bond type (meth) acrylate (B) is an acid-modified (meth) acrylate oligomer formed by reaction of the (meth) acrylate monomer containing an acid anhydride and a hydroxyl group.

The acid-modified (meth) acrylate oligomer may include at least one selected from the group consisting of compounds represented by the following Formulas 4a to 4f.

&Lt; Formula 4a &

<Formula 4b>

<Formula 4c>

<Formula 4d>

<Formula 4e>

<Formula 4f>

,

,

,

또는

에서 선택되며, 상기 n 은 1 내지 10 의 정수이며, R₃는 각각 독립적으로 수소, 탄소수 1 내지 10 의 포화 또는 불포화알킬기, 헤테로알킬기, 벤질기, 카르복실기기, 히드록시기 또는 할로겐 원소에서 선택되며, R₄는 탄소수 1 내지 10 의 포화 또는 불포화알킬렌기이다.)In Formulas 4a to 4f, R ₁ is each independently hydrogen or a methyl group, and R ₂ is each independently

,

,

,

or

N is an integer of 1 to 10, R ₃ is each independently selected from hydrogen, a saturated or unsaturated alkyl group of 1 to 10 carbon atoms, heteroalkyl group, benzyl group, carboxyl group, hydroxy group or halogen element, R ₄ is a saturated or unsaturated alkylene group having 1 to 10 carbon atoms.)

The hydrogen bondable (meth) acrylate (B) is included in an amount of 10 to 40 parts by weight, and the (meth) acrylate monomer (C) is contained in an amount of 10 to 60 parts by weight based on 100 parts by weight of the total composition for the resin light guide plate. The photoinitiator (D) is preferably included in 0.1 to 10 parts by weight.

The resin type light guide plate composition may further include a trifunctional or higher (meth) acrylate curing agent (E) having a maximum shrinkage ratio of Equation 5 below 20%.

<Equation 5>

Maximum shrinkage percentage (%) = -2.58 + 3000 × [molecular weight of (meth) acrylic functional group / (meth) acrylic monomer (E) of (meth) acrylic monomer (E)]

 The (meth) acrylate curing agent (E) may be included 1 to 5 parts by weight based on 100 parts by weight of the total composition.

The resin-type light guide plate composition includes at least two kinds of the (meth) acrylic monomer (C) and preferably has a maximum shrinkage ratio of 3 to 7% calculated by the following formula (4).

&Quot; (4) &quot;

Max Shrinkage (%) =

(In the above formula (4), i represents the number of (meth) acrylic monomer (C) contained in the composition for forming a dot pattern, when each (meth) acrylic monomer is referred to as the n-th monomer regardless of the order of inclusion ,

XnSn represents the product of Xn and Sn,

Xn represents the mass fraction of the nth monomer,

Sn represents the maximum shrinkage rate of the n-th monomer and is calculated by Equation (1).)

In order to achieve the above object of the present invention, the present invention provides a backlight unit comprising a light emitting diode formed on a reflecting plate and a light guide plate formed to cover the light emitting diode with the composition.

It is preferable that the thickness of the said light guide plate is 0.2-2 mm.

In order to achieve another object of the present invention described above, the present invention provides a liquid crystal display device comprising the backlight unit.

The resin-type light guide plate composition according to the present invention has a very small shrinkage rate as the urethane (meth) acrylate oligomer comprises an asymmetric urethane (meth) acrylate oligomer represented by the formula (1) having a number average molecular weight of 2,000 to 10,000, Good transparency, low viscosity and excellent mechanical properties as well as excellent compatibility with other components exhibits a low haze value. The resin light guide plate composition according to the present invention can be formed as a light guide plate for converting a point light source into a surface light source by a simple curing method irrespective of the position of the light emitting diode, and exhibits excellent adhesion to the substrate. In particular, the resin light guide plate composition according to the present invention may be usefully applied to a mixed modular backlight unit in which an edge type and a direct type are mixed.

1 is a view illustrating a structure of a general edge type backlight unit.
2 is a view showing the structure of a general direct type backlight unit.
3 is a diagram illustrating a structure of a mixed modular backlight unit.
4 is a diagram schematically illustrating a structure of a mixed modular backlight unit in which a light guide plate is not formed.

Hereinafter, described in detail so that those skilled in the art can easily implement the present invention.

The resin-type light guide plate composition according to the embodiment of the present invention comprises a urethane (meth) acrylate oligomer (A). The composition may comprise a hydrogen bondable (meth) acrylate (B), a (meth) acrylate monomer (C) and a photoinitiator (D). The photocurable composition may further include a (meth) acrylate curing agent (E).

urethane ( Meta ) Acrylate Oligomer (A)

The urethane (meth) acrylate oligomer is represented by the following formula (1) as an asymmetric type prepared by reacting a compound prepared by reacting a divalent polyol with a divalent isocyanate with a (meth) acrylate monomer containing an alcohol and a hydroxyl group.

&Lt; Formula 1 >

,

,

,

또는

이며, n 은 1 내지 10 의 정수이고, 상기 R₄는 수소 또는 메틸기이며, R₅는 헤테로 원자를 포함해도 좋은 탄소수 1 내지 50의 말단 히드록시기를 갖는 알코올에서 말단의 히드록시기를 제외한 잔여 구조를 나타낸다.)(In Formula 1, R ₁ represents a residual structure excluding a terminal hydroxyl group in the divalent polyol, wherein R ₂ means a residual structure excluding the terminal isocyanate group from the divalent isocyanate, wherein R ₃ is

,

,

,

or

And n is an integer of 1 to 10, R ₄ is hydrogen or a methyl group, and R ₅ represents a residual structure excluding terminal hydroxy groups from an alcohol having a C 1 to C 50 terminal hydroxy group which may contain a hetero atom. )

Asymmetric urethane (meth) acrylate oligomers represented by Formula 1 provide transparency, low viscosity properties and excellent mechanical properties. In particular, the urethane (meth) acrylate oligomer represented by the formula (1) is excellent in compatibility with other components exhibits a low haze value.

The asymmetric urethane (meth) acrylate oligomer represented by Formula 1 may be prepared by reacting a compound prepared by reacting a divalent polyol with a divalent isocyanate with a (meth) acrylate monomer containing an alcohol and a hydroxyl group. have. In other words, a divalent polyol is reacted with an excess of divalent isocyanate to prepare a prepolymer having an isocyanate group at the terminal, and the prepolymer thus prepared is sequentially reacted with a (meth) acrylate monomer containing an alcohol and a hydroxyl group. Can be.

Specifically, the divalent polyol is a group consisting of polyester polyol, polycaprolactone modified polyol, polycarbonate polyol, polybutadiene polyol, polyisophorene polyol, polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol and polytetramethyl glycol It can be used alone or a mixture thereof selected from, but is not limited thereto. The divalent polyol is not necessarily limited, but it is preferable to use a number average molecular weight of 800 or more, more preferably 1000 or more.

Specific examples of the divalent isocyanate include toluene-2,4-diisocyanate and isomers, xylene diisocyanate, isophorone diisocyanate, tetramethyl xylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, 2,2-bis- 4'-propane isocyanate, 6-isopropyl-1,3-phenyldiisocyanate, bis (2-isocyanate ethyl) -fumarate, 1,6-hexanediisocyanate, 4,4'-biphenylene diisocyanate, 3, 3'-dimethylphenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, p-phenylene diisocyanate, m-phenylenedi isocyanate, 1,5-naphthalene diisocyanate, 1,4- Single or mixtures thereof selected from the group consisting of xylene diisocyanate and 1,3-xylene diisocyanate and 4,4-dicyclohexylmethane diisocyanate Can be used, preferably toluene-2,4-diisocyanate and isomer, isophorone diisocyanate, 1,5-naphthalene diisocyanate, 1,4-xylene diisocyanate, 1,3-xylene diisocyanate, 4,4 It is possible to use alone or a mixture thereof selected from the group consisting of -dicyclohexylmethane diisocyanate and 1,6-hexamethylene diisocyanate, but is not limited thereto.

The said alcohol can use the compound which has a C1-C50 terminal hydroxyl group which may contain a hetero atom without limitation. Preferably the alcohol is at least one selected from the group consisting of methyl alcohol, ethyl alcohol, butyl alcohol, isodecyl alcohol, decyl alcohol, ethyl hexyl alcohol, tridecyl alcohol, isotridecyl alcohol, dodecyl alcohol, isododecyl alcohol Compounds can be used, but are not limited thereto.

Specific examples of the (meth) acrylate monomer containing the hydroxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and caprolactone Modified (meth) acrylate, polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate may be used alone or a mixture thereof selected from the group consisting of, but is not limited thereto.

The divalent polyol is preferably reacted in an amount of 0.2 to 0.95 equivalents, particularly 0.4 to 0.9 equivalents, based on 1 equivalent of divalent isocyanate. When the reaction equivalent of the divalent polyol exceeds 0.95 equivalents to 1 equivalent of the divalent isocyanate, the molecular weight of the prepolymer having an isocyanate group at the terminal to be produced increases the molecular weight, thereby reducing the shrinkage rate but increasing the viscosity, thereby decreasing applicability. If there is a problem, less than 0.2 equivalent, the molecular weight of the prepolymer is not large enough, there is a problem that the shrinkage is large.

The prepolymer having an isocyanate group at the terminal obtained by reacting the divalent polyol and divalent isocyanate is reacted with a (meth) acrylic monomer containing hydroxy and an alcohol.

At this time, the (meth) acrylic monomer and the alcohol containing hydroxy are respectively bonded to one terminal of the sock end of the prepolymer and 0.5 to 0.6 equivalents, respectively, per 1 equivalent of isocyanate of the prepolymer so that no isocyanate group remains. It is preferable to use as much as possible. When the (meth) acrylic monomer and alcohol containing hydroxy in the above range are used, the asymmetric urethane represented by the formula (1) having not only transparency, viscosity characteristics and excellent mechanical properties but also excellent compatibility with other components ( Meth) acrylate oligomer can be obtained.

A catalyst may be used to improve reactivity in the process of preparing the urethane (meth) acrylate oligomer, and a polymerization inhibitor may be used to improve reaction stability and storage stability.

The catalyst is specifically triethylamine, triethanolamine, 1,4-diazabiscyclo- (2,2,2) -octane, N, N-diethylcyclohexylamine, N-methylmorpholine, N, N Tertiary amines such as, N ', N'-tetramethyl-methanediamine or dibutyltindilaurate, dibutyltindibutoxide, di- (2-ethylhexyl) tinoxide, dibutyltindiisooctyl maleate, di One or more types of tin-based catalysts such as butyl tin bis- (acetylacetonate), butyl tin trichloride, tributyl tin cyanate can be selected and used, and preferably dibutyl tin dilaurate may be used. The said polymerization inhibitor can use a small amount of phenol type polymerization inhibitors, such as methoxy hydroquinone, hydroquinone, and t-butyl hydroquinone.

The urethane (meth) acrylate oligomer may have a number average molecular weight of 2,000 to 10,000. When the number average molecular weight of the urethane- (meth) acrylate oligomer is less than 2,000, the curing shrinkage may be increased, and when the number average molecular weight is greater than 10,000, the viscosity of the composition may be increased to reduce workability.

The asymmetric urethane (meth) acrylate oligomers according to the present invention exhibit not only low viscosity characteristics but also excellent compatibility with other materials compared to the symmetrical urethane (meth) acrylate oligomers of the general formula (5) presented by the present applicant. do. In particular, due to the low viscosity characteristics, not only can the productivity be improved, but also have a low haze value due to the excellent compatibility with other materials.

The asymmetric urethane (meth) acrylate oligomer represented by Chemical Formula 1 may be included in an amount of 10 to 70 parts by weight, and preferably 20 to 60 parts by weight, based on 100 parts by weight of the total composition for a resin type light guide plate. When the content of the urethane (meth) acrylate oligomer is included in less than 10 parts by weight based on the above reference, sufficient mechanical properties such as adhesion to the substrate can not be obtained, and when included in excess of 70 parts by weight of the photocurable composition There is a problem that the viscosity is too high, not only the workability is lowered but also the shrinkage rate is increased.

Hydrogen Bond Type Meta ) Acrylate (B)

The hydrogen bond type (meth) acrylate (B) may form an ionic bond with the substrate or dissolve a portion of the substrate to impart adhesion to the physical bond.

The hydrogen bond type (meth) acrylate (B) can be used without limitation as long as it can form a hydrogen bond, preferably (meth) acrylate containing a hydroxy group or a carboxyl group can be used.

The hydrogen bond type (meth) acrylate (B) may preferably include at least one selected from the group consisting of compounds represented by the following Chemical Formulas 2 and 3.

<Formula 2>

In Formula 2, R ₁ Is a single bond, alkylene or heteroalkylene having 1 to 10 carbon atoms, cycloalkylene having 3 to 8 carbon atoms, phenylene, alkylphenylene having 1 to 10 carbon atoms, phosphorus, alkoxyphosphonoyl group having 1 to 10 carbon atoms, or Phosphinicosuccinic Nikko group and, R ₂ is H when R ₁ is a single bond, a hydroxy group or a carboxyl group when R ₁ is not a single bond, R ₃ is hydrogen or a methyl group.)

<Formula 3>

In Formula 3, R ₁ Is an alkyl or heteroalkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group, an alkylphenyl group having 1 to 10 carbon atoms, and R ₃ is hydrogen or a methyl group.)

Specific examples of the (meth) acrylate having a hydroxy group introduced therein among the compounds represented by Formula 2 include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth). Acrylate, caprolactone modified (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phosphoric acid (meth) acrylate, and the like (meth) acrylic with carboxyl group Specific examples of the rate include (meth) acrylic acid.

The compound represented by Chemical Formula 3 may be prepared by reacting a monomer having an epoxy functional group with (meth) acrylic acid. Although the number of the said epoxy functional groups is preferable monofunctional, when molecular weight is large, polyfunctional may be sufficient. Specific examples of the monomer having an epoxy functional group include ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and phenol glycidyl ether. , Nonylphenol glycidyl ether, polybisphenol A diglycidyl ether, polybisphenol F diglycidyl ether, polybisphenol S diglycidyl ether, polybisphenol AD diglycidyl ether, and the like may be used. It is not limited.

A catalyst may be used in the reaction of the monomer having the epoxy functional group with (meth) acrylic acid. As the catalyst, tertiary amine-based, quaternary ammonium salt-based, inorganic alkali salt-based and phosphorus-based catalysts may be used. Specifically, triethylamine, pyridine, trimethylamine, tributylamine, triethylamine benzyl chloride, triethylamine Benzyl bromide, tributylamine benzyl chloride, tributylamine benzyl bromide, tetrabutylamine chloride, tetrabutylamine bromide, triphenylphosphine, chromium octate and the like may be used, but is not limited thereto.

The hydrogen bond type (meth) acrylate (B) may be an acid-modified (meth) acrylate oligomer formed by the reaction of an (meth) acrylate monomer containing an acid anhydride and a hydroxy group in the presence of a catalyst.

The acid anhydride is preferably a cyclic acid anhydride, and the (meth) acrylate monomer containing the hydroxy group is specifically 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4 Hydroxybutyl (meth) acrylate, caprolactone modified (meth) acrylate, polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate alone or mixtures thereof may be used. However, the present invention is not limited thereto.

As the catalyst, tertiary amine-based, quaternary ammonium salt-based, inorganic alkali salt-based and phosphorus-based catalysts may be used. Specifically, triethylamine, pyridine, trimethylamine, tributylamine, triethylamine benzyl chloride, triethylamine Benzyl bromide, tributylamine benzyl chloride, tributylamine benzyl bromide, tetrabutylamine chloride, tetrabutylamine bromide, triphenylphosphine, chromium octate and the like may be used, but is not limited thereto.

Preferably, the acid-modified (meth) acrylate oligomer may include at least one selected from the group consisting of compounds represented by the following Chemical Formulas 4a to 4f.

&Lt; Formula 4a &

<Formula 4b>

<Formula 4c>

<Formula 4d>

<Formula 4e>

<Formula 4f>

,

,

,

또는

에서 선택되며, 상기 n 은 1 내지 10 의 정수이며, R₃는 각각 독립적으로 수소, 탄소수 1 내지 10 의 포화 또는 불포화알킬기, 헤테로알킬기, 벤질기, 카르복실기기, 히드록시기 또는 할로겐 원소에서 선택되며, R₄는 탄소수 1 내지 10 의 포화 또는 불포화알킬렌기이다.)In Formulas 4a to 4f, R ₁ is each independently hydrogen or a methyl group, and R ₂ is each independently

,

,

,

or

N is an integer of 1 to 10, R ₃ is each independently selected from hydrogen, a saturated or unsaturated alkyl group of 1 to 10 carbon atoms, heteroalkyl group, benzyl group, carboxyl group, hydroxy group or halogen element, R ₄ is a saturated or unsaturated alkylene group having 1 to 10 carbon atoms.)

The hydrogen bond type (meth) acrylate (B) may include at least one selected from the group consisting of compounds represented by Formulas 2, 3, 4a to 4f as necessary.

The hydrogen bond type (meth) acrylate (B) may be included in an amount of 10 to 40 parts by weight, preferably 15 to 35 parts by weight, based on 100 parts by weight of the total composition for the resin light guide plate. When the hydrogen bond type (meth) acrylate (B) is included in less than 10 parts by weight on the basis of the above, the viscosity of the entire composition may be increased workability and adhesion may be lowered, if included in more than 40 parts by weight, There is a problem that the viscosity may be lowered to cover the LED package, the compatibility may be lowered.

( Meta Acrylic monomer (C)

The (meth) acrylic monomer (C) serves to lower the viscosity of the composition for workability without affecting the physical properties of the composition.

As the (meth) acrylic monomer (C), a maximum shrinkage ratio of the following Equation 1 may be 15% or less, and preferably 3 to 10%. If the maximum shrinkage is greater than 15%, the curing speed is high, but the degree of curing is low, making it difficult to realize sufficient physical properties. In addition, when the shrinkage difference with the substrate is large, the adhesive force is lowered due to the warpage phenomenon. However, the maximum shrinkage rate may not have a value smaller than zero in meaning.

&Quot; (1) &quot;

Maximum shrinkage percentage (%) = -2.58 + 3000 × [the molecular weight of the (meth) acrylic functional group number / (meth) acrylic monomer (C) of the (meth) acrylic monomer (C)]

Typically, the shrinkage may be expressed as the ratio of specific gravity before curing and specific gravity after curing, as shown in Equation 2 below, but by using Equation 1, shrinkage may be easily estimated. The maximum shrinkage ratio of Equation 1 is shown on the assumption that the degree of curing is 100%, Pezron, E., and Magny, B., "Modeling of UV oligomers and monomers properties: viscosity and shrinkage", RadCure Letter ., 2 (1997).

Herein, the degree of curing may vary depending on the curing conditions, but the following Equation 3 expressed as the product of the maximum shrinkage rate and the degree of cure of Equation 1 shows the same result as the shrinkage rate of Equation 2 below.

&Quot; (2) &quot;

Shrinkage (%) = {(specific gravity before cure-specific gravity after cure) / (specific gravity before cure)} × 100

&Quot; (3) &quot;

Shrinkage (%) = Hardness (%) x [Equation 1] / 100

Specific examples of the (meth) acrylic monomer (C) having a maximum shrinkage of 15% or less include 2-phenoxyethyl acrylate (13%), cyclic trimethylolpropane foam acrylate (12.4%), and tridecyl acrylate (9.2). %), Octyldecyl acrylate (12.6%), isobornyl acrylate (11.8%), 2- (2-ethoxyethoxy) ethyl acrylate (13.4%) isodecyl acrylate (11.6%), caprolactone acryl Rate (6.1%), lauryl acrylate (9.9%), stearic acrylate (6.7%), methoxy polyethylene glycol 600 monoacrylate (2.1%), nonylphenol ethylene oxide (4 mol) acrylate (4.1% ), Nonylphenol ethylene oxide (8 mol) acrylate (2.2%), methoxy polyethylene glycol 600 monoacrylate (1.8%), isodecyl methacrylate (10.7%), stearic methacrylate (6.3%), 2-phenoxyethyl methacrylate (12%), isobornyl methacrylate (11%), tridecylmetha Relate (8.6%) and the like.

The (meth) acrylic monomer (C) of the present invention may include two or more kinds of compounds, and in this case, the maximum shrinkage rate calculated by Equation 4 below is preferably 3 to 7%.

The maximum shrinkage rate in the case where various kinds of (meth) acrylic monomers are mixed by the following Equation 4 can be calculated.

&Quot; (4) &quot;

Max Shrinkage (%) =

(In formula (4), i represents the number of the number of the (meth) acrylic monomer (C) contained in the composition for dot pattern formation,

Regardless of the order of inclusion, when each (meth) acrylic monomer is referred to as the nth monomer,

XnSn represents the product of Xn and Sn,

Xn represents the mass fraction of the nth monomer,

Sn represents the maximum shrinkage rate of the n-th monomer and is calculated by Equation (1).)

When the maximum shrinkage rate expressed by Equation 4 is increased, the adhesive force decreases, the hardenability is increased, and when the maximum shrinkage rate decreases, the opposite tendency is shown. Therefore, when the maximum shrinkage expressed by Equation 4 is 3 to 7%, sufficient curing property of 90% or more can be ensured, thereby ensuring sufficient physical properties.

The (meth) acrylic monomer (C) may be included in 10 to 60 parts by weight, preferably 20 to 50 parts by weight based on 100 parts by weight of the total composition for the resin light guide plate. When the (meth) acrylate monomer is included in less than 10 parts by weight based on the above standards, there is a problem in that the workability is high due to the high viscosity of the composition, and when included in excess of 60 parts by weight, mechanical properties may be lowered and adhesive strength may be lowered. There is a problem.

Photoinitiator (D)

The photoinitiator (D) can be used without limitation what is generally known.

The photoinitiator (D) coexists with the first type initiator and the tertiary amine, in which radicals are generated by the decomposition of molecules due to the difference in chemical structure or molecular bond energy, so that there is a hydrogen release type second initiator.

Specific examples of the type 1 initiator include 4-phenoxydichloroacetphenone, 4-t-butyldichloroacetphenone, 4-t-butyltrichloroacetphenone, diethoxyacetphenone, 2-hydroxy-2-methyl -l-phenylpropane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-l-one, 1- (4-dodecylphenyl) -2-hydroxy-2 Acetphenones such as -methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, and 1-hydroxycyclohexylphenyl ketone, benzoin, benzo Benzoin, such as phosphine ether, benzoin ethyl ether, benzyl dimethyl ketal, an acyl phosphine oxide, a titanocene compound, etc. are mentioned.

Specific examples of the type 2 initiators include benzophenone, benzoyl benzoic acid, benzoyl benzoic acid methyl ether, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzol-4'-methyldiphenyl sulfide, 3, Benzophenones, such as 3'-methyl-4- methoxy benzophenone, thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, 2, 4-dimethyl thioxanthone, isopropyl thioxanthone, etc. And thioxanthones. These photoinitiators (D) can be used individually or in mixture of these, You may use together a 1st type and a 2nd type.

The photoinitiator (D) may be included in an amount of 0.1 to 10 parts by weight, and preferably 0.2 to 3 parts by weight, based on 100 parts by weight of the total composition for the resin light guide plate. When the photoinitiator (D) is included in less than 0.1 parts by weight, it is difficult to realize sufficient mechanical properties or adhesive strength due to insufficient curing, and when included in more than 10 parts by weight, such as poor adhesion or cracks on the surface due to curing shrinkage Problems may arise.

( Meta ) Acrylate  Curing agent (E)

The composition for dot pattern formation of this invention may further contain the trifunctional or more (meth) acrylate hardening | curing agent (E) in order to improve sclerosis | hardenability.

As the trifunctional or higher functional (meth) acrylate curing agent (E), one having a maximum shrinkage ratio of the following Equation 5 is 20% or more.

<Equation 5>

Maximum shrinkage percentage (%) = -2.58 + 3000 × [molecular weight of (meth) acrylic functional group / (meth) acrylic monomer (E) of (meth) acrylic monomer (E)]

Here, Equation 5 corresponds to the same content as Equation 1, and described as above to distinguish the monomers used. Therefore, when using more than one compound, those skilled in the art will understand that the application of formula (4) is possible.

The maximum shrinkage ratio of Equation 5 is 20% or more, specifically, reaction with glycerolpropyl addition tri (meth) acrylate, ditrimethylol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and diisocyanate One pentaerythritol tri (meth) acrylate urethane oligomer, the dipenta (meth) acrylate urethane oligomer which reacted with diisocyanate, etc. are mentioned. These can be used individually or in combination of 2 or more, respectively.

The trifunctional or higher (meth) acrylate curing agent (E) may be included in an amount of 1 to 5 parts by weight based on 100 parts by weight of the total composition. When included in less than 1 part by weight is insufficient improvement in curability, when included in more than 5 parts by weight there is a problem that the shrinkage is severe and the adhesive strength is lowered.

The resin-type light guide plate composition of the present invention can be added to the UV stabilizer and heat stabilizer, or additives commonly used in the art as necessary to those skilled in the art to adjust the content according to the needs within the scope of not impairing the object of the present invention. have.

The UV stabilizer serves to block or absorb UV light to prevent degradation by prolonged UV exposure of the cured composition.

The UV stabilizers are classified into absorbers, quenchers, and hindered amine light stabilizers (HALS) according to functional mechanisms. Depending on the chemical structure, it can be classified into phenyl salicylates (sorbents), benzophenones (sorbents), benzotriazoles (sorbents), nickel derivatives (quenchers), and radical scavengers. Can be. It will not specifically limit, if it is an ultraviolet stabilizer which does not change the initial color of a composition largely in this invention.

The heat stabilizer may be used both commercially applicable polyphenol-based, phosphite-based, lactone-based. The UV stabilizer and the heat stabilizer may be used by appropriately adjusting the content at a level that does not affect the curability.

The present invention provides a backlight unit including a light emitting diode formed on a reflecting plate and a light guide plate formed by using the resin type light guide plate composition according to the present invention so as to cover the light emitting diode.

For example, the resin type light guide plate composition according to the present invention may be applied to form a light guide plate of a locally dimmable modular backlight structure in which an edge type and a direct type shown in FIG. 3 are mixed.

For example, the light guide plate may be formed in a simple manner by applying the resin-type light guide plate composition to a predetermined thickness on a reflecting plate and curing the same. In this case, the thickness of the light guide plate is preferably 0.2 to 2 mm.

The light guide plate serves to convert the point light source into a surface light source and exhibits excellent adhesion to the reflective plate as a substrate and excellent brightness.

The backlight unit according to the present invention may further include a diffusion plate, a diffusion film, a light collecting film, a reflective polarizing film, and the like, which are generally used in the art as an upper surface of the light guide plate. Since this is known in the art, detailed description thereof will be omitted.

In addition, the present invention provides a liquid crystal display device having the backlight unit. Since the liquid crystal display device may adopt a configuration generally known in the art, a detailed description thereof will be omitted.

The present invention will be further illustrated by the following examples, which are only specific examples of the present invention, and are not intended to limit or limit the protection scope of the present invention.

Synthesis Example 1 Preparation of Urethane (meth) acrylate Oligomer

In a 1000 ml glass reactor equipped with a stirrer, a heating mantle, a cooling tube, and a temperature control device, 400 parts by weight of polypropylene glycol (Hanongseong, PPG 2000) having an average molecular weight of 2,000, 0.3 parts by weight of methoxyhydroquinone (Eastman, HQMME), 111 parts by weight of isophorone diisocyanate (ALDRICH, IPDI) and 0.1 part by weight of dibutyl tin dilaurate (Achemy, Fascat 4202) were placed in a reactor, and the reaction temperature was maintained at 70 ° C. for 2 hours. After cooling the reactor temperature to 40 ℃ and put 47.5 parts by weight of 1-decanol (TCI, 2-Decanol) in the reactor was heated to 70 ℃ and the reaction was performed for 2 hours. The reactor temperature was cooled to 40 ° C., 65 parts by weight of 2-hydroxyethyl methacrylate (large gold, 2-HEMA) was added to the reactor, and the reaction was performed at 80 ° C. for 3 hours. An isocyanate characteristic peak (2260 cm ⁻¹ ) The reaction was terminated after confirming that it was completely gone. At this time, the resin viscosity was 18500 cps (25 ° C) and the number average molecular weight was 3700. The overall scheme is as shown in Scheme 1 below.

[Reaction Scheme 1]

Synthesis Example 2 Preparation of Urethane (meth) acrylate Oligomer

In a 1000 ml glass reactor equipped with a stirrer, a heating mantle, a cooling tube, and a temperature control device, 400 parts by weight of polypropylene glycol (Hanongseong, PPG 2000) having an average molecular weight of 2,000, 0.3 parts by weight of methoxyhydroquinone (Eastman, HQMME), 111 parts by weight of isophorone diisocyanate (ALDRICH, IPDI) and 0.1 part by weight of dibutyl tin dilaurate (Achemy, Fascat 4202) were placed in a reactor, and the reaction temperature was maintained at 70 ° C. for 2 hours. After the reactor temperature was cooled to 40 ℃ and 56 parts by weight of 1-dodecanol (TCI, 2-Dodecanol) was put in the reactor and the temperature was raised to 70 ℃ and the reaction proceeded for 2 hours. The reactor temperature was cooled to 40 ° C., 65 parts by weight of 2-hydroxyethyl methacrylate (large gold, 2-HEMA) was added to the reactor, and the reaction was performed at 80 ° C. for 3 hours. An isocyanate characteristic peak (2260 cm ⁻¹ ) The reaction was terminated after confirming that was completely gone . At this time, the resin viscosity was 24000 cps (25 ° C.) and the number average molecular weight was 4200. The overall scheme is as shown in Scheme 2 below.

Scheme 2

Synthesis Example 3 Preparation of Urethane (meth) acrylate Oligomer

In a 1000 ml glass reactor equipped with a stirrer, a heating mantle, a cooling tube, and a temperature control device, 400 parts by weight of polypropylene glycol (Hanongseong, PPG 2000) having an average molecular weight of 2,000, 0.3 parts by weight of methoxyhydroquinone (Eastman, HQMME), 111 parts by weight of isophorone diisocyanate (ALDRICH, IPDI) and 0.1 part by weight of dibutyl tin dilaurate (Achemy, Fascat 4202) were placed in a reactor, and the reaction temperature was maintained at 70 ° C. for 2 hours. Thereafter, the reactor was cooled to 40 ° C., 39 parts by weight of 2-ethylhexyl alcohol (TCI, 2-ethylhexyl alcohol) was added to the reactor, and the temperature was raised to 70 ° C., followed by reaction for 2 hours. The reactor temperature was cooled to 40 ° C., 65 parts by weight of 2-hydroxyethyl methacrylate (large gold, 2-HEMA) was added to the reactor, and the reaction was performed at 80 ° C. for 3 hours. An isocyanate characteristic peak (2260 cm ⁻¹ ) The reaction was terminated after confirming that it was completely gone. At this time, the resin viscosity was 26000 cps (25 ° C.) and the number average molecular weight was 4500. The overall scheme is as shown in Scheme 3 below.

Scheme 3

Synthesis Example 4 Preparation of Urethane (meth) acrylate Oligomer

In a 1000 ml glass reactor equipped with a stirrer, a heating mantle, a cooling tube, and a temperature control device, 400 parts by weight of polypropylene glycol (Hanongseong, PPG 2000) having an average molecular weight of 2,000, 0.3 parts by weight of methoxyhydroquinone (Eastman, HQMME), 131 parts by weight of hexamethylene diisocyanate (ALDRICH, Desmodur W) and 0.1 parts by weight of dibutyl tin dilaurate (Achemy, Fascat 4202) were placed in a reactor, and the reaction was performed for 2 hours while maintaining the reaction temperature at 70 ° C. Thereafter, the reactor was cooled to 40 degrees, 47.5 parts by weight of 1-decanol (TCI, 2-Decanol) was put in the reactor, and the temperature was raised to 70 ° C., followed by reaction for 2 hours. The reactor temperature was cooled to 40 ° C, 107.2 parts by weight of 2-hydroxyethyl methacrylate (large gold, 2-HEMA) was added to the reactor, and the reaction was performed at 80 ° C for 3 hours. An isocyanate characteristic peak (2260cm ^-1 ) The reaction was terminated after confirming that it was completely gone. At this time, the resin viscosity was 78,000cp (25 ° C) and the number average molecular weight was 5500. The overall scheme is as shown in Scheme 4 below.

[Reaction Scheme 4]

Synthesis Example 5 Preparation of Urethane (meth) acrylate Oligomer

In a 1000 ml glass reactor equipped with a stirrer, a heating mantle, a cooling tube, and a temperature control device, 400 parts by weight of polypropylene glycol (Hanongseong, PPG 2000) having an average molecular weight of 2,000, 0.3 parts by weight of methoxyhydroquinone (Eastman, HQMME), 131 parts by weight of hexamethylene diisocyanate (ALDRICH, Desmodur W) and 0.1 parts by weight of dibutyl tin dilaurate (Achemy, Fascat 4202) were placed in a reactor and the reaction was performed for 2 hours while maintaining the reaction temperature at 70 ° C. After the reactor temperature was cooled to 40 ℃ and 56 parts by weight of 1-dodecanol (TCI, 2-Dodecanol) was put in the reactor and the temperature was raised to 70 ℃ and the reaction proceeded for 2 hours. The reactor temperature was cooled to 40 ° C., 107.2 parts by weight of 2-hydroxyethyl methacrylate (large gold, 2-HEMA) was added to the reactor, and the reaction proceeded at 80 ° C. for 3 hours. An isocyanate characteristic peak (2260 cm ⁻¹ ) The reaction was terminated after confirming that disappeared completely . At this time, the resin viscosity was 66,000 cps (25 ° C.), and the number average molecular weight was 4900. The overall scheme is as shown in Scheme 5 below.

Scheme 5

Synthesis Example 6 Preparation of Urethane (meth) acrylate Oligomer

In a 1000 ml glass reactor equipped with a stirrer, a heating mantle, a cooling tube, and a temperature control device, 400 parts by weight of polypropylene glycol (Hanongseong, PPG 2000) having an average molecular weight of 2,000, 0.3 parts by weight of methoxyhydroquinone (Eastman, HQMME), 131 parts by weight of hexamethylene diisocyanate (ALDRICH, Desmodur W) and 0.1 parts by weight of dibutyl tin dilaurate (Achemy, Fascat 4202) were put into a reactor and the reaction was carried out for 2 hours while maintaining the temperature at 70 ° C. Thereafter, the reactor was cooled to 40 ° C., 39 parts by weight of 2-ethylhexyl alcohol (TCI, 2-ethylhexyl alcohol) was added to the reactor, and the temperature was raised to 70 ° C., followed by reaction for 2 hours. The reactor temperature was cooled to 40 ° C., 107.2 parts by weight of 2-hydroxyethyl methacrylate (large gold, 2-HEMA) was added to the reactor, and the reaction proceeded at 80 ° C. for 3 hours. An isocyanate characteristic peak (2260 cm ⁻¹ ) Confirm that the disappeared completely and terminate the reaction . At this time, the resin viscosity was 68,000cp (25 ° C), and the number average molecular weight was 4800. The overall scheme is as shown in Scheme 6 below.

[Reaction Scheme 6]

Synthesis Example 7 Preparation of Urethane (meth) acrylate Oligomer

600 parts by weight of polytetraethylene glycol (Polyethylene Korea, PTMG 3000) having an average molecular weight of 3,000 in a 2000 ml glass reactor equipped with a stirrer, a heating mantle, a cooling tube and a temperature control device, hexamethylene diisocyanate (Bieler, Desmodur W) 131 By weight, 0.1 parts by weight of dibutyl tin dilaurate (Achemy, Fascat 4202) was put into the reactor and the reaction was performed for 3 hours while maintaining the reaction temperature at 70 ℃. The reactor temperature was cooled to room temperature, 107.2 parts by weight of 2-hydroxyethyl methacrylate (Cognis, 2-HEMA) and 93.3 parts by weight of isobonol acrylate (Osaka Yuki Co., IBXA), smistizer zipi (Sumitomo Chemical) 0.7 parts by weight, 0.8 parts by weight of methoxyhydroquinone (Eastman, HQMME), 0.2 parts by weight of dibutyl tin dilaurate (Achemy, Fascat 4202) was added and the reaction was carried out at 75 ° C. for 6 hours, and an isocyanate characteristic peak (2260 cm) ^-1 ) confirmed complete disappearance and the reaction was terminated. At this time, the resin viscosity was 95,000 cps (25 ° C.), and the number average molecular weight was 3,800. The overall scheme is as shown in Scheme 7 below.

[Reaction Scheme 7]

Synthesis Example 8 Preparation of Urethane (meth) acrylate Oligomer

800 parts by weight of polyethylene glycol (Hanong Chemical Co., Ltd., PEG 4000 (F)) with an average molecular weight of 4,000 in a 2000 ml glass reactor equipped with a stirrer, heating mantle, cooling tube and temperature control unit, 111 isophorone diisocyanate (Bieler, IPDI) Part, dibutyl tin dilaurate (Achemy, Fascat 4202) 0.1 parts by weight was put in a reactor and the reaction was carried out for 3 hours while maintaining the reaction temperature at 70 ℃. The reactor temperature was cooled to room temperature, 107.2 parts by weight of 2-hydroxyethyl methacrylate (Cognis Co., 2-HEMA), 115.5 parts by weight of isobonol acrylate (Osaka Yuki Co., IBXA), Smilage Phi (Sumitomo Chemical) ) 0.7 parts by weight, methoxyhydroquinone (Eastman, HQMME) 0.8 parts by weight, dibutyl tin dilaurate (Akemi, Fascat 4202) 0.2 parts by weight of the reaction proceeded at 75 ℃ for 6 hours, the isocyanate characteristic peak ( 2260 cm ^-1 ) completely disappeared and the reaction was terminated. At this time, the resin viscosity was 125,000 cps (25 ° C.), and the number average molecular weight was 4,700. The overall scheme is as shown in Scheme 8 below.

[Reaction Scheme 8]

<Examples 1 to 8 and Comparative Examples 1 to 6> Preparation of the composition for resin type light guide plate

Each component was mixed with the composition shown in following Table 1, and the composition for resin type light-guide plates was manufactured.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Synthesis Example 1 50 - - - - - 5 - - - - - - Synthesis Example 2 - 40 - - - - - - - - - - - - Synthesis Example 3 - - 30 - - - - - - - - - - - Synthesis Example 4 - - - 60 - - - - - - - - - - Synthesis Example 5 - - - - 20 - - - - - - - - Synthesis Example 6 - - - - - 50 - 70 - - - - - Synthesis Example 7 - - - - - - - - 40 50 - - - - Synthesis Example 8 - - - - - - - - - - 50 30 40 50 1) IBOA - - 13 15 20 10 45 10 13 10 20 30 20 - 2) TDA 15 26 - - 20 5 15 - 13 5 10 30 30 24 3) TMPTA - One 2 One - - - - One - One - - 10 4) NPEA 25 23 50 23 35 25 25 10 23 25 9 5 9 - 5) 2-HEMA 9 9 4 - 4 9 9 9 9 9 9 4 - 15 6) D-TPO 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 7) Iganox 1010 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Maximum Shrinkage (%) 4.6 5.8 4.8 4.0 5.4 4.6 9.2 8.8 9.8 11.6 10.5 9.1 9.1 11.5

1) IBOA: Isobonylacrylate (Agi), shrinkage rate 11.8%

2) TDA: Tridecyl acrylate (Agi, TM2853), shrinkage rate 9.6%

3) TMPTA: trimethylpropanol triacrylate (Mwon Sang, M300), shrinkage 28%

4) NPEA: Nonylphenol Ethylene Oxide (4mol) Acrylate (Hanpense, NP-041), Shrinkage 4.1%

  5) 2-HEMA: 2-hydroxyethyl methacrylate (Cognis), shrinkage rate 19.8%

6) D-TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Chiba gauge)

7) Iganox 1010: Phenolic Thermal Stabilizer (Shiba Gauge)

Experimental Example 1 Specimen Preparation

The compositions prepared in Examples and Comparative Examples, the structure as shown in Fig. 4 in the table and the coating metal and then let 350mJ / cm ² 1 in the primary curing Black Light lamp in a nitrogen atmosphere halide lamp with a thickness of 1.5mm 1J / cm ² intensity Secondary curing was performed to prepare a specimen.

<Experimental Example 2>

Using the specimen prepared in Experimental Example 1 to evaluate the physical properties as follows and the results are shown in Table 2 below.

1. Adhesion Measurement

Each specimen prepared in Experimental Example 1 was subjected to a T test using Instron's UTM. The adhesive force was measured at a rate of 2 mm / min, and the adhesive strength between the two types of glass and metal was evaluated using the average value except the maximum and minimum values.

2. Initial color value

The specimen prepared in Experimental Example 1 was separated from the base and attached to a glass plate to measure ΔE * ab by measuring the color values of the glass plate and the specimen in a transmission mode using a Spectro color meter SE200 manufactured by Nippon Denshoku Corporation.

3. Measurement of Hardness and Shrinkage

Take the resin part of the specimen prepared in Experimental Example 1 to about 1 g and accurately measure the weight (Wo), and leave it in 10 g of ethyl acetate solution for 24 hours, and dry the specimen in an oven at 60 ° C. for 4 hours to weigh Wi) was measured to calculate the degree of cure by the following equation (6), the actual shrinkage was calculated by the following equation (3).

Equation 6

Gel fraction (%) = (Wi / Wo) x 100

&Quot; (3) &quot;

Shrinkage (%) = Hardness (%) x [Equation 1] / 100

&Quot; (1) &quot;

Maximum shrinkage percentage (%) = -2.58 + 3000 × [the molecular weight of the (meth) acrylic functional group number / (meth) acrylic monomer (C) of the (meth) acrylic monomer (C)]

4. Light resistance

The specimen produced in Experimental Example 1 was left to stand for 100 hours in CT-UVT equipment (UV-B, 280 ~ 360nm) of KOTECH, and after initial value and light resistance test in transmission mode using Spectro color meter SE200 of Nippon Denshoku Corporation. Color value was measured and ΔE * ab was calculated.

ΔE * ab = {(ΔL *) ² + (Δa *) ² + (Δb *) ² } ^1/2

5. High temperature and high humidity

The specimens were prepared in the same manner as the specimens prepared for the elongation measurement of the composition of each experimental example in a constant temperature and humidity chamber with a humidity of 60 degrees 95%, and the difference from the initial color difference value after 500 hours was expressed as ΔE * ab value.

6. Haze

Haze was measured using the spectrophotometer (HZ-1, the Japan Corporation make).

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Adhesiveness
(N) 32 41 26 29 44 45 12 35 12 19 9 3 10 15 Hayes 0.2 0.3 0.2 0.2 0.3 0.3 0.2 0.3 0.5 0.6 0.6 0.7 0.5 0.5 Initial color
value 0.3 0.4 0.4 0.5 0.3 0.2 0.3 0.3 1.2 1.5 1.2 1.9 1.1 2.0 Curing degree
(%) 94 95 94 96 93 98 98 98 80 66 81 85 88 85 Contraction ratio
(%) 4.3 5.5 4.5 3.8 5.0 6.0 5.5 7.0 6.4 4.7 5.6 9.8 10.0 11.0 Light resistance 4.2 5.1 4.4 5.2 3.7 4.1 5.2 4.4 11.5 12.7 11.2 15.7 12.0 13.5 High temperature
High humidity 1.5 1.8 1.3 2.8 2.5 2.5 2.5 2.6 9.1 8.7 9.8 10.8 8.5 8.9

As shown in Table 2, in the case of Examples 1 to 8 in which the light guide plate was manufactured using the composition for a resin type light guide plate including the asymmetric urethane (meth) acrylate oligomer represented by Chemical Formula 1 according to the present invention, It can be seen that the haze value and the initial color value are lower than those of Comparative Examples 1 to 6, in which the light guide plate was manufactured by using the composition for the resin type light guide plate including the symmetric urethane (meth) acrylate oligomer represented by the present applicant. . This is due to the excellent compatibility with other materials, and low haze value and initial color value mean high luminance.

Therefore, the composition for a resin type light guide plate including an asymmetric urethane (meth) acrylate oligomer represented by the formula (1) according to the present invention comprises a symmetrical urethane (meth) acrylate oligomer of the formula (5) conventionally proposed by the present applicant It can be seen that it exhibits excellent luminance characteristics compared with the resin-type light guide plate composition.

In addition, as shown in the synthesis example, the asymmetric urethane (meth) acrylate oligomer according to the present invention shows a low viscosity characteristics it can be seen that workability can be improved.

In addition, in the case of Examples 1 to 8, in which the light guide plate was manufactured using the composition for resin light guide plate including the asymmetric urethane (meth) acrylate oligomer represented by Chemical Formula 1 according to the present invention, in addition to the haze and the initial color value. It can be seen that the overall excellent properties as compared to Comparative Examples 1 to 6 for the light guide plate prepared by using the composition for a resin light guide plate comprising a symmetric urethane (meth) acrylate oligomer of the formula (5) presented by the applicant.

Claims (14)

It is prepared by reacting a compound prepared by reacting a divalent polyol with a divalent isocyanate with a (meth) acrylate monomer containing an alcohol and a hydroxy group. The asymmetric urethane (meth) acrylate (A) A composition for resin type light guide plate comprising the.
<Formula 1>

(In Formula 1, R ₁ represents a residual structure excluding a terminal hydroxyl group in the divalent polyol, wherein R ₂ means a residual structure excluding the terminal isocyanate group from the divalent isocyanate, wherein R ₃ is

,

,

,

or

And n is an integer of 1 to 10, R ₄ is hydrogen or a methyl group, and R ₅ represents a residual structure excluding terminal hydroxy groups from an alcohol having a C 1 to C 50 terminal hydroxy group which may contain a hetero atom. ) The resin light guide plate composition according to claim 1, wherein the number average molecular weight of the asymmetric urethane (meth) acrylate (A) represented by the formula (1) is 2,000 to 10,000. The composition of claim 1, wherein the asymmetric urethane (meth) acrylate (A) represented by Chemical Formula 1 is contained in an amount of 10 to 70 parts by weight based on 100 parts by weight of the total composition. The method of claim 1, wherein the resin-type light guide plate composition
Hydrogen bond (meth) acrylate (B) containing a hydroxyl group or a carboxyl group;
(Meth) acrylate monomer (C) having a maximum shrinkage ratio of 15% or less; And
A photoinitiator (D) is included, The resin type light-guide plate composition characterized by the above-mentioned.
&Quot; (1) &quot;
Maximum shrinkage percentage (%) = -2.58 + 3000 × [the molecular weight of the (meth) acrylic functional group number / (meth) acrylic monomer (C) of the (meth) acrylic monomer (C)] 5. The composition of claim 4, wherein the hydrogen bondable (meth) acrylate (B) comprises at least one selected from the group consisting of compounds represented by the following Chemical Formulas 2 and 3. 6.
(2)

In Formula 2, R ₁ Is a single bond or alkylene or heteroalkylene having 1 to 10 carbon atoms, cycloalkylene having 3 to 8 carbon atoms, phenylene, alkylphenylene having 1 to 10 carbon atoms, phosphorus, alkoxyphosphonoyl group having 1 to 10 carbon atoms or phosph; blood and Nikko group, R ₂ is H when R ₁ is a single bond, R ₁ is a hydroxy group or a carboxyl group is not a single bond R ₃ is hydrogen or a methyl group. )
(3)

In Formula 3, R ₁ Is a C1-C10 alkyl group or heteroalkyl group, a C3-C8 cycloalkyl group, a phenyl group, a C1-C10 alkylphenyl group, R <_3> is hydrogen or a methyl group. ) The method according to claim 4, wherein the hydrogen bond type (meth) acrylate (B) is an acid-modified (meth) acrylate oligomer formed by the reaction of an acid anhydride and a (meth) acrylate monomer containing a hydroxyl group. Topographic light guide plate composition. The composition of claim 6, wherein the acid-modified (meth) acrylate oligomer comprises at least one selected from the group consisting of compounds represented by the following Chemical Formulas 4a to 4f.
<Formula 4a>

<Formula 4b>

<Formula 4c>

<Formula 4d>

<Formula 4e>

<Formula 4f>

In Formulas 4a to 4f, R ₁ is each independently hydrogen or a methyl group, and R ₂ is each independently

,

,

,

or

N is an integer of 1 to 10, R ₃ is each independently selected from hydrogen, a saturated or unsaturated alkyl group of 1 to 10 carbon atoms, heteroalkyl group, benzyl group, carboxyl group, hydroxy group or halogen element, R ₄ is a saturated or unsaturated alkylene group having 1 to 10 carbon atoms.) The method according to claim 4, wherein the hydrogen bondable (meth) acrylate (B) is contained in 10 to 40 parts by weight, the (meth) acrylate monomer (C) is contained in 10 to 60 parts by weight based on 100 parts by weight of the total composition The photoinitiator (D) is a resin type light guide plate composition, characterized in that it comprises 0.1 to 10 parts by weight. The resin light guide plate composition according to claim 1, wherein the resin light guide plate composition further comprises a trifunctional or higher (meth) acrylate curing agent (E) having a maximum shrinkage ratio of the following Equation 5: 20% or more.
<Equation 5>
Maximum shrinkage percentage (%) = -2.58 + 3000 × [molecular weight of (meth) acrylic functional group / (meth) acrylic monomer (E) of (meth) acrylic monomer (E)] The composition for a resin light guide plate according to claim 9, wherein the (meth) acrylate curing agent (E) is contained in an amount of 1 to 5 parts by weight based on 100 parts by weight of the total composition. The resin type light guide plate according to claim 4, wherein the resin type light guide plate composition includes at least two kinds of the (meth) acrylic monomer (C), and the maximum shrinkage ratio calculated by Equation 4 is 3 to 7%. Composition.
<Equation 4>
Max Shrinkage (%) =

(In formula (4), i represents the number of the number of the (meth) acrylic monomer (C) contained in the composition for dot pattern formation,
Regardless of the order of inclusion, when each (meth) acrylic monomer is referred to as the nth monomer,
XnSn represents the product of Xn and Sn,
Xn represents the mass fraction of the nth monomer,
Sn represents the maximum shrinkage rate of the n-th monomer and is calculated by Equation (1).) A light emitting diode formed on the reflecting plate; And a light guide plate formed to cover the light emitting diode with the composition of any one of claims 1 to 11. The backlight unit of claim 12, wherein the light guide plate has a thickness of 0.2 to 2 mm. A liquid crystal display device comprising the backlight unit of claim 12.

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