KR20140099294A

KR20140099294A - Active energy beam-cured composition for optical film, optical film, polarizer protective film, and polarizing plate

Info

Publication number: KR20140099294A
Application number: KR1020147017610A
Authority: KR
Inventors: 겐타로 야치; 다카유키 다케모토; 가츠노부 모치즈키; 히사오 가토
Original assignee: 도아고세이가부시키가이샤
Priority date: 2011-12-01
Filing date: 2012-11-30
Publication date: 2014-08-11
Also published as: TW201329628A; CN104024294A; JPWO2013081101A1; WO2013081101A1

Abstract

(PROBLEMS) To provide an active energy ray curable composition for forming an optical film capable of achieving both a low photoelastic coefficient and a retardation, having good heat and humidity resistance, and also having flexibility, an optical film obtained from the composition, a polarizer protective film and a polarizer .
(Meth) acrylate (A) having a photoelastic coefficient (hereinafter simply referred to as " photoelastic coefficient ") of not more than 30 × 10 ^-12 Pa ^-1 at 23 ° C. and a photoelastic coefficient of 5 10 ^-12 Pa ^-1 or less have × value, and (a) and a polymer (B) other than the component, and a cured product of the photoelastic coefficient of the composition 10 × 10 ^-12 Pa ^-1 or less, measured at a thickness 40 ㎛ The in-plane retardation of the cured product in the front and the inclination of 40 deg., And the retardation in the thickness direction of the cured product in both cases is 5 nm or less.

Description

TECHNICAL FIELD [0001] The present invention relates to an active energy ray-curable composition for forming an optical film, an optical film, a polarizer protective film and a polarizer,

The present invention relates to an active energy ray curable composition used for forming an optical film, an optical film obtained by curing the composition, and a polarizing plate using the same as a polarizer protective film.

The term "optical film" in the present invention means "optical film or sheet", and the thickness is not particularly limited. Also, acrylate or methacrylate is represented by (meth) acrylate.

In recent years, along with the enlargement of the liquid crystal display, it has become necessary to enlarge the optical films such as the polarizer protective film and the retardation film for optically compensating the liquid crystal.

However, when the optical film is enlarged, an external force is deflected. Therefore, when the optical film is made of a material which easily causes birefringence change due to an external force, a birefringence distribution occurs and the contrast becomes uneven. Though the ease of occurrence of birefringence change due to external force is represented by the absolute value of the photoelastic coefficient, the film of triacetyl cellulose (hereinafter also referred to as " TAC "), which is generally used as a polarizer protective film, , Light leakage and whitening are caused by the occurrence of stress birefringence accompanying the shrinkage of the polarizer.

The TAC film has retardation in the thickness direction although it has a small retardation with respect to the incident light in the front direction. Such retardation, as the liquid crystal display becomes larger in size, significantly affects the viewing angle characteristics.

Therefore, a material capable of achieving both low photoelasticity coefficient and low retardation is required.

Patent Document 1 discloses that photoelasticity is reduced by blending an acrylic resin having negative photoelasticity with a cellulose ester resin having positive photoelasticity.

Patent Document 2 discloses that a low photoelastic coefficient and a low retardation are both achieved by blending polyvinyl pyrrolidone with a cellulose ester resin.

Patent Document 3 discloses that the photoelastic coefficient of an urethane (meth) acrylate optical film is small.

Reissue Patent Publication WO2009 / 081607 Japanese Patent Application Laid-Open No. 2008-111056 Japanese Laid-Open Patent Publication No. 2011-145330

In the invention described in Patent Document 1, the retardation is large, and the low photoelastic coefficient and the retardation can not be compatible with each other. In addition, when a polarizer using such a film as a polarizer protective film is used at a high temperature or a high humidity, the polarizer may be deformed, or a polarizer such as a polarizer or a polarizer There is a drawback that performance is deteriorated.

In the invention described in Patent Document 2, since the combination of cellulose ester resin and polyvinylpyrrolidone has a problem that the moisture resistance and heat resistance are worse than the composition described in Patent Document 1.

In the invention described in Patent Document 3, the absolute value of the photoelastic coefficient is as large as TAC (13 × 10 ^-12 Pa ^-1 ) and is not sufficiently satisfactory. In addition, the retardation was large, and the low photoelastic coefficient and retardation could not be satisfied at the same time.

As described above, an optical film which has been studied as a material for a polarizer protective film replacing triacetyl cellulose in the prior art can not both achieve a low photoelastic coefficient and retardation, or even if it can be compatible, When the polarizing plate using the film as a polarizer protective film is used under high temperature or high humidity, there is a drawback that the polarizing plate is deformed and the performance of the polarizing plate such as polarizability and color is lowered.

An object of the present invention is to provide an active energy ray curable composition for forming an optical film that can obtain an optical film having both low photoelasticity coefficient and low retardation and excellent heat and humidity resistance.

It is another object of the present invention to provide an optical film which can be preferably used for polarizer protective film applications, has excellent viewing angle characteristics, and is excellent in heat resistance and adhesion.

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted intensive studies to solve the above problems and found that the following active energy ray curable compositions can solve the above problems and have completed the present invention.

The optical film of the active energy ray-curable composition for forming the present invention provides a cured photoelastic coefficient is 1 × 10 ^-12 Pa ^-1 or less Urethane 30 (meth) acrylate (A), and, to the photoelastic coefficient is 2 5 × 10 ^- has a value of less than ¹² ^-1 Pa, also (a) and a polymer (B) other than the component, and to a cured composition of the photoelastic coefficient of 10 × 10 ^-12 Pa ^-1 or less 1, measured with a thickness 40 ㎛ The in-plane retardation of the cured product in one case and the retardation in the thickness direction of both the front face and the inclined face of 40 DEG are 5 nm or less.

The photoelastic coefficient 1 means a photoelastic coefficient at 23 ° C and the photoelastic coefficient 2 means that the optical film obtained by adding the component (B) at an optional ratio to the component (A) used has a photoelasticity Means a value obtained when the value of the coefficient is measured and the addition amount is 100%, which is extrapolated from the linear graph of the addition amount and the photoelastic coefficient.

According to the present invention, it is possible to provide an active energy ray curable composition for optical film formation which can obtain an optical film having both a low photoelastic coefficient and a low retardation and having excellent heat and humidity resistance.

Further, according to the present invention, it is possible to provide an optical film which can be preferably used for polarizer protective film applications, has excellent viewing angle characteristics, and is excellent in heat resistance and adhesion.

1 is a schematic view showing an example of the production of an optical film using the composition of the present invention.
2 is a schematic view showing another example of the production of an optical film using the composition of the present invention.

The active energy ray-curable composition (hereinafter, simply referred to as "composition") for forming an optical film of the present invention contains urethane (meth) acrylate (A) having a photoelastic coefficient 1 of 30 × 10 ^-12 Pa ^-1 or less (B) (hereinafter, simply referred to as "component (B)") having a value of not more than 5 × 10 ^-12 Pa ^-1 and having the following photoelasticity coefficient 2, ) Component], and the cured product of the composition has the following photoelastic coefficient 1 of 10 x 10 < ^-12 > Pa < ^-1 & And retardation in the thickness direction are both 5 nm or less.

Hereinafter, the present invention will be described in detail. In the present specification, the crosslinked product obtained by irradiating the composition with active energy rays and the cured product are collectively referred to as " cured product ".

1. Component (A)

Component (A) is a cured product of the photoelastic coefficient is 1 × 10 ^-12 Pa ^-1 or less Urethane 30 (meth) acrylate.

Can be a photoelastic coefficient of 1, the cured product of the composition to less than 10 × 10 ^-12 Pa ^-1 by using a × 10 ^-12 Pa ^-1 or less compound 30 as a photoelastic coefficient of 1, the cured product of the component (A). In addition, a photoelastic coefficient of 1, the cured product of the component (A) is preferably not less than 5 × 10 ^-12 Pa ^-1.

A ¹ ^- (A) 1 roneun photoelastic coefficient of the cured product of the ^{composition, 10 × 10 -12 ~ 20 ×} 10 -12 Pa -1 is preferable, and more preferably ^{10 × 10 -12 ~ 15 × 10} -12 Pa.

In the present invention, the photoelastic coefficient is a coefficient indicating the tendency of a change in birefringence due to an external force to occur, and the photoelastic coefficient 1 is a photoelastic coefficient at 23 deg. The closer the value of the photoelastic coefficient is to zero, the smaller the change of the birefringence due to the external force is.

Specifically, the photoelastic coefficient 1 (C) is a value defined by the following formula (1) when? Is the elongation stress and? N is the birefringence at the time of stress application.

C [Pa ^-1 ] =? N /? (1)

Here,? N is defined by the following formula (2) when n ₁ is a refractive index in a direction parallel to the stretching direction and n ₂ is a refractive index in a direction perpendicular to the stretching direction.

N = n ₁ - n ₂ (2)

The photoelastic coefficient 1 in the present invention means a value measured at a temperature of 23 ° C.

As a method of measuring the photoelastic coefficient 1, an optical film obtained by curing the composition of the present invention or a film obtained by curing only the component (A) may be measured by a known birefringence meter. Specifically, for example, an optical film obtained by curing the composition of the present invention or a film obtained by curing only the component (A) is cut into 15 mm x 60 mm, and the film is cut by an automatic birefringence system (KOBRA-WR, ) Was used to measure the in-plane retardation value when the 5-point tensile strength σ was changed in the range of 0 N to 10 N at room temperature. From the slope of the approximate straight line prepared according to the formula (1), the photoelastic coefficient 1 Can be obtained.

Examples of the component (A) include a reaction product of a polyol, an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate, and a raw material is selected so that the obtained compound satisfies the photoelastic coefficient 1. [

As the component (A), urethane (meth) acrylate having two or more (meth) acryloyl groups is preferable, and urethane (meth) acrylate having two (meth) acryloyl groups is more preferable .

As the component (A), urethane (meth) acrylate having no aromatic group is preferable because it has low photoelasticity. The urethane (meth) acrylate not having an aromatic group can be produced by using a compound having no aromatic group as a starting polyol and an organic polyisocyanate.

(Mw) of the component (A) is preferably 1,000 to 15,000, more preferably 1,000 to 10,000.

In the present invention, Mw is a value obtained by converting a molecular weight measured by gel permeation chromatography (hereinafter also referred to as " GPC ") into polystyrene.

The component (A) may be used alone or in combination of two or more.

Hereinafter, a method for producing the polyol, the organic polyisocyanate, the hydroxyl group-containing (meth) acrylate, and the component (A), which are the starting compounds of the component (A), will be described.

1-1. Polyol

As the polyol, it is preferable to use a diol, and various diols can be used.

Examples of the diol include an aliphatic diol having 2 to 12 carbon atoms, an alicyclic diol having 2 to 12 carbon atoms, a polycarbonate diol, a polyester diol, and a polyether diol.

Examples of the aliphatic diol having 2 to 12 carbon atoms include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, polytetramethylene glycol , 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-ethyl-1,3-hexaneglycol, 2,2,4- , 3-pentanediol, 3,3-dimethylolheptane, 1,9-nonanediol, and 2-methyl-1,8-octanediol.

Examples of the alicyclic diol having 2 to 12 carbon atoms include cyclohexanedimethanol, hydrogenated bisphenol A, tricyclo [5.2.1.0 ^2,6 ] decanedimethanol (commonly referred to as tricyclodecanedimethanol), 1,4-decahydro Naphthalene diol, 1,5-decahydronaphthalene diol, 1,6-decahydronaphthalene diol, 2,6-decahydronaphthalene diol, 2,7-decahydronaphthalene diol, decahydronaphthalene dimethanol, norbornanediol, Decanoldimethanol, adamantanediol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane Bis (4-hydroxycyclohexyl) propane (commonly called hydrogenated bisphenol A), 4,4'-dihydroxydicyclohexyl methane (commonly referred to as spiroglycol), isosorbide, isomannide, 2,2- Hydrogenated bisphenol F), 1,1-bis (4-hydroxycyclohexyl) -1,1-dicyclohexyl methane (commonly known as hydrogenated bisphenol F) Sphenol Z) and alicyclic diols such as 4,4-bicyclohexanol.

Examples of the polycarbonate diol include a reaction product of a low molecular weight diol and / or a polyether diol with a dialkyl carbonate such as ethylene carbonate and dibutyl carbonate.

Examples of the low molecular weight diol include ethylene glycol, propylene glycol, cyclohexanedimethanol, and 3-methyl-1,5-pentanediol, 1,5-pentanediol, and 1,6-hexanediol.

Examples of the polyether diol include polyalkylene glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, and diols such as block or random polymer such as polyethylene polypropoxy block polymer diol.

Examples of the polyester diol include esterification products of the low molecular weight diol and / or the polyether diol with an acid component such as a dibasic acid such as adipic acid, succinic acid, tetrahydrophthalic acid and hexahydrophthalic acid or anhydride thereof .

Examples of the polyether diol include polyalkylene glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol; blocks such as polyethylene polypropoxy block polymer diol; and diols such as random polymers.

As the polyol, triols are preferably used in combination with diol in order to improve the mechanical strength of the cured product.

The triol is preferably selected from 1,2,6-hexanetriol, 1,2,3-heptanetriol, 1,2,4-butanetriol, trimethylolpropane, trimethylolethane, Glycerin and tris (2-hydroxyethyl) isocyanurate, and adducts of these triols such as? -Caprolactone, ethylene oxide and propylene oxide.

As the caprolactone adduct of triol, a caprolactone adduct of trimethylolpropane and a caprolactone adduct of glycerin are preferable. As the caprolactone adduct of the triol, a compound having an average hydroxyl value of 300 to 600 mgKOH / g and an average hydroxyl number of 3 is preferable.

The triol caprolactone adducts are commercially available, and include, for example, plaque cells 303, 305, 308, 312, and L320ML (manufactured by Daicel Chemical Industries, Ltd.).

These polyols may be used alone or in combination of two or more.

When brittleness and flexibility are required as the component (A), it is more preferable to use an aliphatic diol having 2 to 12 carbon atoms or an alicyclic diol having 2 to 12 carbon atoms as the polyol.

(Hereinafter, also referred to as " P-Mn ") as a polyol when mechanical properties are required as the component (A), more specifically, when an excellent breaking strength and tensile modulus of elasticity are required, And a polyol having a P-Mn of less than 500 are preferably used in combination.

In the present invention, the P-Mn (number average molecular weight) of the polyol refers to a value obtained by the following formula.

More specifically, examples of the polyol having a P-Mn of 500 or more include a polycarbonate diol and a polyester diol. Examples of the polyol having a P-Mn of less than 500 include an aliphatic diol having 2 to 12 carbon atoms and an alicyclic Diols, and combinations thereof. The polyol having P-Mn of 500 or more is preferably a polyol having P-Mn of 500 or more and 10,000 or more. The polyol having a P-Mn of less than 500 is preferably a polyol having a P-Mn of 62 or more and less than 500. [

1-2. abandonment Polyisocyanate

As the organic polyisocyanate, an organic diisocyanate is preferable, and a non-sulfur modified organic diisocyanate is more preferable.

Examples of the non-sulfuric modified organic diisocyanate include aliphatic diisocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and dimeric acid diisocyanate, isophorone diisocyanate (hereinafter referred to as " IPDI ), Alicyclic diisocyanates such as 4,4'-methylenebis (cyclohexyl isocyanate), norbornadiisocyanate and?,? '- diisocyanate dimethylcyclohexane, and the like.

These organic polyisocyanates may be used alone or in combination of two or more.

Of the above-mentioned compounds, IPDI is preferable in that the cured product has excellent mechanical strength and optical characteristics.

1-3. Containing hydroxyl group ( Mat ) Acrylate

Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (Meth) acrylate such as hydroxyethyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxy octyl (meth) acrylate, pentaerythritol tri, di or mono (meth) acrylate, and trimethylol propane di or mono Alkyl (meth) acrylates, and caprolactone adducts of these compounds.

Of the above-mentioned compounds, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like are preferable from the viewpoint of the curability of the composition and the flexibility of the cured product. And caprolactone adducts of 2-hydroxyethyl acrylate are preferred.

1-4. (A) < / RTI >

The component (A) may be prepared by a conventional method.

Examples of the component (A) include compounds prepared by reacting a polyol and an organic polyisocyanate to prepare an isocyanate group-containing compound and reacting the compound with a hydroxyl group-containing (meth) acrylate (hereinafter also referred to as " (Hereinafter also referred to as " compound A2 "), and the like. Compound A1 is preferred because it is easy to control the molecular weight.

In the case of producing the compound A1, the polyol and the organic polyisocyanate to be used are subjected to an addition reaction by heating and stirring in the presence of an urethane-forming catalyst such as dibutyltin dilaurate, and further hydroxyalkyl (meth) acrylate is added , And a method in which the addition reaction is carried out by heating and stirring. In the case of producing the compound A2, a polyol, an organic polyisocyanate and a hydroxyalkyl (meth) acrylate are simultaneously added in the presence of the same catalyst as above, And the like.

1-5. The preferred component (A)

In the present invention, as the component (A), among the above, a polycarbonate diol or a polyester diol (hereinafter collectively referred to as "diol a"), an aliphatic or alicyclic diol having 2 to 12 carbon atoms (Also referred to as " diol b "), urethane (meth) acrylate, which is a reaction product of a non-sulfur modified organic diisocyanate and a hydroxyl group-containing (meth) acrylate.

The component (A) is superior in mechanical strength by using diol a as a polyol, diol b as a single-chain diol, and an organic diisocyanate as compared with other urethane (meth) acrylates, And the photoelastic coefficient 1 of the cured product of the composition is low.

Examples of the diol a include the above-mentioned polycarbonate diol and polyester diol, and examples of the diol b include aliphatic diols having 2 to 12 carbon atoms and alicyclic diols having 2 to 12 carbon atoms.

These diols a and b may be used alone or in combination of two or more.

The ratio of the diols a and b is preferably from 5 to 50 mol% of the diol a and from 50 to 95 mol% of the diol b, more preferably from 5 to 40 mol% of the diol a and from 60 to 95 mol% % to be.

When triols are used in combination, the ratio of the triols is preferably 50 to 95 mol% of the total of the diols a and b and 5 to 50 mol% of the triols, more preferably the diols a and / b: 60 to 95 mol%, and triol: 5 to 40 mol%.

As the component (A), a compound obtained by reacting a diol a and a diol b with an anion-modified organic diisocyanate to prepare an isocyanate group-containing compound and reacting the compound with a hydroxyl group-containing (meth) (Compound A-II) in which diol a and diol b, non-sulfur modified organic diisocyanate and hydroxyl group-containing (meth) acrylate are simultaneously reacted, and compound AI is preferable Do.

In the present invention, as the component (A), among the above, a reaction product of a diol b (a diol having a P-Mn of less than 500), a non-sulfur modified organic diisocyanate and a caprolactone adduct of a hydroxyl group-containing (meth) acrylate (Meth) acrylate is particularly preferred. The component (A) is more excellent in brittleness and flexibility than the cured product of the composition.

As the diol b in this case, a polyol having a P-Mn of 62 to 400 is preferable.

Specific examples of the compound include aliphatic diols having 2 to 6 carbon atoms such as 1,4-butanediol, tricyclo [5.2.1.0 ^2,6 ] decanedimethanol, and 3,9-bis (1,1-dimethyl- -Hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane and the like are preferable, and from the viewpoint of excellent strength of the cured product, 3,9-bis ( 1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane (commonly called spiroglycol) is particularly preferred.

As the caprolactone adduct of a hydroxyl group-containing (meth) acrylate, a caprolactone adduct of hydroxyalkyl (meth) acrylate is preferred. Further, as the reaction ratio of caprolactone to hydroxyl group-containing (meth) acrylate, it is preferably larger than 0.1 mole and smaller than 2.0 mole.

The method for producing the component (A) may be carried out in the same manner as described above, and the preferable production method is the same as described above.

2. Component (B)

(B) is a polymer having a photoelastic coefficient 2 of 5 x 10 < ^-12 > Pa < ^-1 > or less and is a polymer other than the component (A). The photoelastic coefficient 2 of the component (B) is preferably -15 × 10 ^-12 Pa ^-1 or more.

In the present invention, the photoelastic coefficient 2 means that the value of the photoelastic coefficient at 23 캜 of the optical film obtained by adding the component (B) to the component (A) at an arbitrary ratio as described above is measured, Means a value when the addition amount is 100%, which is extrapolated from a straight line graph of the addition amount and the photoelastic coefficient.

When the relationship between the amount of the component (A) and the amount of the component (B) added and the photoelastic coefficient is linearly plotted, it is preferable that three or more measured values are obtained and that the straight line graph is produced by the least squares method.

The cured product of the component (A) or the cured product of the composition can be formed. Therefore, the photoelastic coefficient can be directly measured using the automatic birefringence system. However, since the component (B) The photoelastic coefficient 2 is set as the photoelastic coefficient.

As described above, the cured product of the component (A) has a positive photoelastic coefficient of 30 × 10 ^-12 Pa ^-1 or less, preferably 10 × 10 ^-12 to 30 × 10 ^-12 Pa ^-1, owing to the first, by a photoelastic coefficient of 2 × 10 ^-12 Pa ^-1 blended with not more than 5 (B) component can be a second photoelastic coefficient of the cured product of the composition to less than 10 × 10 ^-12 Pa ^-1.

The photoelastic coefficient 2 of the component (B) is preferably -10 x 10 ^-12 to 5 x 10 ^-12 Pa- ¹ , more preferably -10 x 10 ^-12 to 2 x 10 ^-12 Pa ^- ¹ , And more preferably -10 x 10 ^-12 to -2 x 10 ^-12 Pa ^- ¹ .

The Mw of the component (B) may be suitably set according to the purpose, preferably 1,000 to 100,000, more preferably 1,000 to 50,000.

By setting the Mw to 1,000 or more, the amount of the polymerization initiator and the chain transfer agent can be reduced during the production of the component (B), thereby preventing the increase of the photoelastic coefficient 1 of the cured product and the problem of coloring, , It is excellent in compatibility with the component (A), and the turbidity of the cured product can be prevented.

As the component (B), various compounds can be used as long as the polymer has the photoelastic coefficient 2. The homopolymer or copolymer of a monomer having a (meth) acryloyl group, a copolymer of an N-vinyl-2-pyrrolidone copolymer , homopolymers or copolymers of? -methylstyrene, ethylene-tetracyclododecene copolymers, and the like.

Specific examples of the monomer having a (meth) acryloyl group include (meth) acrylic acid;

(Meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, ethyl (meth) acrylate, ethyl (Meth) acrylates such as dicyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate and glycidyl (meth) acrylate;

(Meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and hydroxyhexyl (meth) acrylate;

N- (meth) acryloylmorpholine; and

(Meth) acrylamide, N, N-dimethylol (meth) acrylamide, N, N-dimethylacrylamide, N, Acrylamides, and the like.

As a copolymer of a monomer having a (meth) acryloyl group, a copolymer having an amide structure or a carboxyl group is preferable because of a large value of negative photoelasticity coefficient 2 and excellent compatibility with the component (A).

In the copolymer having an amide structure, the amide structure is preferably a morpholine structure. As a specific example of the copolymer having an amide structure, a copolymer of (meth) acrylate and N- (meth) acryloylmorpholine is preferable.

In the case of a copolymer having an amide structure, the proportion of the monomer having an amide structure is preferably 5 to 50 parts by weight based on 100 parts by weight of the total amount of the total monomers to be used.

As specific examples of the copolymer having a carboxyl group, a copolymer of (meth) acrylate and acrylic acid or methacrylic acid is preferable.

In the case of a copolymer having a carboxyl group, the acid value is preferably 5 to 65 mgKOH / g.

Commercially available homopolymers or copolymers of monomers having (meth) acryloyl groups can also be used. (Manufactured by Mitsubishi Rayon Co., Ltd.), KT 75 (manufactured by Denki Kagaku Kogyo Co., Ltd.), DERAL PET 60N and 80N (manufactured by Asahi Kasei Chemicals Corporation), Dianal BR52, BR80, BR83, BR85, And the like.

Dianal is a copolymer of a monomer having a (meth) acryloyl group, and BR83, BR87 and BR88 are commercially available products of a copolymer having a carboxyl group.

In the N-vinyl-2-pyrrolidone copolymer, copolymerizable monomers of N-vinyl-2-pyrrolidone include vinyl acetate and alkyl (meth) acrylates.

Specific examples of the N-vinyl-2-pyrrolidone copolymer include vinylpyrrolidone · vinyl acetate copolymer, vinylpyrrolidone · methyl (meth) acrylate copolymer, vinylpyrrolidone · ethyl (meth) Acrylate copolymer, vinylpyrrolidone-butyl (meth) acrylate copolymer, and the like.

As the N-vinyl-2-pyrrolidone copolymer, commercially available ones can also be used. For example, PVP / VA S-630 [manufactured by ISP Japan Co., Ltd.] and the like.

The method for producing the component (B) is not particularly limited, and any of known methods such as suspension polymerization, emulsion polymerization, bulk polymerization, or solution polymerization may be used by using the above-mentioned monomers. As the polymerization initiator, a conventional peroxide-based or azo-based polymerization initiator may be used, or a redox-based polymerization initiator may be used.

The polymerization temperature is preferably 30 to 100 ° C for suspension or emulsion polymerization and 80 to 300 ° C for bulk polymerization or solution polymerization. Polymerization may also be carried out using an alkyl mercaptan or the like as a chain transfer agent.

As the component (B) in the present invention, a polymer having an ethylenic unsaturated group (hereinafter also referred to as " (UB) component ") is preferable.

(UB) component is chemically crosslinked with the component (A) by irradiation of an active energy ray. Therefore, when a polymer having a negative value of photoelastic coefficient 2 having no ethylenic unsaturated group is blended, there is a problem that flexibility and brittleness of the resulting cured product are lowered. However, a polymer having a photoelastic coefficient of 2 has a negative value The photoelastic coefficient 2 of the cured product can be significantly reduced.

Hereinafter, the component (UB) will be described.

2-1. ( UB ) ingredient

Examples of the ethylenic unsaturated group in the component (UB) include a vinyl group, a vinyl ether group, a (meth) acryloyl group, and a (meth) acrylamide group. Among these, the (meth) acryloyl group is particularly preferable, and the acryloyl group is more preferable because the component (B) is easily produced and the curing property by the active energy ray is excellent.

As the component (UB), various compounds can be used as long as the photoelastic coefficient 2 is 5 × 10 ^-12 Pa ^-1 or less and the polymer has an ethylenic unsaturated group. Examples of the polymer include the following polymers.

1) polymer UB1: a polymer having an isocyanate group and an ethylenic unsaturated group in a polymer containing a carboxyl group (hereinafter also referred to as a " carboxyl group-containing prepolymer ") and / or a polymer containing a hydroxyl group A polymer obtained by adding a compound (hereinafter also referred to as " isocyanate-based unsaturated compound ")

2) Polymer UB2: A polymer obtained by adding a compound having an epoxy group and an ethylenic unsaturated group (hereinafter also referred to as " epoxy-based unsaturated compound ") to a carboxyl group-containing prepolymer

3) Polymer UB3: A polymer obtained by adding a compound having a carboxyl group and an ethylenic unsaturated group (hereinafter also referred to as a " carboxyl-based unsaturated compound ") to a polymer containing an epoxy group (hereinafter also referred to as an " epoxy group-containing prepolymer &

Hereinafter, the polymers UB1 to UB3 will be described.

2-1-1. Prepolymer Manufacturing method

The monomer constituting the prepolymer may be appropriately selected from monomers having a photoelastic coefficient of 5 × 10 ^-12 Pa ^-1 or less of the obtained prepolymer. Among them, a compound having a (meth) acryloyl group can be preferably used.

Hereinafter, a method for producing a carboxyl group-containing prepolymer, a hydroxyl group-containing prepolymer and an epoxy group-containing prepolymer will be described.

2-1-1-1. Carboxyl group content Prepolymer Manufacturing method

Examples of the carboxyl group-containing prepolymer used in the production of the polymer UB1 and the polymer UB2 include copolymers of a carboxyl-based unsaturated compound and an ethylenically unsaturated compound other than the carboxyl-unsaturated compound (hereinafter also referred to as " other unsaturated compound "), And a polymer containing a carboxyl group at the terminal (hereinafter referred to as a terminal carboxyl group-containing polymer) obtained by polymerizing other unsaturated compounds in the presence of a transfer agent.

First, a copolymer of a carboxylic unsaturated compound and another unsaturated compound will be described.

Examples of the carboxyl-based unsaturated compound include carboxyl group-containing compounds such as (meth) acrylic acid, polycaprolactone modified product of (meth) acrylic acid, monohydroxyethyl (meth) acrylate and succinic acid monohydroxyethyl (meth) Methacrylate, and the like.

Of these, it is preferable to use (meth) acrylic acid because the photoelastic coefficient 2 of the component (UB) to be obtained is lower than that of the component (UB).

Other unsaturated compounds are, when the photoelastic coefficient of the resulting 2 (UB) × 10 ^-12 Pa ^-1 or less components, but 5 not limited, in the carboxylic type is excellent in terms of copolymerizability with the unsaturated compound (meth) acrylic A compound having a diazo group is preferable.

Examples of the compound having a (meth) acryloyl group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (Meth) acrylates such as neo (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate and glycidyl (meth) acrylate;

N- (meth) acryloylmorpholine;

(Meth) acrylamide, N, N-dimethylol (meth) acrylamide, N, N-dimethylacrylamide, N, Acrylamides; and

(Meth) acrylonitrile, and the like.

If necessary, compounds other than the compound having a (meth) acryloyl group may also be used, and examples thereof include styrene,? -Methylstyrene, and vinyl acetate.

Among them, it is particularly preferable to use methyl (meth) acrylate and N- (meth) acryloylmorpholine in that the photoelastic coefficient 2 of the component (B) to be obtained is lower than that.

The prepolymer may also be a copolymer of a compound having a hydroxyl group and an ethylenic unsaturated group (hereinafter also referred to as a " hydroxyl group-containing unsaturated compound ").

Examples of the hydroxyl group-containing unsaturated compound include a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and hydroxyhexyl (Meth) acrylate, and hydroxyalkyl vinyl ethers such as hydroxybutyl vinyl ether.

A method for producing a copolymer of a carboxyl-based unsaturated compound and other unsaturated compounds is not particularly limited, and known methods such as suspension polymerization, emulsion polymerization, bulk polymerization and solution polymerization can be carried out using the above-mentioned compounds .

Of these, the solution polymerization method is preferable because the preparation of the polymer is easy, and unnecessary impurities such as an emulsifier are not contained.

In the case of the solution polymerization method, the raw material monomer to be used is dissolved in an organic solvent, a thermal polymerization initiator is added, and the mixture is heated and stirred. In the case of synthesizing by radical polymerization by solution polymerization, the raw material monomer to be used is dissolved in an organic solvent, a thermal radical polymerization initiator is added, and the mixture is heated and stirred. If necessary, a chain transfer agent may be used to control the molecular weight of the polymer.

Examples of the organic solvent used in the solution polymerization method include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and butyl acetate, ethers such as propylene glycol monomethyl ether, Aromatic hydrocarbons such as hexane, heptane and mineral spirit, and the like.

Examples of the thermal polymerization initiator include azo type initiators such as azobisisobutyronitrile, azobisisobalonitrile, azobiscyclohexanecarbonitrile and azobiscyano valeric acid solution;

organic peroxides such as t-butyl peroxypivalate, t-hexyl peroxypivalate, diarooyl peroxide, di (2-ethylhexyl) peroxydicarbonate, di-t-butyl peroxide and dicumyl peroxide;

Hydrogen peroxide-iron (II) salt, peroxosulfate-sodium hydrogen sulfite, cumene hydroperoxide-iron (II) salt and the like.

The use ratio of the thermal polymerization initiator may be suitably set according to the target molecular weight. The proportion of the thermal polymerization initiator to be used is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the total of all the monomers used.

The chain transfer agent may be used if necessary in order to adjust the range of Mw described above. However, since the photoelastic coefficient 2 of the component (B) may increase by the use of the chain transfer agent, the chain transfer agent may be adjusted .

As the chain transfer agent, known chain transfer agents can be used. For example, there may be mentioned, for example, dodecyl mercaptan, lauryl mercaptan, glycidyl mercaptan, 2-mercaptoethanol, 3-mercaptopropionic acid, mercaptoacetic acid, 2-ethylhexyl thioglycolate, Mercapto-1-propanol and other mercaptans, and? -Methylstyrene dimer.

These chain transfer agents may be used alone or in combination of two or more.

The ratio of the chain transfer agent to be used may be the same as that normally used and is preferably 0.01 to 7 parts by weight per 100 parts by weight of the total amount of all the monomers to be used.

The polymer thus obtained is a polymer having a carboxyl group in the side chain.

The copolymerization ratio of the carboxyl-based unsaturated compound and the other unsaturated compound may be suitably set according to the proportion of the ethylenically unsaturated group to be finally introduced, and the carboxyl-based unsaturated compound and the other unsaturated compound 1 to 40% by weight of an unsaturated compound and 60 to 99% by weight of other unsaturated compounds are preferable.

The Mw of the copolymer of the carboxyl-based unsaturated compound and the other unsaturated compound may be suitably set according to the purpose, and is preferably 1,000 to 100,000, more preferably 1,000 to 50,000.

Next, a method for producing a terminal carboxyl group-containing polymer will be described.

Examples of the method for producing a terminal carboxyl group-containing polymer include a method of polymerizing other unsaturated compounds in the presence of a chain transfer agent having a carboxyl group, and the like.

As other unsaturated compounds, the same compounds as mentioned above can be mentioned, and the same compounds as those described above are preferable.

Examples of the chain transfer agent having a carboxyl group include 3-mercaptopropionic acid, mercaptoacetic acid and the like.

The ratio of the chain transfer agent having a carboxyl group may be suitably set according to the proportion of the ethylenically unsaturated group finally introduced, and is preferably 0.01 to 7 parts by weight per 100 parts by weight of the total amount of the total monomers to be used.

As the polymerization method, the same method as described above can be employed.

The polymer thus obtained is a polymer having a carboxyl group at the terminal.

The Mw of the terminal carboxyl group-containing polymer may be suitably set according to the purpose, and is preferably 1,000 to 100,000, more preferably 10,000 to 50,000.

As the carboxyl group-containing prepolymer, a terminal carboxyl group-containing polymer is preferable because the number and position of the ethylenic unsaturated groups introduced into one molecule can be controlled.

2-1-1-2. Hydroxyl group content Prepolymer Manufacturing method

Examples of the hydroxyl group-containing prepolymer used in the polymer UB1 include a copolymer of a hydroxyl group-containing unsaturated compound and another unsaturated compound and a polymer having a terminal hydroxyl group in the presence of a chain transfer agent having a hydroxyl group and other unsaturated compounds (hereinafter, Containing polymer ") and the like.

Examples of the hydroxyl group-containing unsaturated compound include the same compounds as those described above.

A copolymer of a hydroxyl-containing unsaturated compound and another unsaturated compound can be produced by the same method as described above.

The copolymer thus obtained is a copolymer having a hydroxyl group in the side chain.

The copolymerization ratio of the hydroxyl group-containing unsaturated compound and the other unsaturated compound may be suitably set in accordance with the proportion of the ethylenically unsaturated group finally introduced, and the hydroxyl group-containing unsaturated compound may be used in an amount of 1 to 40 By weight and 60 to 99% by weight of other unsaturated compounds.

The Mw of the copolymer of the hydroxyl group-containing unsaturated compound and the other unsaturated compound may be appropriately set depending on the purpose, and is preferably 1,000 to 100,000, more preferably 1,000 to 50,000.

Next, a method for producing a terminal hydroxyl group-containing polymer will be described.

Examples of the method for producing the terminal hydroxyl group-containing polymer include a method of polymerizing other unsaturated compounds in the presence of a chain transfer agent having a hydroxyl group.

Examples of the chain transfer agent having a hydroxyl group include 2-mercaptoethanol and the like.

The ratio of the chain transfer agent having a hydroxyl group may be suitably set according to the proportion of the ethylenically unsaturated group finally introduced, and is preferably 0.01 to 7 parts by weight per 100 parts by weight of the total amount of the total monomers to be used.

The polymer thus obtained is a polymer having a hydroxyl group at the terminal.

The Mw of the terminal hydroxyl group-containing polymer may be appropriately set depending on the purpose, and is preferably 1,000 to 100,000, and more preferably 1,000 to 50,000.

As the hydroxyl group-containing prepolymer, the terminal hydroxyl group-containing polymer is preferable because the number and position of the ethylenic unsaturated groups to be introduced into one molecule can be controlled.

2-1-1-3. Epoxy group content Prepolymer Manufacturing method

Examples of the epoxy group-containing prepolymer used in the polymer UB3 include copolymers of an epoxy-based unsaturated compound and other unsaturated compounds.

Examples of the epoxy-based unsaturated compound include epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate and cyclohexene oxide-containing (meth) acrylate.

The copolymer of the epoxy-based unsaturated compound and the other unsaturated compound can be produced by the same method as described above.

The copolymer thus obtained is a copolymer having an epoxy group in the side chain.

The ratio of the epoxy-based unsaturated compound to the other unsaturated compound may be appropriately set according to the proportion of the ethylenically unsaturated group to be finally introduced, and the epoxy-based unsaturated compound may be added to the total amount of the epoxy- 1 to 40% by weight and other unsaturated compounds 60 to 99% by weight.

The Mw of the copolymer of the epoxy-based unsaturated compound and the other unsaturated compound may be suitably set according to the purpose, and is preferably 1,000 to 100,000, more preferably 1,000 to 50,000.

2-1-2. ( UB ) Method of manufacturing a component

(UB) component is introduced into a carboxyl group-containing prepolymer, a hydroxyl group-containing prepolymer and an epoxy group-containing prepolymer by addition reaction with a compound having a functional group capable of reacting with the prepolymer and an ethylenically unsaturated group.

The addition reaction may be carried out by a conventional method.

For example, in any case, it can be produced by adding each compound to the prepolymer in an organic solvent, in a water medium or in the absence of a solvent. As the conditions for the addition reaction, the reaction temperature, the reaction time, and the catalyst may be selected according to each reaction.

The addition reaction will be described below.

The polymer UB1 is prepared by adding an isocyanate-based unsaturated compound to a carboxyl group-containing prepolymer and / or a hydroxyl group-containing prepolymer by a urethanation reaction.

Examples of the isocyanate-based unsaturated compounds include the organic polyisocyanates exemplified in the production of the component (A), preferably 2-isocyanatoethyl (meth) acrylate, mono-valent acrylic acid ester of IPDI and 2-hydroxyethyl acrylate Duct bodies, and the like.

The catalyst for the urethanization reaction includes, for example, an organometallic compound.

Examples of the organometallic compound include di-n-butyltin oxide, di-n-butyltin dilaurate, di-n-butyltin, organic tin compounds such as n-octyltin dilaurate, monobutyltin trichloride, di-n-butyltin dialkyl mercaptan and di-n-octyltin dialkyl mercaptan; Organic lead compounds such as lead naphthenate and lead octenate, and organic bismuth compounds such as bismuth octylate.

The ratio of the catalyst used in the urethanization reaction is preferably from 0.001 to 0.5 parts by weight, and more preferably from 0.001 to 0.1 parts by weight, per 100 parts by weight of the total amount of the carboxyl group-containing prepolymer and the isocyanate-based unsaturated compound.

The reaction ratio of the isocyanate-based unsaturated compound to the carboxyl group-containing prepolymer is preferably 0.8 to 1.0 mole of the isocyanate-based unsaturated compound per mole of the total carboxyl groups in the carboxyl group-containing prepolymer.

The reaction ratio of the isocyanate-based unsaturated compound to the hydroxyl group-containing prepolymer is preferably 0.8 to 1.0 mole of the isocyanate-based unsaturated compound per mole of the total number of hydroxyl groups in the hydroxyl group-containing prepolymer.

By making the reaction ratio of the isocyanate-based unsaturated compound to 1 mol of the carboxyl group and / or the hydroxyl group in the prepolymer less than 1 mol, the component (UB) can be a polymer having a carboxyl group and / or a hydroxyl group.

In the polymer B2, an epoxy-based unsaturated compound is added to the carboxyl group-containing prepolymer.

In the polymer B3, a carboxyl group-containing unsaturated compound is added to an epoxy group-containing prepolymer.

Examples of the epoxy-based unsaturated compound include the same compounds as described above, and examples of the carboxyl-based unsaturated compound include the same compounds as described above.

Examples of the catalyst for the addition reaction between a carboxyl group and an epoxy group include tertiary amines such as triethylamine, tripropylamine, tributylamine, dimethyllaurylamine, triethylenediamine and tetramethylethylenediamine, triethylbenzylammonium chloride, Quaternary phosphonium salts such as quaternary ammonium salts such as ammonium bromide and tetrabutylammonium bromide, triphenylbutylphosphonium bromide and tetrabutylphosphonium bromide, and phosphine compounds such as triphenylphosphine and tributylphosphine. . Among them, it is preferable to use triphenylphosphine because the coloration of the resin is small.

The ratio of the catalyst in the reaction is preferably 100 parts by weight of the total amount of the carboxyl group-containing prepolymer and the epoxy-based unsaturated compound, or 0.1 to 5.0 parts by weight per 100 parts by weight of the epoxy group-containing prepolymer and the carboxyl- And more preferably 0.1 to 3.0 parts by weight.

The reaction ratio of the epoxy-based unsaturated compound to the carboxyl group-containing prepolymer is preferably 0.8 to 1.2 moles of the epoxy-based unsaturated compound per mole of the total carboxyl groups in the carboxyl group-containing prepolymer.

The reaction ratio of the carboxyl-based unsaturated compound to the epoxy group-containing prepolymer is preferably from 0.8 to 1.2 moles of the carboxyl-based unsaturated compound per mole of the total of the epoxy groups in the epoxy group-containing prepolymer.

In the above addition reaction, in any case, subsequent to the preparation of the above-described prepolymer, preferably, the solution polymerization may be carried out.

At that time, a polymerization inhibitor is used to inhibit the polymerization during the addition reaction. Examples of the polymerization inhibitor include dibutyl hydroxytoluene, hydroquinone, hydroquinone monomethyl ether and the like, and it is preferable to add 50 to 1,000 ppm to the reaction solution.

2-3. ( UB ) Component Ethylenic Unsaturated group

The average number of ethylenic unsaturated groups in the component (UB) may be appropriately set according to the purpose.

The average number of ethylenically unsaturated groups in the component (UB) is preferably 0.5-5.0 on average, and more preferably 1.0-3.0 on average per molecule. When the average number of ethylenic unsaturated groups contained in one molecule is 0.5 or more on average, it is sufficiently inserted into the matrix of the component (A) to provide sufficient heat resistance, moist heat resistance and brittleness. When the average is 5.0 or less, crosslinking density is suitable, toughness as a film is excellent, and the photoelastic coefficient 1 of the cured product of the composition can be made low.

(F) of the ethylenic unsaturated group in the component (UB) can be represented by the following formula (3).

X: Number-average molecular weight Mn of the prepolymer measured by GPC

Y: molecular weight of the compound unit having a reactive group in the prepolymer

Z: Weight fraction of the compound having a reactive group in the prepolymer

The unit of the compound having a reactive group in the prepolymer means a monomer unit derived from a carboxyl group-containing unsaturated compound, a monomer unit derived from a hydroxyl group-containing unsaturated compound, or a monomer unit derived from an epoxy group-containing prepolymer if the prepolymer contains a carboxyl group. Respectively.

(UB) component, since an ethylenically unsaturated group can be introduced efficiently at the molecular end, it is possible to produce a copolymer having a terminal carboxyl group-containing polymer or a terminal hydroxyl group-containing polymer as a prepolymer (Hereinafter, also referred to as macromonomer) is preferable.

Specific examples of the macromonomer include polymers B1 and B2 made of a polymer having a terminal carboxyl group, and polymer B1 made of a polymer having a terminal hydroxyl group. The f value thereof is 1.0.

3. Activity for optical film formation Energy line Curable composition

The present invention is an active energy ray curable composition for forming an optical film comprising the above component (A) and the component (B) as essential components.

The composition may be produced by a conventional method, and the components (A) and (B) may be used and, if necessary, other components may be further added and the mixture may be stirred and mixed.

The composition of the present invention needs to have a photoelastic coefficient 1 of the cured product of 10 x 10 < ^-12 > Pa < ^-1 > or less. As a result, the cured product does not readily undergo birefringence change due to an external force, and light leak and whitening can be prevented when the cured product is used as a polarizer protective film. The photoelastic coefficient 1 of the cured product of the composition of the present invention is preferably -10 10 ^-12 Pa ^-1 or more.

The composition of the present invention needs to have both the in-plane retardation of the cured product measured at a thickness of 40 占 퐉 and the inclination angle of 40 占 and the retardation in the thickness direction of 5 nm or less. Thus, when used as a polarizer protective film, a liquid crystal display having excellent viewing angle characteristics can be obtained. If the retardation of the cured product is larger than 5 nm, there is a problem that the viewing angle characteristics are deteriorated.

It is also preferable that the in-plane retardation of the front surface of the cured product measured at a thickness of 40 占 퐉 is 1 nm or less, the in-plane retardation of 40 占 is 5 nm or less and the retardation in the thickness direction is 5 nm or less . The value of the retardation is preferably -5 nm or more.

In the present invention, the retardation means a phase difference generated by birefringence when the transmitted light is decomposed into two linearly polarized lights orthogonal to each other when the linearly polarized light enters the optical film.

Specifically, the retardation Re in the plane and the retardation Rth in the thickness direction satisfy nx and ny (where nx > ny), the refractive index in the thickness direction is nz, and the film thickness d Is a value defined by the following formula.

Further, in the present invention, in-plane retardation of 40 deg. Means in-plane retardation when linearly polarized light is incident on the optical film at an inclination of 40 deg.

The amount of the component (A) and the amount of the component (B) may be suitably set according to the purpose. The amount of the component (A) is preferably 30 to 90% by weight and the content of the component (B) Is preferably 10 to 70% by weight, more preferably 40 to 80% by weight of the component (A) and 20 to 60% by weight of the component (B).

When the proportion of the component (A) is 30% by weight or more, mechanical properties of the obtained cured product can be excellent. On the other hand, when it is 90% by weight or less, low photoelasticity coefficient and low retardation can be achieved.

The composition of the present invention comprises the above components (A) and (B) as essential components, but various components may be blended according to the purpose.

Concretely, an ethylenically unsaturated compound other than the component (A) (hereinafter also referred to as component (C)), a photopolymerization initiator (hereinafter also referred to as component (D)) and an organic solvent ], A polymerization inhibitor and / or an antioxidant, and a light resistance improver.

Hereinafter, these components will be described.

(C) Component

(C) is an ethylenically unsaturated compound other than the component (A).

The component (C) is a component which is blended as needed for the purpose of lowering the viscosity of the entire composition, and for adjusting other physical properties.

Specific examples of the component (C) include (meth) acrylates other than the component (A) [hereinafter also referred to as "other (meth) acrylate"] and N-vinyl-2-pyrrolidone .

Examples of other (meth) acrylates include compounds having one (meth) acryloyl group [hereinafter referred to as "monofunctional (meth) acrylate"] and compounds having two or more (meth) acryloyl groups , And "polyfunctional (meth) acrylate"], and the like.

Specific examples of the monofunctional (meth) acrylate include isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i Acrylates such as butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, diethylaminoethyl (meth) acrylate, benzyl (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, (N = 1 to 4) (meth) acrylate, p-cumylphenol EO-modified (n = 1 to 4) (meth) acrylate, phenoxyethyl (Meth) acrylate, N- (meth) acryloylmorpholine, N-vinylformamide, N- (meth) acrylate, Acryloyloxyethylhexahydrophthalimide, N- (meth) acryloyloxyethyltetrahydrophthalimide, and the like.

Specific examples of the polyfunctional (meth) acrylate include di (meth) acrylate, bisphenol A di (meth) acrylate, ethylene glycol di (meth) acrylate, di Acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol (n = 5 to 14) di (meth) acrylate, propylene glycol di ) Acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol (n = 5 to 14) di (N = 3 to 16) di (meth) acrylate, poly (1-methyl (meth) acrylate), 1,3-butylene glycol di Butylene glycol) (n = 5 to 20) Di (meth) acrylate Acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalic neopentyl glycol di Acrylate, and bifunctional (meth) acrylates of tricyclodecane dimethylol (meth) acrylate.

In the above, EO denaturation means ethylene oxide denaturation, and n means the number of repeating alkylene oxide units.

As the component (C), only one kind of the above-mentioned compounds may be used, or two or more kinds of them may be used in combination.

As the component (C), among the above-mentioned compounds, a compound having a photoelastic coefficient 1 of the homopolymer smaller than that of the component (A) is preferable, and a compound having a photoelastic coefficient 1 of the homopolymer is more preferably negative.

Specific examples of the compound are preferably isobornyl (meth) acrylate, t-butyl (meth) acrylate, N- (meth) acryloylmorpholine and N- Do.

The proportion of the component (C) may be appropriately set according to the purpose, and it may be an amount that does not lower the flexibility of the resulting cured product. The amount of the component (C) is preferably 1 to 100% By weight, more preferably 1 to 80% by weight.

(D) Component

(D) is a photopolymerization initiator.

Component (D) is a component to be blended when ultraviolet rays and visible rays are used as active energy rays. In the case of using an electron beam as the active energy ray, it is not always necessary to blend the component (D), but a small amount of the component (D) may be blended as needed for improving the curability.

Examples of the component (D) include benzyl dimethyl ketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2- Hydroxy-2-methyl-1-propan-1-one, oligo [2-hydroxy- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} - 1 - [4- 2-methylpyrrolidin-1-one, 2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) -Morpholinophenyl) butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) N-1414 (manufactured by ADEKA Corporation), phenylglyoxylic acid liquid methyl ester, ethyl anthraquinone, and phenanthrenequinone;

Benzophenone, 4-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4- (methylphenylthio) phenylphenylmethane, methyl- (4-methylphenylsulfonyl) propan-1-one, 4,4'-bis (dimethylamino) benzo Phenanone, 4,4'-bis (diethylamino) benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone, N, N'-tetraethyl-4,4'-diaminobenzo Benzophenone-based compounds such as phenone and 4-methoxy-4'-dimethylaminobenzophenone;

Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate and bis 6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide;

Chloro-4-propylthioxanthone, 3- [3,4-dimethyl-9-oxo-9H-thioxanthone, -2-yl] oxy] -2-hydroxypropyl-N, N, N-trimethylammonium chloride and fluorothioxanthone;

Acridine-based compounds such as acridone and 10-butyl-2-chloroacridone;

1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 Oxime] esters such as [yl] -1- (O-acetyloxime);

A dimer of 2- (o-chlorophenyl) -4,5-diphenylimidazole, a dimer of 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole, (o-fluorophenyl) -4,5-phenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p- methoxyphenyl) (P-methoxyphenyl) -5-phenylimidazole dimer and 2- (2,4-dimethoxyphenyl) -4,5- 2,4,5-triarylimidazole dimer such as diphenylimidazole dimer and the like; and

Acridine derivatives such as 9-phenylacridine and 1,7-bis (9,9'-acridinyl) heptane.

These compounds may be used alone or in combination of two or more.

(A), (B), and (C) when the component (C) is contained relative to the total of 100 parts by weight of the components (A) and (B) Is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight based on 100 parts by weight of the total amount of the components.

When the proportion of the component (D) is 0.01% by weight or more, the composition can be cured with an appropriate amount of ultraviolet rays or visible light, thereby improving productivity. On the other hand, when the content is 10% by weight or less, .

(E) Component

The composition of the present invention preferably contains an organic solvent which is a component (E) for the purpose of improving the coatability to a substrate.

Specific examples of the component (E) include hydrocarbon solvents such as n-hexane, benzene, toluene, xylene, ethylbenzene and cyclohexane;

Butanol, isobutyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2- (methoxymethoxy) ethanol, 2-isopropanol Butoxyethanol, 2-butoxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, diethylene glycol, diethylene Alcohol solvents such as glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol and propylene glycol monomethyl ether;

(2-methoxyethyl) ether, bis (2-ethoxyethyl) ether and bis (2-ethoxyethyl) ether, such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, bis Ethyl) ether;

Examples of the solvent include acetone, methyl ethyl ketone, methyl n-propyl ketone, diethyl ketone, butyl methyl ketone, methyl isobutyl ketone, methyl pentyl ketone, di- , Ketone solvents such as cyclohexanone and methylcyclohexanone;

Ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, methyl glycol acetate, propylene glycol monomethyl ether acetate and cellosolve acetate;

And aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone and? -Butyrolactone.

As the component (E), one or more of the above-described compounds may be used.

The organic solvent may be added separately, or the organic solvent used in the production of the component (A) may be used without isolation.

The proportion of the component (E) is appropriately set, and it is preferably 10 to 90% by weight, more preferably 40 to 80% by weight in the composition.

polymerization Prohibition Or / and antioxidant

It is preferable to add a polymerization inhibitor and / or an antioxidant to the composition of the present invention because it can improve the storage stability of the composition of the present invention.

As the polymerization inhibitor, hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol and various phenol antioxidants are preferable, but a sulfur secondary antioxidant, Etc. may be added.

(A), (B) and (C) when the total amount of the polymerization inhibitor and / or the antioxidant is 100 parts by weight based on 100 parts by weight of the total of the components (A) and (B) Is preferably 0.001 to 3% by weight, more preferably 0.01 to 0.5% by weight based on 100 parts by weight of the total amount of the components (A) and (B).

Light resistance Enhancer

To the composition of the present invention, a light resistance improving agent such as an ultraviolet absorber or a light stabilizer may be added.

Examples of the ultraviolet absorber include 2- (2'-hydroxy-5-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole;

Triazine compounds such as 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-isooctyloxyphenyl) -s-triazine;

Dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy- Methoxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2 , 3 ', 4,4'-tetrahydroxybenzophenone, or benzophenone compounds such as 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.

Examples of the light stabilizer include N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -N, N'-diformylhexamethylenediamine, bis (3,5-ditertiarybutyl-4-hydroxybenzyl) -2-n-butylmalonate, bis (1,2,2,6,6-pentamethyl- N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -N, N A high molecular weight hindered amine compound such as bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, or the like, .

The blending ratio of the light resistance improver is preferably such that the total amount of the component (A), the component (B) and the component (C) when the component (C) is contained relative to the total of 100 parts by weight of the components (A) Is preferably 0 to 5% by weight, more preferably 0 to 1% by weight, based on 100 parts by weight of the composition.

4. How to use

The composition of the present invention may employ various methods of use depending on the purpose of forming an optical film.

Specifically, there are a method of applying a composition to a base material and irradiating an active energy ray to cure the base material, a method of applying the composition to the base material and bonding the base material to another base material, And a method in which the composition is cured by irradiating an active energy ray.

As the substrate, a peelable substrate and a substrate having no releasability (hereinafter also referred to as " non-formed substrate ") can be used.

Examples of the peelable substrate include a film subjected to a releasing treatment, a surface untreated film having releasability, and a metal (hereinafter collectively referred to as " releasing material ").

Examples of the releasing material include a siliconized polyethylene terephthalate film, a surface untreated polyethylene terephthalate film, a surface untreated cycloolefin polymer film, and a surface untreated OPP film (polypropylene).

In order to suppress the haze of the cured product of the composition of the present invention to 1.0% or less, it is preferable to use a surface-untreated polyethylene terephthalate film or a surface-untreated OPP film (polypropylene).

For the optical film obtained from the composition of the present invention, a base having a surface roughness (center line average roughness) Ra of 150 nm or less is preferably used as the peelable base material in order to lower the haze or impart surface smoothness, 100 nm is more preferable. The haze is preferably 3.0% or less. The haze is preferably 0.01% or more.

Specific examples of the substrate include a surface-untreated polyethylene terephthalate film and a surface-untreated OPP film (polypropylene).

In the present invention, the surface roughness Ra means that the roughness of the film surface is measured and the average roughness is calculated.

Examples of the non-forming substrate include various plastics other than the above, and include cellulose acetate resins such as polyvinyl alcohol, triacetylcellulose and diacetylcellulose, acrylic resins, polyesters, polycarbonates, polyarylates, And cyclic polyolefin resins in which cyclic olefins such as norbornene are used as monomers.

In the application of the composition of the present invention, as the composition, the raw material component is stirred and mixed so as to prevent the occurrence of defects such as the prevention of mixing of foreign matters and voids such as voids, or to obtain excellent optical properties, Is preferably used.

As a method of purifying the composition, a method of filtering the composition is simple and preferable. Examples of the filtration method include pressure filtration and the like.

The filtration accuracy is preferably 10 占 퐉 or less, and more preferably 5 占 퐉 or less. The smaller the filtration accuracy, the more preferable. However, if the filtration accuracy is too small, the filter tends to be clogged, the frequency of replacement of the filter increases, and the productivity is lowered.

The coating method may be suitably set in accordance with the purpose and may be carried out by a known method such as a bar coater, an applicator, a doctor blade, a knife coater, a comma coater, a reverse roll coater, a die coater, a lip coater, a gravure coater and a micro gravure coater Method.

Examples of the active energy ray include electron beams, ultraviolet rays and visible rays. Of these, electron beams are more preferable because they do not necessarily contain a photopolymerization initiator and are excellent in heat resistance and light resistance of a cured product.

The irradiation conditions such as the dose and the irradiation intensity in the active energy ray irradiation may be suitably set in accordance with the composition, the substrate and the purpose of use.

5. Optical film

The composition of the present invention can be preferably used for producing an optical film.

Hereinafter, the optical film will be described.

In the following, some explanation will be given based on Fig. 1 and Fig.

5-1. Method for producing optical film

The optical film may be produced by a conventional method, for example, by applying a composition to a substrate and then irradiating with an active energy ray.

Fig. 1 is a schematic view showing an example of a preferable method for producing an optical film composed of a release material / a cured product.

In Fig. 1, (1) means a release material.

When the composition is a non-solvent type (Fig. 1: F1), the composition is applied to a release material (Fig. 1 (1)). In the case where the composition contains an organic solvent or the like (Fig. 1: F2), the composition is applied to a release material (Fig. 1: (1)) and then dried to evaporate the organic solvent or the like (Fig.

By irradiating an active energy ray to a sheet formed by forming the composition layer 2 on a release material, an optical film composed of a release material / a cured product is obtained. The irradiation of the active energy ray is usually carried out from the side of the composition layer, but it can also be irradiated from the release material side.

In the above, if a release material is used as the substrate 1, an optical film composed of a release material / a cured product can be produced.

The coating amount of the composition of the present invention may be appropriately selected depending on the intended use. It is preferable that the organic solvent or the like is applied so as to have a film thickness of 5 to 200 占 퐉 after drying, more preferably 10 to 100 占 퐉 .

When the composition contains an organic solvent or the like, it is heated and dried after application to evaporate an organic solvent or the like.

The heating and drying method may be a method of passing through a furnace equipped with a heating device or a blowing method.

The heating and drying conditions may be appropriately set according to the organic solvent to be used and the like, and a method of heating at a temperature of 40 to 150 ° C.

As the composition after heating and drying, the proportion of the organic solvent is preferably 1% by weight or less.

The irradiation conditions such as the dose and the irradiation intensity in the active energy ray irradiation may be suitably set according to the composition, the substrate, the purpose, and the like to be used.

Fig. 2 is a schematic view showing an example of a preferable method for producing an optical film composed of a releasing member / a cured product / a releasing member.

In Fig. 2, (1), (3) and (4) refer to a release material.

When the composition is a non-solvent type (Fig. 2: F1), the composition is applied to a release material (Fig. 2 (1)). When the composition contains an organic solvent or the like (Fig. 2: F2), the composition is applied to a release material (Fig. 2 (1)) and then dried to evaporate the organic solvent or the like (Fig. 2: 2-1). The composition layer 2 is laminated with a releasing member 3 and then subjected to active energy ray irradiation or activation energy ray irradiation, and then the releasing member 4 is laminated to obtain an optical film in which a releasing member, a cured product and a releasing member are formed in this order Loses.

In Figs. 1 and 2, an example using a release material is described as a base material, but an optical film can also be produced using a non-formation base material.

For example, in FIG. 1, it is also possible to produce an optical film composed of a non-formed substrate / cured product by using a non-forming substrate instead of the releasing member of (1) have.

2, a non-forming base material is used as a releasing material of any one of (1), (3) and (4), and is irradiated with active energy rays in the same manner as described above to cure the releasing material / An optical film composed of a non-forming substrate / a cured product / a non-forming substrate may be produced.

Specific examples of this embodiment include a method of forming a protective film directly on a polarizer by using a polarizer as a non-forming substrate, applying the composition, and irradiating an active energy ray.

In the case of producing a lens sheet, a transparent plastic film is used as a non-forming substrate, a composition is applied, a metal mold is applied as a releasing material to the applied film, and an active energy ray is irradiated from the transparent plastic film side And the like.

In the above example, an example in which a composition is applied to a substrate to produce an optical film is described. In the case of producing an optical film having a large film thickness, a composition is poured into a mold having a specific concave portion, An optical film may also be prepared by irradiating an energy ray to cure the composition.

5-2. Use of optical film

The optical film formed from the composition of the present invention can be used in various optical applications. More specifically, examples thereof include a polarizer protective film, a support film for a prism sheet, and a light guide film of a polarizing plate used in a liquid crystal display device or the like. Other applications include lens sheets such as Fresnel lenses and lenticular lenses, and lenticular lenses can also be used in nano 3D displays.

Hereinafter, a polarizer using a polarizer protective film (hereinafter simply referred to as " protective film ") formed from the composition of the present invention will be described.

Polarizer

The polarizing plate has a structure in which a protective film is laminated on at least one surface of the polarizer.

As the polarizing plate, a polarizing plate may be prepared by directly applying the composition of the present invention to a polarizer and curing the polarizing plate to form a protective film. Alternatively, the polarizing plate may be manufactured by bonding a polarizing plate and a protective film.

As the polarizer, various materials can be used as long as they have a function of selectively transmitting linearly polarized light in one direction from natural light.

For example, there are a iodine-based polarizing film in which iodine is adsorbed and oriented on a polyvinyl alcohol-based film, a dye-based polarizing film in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol film, a dichroic dye is coated, A coating type polarizer and the like. These iodine-based polarizing films, dye-based polarizing films and coated polarizers have a function of selectively transmitting linearly polarized light in one direction from natural light and absorbing another linearly polarized light in one direction, which is called an absorbing polarizer. Of these polarizers, it is preferable to use an absorptive polarizer excellent in visibility. The thickness of the absorptive polarizer is preferably from 5 to 40 mu m.

The polarizing plate of the present invention is a polarizing plate in which an optical film of the present invention is laminated on at least one surface of a polarizer as a protective film, and is bonded by an adhesive.

The adhesive used for bonding the polarizer and the protective film may be selected arbitrarily in consideration of the respective adhesiveness.

Specific examples of the adhesive include a polyvinyl alcohol-based adhesive, a solvent-based adhesive, a hot-melt adhesive and a solvent-based adhesive, and a solvent-free active energy ray curable adhesive can be preferably used.

Examples of the active energy ray curable adhesive include a photo cationic curable adhesive, a photo-radical curable adhesive, and a hybrid adhesive using a combination of optical cationic curing and photo-radical curing.

Examples of the photo cationically curable adhesives include photo cationic curable compounds such as epoxy compounds and oxetane compounds, and adhesives containing a photo cationic polymerization initiator.

Examples of the photo-radical curable adhesives include photo radical curable compounds such as (meth) acrylate, vinyl ether and vinyl compounds, and adhesives containing a photo radical polymerization initiator.

Examples of the hybrid adhesive include adhesives including the above-mentioned photocathione curable compounds, photo-radical curable compounds, photocathode polymerization initiators, and photo radical polymerization initiators.

When a protective film is provided on both surfaces of the polarizer, it is most preferable to have the protective film of the present invention on both surfaces. If necessary, the protective film of the present invention may be used for one side and the other side may be provided with a protective film other than the protective film of the present invention (hereinafter also referred to as " other protective film ").

Other protective films include, for example, cellulose acetate resin films such as triacetyl cellulose and diacetyl cellulose, acrylic resin films, polyester resin films, cyclic polyolefin resin films using cyclic olefins such as norbornene as monomers, and the like . When these are used as a protective film on the display side, a film having a retardation may be used.

Example

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. In the following, " parts " means parts by weight.

○ [Preparation of Component (A)] Preparation Example A1

145.9 g of IPDI as an isocyanate and 0.07 g of dibutyltin dilaurate as a catalyst were fed into a 500 ml reaction vessel equipped with a stirrer, a thermometer and a condenser at room temperature (25 DEG C, the same applies) Under nitrogen atmosphere containing oxygen, they were heated with stirring until the liquid temperature reached 70 占 폚.

43.0 g of 1,4-butanediol: 33.5 g, and methyl ethyl ketone (hereinafter also referred to as " MEK ") were added as an alcohol solution in the same manner as in Example 1, except that polycarbonate diol (Duoran T-5651 manufactured by Asahi Chemical Industry Co., ): 65.0 g of a mixed solution was dropped so that the internal temperature was 75 占 폚 or less, and the mixture was reacted at an internal temperature of 80 占 폚 for 2 hours.

Thereafter, 57.6 g of 2-hydroxyethyl acrylate (hereinafter also referred to as "HEA") and 2,6-di-t-butyl-4-methylphenol (hereinafter also referred to as "BHT" , 0.28 g of MEK, 5.0 g of dibutyltin dilaurate and 0.07 g of dibutyltin dilaurate was added dropwise so that the inner temperature became 75 캜 or lower, and the mixture was reacted for 3 hours. The resulting mixture was subjected to an infrared absorption spectrometer (FT-IR Spectrum 100 ) To confirm that the isocyanate group was completely consumed, and a MEK solution (solid content 80%) containing urethane acrylate (hereinafter referred to as "UA-1") was obtained.

The polystyrene reduced weight average molecular weight (hereinafter, also referred to as Mw) of UA-1 was measured by GPC (solvent: tetrahydrofuran, column: HSPgel HR MB-L, manufactured by Waters Corporation).

The photoelastic coefficient 1 was measured to be 12.3 x 10 < ^-12 > Pa & lt ^; ^-1 >

○ [Preparation of Component (A)] Preparation Example A2

In Synthesis Example A1, 127.8 g of IPDI as an isocyanate, 37.6 g of Duranol T5651 as an alcohol solution, 64.1 g of tricyclo [5.2.1.0 ^2,6 ] decane dimethanol (TCDDM manufactured by Oak Acres) and MEK: 65.0 g) and HEA (50.5 g) to obtain an MEK solution (solid content: 80%) containing urethane acrylate (hereinafter referred to as "UA-2").

After a same measure Mw and the photoelastic coefficient of the obtained 1-UA 2 as in Preparation Example A1, Mw is 2300, the photoelastic coefficient of 1 is 9.7 × 10 ^-12 Pa ^- ^1.

○ [Preparation of Component (A)] Preparation Example A3

In Production Example A1, 151.4 g of IPDI as an isocyanate, 18.3 g of polycaprolactone triol (Placel 303, number average molecular weight 300) (produced by Daicel Chemical Industries, Ltd.) and 20.4 g of Duranol T5651 , A mixture solution of 28.2 g of 1,4-butanediol and 65.0 g of MEK, and HEA (61.6 g) were used in the same manner as in Example 1, except that MEK containing urethane acrylate (hereinafter referred to as "UA- To obtain a solution (solid content 80%).

After a same measure Mw and the photoelastic coefficient of the obtained 1 UA-3 in Preparation Example A1, Mw 2,400, the photoelastic coefficient of 1 is 13.5 × 10 ^-12 Pa ^- ^1.

○ [Preparation of Component (A)] Preparation Example A4

In Production Example A1, 148.8 g of IPDI as an isocyanate, 42.1 g of polyester diol (Exp4358, an ester of adipic acid and ethylene glycol, number average molecular weight 500) as an alcohol solution, 42.1 g of 1,4-butanediol (80% solids) containing urethane acrylate (hereinafter referred to as " UA-4 ") was obtained in the same manner as in Example 1, except that the amount of the solution was changed to 30.4 g and a mixed solution of 65.0 g of MEK and 58.7 g of HEA. &Lt; / RTI >

After a same measure Mw and the photoelastic coefficient of the obtained 1 UA-4 in Production Example A1, Mw is 1900, the photoelastic coefficient of 1 is 12.6 × 10 ^-12 Pa ^- ^1.

○ [Preparation of Component (A)] Preparation Example A5

A mixed solution of 99.6 g of IPDI and 50.0 g of MEK as an isocyanate was used as the isocyanate in the production example A1 and a mixed solution of spiroglycol (hydroxyl value: 369 mgKOH / g, P-Mn: 304) as an alcohol (manufactured by Mitsubishi Gas Chemical Co., ]: 74.4 g and MEK (used for washing attached to the reaction vessel after addition of powdered SPG): 25.5 g, as hydroxyl-containing acrylate, 1 mole of? -Caprolactone adduct of 2-hydroxyethyl acrylate [ (Manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), 95.6 g of MEK and 5.0 g of MEK, to obtain a MEK solution containing a urethane acrylate (hereinafter referred to as "UA-5" %).

It was measured in the same manner as in Preparation Example A1, and the Mw of the obtained photoelastic coefficient 1 UA-5, Mw 2,400, the photoelastic coefficient of 1 is 11.6 × 10 ^-12 Pa ^- ^1.

○ [Preparation of Component (A)] Preparation Example A6

Except that 134.0 g of IPDI as an isocyanate, a mixed solution of 34.2 g of 1,4-butanediol and 65.0 g of MEK as a solution of alcohol and 104.8 g of FA1DDM as a hydroxyl group-containing acrylate were used in Production Example A1 To obtain an MEK solution (solid content 80%) containing urethane acrylate (hereinafter referred to as " UA-6 ").

Was measured in the same manner as in Preparation Example A1, and the Mw of the obtained photoelastic coefficient 1 UA-6, Mw is 2200, the photoelastic coefficient of 1 is 17.5 × 10 ^-12 Pa ^- ^1.

○ Preparation A'1 [preparation of urethane acrylate other than component (A);

In a 500 ml reaction vessel equipped with a stirrer, a thermometer and a condenser, 196.0 g of IPDI as an isocyanate and 0.035 g of dibutyltin dilaurate as a catalyst were charged at room temperature. Under an atmosphere of nitrogen containing 5% by volume of oxygen, These were heated with stirring until the liquid temperature reached 70 ° C.

As an alcohol, 49.5 g of Duranol T5651 was added dropwise so that the inner temperature became 75 캜 or lower, and the mixture was reacted at an inner temperature of 80 캜 for 2 hours.

Thereafter, 104.5 g of HEA and 0.09 g of BHT were added dropwise at an internal temperature of 75 占 폚 or lower and reacted for 3 hours to obtain urethane acrylate (hereinafter referred to as "UA'1").

After a same measure Mw and the photoelastic coefficient of the obtained 1 UA'1 as in Preparation Example A1, Mw is 4400, the photoelastic coefficient is 1 153 × 10 ^-12 Pa ^- ^1.

○ [Preparation of the component (B)] Production Example B1

20.0 g of methyl methacrylate (hereinafter also referred to as " MMA "), 20.0 g of N-acryloylmorpholine (hereinafter also referred to as " ACMO "), 200 g of methyl isobutyl ketone (hereinafter, also referred to as " MIBK ") was added and dissolved uniformly at room temperature.

80.0 g of MMA was fed for 4 hours and 80.0 g of ACMO was fed over 3 hours while stirring the contents of the flask, the inner temperature was raised to 92 캜 under a nitrogen atmosphere and the inner temperature was fixed. V-65 Azobis-2,4-dimethylvaleronitrile (manufactured by JunYaku Kogyo Co., Ltd.) and 40 parts of MIBK were fed continuously over 5 hours.

After completion of the continuous feeding, the solution was kept at an inner temperature of 92 캜 for 3 hours for aging. As a result, a solution (solid content: 47%) containing a polymer having a negative photoelasticity coefficient of 2 (hereinafter referred to as "LP-1") was obtained.

The Mw of the obtained LP-1 was measured in the same manner as in Production Example A1. As a result, Mw was 10,000. The results of measurement according to the photoelastic coefficient of 2 ^{LP-1, -5.0 × 10 -12} Pa - ^1.

With respect to the photoelastic coefficient 2 of the component (B), the photoelastic coefficient value at 23 캜 of the obtained optical film obtained by adding the component (B) to the used urethane acrylate in an optional ratio was measured, The photoelastic coefficient value when the addition amount is 100%, which is extrapolated from a linear graph of the coefficient, is calculated and described.

(1) Examples 1 to 12 and Comparative Examples 1 to 7 (Preparation of composition)

The components shown in the following Table 1 were put into a container made of stainless steel at the ratios shown in Table 1 and stirred while being warmed with a magnetic stirrer to obtain a composition.

The abbreviations in Table 1 mean the following.

· LP-2: polymethyl methacrylate-based resin, manufactured by Mitsubishi Rayon Co., diamond day BR-87 [solid content; 100%, Mw; 25,000, acid value; 10.5 ㎎KOH / g, the photoelastic coefficient of 2; -6 × 10 ^{- 12} Pa ^-1 ]

· LP-3: N-vinyl-2-pyrrolidone / vinyl acetate copolymer, PVP / VA S-630 (solid content: 100%, Mw: 45,000, photoelastic coefficient: × 10 ^-12 Pa ^-1 ]

Dc1173: 2-hydroxy-2-methyl-1-phenylpropan-1-one, DAROCUR-1173 manufactured by BASF Japan

(2) Examples F1 to F10 and Comparative Examples F1 to F6 (Production of optical film by electron beam curing)

(Manufactured by Toray Industries, Inc.) having a width of 300 mm and a length of 300 mm ("Lamier 50-T60" (surface untreated polyethylene terephthalate film, thickness 50 μm, hereinafter referred to as " The compositions obtained in Examples 1 to 6 were dried at 80 占 폚 for 10 minutes and then applied with an applicator so that the film thickness became 40 占 퐉.

Thereafter, a laminae having a width of 300 mm and a length of 300 mm was laminated on the composition layer, and then an electron beam irradiating device manufactured by NHV Corporation was used to measure an acceleration voltage of 200 kV and a dose of 50 kGy (adjusted by beam current and conveying speed ) And electron beam irradiation under an oxygen concentration of 300 ppm or less to obtain an optical film.

After curing, the laminate was peeled off from the Lou mirror and used for evaluating the photoelastic coefficient 1, the retardation in the plane and the thickness direction as described later.

(3) Examples F11 to F12 and Comparative Example 7 (Production of optical film by ultraviolet curing)

The UV curable composition obtained in Examples 11 to 12 and Comparative Example 7 was dried at 80 캜 for 10 minutes and coated with an applicator so as to have a film thickness of 40 탆 in a luminous mirror having a width of 300 mm and a length of 300 mm.

Thereafter, a laminae having a width of 300 mm and a length of 300 mm was laminated on the composition layer, and then the laminate was irradiated with ultraviolet light having an intensity of irradiation of 400 mW / cm < 3 > Cm 2 (measurement value of UV POWER PUCK manufactured by Fusion UV Systems Japan Co., Ltd.)) and irradiated with ultraviolet rays with an accumulated light quantity of 1,000 mJ / cm 2 to obtain an ultraviolet curable optical film.

After curing, it was peeled off from the Lu mirror and used for later evaluation.

[Photoelastic coefficient 1]

Optical films obtained in Examples and Comparative Examples were cut into 15 mm x 60 mm and stretched at room temperature using an automatic birefringence system (KOBRA-WR, Oji Instruments Co., Ltd.) at 5 point tension the in-plane retardation value at the time of changing? was measured, and the photoelastic coefficient 1 was determined from the slope of the approximate straight line prepared according to the following formula. The results are shown in Table 2.

Δn = C · σ

(Wherein DELTA n is stress birefringence, sigma is tension, and C is photoelastic coefficient 1.)

With respect to the photoelastic coefficient 1 of the cured product of the component (A), only the component (A) was cured by the same method as in the production of the optical film by electron beam hardening to prepare a film.

[In-plane and thickness direction retardation]

(Hereinafter, referred to as " 0 DEG Re " and " 40 DEG ", respectively) were formed on the optical films obtained in Examples and Comparative Examples using a phase difference detector (KOBRA-21ADH manufactured by Oji Instruments Co., (Hereinafter also referred to as " Rth ") and thickness direction retardation (hereinafter also referred to as " Rth "). The results are shown in Table 2.

Examples F1 to F12 are optical films obtained from the compositions of Examples 1 to 12 which are the compositions of the present invention, and the photoelastic coefficient 1 is 13 × 10 ^-12 Pa ^-1 of the photoelastic coefficient 1 of TAC used as a conventional polarizer protective film It was small, and there was no fear of light leakage or white light. The retardation in the thickness direction was smaller than the Rth of 30 to 40 nm of TAC (40 占 퐉) and excellent in viewing angle characteristics.

On the other hand, Comparative Examples F1 to F5 did not contain the component (B), so that the photoelastic coefficient 1 or the retardation in the thickness direction was large, and both of them could not be made small at the same time. In addition, although Comparative Examples F6 to F7 contained the component (B), since the photoelastic coefficient 1 of the UA-5 group was large, the photoelastic coefficient 1 could not be sufficiently reduced.

○ Production Example B2 [prepared carboxyl group-containing prepolymer;

52.0 g of methyl methacrylate (hereinafter also referred to as " MMA ") and 2-hydroxyethyl methacrylate (hereinafter also referred to as " HEMA ") were added to a 1 L reaction vessel equipped with a stirrer, a thermometer, (hereinafter also referred to as " MIBK "): 2 g of 3-mercaptopropionic acid (hereinafter also referred to as " MPA "), 480 g were added and dissolved homogeneously at room temperature.

While the contents of the flask were stirred, the internal temperature was raised to 92 ° C under a nitrogen atmosphere. After the internal temperature was fixed, 748.8 g of a mixed solution of 468.0 g of MMA, 144.0 of HEMA, 108.0 of MAA and 28.8 g of MPA was added over 5 hours On the other hand, 2,2'-azobis-2,4-dimethylvaleronitrile (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) Hereinafter also referred to as "V-65") and 80 g of MEK were continuously added over 5.5 hours, respectively.

After the continuous addition was completed, the inner temperature was maintained at 92 캜 and aging was carried out for 2 hours to obtain a solution (solid content: 62%) of a carboxyl group-containing prepolymer (hereinafter referred to as "LP-4").

Mn, Mw, and photoelasticity coefficient 2 of the obtained LP-4 were measured in the same manner as in Production Example B1. As a result, Mn was 3,200, Mw was 5,800, and the photoelastic coefficient 2 was 0.210 ^-12 Pa ^- ¹ .

The results are shown in Table 3. The numbers in Table 3 are expressed as the ratio when the ratio of the total monomer used is converted to 100% by weight, and the organic solvent used and the ratio thereof are omitted.

○ Production Example B3 [prepared carboxyl group-containing prepolymer;

A solution of a carboxyl group-containing prepolymer (hereinafter referred to as " LP-5 ") having a negative photoelasticity coefficient 2 (solid content 62%).

Mn, Mw, and photoelasticity coefficient 2 of the obtained LP-5 were measured in the same manner as in Production Example B1. As a result, Mn was 4,400, Mw was 11,000, and photoelasticity coefficient 2 was -2.0x10 ^-12 Pa ^- ¹ . The results are shown in Table 3.

○ Production Example B4 [Preparation of a carboxyl-terminated polymer;

400.0 g of MMA, 5.8 g of MPA and 640.0 g of MIBK were put into a 1 L reaction vessel equipped with a stirrer, a thermometer and a condenser, and dissolved homogeneously at room temperature.

400.0 g of MMA and 8.64 g of MPA were added over a period of 3 hours while 1.3 g of V-65 and 1.3 g of MEK were added thereto while stirring the contents of the flask, : 32 g of Polymerization Initiator Solution (1) was continuously added for 4 hours over a period of 2 hours, and a polymerization initiator solution (2) comprising 5.2 g of V-65 and 128.0 g of MEK was continuously added.

After the continuous addition was completed, the inner temperature was maintained at 92 占 폚 and aging was carried out for 2 hours to obtain a solution (solid content: 51%) of a terminal carboxyl group-containing polymer having a negative photoelasticity coefficient 2 (hereinafter referred to as "LP-6").

After a same measure Mn, Mw, the photoelastic coefficient of the resulting 2 LP-6 in Production Example B1, Mn is 6,000, Mw is 12,000 and photoelastic coefficient is 2 -4.0 × 10 ^-12 · Pa ^- ^1. The results are shown in Table 3.

○ [Preparation of the component (B)] Preparation B5

350.0 g (solid content: 62%) of LP-4 was added to a 1-liter reaction vessel equipped with a stirrer, a thermometer and a condenser. The mixture was heated to 92 DEG C and stirred at 180 rpm for 1 hour while blowing a 5% oxygen- Respectively. Then, 0.11 g of BHT as a polymerization inhibitor, 0.05 g of DBTDL as a catalyst, 2 g of 2-acryloyloxyethyl isocyanate (Car lens AOI manufactured by Showa Denko K.K. Hereinafter, also referred to as " AOI "): 43.0 g, and the mixture was stirred for 4 hours.

The termination of this urethanization reaction was confirmed by infrared spectroscopy of disappearance of isocyanate groups in the solution. Thus, a solution (solid content: 64%) of the component (B) (hereinafter referred to as "ULP-1") was obtained.

Mn, Mw, and photoelasticity coefficient 2 of the obtained ULP-1 were measured in the same manner as in Production Example B1. In addition, the f value of ULP-1 was calculated according to equation (3).

Table 4 shows the results of Mn, Mw, f value, unsaturated group introduction site and photoelasticity coefficient 2 of ULP-1.

The numbers in Table 4 are expressed as the ratio when the ratio of the entire monomers used in the preparation of the prepolymer is converted to 100% by weight, and the solvent and the ratio thereof are omitted.

○ [Preparation of the component (B)] Preparation B6 ~ 16

The same operation was carried out as in Production Example B5 except that the kind and ratio of the monomers used in the preparation of the prepolymer were changed as shown in Tables 4 and 5 and the kinds and ratios of the compounds used as the addition reaction were changed , A solution of the component (B) (solid content 51 to 64%) was obtained.

Mn, Mw, f value and photoelasticity coefficient 2 of the obtained ULP-2 to 12 were measured in the same manner as in Production Example B6. The results are shown in Table 4 and Table 5 together with the unsaturated group introduction point.

In Production Examples B11 and B14, the disappearance of the acid value in the reaction solution was confirmed by using an autotitrator (COM-900, manufactured by Hiranuma Industrial Co., Ltd.) at the end of the reaction between the carboxyl group and the epoxy group.

In Table 4 and Table 5, f is the average number of ethylenically unsaturated groups in one molecule.

The abbreviations in Tables 3 to 5 are shown below, including those defined above.

MMA: methyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

· MAA: methacrylic acid

MA: methyl acrylate

GMA: glycidyl methacrylate

· ACMO: acryloylmorpholine

V-65: 2,2'-azobis-2,4-dimethylvaleronitrile

MPA: 3-mercaptopropionic acid

MTG: 2-mercaptoethanol

DM: Dodecyl mercaptan

AOI: 2-acryloyloxyethyl isocyanate

AA: Acrylic acid

MOI: 2-methacryloyloxyethyl isocyanate

· DBTDL: dibutyltin dilaurate

TBAB: tetrabutylammonium bromide

BHT: 2,6-di-t-butyl-4-methylphenol

(4) Examples U1 to U20 and Comparative Examples U1 to U2 (Preparation of composition)

The components shown in Tables 6 to 9 shown in Tables 6 to 9 were put into a container made of stainless steel at the ratios shown in Tables 6 to 9 and stirred while being warmed with a magnetic stirrer to obtain a composition.

In Table 7, M309 means trimethylolpropane triacrylate (Aronix M-309 manufactured by Toa Gosei Co., Ltd.).

(5) Examples UF1 to UF20 and Comparative Examples UF1 and UF2 (Production of optical film by electron beam hardening)

U1 to U20 and comparative examples were measured on a film "Lumirror 50-T60" (surface untreated polyethylene terephthalate film, thickness 50 μm, hereinafter referred to as "Lumirror") manufactured by Toray Industries, Inc., having a width of 300 mm and a length of 300 mm The compositions obtained in Examples U1 to U2 were dried at 120 占 폚 for 10 minutes and then applied with an applicator so as to have a film thickness of 40 占 퐉.

Thereafter, a lamellar mirror having a width of 300 mm and a length of 300 mm was laminated on the composition layer, and then an electron beam irradiating device manufactured by NHV Corporation was used to irradiate an electron beam at an acceleration voltage of 200 kV and a dose of 150 kGy ) And electron beam irradiation was performed under the condition of an oxygen concentration of 300 ppm or less to obtain an optical film.

After curing, it was peeled off from the Loumirer, and the photoelastic coefficient 1, retardation in the plane and thickness direction were evaluated in the same manner as above. In addition, cutting property and bending resistance were evaluated according to the following method.

[Cutting property]

In order to evaluate the flexibility of the produced film, the cuttability when cut with a cutter knife was evaluated according to the following criteria. The results are shown in Table 10.

○: Smooth cutting condition

△: It lacks a little smoothness

X: A state in which a crack occurs in a cross section at the time of cutting

[Endurance curvature]

In order to evaluate the flexibility of the produced film, the resistance when the film cut into 15 mm x 150 mm was bent 180 degrees was evaluated based on the following criteria. The results are shown in Table 10.

○: Three pieces are not cracked

?: Cracking in one to two circuits

×: 1 cycle Crack

Examples UF1 to UF17 are optical films obtained from the compositions of Examples U1 to U17, which are the compositions of the present invention, and the photoelastic coefficient 1 is 13 × 10 ^-12 Pa ^-1 of the photoelastic coefficient 1 of TAC used as a conventional polarizer protective film It was small, and there was no fear of light leakage or white light. The retardation in the thickness direction was smaller than the Rth of 30 to 40 nm of TAC (40 占 퐉) and excellent in viewing angle characteristics. It was also excellent in flexibility.

On the other hand, Examples UF18 to UF20 show optical properties of optical components (compositions of Comparative Examples U18 to U20) including compositions of component (B) 'having no ethylenic unsaturated group (comparative examples U18 to U20) Film, and had a photoelastic coefficient of 1 and excellent retardation as in the examples, but all had poor flexibility.

Comparative Example UF1 was an optical film made of a composition containing no component (B) (Comparative Example U1), and the photoelastic coefficient 1 and the retardation in the thickness direction were large, and both of them could not be made small at the same time. Comparative Example UF2 was an optical film made of a composition using a urethane acrylate different from the component (A) (Comparative Example U2), and had a large photoelastic coefficient of 1.

○ Manufacturing Example PL1 [Production of Polarizer]

A polyvinyl alcohol film having a thickness of 80 탆 was swelled in a water bath at 30 캜 and then dyed in an aqueous iodine solution of 5% by weight (weight ratio: iodine / potassium iodide = 1/10). Subsequently, it was immersed in an aqueous solution containing 3% by weight of boric acid and 2% by weight of potassium iodide, further uniaxially stretched to 5.5 times in an aqueous solution containing 4% by weight of boric acid and 3% by weight of potassium iodide at 55 DEG C And then immersed in an aqueous 5 wt% potassium iodide solution. Thereafter, drying was carried out in an oven at 70 캜 for 1 minute to obtain a polarizer having a thickness of 30 탆 (hereinafter referred to as a polarizer P).

The obtained polarizers P were measured for the degree of polarization and the single transmittance using a spectrophotometer (UV-2200 manufactured by Shimadzu Corporation) equipped with a polarizing prism, and found to be 99.99% and 43.1%, respectively.

○ Manufacturing Example V1 [Preparation of ultraviolet curable adhesive]

, 50 parts of bisphenol A diglycidyl ether (jER807 manufactured by Japan Epoxy Resin Co., Ltd.), 20 parts of tetrahydrofurfuryl acrylate (THF-A manufactured by Osaka Organic Chemical Industry Co., Ltd.), 4 parts of 4-hydroxyl butyl acrylate (4-methylphenyl) [4- (2-methylpropyl) phenyl] hexafluorophosphate (hereinafter referred to as " photoinitiator ") of a photopolymerization initiator 4 parts of IRGACURE 250 manufactured by BASF Japan Ltd.) and 1 part of 2,4-diethylthioxanthone (Kayacure DETX-s, manufactured by Nippon Kayaku Co., Ltd.) were charged into a container made of stainless steel and agitated until uniform with a magnetic stirrer To obtain an ultraviolet curable adhesive (hereinafter referred to as adhesive UVX1).

(6) Example P1, Example P2 and Comparative Example P1 (Production of polarizing plate)

The optical films obtained in Examples F3 and F5 and Comparative Example F6 were used as the polarizer protective films and the adhesive UVX1 was applied on both sides of the polarizer P to a film thickness of 5 mu m and the optical films were laminated. The conveyor speed was adjusted by a conveyor type ultraviolet irradiator (high pressure mercury lamp, lamp height 15 cm, irradiation intensity of 375 mW / cm 2 (measured value of UV POWER PUCK manufactured by Fusion UV Systems Japan Co., Ltd.) And irradiated with ultraviolet light having an accumulated light quantity of 220 mJ / cm 2 to obtain a polarizing plate (100 mm in width x 100 mm in length).

No corona treatment was performed on any of the polarizer protective films.

[Measurement of polarization degree and unit transmittance]

The polarization degree and the single transmittance of the polarizing plate obtained in Examples and Comparative Examples were measured using a spectrophotometer (UV-2200 manufactured by Shimadzu Corporation) equipped with a polarizing prism. The results are shown in Table 11.

[Adhesiveness of Polarizer Protective Film and Polarizer]

The state of the polarizer protective films obtained in Examples and Comparative Examples when the polarizer protective film and the polarizer P were adhered with each other by twisting by hand and cut was evaluated according to the following criteria. The results are shown in Table 11.

?: The polarizer and the polarizer protective film are integrated, and peeling does not occur.

X: peeling between the polarizer and the polarizer protective film is confirmed.

[Humidity Resistance of Polarizer]

After the polarizing plates obtained in Examples and Comparative Examples were allowed to stand in a constant temperature and humidity bath at 60 ° C and 90% RH for 120 hours, the presence or absence of deformation of the samples was visually evaluated based on the following criteria. The results are shown in Table 11.

○: No deformation is seen.

X: Deformation was observed

Examples P1 and P2 are polarizers using the optical film obtained in Examples F3 and F5, which are the compositions of the present invention, and the performance of the polarizer P is maintained, and adhesion and heat and humidity resistance are good.

On the other hand, Comparative Example P1 was a polarizing plate using the optical film obtained in Comparative Example F6, but the performance of the polarizer P was maintained.

(7) Examples P3 to P12 (Production of polarizing plate)

Polarizers were prepared in the same manner as in Example P1 except that the optical films obtained in Examples F1, F2, F4 and F6 to F12 were used as the polarizer protective films, respectively, to evaluate the heat and humidity resistance.

Any of the polarizing plates of Examples P3 to P12 was good in moisture resistance and heat resistance.

○ Manufacturing Example V2 [Preparation of ultraviolet curable adhesive]

, 40 parts of bisphenol A diglycidyl ether (jER807 manufactured by Japan Epoxy Resin Co., Ltd.), 20 parts of tetrahydrofurfuryl acrylate (THF-A manufactured by Osaka Organic Chemical Industry Co., Ltd.), 4 parts of 4-hydroxyl butyl acrylate 10 parts of isocyanuric acid ethylene oxide-modified di- and triacrylate (ARONIX M-313, manufactured by Toa Gosei Co., Ltd.), 10 parts of diphenyl-4- ( 6 parts of a 50 wt% propylene carbonate solution (CPI-100P manufactured by SAN-A PRO) of phenylsulfonium hexafluorophosphate, 1 part of 1-hydroxycyclohexyl phenyl ketone (Irgacure 184 manufactured by BASF Japan) Was added to a container made of stainless steel and stirred until uniform with a magnetic stirrer to obtain an ultraviolet curable adhesive (hereinafter referred to as adhesive UVX2).

(8) Example UP1, Example UP2 and Comparative Example UP1 (Production of polarizing plate)

(100 mm in width × 100 mm in length) was produced in the same manner as in Example P1 except that the optical film obtained in Example UF7, Example UF10 and Comparative Example UF2 was used as the polarizer protective film and UVX2 was used as the adhesive. .

No corona treatment was performed on any of the polarizer protective films.

Polarizability and single transmittance were measured for the polarizers obtained in Examples and Comparative Examples in the same manner as in Example P1, and the adhesion between the polarizer protective film and the polarizers and the heat and humidity resistance of the polarizers were evaluated in the same manner as described above. Table 12 shows the results.

Examples UP1 and UP2 are polarizers using optical films obtained in Examples UF7 and UF10 of the compositions of the present invention, and the performance of the polarizer P is maintained, and adhesion and heat and humidity resistance are good and are effective as a protective film for a polarizer .

On the contrary, Comparative Example UP1 was a polarizing plate using the optical film obtained in Comparative Example UF2, but the performance of the polarizer P was maintained, and the adhesiveness was good, but the heat and humidity resistance deteriorated.

(9) Examples UP3 to UP20 (Production of polarizing plate)

A polarizing plate was produced in the same manner as in Example UP1 except that the optical films obtained in Examples UF1 to UF6, UF8, UF9 and UF11 to F20 were used as the polarizer protective films, respectively, and the resistance to humidity and humidity was evaluated.

Any of the polarizing plates of Examples UP3 to UP20 was good in moisture resistance and heat resistance.

Industrial availability

The active energy ray curable composition for forming an optical film of the present invention can be preferably used for producing an optical film.

Further, the optical film of the present invention is preferably used in the polarizer protective film application, as described in detail above.

Claims

To the cured product photoelastic coefficient is 1 × 10 ^-12 Pa ^-1 or less Urethane 30 (meth) acrylate (A), and,
Wherein the following photoelastic coefficient 2 has a value of 5 x 10 < ^-12 > Pa < ^-1 > or less and further contains a polymer (B)
And to the cured composition of the photoelastic coefficient of 10 × 10 ^-12 Pa ^-1 or less 1,
The in-plane retardation and the retardation in the thickness direction of the cured product when measured at a thickness of 40 占 퐉 are both 5 nm or less
An active energy ray curable composition for forming an optical film.
The photoelastic coefficient 1 means a photoelastic coefficient at 23 캜, and the photoelastic coefficient 2 is a value obtained by adding the component (B) at an arbitrary ratio to the used component (A) , And means a value when the addition amount is 100%, which is extrapolated from a straight line graph of the addition amount and the photoelasticity coefficient.

The method according to claim 1,
Wherein the component (A) is a compound having no aromatic group.

3. The method according to claim 1 or 2,
Wherein the component (A) has two or more (meth) acryloyl groups and is an oligomer having a weight average molecular weight of 1,000 to 15,000.

4. The method according to any one of claims 1 to 3,
Wherein the component (A) is a reaction product of a polyol, an organic polyisocyanate, and a hydroxyl group-containing (meth) acrylate.

5. The method of claim 4,
In the component (A)
The polyol is an aliphatic or alicyclic diol having 2 to 12 carbon atoms or a polycarbonate diol or polyester diol and an aliphatic or alicyclic diol having 2 to 12 carbon atoms,
When the organic polyisocyanate is a non-sulfur-modified organic diisocyanate
An active energy ray curable composition for forming an optical film.

5. The method of claim 4,
In the component (A)
The polyol is an aliphatic or alicyclic diol having 2 to 12 carbon atoms and having a number average molecular weight of 62 or more and less than 500,
Wherein the organic polyisocyanate is a non-sulfur modified organic diisocyanate,
(Meth) acrylate is a caprolactone addition unit of a hydroxyl group-containing (meth) acrylate
An active energy ray curable composition for forming an optical film.

7. The method according to any one of claims 1 to 6,
Wherein the component (B) is a homopolymer or copolymer of a monomer having a (meth) acryloyl group.

8. The method of claim 7,
An active energy ray curable composition for forming an optical film, wherein the component (B) is a copolymer of a monomer having a (meth) acryloyl group and having an amide structure or a carboxyl group.

7. The method according to any one of claims 1 to 6,
Wherein the component (B) is an N-vinyl-2-pyrrolidone copolymer.

10. The method according to any one of claims 1 to 9,
Wherein the component (B) is a polymer having an ethylenic unsaturated group.

11. The method of claim 10,
Wherein the ethylenic unsaturated group in the component (B) is a (meth) acryloyl group.

13. The method according to claim 11 or 12,
The component (B)
A polymer obtained by adding a compound having an epoxy group and an ethylenic unsaturated group to a polymer containing a carboxyl group,
A polymer obtained by adding a compound having an isocyanate group and an ethylenically unsaturated group to a polymer containing a carboxyl group and / or a polymer containing a hydroxyl group,
A polymer obtained by adding a compound having a carboxyl group and an ethylenic unsaturated group to a polymer containing an epoxy group
And an active energy ray curable composition for forming an optical film.

13. The method of claim 12,
An active energy ray curable composition for forming an optical film, wherein the polymer containing a carboxyl group, the polymer containing a hydroxyl group, or the polymer containing an epoxy group is a copolymer of a compound having a (meth) acryloyl group.

The method according to claim 12 or 13,
Wherein the carboxyl group-containing polymer or the hydroxyl group-containing polymer is a polymer containing a carboxyl group at the terminal thereof or a polymer containing a hydroxyl group at the terminal thereof, respectively.

15. The method according to any one of claims 1 to 14,
(A) and 20 to 90% by weight, based on the total amount of the component (A) and the component (B), based on the total amount of the components (A) and (B).

16. The method according to any one of claims 1 to 15,
An active energy ray curable composition for forming an optical film, which is an electron beam curable composition for forming an optical film.

An optical film comprising a cured product of the composition according to any one of claims 1 to 15 formed into a film or a sheet.

A polarizer protective film comprising the optical film according to claim 17.

15. A method for producing an optical film, which comprises applying a composition according to any one of claims 1 to 15 to a sheet-like substrate, and then irradiating an active energy ray from the coated surface side or the sheet-like substrate side.

20. The method of claim 19,
Wherein the sheet-like base material is a peelable base material.

15. A method for producing a sheet-like base material, which comprises applying a composition according to any one of claims 1 to 15 to a sheet-like base material, applying another sheet-like base material to the application surface of the composition, Gt;

22. The method of claim 21,
Wherein one or both of the sheet-like substrates is a peelable substrate.

A polarizing plate in which a polarizer protective film according to claim 18 is laminated on at least one surface of a polarizer formed of a polyvinyl alcohol-based resin, the polarizer being adhered to the polarizer protective film through an adhesive layer.