CN104024294A

CN104024294A - Active energy beam-cured composition for optical film, optical film, polarizer protective film, and polarizing plate

Info

Publication number: CN104024294A
Application number: CN201280059166.XA
Authority: CN
Inventors: 谷内健太郎; 竹本贵之; 望月克信; 加藤久雄
Original assignee: Toagosei Co Ltd
Current assignee: Toagosei Co Ltd
Priority date: 2011-12-01
Filing date: 2012-11-30
Publication date: 2014-09-03
Also published as: TW201329628A; WO2013081101A1; KR20140099294A; JPWO2013081101A1

Abstract

To provide: an active energy beam-curable composition for optical films that combines a low photoelastic coefficient and low retardation, good resistance to moist heat, and outstanding flexibility; an optical film obtained using said composition; a polarizer protective film; and a polarizing plate. An energy beam-curable composition for forming optical films, containing: (A) urethane (meth)acrylate (A) having a photoelastic coefficient at 23 DEG C when cured (hereinafter merely referred to as the "photoelastic coefficient") not exceeding 30 x 10-12Pa-1, and (B) a polymer other than the component (A) and which has a photoelastic coefficient not exceeding 5 x 10-12Pa-1. The photoelastic coefficient when cured does not exceed 10 x 10-12Pa-1, in-plane retardation at the front and at a diagonal of 40 DEG and total retardation in the thickness direction when cured as measured at a thickness of 40mum does not exceed 5nm.

Description

Blooming forms by active energy ray-curable composition, blooming, polaroid protective film and polarization plates

Technical field

The present invention relates to be used to form the active energy ray-curable composition of blooming, solidified and the blooming that obtains and use the polarization plates of this blooming as polaroid protective film by said composition, and while belong to these technical fields.

It should be noted that, described " blooming " expression " blooming or optical sheet " in the present invention, is not particularly limited its thickness.In addition, acrylate or methacrylic ester are expressed as to (methyl) acrylate.

Background technology

In recent years, follow the maximization of liquid-crystal display, polaroid protective film, also become more and more necessary for the maximization of the blooming such as phase retardation film that liquid crystal carried out to optical compensation.

But, in the time that blooming becomes maximization, can produce the inequality of external force, therefore, being formed by the material easily changing because of external force generation double refraction at blooming, exist the birefringent distribution of generation, contrast gradient to become inhomogeneous problem.Because the easy degree that external force generation double refraction changes can utilize the absolute value of photoelastic coefficient to represent, and be often used as cellulose triacetate (below also referred to as " the TAC ") film of polaroid protective film can be large because of the absolute value of photoelastic coefficient, follow polaroid to shrink the stress birefringence producing light leak, whiting (Japanese original text: Bai order >) occur.

In addition, the delay of the incident light of TAC film frontal direction is little, but has the delay of thickness direction.The maximization process of following liquid-crystal display, such delay brings remarkably influenced to field angle characteristic.

For this reason, requirement can have the material of low photoelastic coefficient and low delay concurrently.

In patent documentation 1, disclose by mixing and there is negative stress optic acrylic resin and reduce stress optic technical scheme thering is just stress optic cellulose ester resin.

In patent documentation 2, by cellulose ester resin mix polyethylene pyrrolidone is taken into account to low photoelastic coefficient and low delay.

Following content is disclosed in patent documentation 3: the photoelastic coefficient of the blooming being formed by carbamate (methyl) acrylate is little.

Prior art document

Patent documentation

Patent documentation 1: Japan is public table patent WO2009/081607 communique again

Patent documentation 2: TOHKEMY 2008-111056 communique

Patent documentation 3: TOHKEMY 2011-145330 communique

Summary of the invention

The problem that invention will solve

With regard to the invention of recording in patent documentation 1, it postpones large, cannot take into account low photoelastic coefficient and low delay.In addition; because it is taking the high Mierocrystalline cellulose of water-intake rate as matrix; therefore humidity resistance is insufficient, will use this film when the polarization plates of polaroid protective film is used under high temperature or high humidity, the shortcoming that exists the polarization plates performances such as polarization plates distortion or degree of polarization, form and aspect to reduce.

With regard to the invention of recording in patent documentation 2, because it is the combination of cellulose ester resin and polyvinylpyrrolidone, therefore exist humidity resistance than the worse problem of composition of recording in patent documentation 1.

With regard to the invention of recording in patent documentation 3, the absolute value of its photoelastic coefficient is larger, reaches and TAC (13 × 10 ^-12pa ^-1) equal extent, cannot fully meet the demands.In addition, it postpones large, cannot take into account low photoelastic coefficient and low delay.

As mentioned above; for the polaroid protective film material as alternative cellulose triacetate in the past and for studied blooming; it cannot take into account low photoelastic coefficient and low delay; or allow to take into account low photoelastic coefficient and low delay; also cannot obtain sufficient humidity resistance; to use this film when the polarization plates of polaroid protective film is used under high temperature or high humidity, the shortcoming that exists the polarization plates performances such as polarization plates distortion or degree of polarization, form and aspect to reduce.

The object of the present invention is to provide the blooming formation active energy ray-curable composition that can obtain the blooming of taking into account low photoelastic coefficient and low delay and humidity resistance excellence.

In addition, the object of the present invention is to provide applicable to polaroid protective film purposes and the also blooming of excellence of field angle excellent, humidity resistance and cementability.

For solving the means of above-mentioned problem

The inventor etc. conduct in-depth research in order to solve above-mentioned problem, found that active energy ray-curable composition as follows can solve above-mentioned problem, and then have completed the present invention.

Blooming formation of the present invention comprises carbamate (methyl) acrylate (A) and polymkeric substance (B) with active energy ray-curable composition, and the following photoelastic coefficient 1 of the cured article of described carbamate (methyl) acrylate (A) is 30 × 10 ^-12pa ^-1below, the following photoelastic coefficient 2 of described polymkeric substance (B) has 5 × 10 ^-12pa ^-1following value, and described polymkeric substance (B) is polymkeric substance except (A) composition, the following photoelastic coefficient 1 of the cured article of said composition is 10 × 10 ^-12pa ^-1below, in the time measuring with the thickness of 40 μ m, the interior delay of face positive and oblique 40 ° of cured article and the delay of thickness direction are below 5nm.

It should be noted that, photoelastic coefficient 1 represents the photoelastic coefficient at 23 DEG C, photoelastic coefficient 2 represents following value: used (A) composition is added (B) composition and obtains blooming with arbitrary proportion, and the photoelastic coefficient value at 23 DEG C is measured to obtained blooming, make rectilinear coordinate graph by its addition and photoelastic coefficient, and photoelastic coefficient value when being extrapolated to addition and being 100% by this rectilinear coordinate graph.

Invention effect

According to the present invention, can provide the blooming formation active energy ray-curable composition that can obtain the blooming of taking into account low photoelastic coefficient and low delay and humidity resistance excellence.

In addition, according to the present invention, can provide applicable to polaroid protective film purposes and the also blooming of excellence of field angle excellent, humidity resistance and cementability.

Brief description of the drawings

Fig. 1 shows the schematic diagram of manufacturing an example of blooming with composition of the present invention.

Fig. 2 shows another routine schematic diagram of manufacturing blooming with composition of the present invention.

Embodiment

Blooming formation of the present invention comprises carbamate (methyl) acrylate (A) (below also referred to as " (A) composition ") and polymkeric substance (B) (below also referred to as " (B) composition ") with active energy ray-curable composition (below also referred to as " composition "), and the following photoelastic coefficient 1 of the cured article of described carbamate (methyl) acrylate (A) is 30 × 10 ^-12pa ^-1below, the following photoelastic coefficient 2 of described polymkeric substance (B) has 5 × 10 ^-12pa ^-1following value, and described polymkeric substance (B) is polymkeric substance except (A) composition, the following photoelastic coefficient 1 of the cured article of said composition is 10 × 10 ^-12pa ^-1below, in the time measuring with the thickness of 40 μ m, the interior delay of face positive and oblique 40 ° of cured article and the delay of thickness direction are below 5nm.

Below, the present invention is described in detail.It should be noted that, in this manual, the cross-linking agent and the cured article table of induction that composition are irradiated to active energy beam and obtain are shown to " cured article ".

1. (A) composition

(A) composition is that the photoelastic coefficient 1 of cured article is 30 × 10 ^-12pa ^-1following carbamate (methyl) acrylate.

Making the photoelastic coefficient 1 of the cured article of (A) composition by use is 30 × 10 ^-12pa ^-1following compound, can make the photoelastic coefficient 1 of the cured article of composition is 10 × 10 ^-12pa ^-1below.In addition, (A) photoelastic coefficient 1 of the cured article of composition is preferably 5 × 10 ^-12pa ^-1above.

As the photoelastic coefficient 1 of the cured article of (A) composition, be preferably 10 × 10 ^-12～20 × 10 ^-12pa ^-1, more preferably 10 × 10 ^-12～15 × 10 ^-12pa ^-1.

Described photoelastic coefficient in the present invention is the coefficient that represents the easy degree changing because of external force generation double refraction, and photoelastic coefficient 1 is the photoelastic coefficient at 23 DEG C.The value of photoelastic coefficient, more close to zero, represents that the double refraction causing because of external force changes less.

Particularly, when degree of birefringence σ being made as to tensile stress, when Δ n is made as to stress application, photoelastic coefficient 1 (C) is the value by following formula (1) definition.

C[Pa ^-1]＝Δn/σ…(1)

Herein, by n ₁be made as the specific refractory power of the direction parallel with draw direction, by n ₂while being made as the specific refractory power of the direction vertical with draw direction, Δ n is defined by following formula (2).

Δn＝n ₁-n ₂…(2)

It should be noted that, the photoelastic coefficient 1 in the present invention is illustrated in the value of measuring at 23 DEG C of temperature.

As the measuring method of photoelastic coefficient 1, utilize the blooming that known double refraction instrument obtains being solidified by composition of the present invention or only solidified by (A) composition and the film that obtains is measured.Particularly, preferably enumerate example as described below: by the blooming being solidified by composition of the present invention and obtain or only solidified by (A) composition and the film that obtains cuts into 15mm × 60mm, phase difference value in face while utilizing automatic double refraction instrument (KOBRA-WR, prince's instrumentation machine (strain) system) to be at room temperature determined at respectively to change 5 tension force σ in the scope of 0N～10N, and obtain photoelastic coefficient 1 by the slope of the near linear of making according to above-mentioned formula (1).

As (A) composition, can enumerate the reactant of polyvalent alcohol, organic multiple isocyanate and hydroxyl (methyl) acrylate etc., and select raw material so that gained compound meets the mode of above-mentioned photoelastic coefficient 1.

As (A) composition; be preferably carbamate (methyl) acrylate with 2 above (methyl) acryls, more preferably there is carbamate (methyl) acrylate of 2 (methyl) acryls.

As (A) composition, do not there is carbamate (methyl) acrylate of aromatic series base owing to showing low photoelasticity, therefore preferably.Carbamate (methyl) acrylate without aromatic series base can be by manufacturing as raw polyol and organic multiple isocyanate with the compound without aromatic series base.

As the weight-average molecular weight (hereinafter referred to as " Mw ") of (A) composition, be preferably 1,000～15,000, more preferably 1,000～10,000.

It should be noted that, the described Mw in the present invention is the value of utilizing the molecular weight of gel permeation chromatography (below also referred to as " GPC ") mensuration to obtain through polystyrene conversion.

(A) composition can only be used singly, or in combination of two or more kinds.

Below, to as the starting compound of (A) composition be polyvalent alcohol, organic multiple isocyanate and hydroxyl (methyl) acrylate and (A) manufacture method of composition describe.

1-1. polyvalent alcohol

As polyvalent alcohol, preferably use glycol, can use various glycol.

As glycol, can enumerate the aliphatic diol of carbonatoms 2～12, alicyclic diol, polycarbonate diol, polyester glycol and the polyether glycol of carbonatoms 2～12.

As the aliphatic diol of carbonatoms 2～12, can enumerate: ethylene glycol, Diethylene Glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,2-butyleneglycol, 1,3-butyleneglycol, BDO, polytetramethylene glycol, 1,5-PD, 1,6-hexylene glycol, 3-methyl isophthalic acid, 5-pentanediol, neopentyl glycol, 2-ethyl-1,3-hexylene glycol, 2,2,4-trimethylammonium-1,3-pentanediol, 3,3-dihydroxymethyl heptane, 1,9-nonanediol and 2-methyl isophthalic acid, 8-ethohexadiol etc.

As the alicyclic diol of carbonatoms 2～12, can enumerate: cyclohexanedimethanol, Hydrogenated Bisphenol A, three ring [5.2.1.0 ^2,6] decane dimethanol (being commonly called as: tristane dimethanol), 1, 4-perhydronaphthalene diphenol, 1, 5-perhydronaphthalene diphenol, 1, 6-perhydronaphthalene diphenol, 2, 6-perhydronaphthalene diphenol, 2, 7-perhydronaphthalene diphenol, perhydronaphthalene dimethanol (dehydronaphthalene dimethanol), norbornane glycol, norbornane dimethanol, naphthalane dimethanol (decalin dimethanol), diamantane glycol, 3, 9-two (1, 1-dimethyl-2-hydroxyethyl)-2, 4, 8, 10-tetra-oxaspiros [5.5] undecane (being commonly called as: the spiroglycol), Isosorbide, different mannide (isomannide), 2, two (4-hydroxy-cyclohexyl) propane (being commonly called as: Hydrogenated Bisphenol A) of 2-, 4, 4 '-dihydroxyl dicyclohexyl methane (being commonly called as: A Hydrogenated Bisphenol A F), 1, two (the 4-hydroxy-cyclohexyls)-1 of 1-, 1-dicyclohexyl methyl hydride (being commonly called as: A Hydrogenated Bisphenol A Z) and 4, the alicyclic diols such as 4-dicyclo hexanol etc.

As polycarbonate diol, can enumerate: low molecular weight diols is or/and the reactant of the dialkyl carbonates such as polyether glycol and ethylene carbonate ester and carbonic acid butanediol ester etc.

As low molecular weight diols, can enumerate ethylene glycol, propylene glycol, cyclohexanedimethanol and 3-methyl isophthalic acid, 5-pentanediol, 1,5-PD, 1,6-hexylene glycol etc. herein.

As polyether glycol, can enumerate: the polyalkylene glycols such as polyoxyethylene glycol, polypropylene glycol and polytetramethylene glycol; And the glycol of the block polymer such as polyethylene polyoxypropylene block polymer glycol or unregulated polymer etc.

As polyester glycol, can enumerate: above-mentioned low molecular weight diols is or/and the reactant of esterification that the sour composition such as the diprotic acid such as above-mentioned polyether glycol and hexanodioic acid, succsinic acid, tetrahydrophthalic acid and hexahydrophthalic acid or its acid anhydrides forms etc.

As polyether glycol, can enumerate: the polyalkylene glycols such as polyoxyethylene glycol, polypropylene glycol and polytetramethylene glycol; The glycol of the block polymers such as polyethylene polyoxypropylene block polymer glycol or unregulated polymer etc.

As polyvalent alcohol, in order to improve the physical strength of cured article, preferably except glycol, be also used in combination triol.

As triol, can enumerate 1,2,6-hexanetriol, 1,2,3-triol in heptan, 1,2,4-trihydroxybutane, TriMethylolPropane(TMP), trimethylolethane, Xylitol, pyrogallol, glycerine and isocyanuric acid three (2-hydroxyethyl) ester, also can enumerate affixture of oxyethane and the propylene oxide etc. of 6-caprolactone affixture, these triols of these triols etc.

As the caprolactone affixture of triol, the preferably caprolactone affixture of TriMethylolPropane(TMP), the caprolactone affixture of glycerine.As the caprolactone affixture of this triol, preferably average hydroxyl value is the compound that 300～600mgKOH/g and average hydroxyl number are 3.

The existing commercially available product of caprolactone affixture of above-mentioned triol, for example, can enumerate Plaxcel303,305,308,312, L320ML (Daisel chemical industry Co., Ltd's system) etc.

These polyvalent alcohols can only use a kind, also two or more can be used in combination.

As (A) composition, in the situation that requiring fragility and flexibility, more preferably use the aliphatic diol of carbonatoms 2～12 or the alicyclic diol of carbonatoms 2～12 as above-mentioned polyvalent alcohol.

As (A) composition, in the situation that requiring mechanical properties, more specifically, in the situation that requiring breaking tenacity and modulus in tension excellence, as polyvalent alcohol, be preferably that more than 500 polyvalent alcohol and P-Mn is used in combination lower than 500 polyvalent alcohol by the number-average molecular weight of hydroxyl value benchmark (below also referred to as " P-Mn ").

It should be noted that, the P-Mn (number-average molecular weight) of the described polyvalent alcohol in the present invention refers to the value of obtaining according to the following formula.

[mathematical expression 1]

More specifically, be more than 500 polyvalent alcohols as P-Mn, can enumerate polycarbonate diol and polyester glycol, as P-Mn lower than 500 polyvalent alcohol, can enumerate the aliphatic diol of carbonatoms 2～12 and the alicyclic diol of carbonatoms 2～12, these polyvalent alcohols can be used in combination.P-Mn is that more than 500 polyvalent alcohols is preferably the polyvalent alcohol of P-Mn more than 500 and more than 10,000.In addition, P-Mn is preferably P-Mn more than 62 lower than 500 polyvalent alcohol and lower than 500 polyvalent alcohol.

1-2. organic multiple isocyanate

As organic multiple isocyanate, be preferably organic diisocyanate, more preferably without xanthochromia type organic diisocyanate.

As without xanthochromia type organic diisocyanate, can enumerate: hexamethylene diisocyanate, lysine methyl ester vulcabond, 2,4, aliphatic diisocyanate, the isophorone diisocyanates (below also referred to as " IPDI "), 4 such as 4-trimethyl hexamethylene diisocyanate, dimer acid diisocyanate, 4 '-methylene-bis (cyclohexyl isocyanate), norbornene alkyl diisocyanate and ω, the alicyclic diisocyanates such as ω '-vulcabond dimethyl cyclohexane.

These organic multiple isocyanates can only use a kind, also two or more can be used in combination.

In above-claimed cpd, from the viewpoint of making the physical strength of cured article and optical characteristics excellence, preferred IPDI.

1-3. hydroxyl (methyl) acrylate

As hydroxyl (methyl) acrylate, can enumerate: (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid hydroxyl pentyl ester, the own ester of (methyl) vinylformic acid hydroxyl, (methyl) vinylformic acid hydroxyl monooctyl ester, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, tetramethylolmethane list (methyl) acrylate, TriMethylolPropane(TMP) two (methyl) acrylate, (methyl) vinylformic acid hydroxyalkyl acrylates such as TriMethylolPropane(TMP) list (methyl) acrylate, and the caprolactone affixture of these compounds etc.

In above-claimed cpd, from the viewpoint of making the solidified nature of composition and the flexibility excellence of cured article, the preferably caprolactone affixture of (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester and vinylformic acid 2-hydroxy methacrylate.

the manufacture method of 1-4. (A) composition

(A) composition can be the composition of manufacturing according to ordinary method.

As (A) composition, can enumerate: make polyvalent alcohol react to manufacture the compound that contains isocyanate group with organic multiple isocyanate, and make this compound and hydroxyl (methyl) acrylate reactions and the compound (below also referred to as " compd A 1 ") that obtains; The compound (below also referred to as " compd A 2 ") that makes polyvalent alcohol, organic multiple isocyanate and hydroxyl (methyl) acrylate simultaneous reactions and obtain etc.For the reason of easily molecular weight being controlled, preferred compound A1.

In the situation that manufacturing compd A 1, can be set forth under the urethane catalyzer existence such as dibutyl tin laurate used polyvalent alcohol and organic multiple isocyanate are carried out to heated and stirred, make them that addition reaction occur, then add (methyl) vinylformic acid hydroxyalkyl acrylate carry out heated and stirred, thereby make their that the method etc. of addition reaction occur; In the situation that manufacturing compd A 2, can be set forth in the method etc. of adding polyvalent alcohol, organic multiple isocyanate and (methyl) vinylformic acid hydroxyalkyl acrylate under the existence of catalyzer same as described above simultaneously and carrying out heated and stirred.

preferred (A) composition of 1-5.

As (A) composition in the present invention, in above-mentioned substance, preferably as the aliphatic diol of polycarbonate diol or polyester glycol (also they being referred to as below to " glycol a "), carbonatoms 2～12 or alicyclic diol (also they being referred to as below to " glycol b "), without carbamate (methyl) acrylate of the reactant of xanthochromia type organic diisocyanate and hydroxyl (methyl) acrylate.

Compared with other carbamate (methyl) acrylate, should (A) composition by using glycol a, as the glycol b of short-chain diol as polyvalent alcohol, and use without xanthochromia type organic diisocyanate as organic diisocyanate, can obtain the little composition of xanthochromia degree after physical strength excellence, light fastness test, and then can make the photoelastic coefficient 1 of the cured article of composition reduce.

As glycol a, can enumerate above-mentioned polycarbonate diol and polyester glycol, as glycol b, can enumerate the aliphatic diol of above-mentioned carbonatoms 2～12 and the alicyclic diol of carbonatoms 2～12.

These glycol a and glycol b can only use a kind, also two or more can be used in combination.

As the ratio of glycol a and glycol b, preferably making glycol a is that 5～50 % by mole and glycol b are 50～95 % by mole, and more preferably making glycol a is that 5～40 % by mole and glycol b are 60～95 % by mole.

In addition, in the situation that being used in combination triol, as the ratio of triol, the total amount that preferably makes glycol a and glycol b is that 50～95 % by mole and triol are 5～50 % by mole, and more preferably making glycol a and/or glycol b is that 60～95 % by mole and triol are 5～40 % by mole.

As this (A) composition, with similarly above-mentioned, can enumerate: make glycol a and glycol b and react to manufacture without xanthochromia type organic diisocyanate the compound that contains isocyanate group, and making this compound and hydroxyl (methyl) acrylate reactions and the compound (compd A-I) that obtains; Make glycol a and glycol b, without xanthochromia type organic diisocyanate and hydroxyl (methyl) acrylate simultaneous reactions and compound (compd A-II) obtaining etc.For the reason of easily molecular weight being controlled, preferred compound A-I.

And then, as (A) composition in the present invention, in above-mentioned substance, particularly preferably as glycol b (P-Mn lower than 500 glycol), without carbamate (methyl) acrylate of the reactant of the caprolactone affixture of xanthochromia type organic diisocyanate and hydroxyl (methyl) acrylate.Should (A) composition can make fragility and the flexibility of cured article of composition more excellent.

As glycol b now, preferably P-Mn is the polyvalent alcohol more than 62 and below 400.

As the concrete example of this compound, the aliphatic diol of the carbonatomss 2～6 such as preferred BDO, three ring [5.2.1.0 ^2,6] decane dimethanol and two (1, the 1-dimethyl-2-hydroxyethyls)-2 of 3,9-, 4,8,10-, tetra-oxaspiros [5.5] undecane etc. has the alicyclic diol of multiple rings, from making the aspect of excellent strength of cured article, particularly preferably 3, two (1, the 1-dimethyl-2-hydroxyethyls)-2,4 of 9-, 8,10-, tetra-oxaspiros [5.5] undecane (being commonly called as: the spiroglycol).

As the caprolactone affixture of hydroxyl (methyl) acrylate, the preferably caprolactone affixture of (methyl) vinylformic acid hydroxyalkyl acrylate.In addition, the reaction ratio as caprolactone with respect to hydroxyl (methyl) acrylate, is preferably greater than 0.1 mole and be less than 2.0 moles.

The manufacture method of being somebody's turn to do (A) composition is also similarly implemented with above-mentioned, and preferred manufacture method is also same as described above.

2. (B) composition

(B) composition is that photoelastic coefficient 2 has 5 × 10 ^-12pa ^-1the polymkeric substance of following value, and (B) composition is polymkeric substance except (A) composition.In addition, (B) photoelastic coefficient 2 of composition is preferably-15 × 10 ^-12pa ^-1above.

Described photoelastic coefficient 2 in the present invention refers to: as mentioned above, used (A) composition is added (B) composition and obtains blooming with arbitrary proportion, and the photoelastic coefficient value at 23 DEG C is measured to the blooming of gained, make rectilinear coordinate graph by its addition and photoelastic coefficient, and photoelastic coefficient value when being extrapolated to addition and being 100% by this rectilinear coordinate graph.

In the time that by (A) composition and (B) addition of composition and the relation of photoelastic coefficient are made into rectilinear coordinate graph, preferably obtain 3 above measured values, in addition, rectilinear coordinate graph is preferably made by method of least squares.

For the cured article of the cured article of (A) composition, composition, because it can film forming, therefore can use automatic double refraction instrument directly to measure photoelastic coefficient, but for (B) composition, due to its film forming difficulty, therefore cannot directly measure photoelastic coefficient, thereby using above-mentioned photoelastic coefficient 2 as photoelastic coefficient.

As mentioned above, (A) cured article of composition has 30 × 10 ^-12pa ^-1following positive photoelastic coefficient 1, preferably have 10 × 10 ^-12～30 × 10 ^-12pa ^-1therefore the positive photoelastic coefficient 1 of scope is 5 × 10 by coordinating photoelastic coefficient 2 ^-12pa ^-1following (B) composition, can make the photoelastic coefficient 2 of the cured article of composition reach 10 × 10 ^-12pa ^-1below.

As the photoelastic coefficient 2 of (B) composition, be preferably-10 × 10 ^-12～5 × 10 ^-12pa ^-1, more preferably-10 × 10 ^-12～2 × 10 ^-12pa ^-1, more preferably-10 × 10 ^-12～-2 × 10 ^-12pa ^-1.

(B) Mw of composition suitably sets according to target, is preferably 1,000～100,000, more preferably 1,000～50,000.

Be 1 by making Mw, more than 000, polymerization starter can reduce manufacture (B) composition time, the amount of chain-transfer agent, can prevent thus the rising of photoelastic coefficient 1 of cured article and painted problem, on the other hand, be below 100,000 by making Mw, can make (B) composition and (A) composition consistency excellence, prevent cured article muddiness.

As (B) composition; as long as thering is the polymkeric substance of above-mentioned photoelastic coefficient 2; can use various compounds, can enumerate: homopolymer or multipolymer, ethene-tetracyclododecane multipolymer etc. with the homopolymer of monomer of (methyl) acryl or multipolymer, NVP multipolymer, alpha-methyl styrene.

As the monomer with (methyl) acryl, specifically can enumerate:

(methyl) vinylformic acid;

(methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) tert-butyl acrylate, (methyl) isobornyl acrylate, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid two encircle (methyl) acrylate such as pentyl ester, (methyl) vinylformic acid two cyclopentenes esters, (methyl) glycidyl acrylate;

Hydroxyl (methyl) acrylate such as (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid hydroxyl butyl ester, the own ester of (methyl) vinylformic acid hydroxyl;

N-(methyl) acryloyl morpholine; And

(methyl) acrylamide, N hydroxymethyl acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide and N, the acrylic amides such as N-dimethylaminopropyl (methyl) acrylamide etc.

As the multipolymer of monomer with (methyl) acryl; have the value of negative photoelastic coefficient 2 of the multipolymer of amide structure or carboxyl large and with the consistency excellence of (A) composition, preferably there is in this multipolymer of amide structure or carboxyl.

In the multipolymer with amide structure, as amide structure, preferably morpholine structure.As the concrete example of multipolymer with amide structure, the preferably multipolymer of (methyl) acrylate and the formation of N-(methyl) acryloyl morpholine.

In the case of the multipolymer with amide structure, as the ratio of monomer with amide structure, be preferably 5～50 weight parts with respect to total amount 100 weight parts of used whole monomers.

As the concrete example of multipolymer with carboxyl, the preferably multipolymer of (methyl) acrylate and acrylic or methacrylic acid formation.

In the case of the multipolymer with carboxyl, as acid number, be preferably 5～65mgKOH/g.

As homopolymer or the multipolymer of monomer with (methyl) acryl, can also use commercially available product.For example, can enumerate: Delpet60N, 80N (Asahi Kasei Chemicals (strain) system), Dainal BR52, BR80, BR83, BR85, BR87, BR88 (Mitsubishi Rayon (strain) system), KT75 (electrochemical industry (strain) system) etc.

Dainal is the multipolymer with the monomer of (methyl) acryl, and BR83, BR87, BR88 are the commercially available products with the multipolymer of carboxyl.

In NVP multipolymer, as the comonomer of NVP, can enumerate vinyl-acetic ester and (methyl) alkyl acrylate etc.

As the concrete example of NVP multipolymer, can enumerate: vinylpyrrolidone/vinyl acetate copolymer, vinyl pyrrolidone-(methyl) methyl acrylate copolymer, vinyl pyrrolidone-(methyl) ethyl acrylate copolymer, vinyl pyrrolidone-(methyl) butyl acrylate copolymer etc.

As NVP multipolymer, can also use commercially available product.For example can enumerate PVP/VA S-630 (ISP Japan (strain) system) etc.

As the manufacture method of (B) composition, be not particularly limited, can use above-mentioned monomer and adopt any means in the known methods such as suspension polymerization, letex polymerization, mass polymerization or solution polymerization., as polymerization starter, the polymerization starter of common peroxidation system and azo system can be used herein, in addition, reducto oxydative system can also be made.

With regard to polymerization temperature, in suspension polymerization or letex polymerization, preferably at 30～100 DEG C, implement; In mass polymerization or solution polymerization, preferably at 80～300 DEG C, implement.In addition, can also implement polymerization as chain-transfer agent with alkyl sulfhydryl etc.

As (B) composition in the present invention, preferably there is the polymkeric substance (below also referred to as " (UB) composition ") of ethylenically unsaturated group.

(UB) composition meeting and (A) composition generation chemically crosslinked under the irradiation of active energy beam.Therefore, do not have ethylenically unsaturated group and the polymkeric substance of photoelastic coefficient 2 for negative value in the case of coordinating, existence causes the flexibility of gained cured article, the problem that fragility declines, but while using (UB) composition, the polymkeric substance that photoelastic coefficient 2 is negative value can be coordinated more, the photoelastic coefficient 2 of cured article can be reduced by a larger margin.

Below, (UB) composition is described.

2-1. (UB) composition

As the ethylenically unsaturated group in (UB) composition, can enumerate vinyl, vinyl ether group, (methyl) acryl and (methyl) acrylamido etc.Wherein, from the aspect of easy manufacture (B) composition, solidified nature excellence based on active energy beam, be particularly preferably (methyl) acryl, acryl more preferably.

As (UB) composition, as long as photoelastic coefficient 2 is 5 × 10 ^-12pa ^-1below and there is the polymkeric substance of ethylenically unsaturated group, can use various compounds, for example, polymkeric substance shown in can being listed below.

1) polymkeric substance UB1: the polymkeric substance that obtains containing that the polymkeric substance of carboxyl (below also referred to as " containing carboxyl prepolymer ") and/or the upper addition of the polymkeric substance (below also referred to as " hydroxyl prepolymer ") that contains hydroxyl have the compound (below also referred to as " isocyanic ester unsaturated compounds ") of isocyanate group and ethylenically unsaturated group;

2) polymkeric substance UB2: at the polymkeric substance obtaining containing addition on carboxyl prepolymer has the compound (below also referred to as " epoxies unsaturated compound ") of epoxy group(ing) and ethylenically unsaturated group;

3) polymkeric substance UB3: the polymkeric substance that obtains containing that the upper addition of the polymkeric substance of epoxy group(ing) (below also referred to as " containing epoxy group(ing) prepolymer ") has the compound (below also referred to as " carboxyl unsaturated compounds ") of carboxyl and ethylenically unsaturated group.

Below, polymkeric substance UB1～UB3 is described.

2-1-1. the manufacture method of prepolymer

As the monomer that forms prepolymer, be 5 × 10 as long as suitably select the photoelastic coefficient 2 of gained prepolymer ^-12pa ^-1following monomer, but wherein can preferably use the compound with (methyl) acryl.

Below, to describing containing carboxyl prepolymer, hydroxyl prepolymer and the manufacture method containing epoxy group(ing) prepolymer.

2-1-1-1. containing the manufacture method of carboxyl prepolymer

As in the manufacture of polymkeric substance UB1 and polymkeric substance UB2, use containing carboxyl prepolymer, can enumerate: the polymkeric substance (below also referred to as containing terminal carboxyl(group) polymkeric substance) that the multipolymer that carboxyl unsaturated compounds and the alefinically unsaturated compounds (below also referred to as " other unsaturated compound ") except it form and the end being polymerized under the existence of chain-transfer agent with carboxyl by other unsaturated compound contain carboxyl etc.

First, the multipolymer of carboxyl unsaturated compounds and the formation of other unsaturated compound is described.

As carboxyl unsaturated compounds, can enumerate: (methyl) vinylformic acid, (methyl) acrylic acid polycaprolactone modifier and phthalic acid list hydroxyethyl (methyl) acrylate, mono succinate hydroxyethyl (methyl) acrylate etc. contain carboxyl (methyl) acrylate etc.

In these compounds, particularly from making the lower angle of photoelastic coefficient 2 of gained (UB) composition, preferably use (methyl) vinylformic acid.

As other unsaturated compound, be 5 × 10 as long as make the photoelastic coefficient 2 of gained (UB) composition ^-12pa ^-1below, there is no particular determination, but from the viewpoint of what make with the copolymerizable excellence of above-mentioned carboxyl unsaturated compounds, preferably there is the compound of (methyl) acryl.

As the compound with (methyl) acryl, can enumerate:

N-(methyl) acryloyl morpholine;

(methyl) acrylamide, N hydroxymethyl acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide and N, the acrylic amides such as N-dimethylaminopropyl (methyl) acrylamide; And

(methyl) vinyl cyanide etc.

Can also be as required and use the compound except thering is the compound of (methyl) acryl, can enumerate vinylbenzene, alpha-methyl styrene and vinyl-acetic ester etc.

In these compounds, particularly from making the lower angle of photoelastic coefficient 2 of gained (B) composition, preferably use (methyl) methyl acrylate and N-(methyl) acryloyl morpholine.

As this prepolymer, further copolymerization has the compound (below also referred to as " hydroxy kind unsaturated compound ") of hydroxyl and ethylenically unsaturated group.

As hydroxy kind unsaturated compound, can enumerate: the hydroxyalkyl vinyl ether such as hydroxyl (methyl) acrylate and hydroxybutyl vinyl ether such as (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid hydroxyl butyl ester and the own ester of (methyl) vinylformic acid hydroxyl etc.

The manufacture method of the multipolymer forming as carboxyl unsaturated compounds and other unsaturated compound, there is no particular restriction, can adopt the known method such as suspension polymerization, letex polymerization, mass polymerization, solution polymerization that uses above-claimed cpd.

In these methods, from easy manufacture polymkeric substance and not containing the angle of the unnecessary impurity such as emulsifying agent, preferred solution polymerization.

In the situation that utilizing solution polymerization process to manufacture, can obtain above-mentioned multipolymer by used starting monomer being dissolved in to organic solvent, adding thermal polymerization and carrying out heated and stirred.Utilizing solution polymerization process and undertaken synthetic in the situation that by radical polymerization, can be by used starting monomer being dissolved in to organic solvent, add hot radical polymerization starter and carry out heated and stirred and obtain above-mentioned multipolymer.In addition, can also use as required the chain-transfer agent in order to regulate polymer molecular weight.

As the organic solvent for solution polymerization process, can enumerate: the ketones such as acetone, methylethylketone and methyl iso-butyl ketone (MIBK); The ester such as ethyl acetate, butylacetate class; The ethers such as propylene glycol monomethyl ether; Toluene, dimethylbenzene etc. are aromatic hydrocarbon based; And the aliphatic hydrocarbon such as hexane, heptane and mineral turpentine (mineral spirit) etc.

As thermal polymerization, can enumerate:

The azo-initiators such as Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), the two cyclohexanenitriles of azo and azo dicyano valeric acid;

The organo-peroxides such as tert-Butyl peroxypivalate, the tertiary own ester of peroxidation PIVALIC ACID CRUDE (25), dilauroyl peroxide, peroxy dicarbonate two (2-ethylhexyl) ester, di-t-butyl peroxide and dicumyl peroxide; And

Hydrogen peroxide-iron (II) salt, peroxydisulfate-sodium bisulfite, cumene hydroperoxide-iron (II) salt etc.

The usage ratio of thermal polymerization is suitably set according to target molecular weight.With respect to total amount 100 weight parts of used whole monomers, the usage ratio of thermal polymerization is preferably 0.1～10 weight part.

In order to be adjusted to above-mentioned Mw scope, can use as required chain-transfer agent, but due to sometimes because of use chain-transfer agent cause the photoelastic coefficient 2 of (B) composition to increase, therefore preferably the amount of chain-transfer agent is adjusted into the least possible amount.

As chain-transfer agent, can use known chain-transfer agent.For example can enumerate: lauryl mercaptan, lauryl mercaptan, glycidyl mercaptan, 2 mercapto ethanol, 3-thiohydracrylic acid, Thiovanic acid, 2-ethylhexyl mercaptoacetate, 2, the thio-alcohols such as 3-dimercapto-1-propyl alcohol; And alpha-methyl styrene dimer etc.

These chain-transfer agents may be used alone, or two or more kinds may be used in combination.

The usage ratio of chain-transfer agent and normally used consumption are equal extent, in the time that the total amount of used whole monomers is made as to 100 weight part, are preferably 0.01～7 weight part.

The polymkeric substance that side chain has carboxyl according to the polymkeric substance obtaining with upper type.

As the copolymerization ratio of carboxyl unsaturated compounds and other unsaturated compound, suitably set according to the ratio of the ethylenically unsaturated group of final importing, preferably making carboxyl unsaturated compounds with respect to total amount 100 weight of carboxyl unsaturated compounds and other unsaturated compound is that 1～40 % by weight and other unsaturated compound are 60～99 % by weight.

The Mw of the multipolymer forming as carboxyl unsaturated compounds and other unsaturated compound, suitably sets according to target, is preferably 1,000～100,000, more preferably 1,000～50,000.

Below, the manufacture method containing terminal carboxyl(group) polymkeric substance is described.

As containing the manufacture method of terminal carboxyl(group) polymkeric substance, can enumerate the method that for example makes other unsaturated compound carry out polymerization under the existence of chain-transfer agent with carboxyl etc.

As other unsaturated compound, can enumerate compound same as described above, and preferred compound same as described above.

As the chain-transfer agent with carboxyl, can enumerate 3-thiohydracrylic acid, Thiovanic acid etc.

As the ratio of chain-transfer agent with carboxyl, suitably set according to the ratio of the ethylenically unsaturated group of final importing, be preferably 0.01～7 weight part with respect to total amount 100 weight parts of used whole monomers.

As polymerization process, can adopt method same as described above.

The polymkeric substance that end has carboxyl according to the polymkeric substance obtaining with upper type.

As the Mw containing terminal carboxyl(group) polymkeric substance, suitably set according to target, be preferably 1,000～100,000, more preferably 10,000～50,000.

As containing carboxyl prepolymer, for can, to being directed in the number of the ethylenically unsaturated group in every 1 molecule and the reason that position is controlled, preferably containing terminal carboxyl(group) polymkeric substance.

the manufacture method of 2-1-1-2. hydroxyl prepolymer

As the hydroxyl prepolymer using in polymkeric substance UB1, can enumerate: the polymkeric substance (below also referred to as " containing terminal hydroxyl polymkeric substance ") that the multipolymer that hydroxy kind unsaturated compound and other unsaturated compound form and the end being polymerized under the existence of chain-transfer agent with hydroxyl by other unsaturated compound contain hydroxyl etc.

As hydroxy kind unsaturated compound, can enumerate compound same as described above.

The manufacture method of the multipolymer forming as hydroxy kind unsaturated compound and other unsaturated compound, can manufacture according to method same as described above.

The multipolymer that side chain has hydroxyl according to the multipolymer obtaining with upper type.

As the copolymerization ratio of hydroxy kind unsaturated compound and other unsaturated compound, suitably set according to the ratio of the ethylenically unsaturated group of final importing, preferably making hydroxy kind unsaturated compound with respect to total amount 100 weight of hydroxy kind unsaturated compound and other unsaturated compound is that 1～40 % by weight and other unsaturated compound are 60～99 % by weight.

The Mw of the multipolymer forming as hydroxy kind unsaturated compound and other unsaturated compound, suitably sets according to target, is preferably 1,000～100,000, more preferably 1,000～50,000.

Below, the manufacture method containing terminal hydroxyl polymkeric substance is described.

As containing the manufacture method of terminal hydroxyl polymkeric substance, can enumerate the method that for example makes other unsaturated compound carry out polymerization under the existence of chain-transfer agent with hydroxyl etc.

As the chain-transfer agent with hydroxyl, can enumerate 2 mercapto ethanol etc.

As the ratio of chain-transfer agent with hydroxyl, suitably set according to the ratio of the ethylenically unsaturated group of final importing, be preferably 0.01～7 weight part with respect to total amount 100 weight parts of used whole monomers.

As polymerization process, can adopt method same as described above.

The polymkeric substance that end has hydroxyl according to the polymkeric substance obtaining with upper type.

As the Mw containing terminal hydroxyl polymkeric substance, suitably set according to target, be preferably 1,000～100,000, more preferably 1,000～50,000.

As hydroxyl prepolymer, for can, to being directed in the number of the ethylenically unsaturated group in every 1 molecule and the reason that position is controlled, preferably containing terminal hydroxyl polymkeric substance.

2-1-1-3. containing the manufacture method of epoxy group(ing) prepolymer

As in polymkeric substance UB3, use containing epoxy group(ing) prepolymer, can enumerate: the multipolymer of epoxies unsaturated compound and the formation of other unsaturated compound.

As epoxies unsaturated compound, can enumerate: (methyl) glycidyl acrylate and (methyl) acrylate of containing cyclohexene oxide etc. are containing epoxy group(ing) (methyl) acrylate etc.

The manufacture method of the multipolymer forming as epoxies unsaturated compound and other unsaturated compound, can manufacture according to method same as described above.

The multipolymer that side chain has epoxy group(ing) according to the multipolymer obtaining with upper type.

As the copolymerization ratio of epoxies unsaturated compound and other unsaturated compound, suitably set according to the ratio of the ethylenically unsaturated group of final importing, preferably making epoxies unsaturated compound with respect to total amount 100 weight of epoxies unsaturated compound and other unsaturated compound is that 1～40 % by weight and other unsaturated compound are 60～99 % by weight.

The Mw of the multipolymer forming as epoxies unsaturated compound and other unsaturated compound, suitably sets according to target, is preferably 1,000～100,000, more preferably 1,000～50,000.

the manufacture method of 2-1-2. (UB) composition

Can by make containing carboxyl prepolymer, hydroxyl prepolymer, containing epoxy group(ing) prepolymer with there is the functional group that can react with these prepolymers and the compound generation addition reaction of ethylenically unsaturated group and import (UB) composition.

As the method for addition reaction, according to ordinary method.

For example, no matter in which kind of situation, all can by organic solvent, in water medium or in solvent-free situation on prepolymer the each compound of addition manufacture.As the condition of each addition reaction, according to each reaction and selective reaction temperature, reaction times and catalyzer.

Below, addition reaction is described.

Polymkeric substance UB1 can be by containing utilizing urethane reaction on carboxyl prepolymer and/or hydroxyl prepolymer, addition isocyanic ester unsaturated compounds be manufactured.

As isocyanic ester unsaturated compounds, the organic multiple isocyanate of enumerating in the manufacture of above-mentioned (A) composition can be set forth in, the monoadduct of 2-isocyanic ester (methyl) ethyl propenoate, IPDI and the formation of vinylformic acid 2-hydroxy methacrylate etc. can be preferably enumerated.

As the catalyzer of urethane reaction, can enumerate for example organometallic compound.

As organometallic compound, can enumerate: the organo-tin compounds such as di-n-butyl stannic oxide, di-n-butyltin dilaurate, di-n-butyl tin, oxalic acid di-n-butyl tin, di-n-octyl tin oxide, Bis(lauroyloxy)dioctyltin, monobutyl-tin-trichloride, di-n-butyl tin dialkyl group mercaptan, dioctyltin dialkyl group mercaptan; The organo-lead compounds such as lead oleate, 2 ethyl hexanoic acid lead, lead naphthenate, octene lead plumbate; The bismuth organic compounds such as Bismuth Octoate etc.

As the usage ratio of urethane reacting middle catalyst, preferably with respect to containing total amount 100 weight parts of carboxyl prepolymer and isocyanic ester unsaturated compounds being 0.001～0.5 weight part, more preferably 0.001～0.1 weight part.

As isocyanic ester unsaturated compounds, with respect to the reaction ratio containing carboxyl prepolymer, preferably making isocyanic ester unsaturated compounds with respect to 1 mole of the carboxyl total amount containing in carboxyl prepolymer is 0.8～1.0 mole.

Reaction ratio as isocyanic ester unsaturated compounds with respect to hydroxyl prepolymer, preferably making isocyanic ester unsaturated compounds with respect to 1 mole of the carboxyl total amount in hydroxyl prepolymer is 0.8～1.0 mole.

By making reaction ratio with respect to the isocyanic ester unsaturated compounds of 1 mole of the carboxyl in prepolymer and/or hydroxyl lower than 1 mole, can make (UB) to become to be divided into the polymkeric substance with carboxyl and/or hydroxyl.

Polymkeric substance UB2 is by manufacturing containing addition epoxies unsaturated compound on carboxyl prepolymer.

In addition, polymkeric substance UB3 is by manufacturing containing addition carboxyl unsaturated compounds on epoxy group(ing) prepolymer.

As epoxies unsaturated compound, can enumerate compound same as described above, carboxyl unsaturated compounds also can be enumerated compound same as described above.

As the catalyzer of the addition reaction of carboxyl and epoxy group(ing), can enumerate: the tertiary amines such as triethylamine, tripropyl amine, Tributylamine, dimethyl lauryl amine, triethylenediamine and tetramethylethylened; The quaternary ammonium salts such as triethyl benzyl ammonia chloride, trimethylammonium hexadecyl brometo de amonio, Tetrabutyl amonium bromide; The quaternary alkylphosphonium salts such as triphenyl butyl phosphonium bromide and four butyl phosphonium bromides; And the phosphine compound such as triphenylphosphine and tributylphosphine.In these catalyzer, from painted few viewpoint of resin, preferably use triphenylphosphine.

As the ratio of catalyzer in reaction, preferably with respect to total amount 100 weight parts containing carboxyl prepolymer and epoxies unsaturated compound or with respect to containing total amount 100 weight parts of epoxy group(ing) prepolymer and carboxyl unsaturated compounds being 0.1～5.0 weight part, more preferably 0.1～3.0 weight part.

As epoxies unsaturated compound, with respect to the reaction ratio containing carboxyl prepolymer, preferably making epoxies unsaturated compound with respect to 1 mole of the carboxyl total amount containing in carboxyl prepolymer is 0.8～1.2 mole.

As carboxyl unsaturated compounds, with respect to the reaction ratio containing epoxy group(ing) prepolymer, preferably making carboxyl unsaturated compounds with respect to 1 mole of the epoxy group(ing) total amount containing in epoxy group(ing) prepolymer is 0.8～1.2 mole.

In any case, all can be after immediately above-mentioned prepolymer manufacture, preferably immediately implementing above-mentioned addition reaction after solution polymerization.

Now, the polymerization while suppressing addition reaction with stopper.As stopper, can enumerate butylated hydroxytoluene, quinhydrones, hydroquinone monomethyl ether etc., preferably add the stopper of 50～1,000ppm with respect to reaction soln.

ethylenically unsaturated group in 2-3. (UB) composition

As the mean number of the ethylenically unsaturated group in (UB) composition, suitably set according to target.

As the mean number of the ethylenically unsaturated group in (UB) composition, preferably 0.5～5.0 of average out to, more preferably average 1.0～3.0 in every 1 molecule.The ethylenically unsaturated group number having in every 1 molecule is average when more than 0.5, can enter into fully the matrix of (A) composition, makes thermotolerance, humidity resistance, fragility become abundant.The ethylenically unsaturated group number having in every 1 molecule is average below 5.0 time, can make cross-linking density moderate, as the also step-down of photoelastic coefficient 1 of the cured article of the tenacity excellent of film, composition.

(UB) mean number of the ethylenically unsaturated group in composition (f) can be represented by following formula (3).

[mathematical expression 2]

X: the number-average molecular weight Mn that utilizes the prepolymer of GPC mensuration

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

Z: the parts by weight in prepolymer with the compound unit of reactive group

It should be noted that, for thering is the compound unit of reactive group in prepolymer, if containing carboxyl prepolymer, represent the monomeric unit from carboxyl unsaturated compounds; If hydroxyl prepolymer represents the monomeric unit from hydroxy kind unsaturated compound; If containing epoxy group(ing) prepolymer, represent the monomeric unit from epoxies unsaturated compound.

For (UB) composition, in order effectively to import ethylenically unsaturated group in molecular end, and from taking into account the viewpoint of fragility and photoelastic coefficient 2 higher-dimension, preferably by containing terminal carboxyl(group) polymkeric substance or containing the polymkeric substance (below also referred to as macromonomer) of terminal hydroxyl polymers manufacturing as prepolymer.

As macromonomer, specifically can enumerate by containing the polymkeric substance UB1 of terminal carboxyl(group) polymers manufacturing and UB2, by the polymkeric substance UB1 containing terminal hydroxyl polymers manufacturing, their f value is 1.0.

3. blooming formation active energy ray-curable composition

The present invention relates to comprise above-mentioned (A) composition and (B) composition as the blooming formation active energy ray-curable composition of essential composition.

As the manufacture method of composition, according to ordinary method, can obtain as follows composition: use (A) composition and (B) composition, and use as required and further other composition, these compositions are stirred, mixed.

With regard to composition of the present invention, need to make the photoelastic coefficient 1 of its cured article is 10 × 10 ^-12pa ^-1below.Thus, cured article is difficult for, because external force generation double refraction changes, when as polaroid protective film, can preventing light leak and whiting.In addition, the photoelastic coefficient 1 of the cured article of composition of the present invention is preferably-10 × 10 ^-12pa ^-1above.

With regard to composition of the present invention, in the front of the cured article need to make to measure with the thickness of 40 μ m time and the face of oblique 40 °, the delay of delay and thickness direction is below 5nm.Thus, when as polaroid protective film, can obtain the liquid-crystal display of field angle excellent.Delay at cured article is greater than 5nm, has the problem of field angle characteristic variation.

In addition, preferably: in the time measuring with the thickness of 40 μ m, in the positive face of cured article, postpone, for below 1nm, in the face of oblique 40 °, postpone for below 5nm, and the delay of thickness direction to be below 5nm.In addition, preferably make the value of this delay be-more than 5nm.

Described delay in the present invention refers to: in the time that rectilinearly polarized light is incident to blooming, think that transmitted light can be decomposed into orthogonal 2 bundle rectilinearly polarized lights, the double refraction based on now and the phase differential that produces.

Particularly, the principal refractive index in face is made as to nx, ny (wherein, nx >=ny), by the specific refractory power of thickness direction be made as nz, when thickness is made as to d, the delay (Re) in face and the delay (Rth) of thickness direction are the values being defined by following formula.

Re＝(nx-ny)×d

Rth＝{(nx+ny)/2-nz}×d

In addition, postpone in the face of described oblique 40 ° in the present invention to refer to: in the face when tilting 40 ° of incident rectilinearly polarized lights with respect to blooming, postpone.

As (A) composition and (B) ratio of composition, suitably set according to target, in the time that taking (A) composition and (B) total amount of composition is as benchmark, preferably make (A) composition be 30～90 % by weight and (B) composition be 10～70 % by weight, more preferably make (A) composition be 40～80 % by weight and (B) composition be 20～60 % by weight.

Being more than 30 % by weight by making the ratio of (A) composition, can making the mechanical properties excellence of gained cured article, on the other hand, is below 90 % by weight by making the ratio of (A) composition, can take into account low photoelastic coefficient and low delay.

Composition of the present invention be taking above-mentioned (A) composition and (B) composition as the composition of essential composition, but can coordinate various compositions according to target.

Particularly, can enumerate: alefinically unsaturated compounds (below also referred to as (C) composition) except (A) composition, Photoepolymerizationinitiater initiater (below also referred to as (D) composition), organic solvent (below also referred to as (E) composition), stopper are or/and antioxidant, photostabilization activator etc.

Below, these compositions are described.

(C) composition

(C) composition is the alefinically unsaturated compounds except (A) composition.

(C) composition be for make composition in its entirety reduced viscosity object, object that other physical property is adjusted and need the composition coordinating.

As the concrete example of (C) composition, can enumerate (methyl) acrylate (below also referred to as " other (methyl) acrylate "), NVP etc. except (A) composition.

As other (methyl) acrylate, can enumerate: have 1 (methyl) acryl compound (below also referred to as " simple function (methyl) acrylate "), there is the compound (below also referred to as " multifunctional (methyl) acrylate ") etc. of 2 above (methyl) acryls.

As the concrete example of simple function (methyl) acrylate, can enumerate: (methyl) isobornyl acrylate, (methyl) vinylformic acid two cyclopentenes esters, (methyl) vinylformic acid two encircles pentyl ester, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid 3-methyl cyclohexanol ester, (methyl) vinylformic acid 1-adamantane esters, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) Ethyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester, (methyl) tetrahydrofurfuryl acrylate, (methyl) glycidyl acrylate, (methyl) vinylformic acid dimethylamino ethyl ester, (methyl) vinylformic acid diethylamino ethyl ester, (methyl) benzyl acrylate, (methyl) allyl acrylate, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid phenoxy ethyl, orthoxenol EO modification (n=1～4) (methyl) acrylate, to cumyl phenol EO modification (n=1～4) (methyl) acrylate, (methyl) phenyl acrylate, the adjacent phenyl phenyl ester of (methyl) vinylformic acid, (methyl) vinylformic acid is to cumyl phenyl ester, N-(methyl) acryloyl morpholine, N-vinyl formamide, N-(methyl) acryloxy ethyl hexahydrophthalic phthalimide, N-(methyl) acryloxy ethyl tetrahydric phthalimide etc.

As the concrete example of multifunctional (methyl) acrylate, can enumerate: dihydroxyphenyl propane EO modification (n=1～2) two (methyl) acrylate, dihydroxyphenyl propane two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, polyoxyethylene glycol (n=5～14) two (methyl) acrylate, propylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, four propylene glycol two (methyl) acrylate, polypropylene glycol (n=5～14) two (methyl) acrylate, 1,3 butylene glycol two (methyl) acrylate, BDO two (methyl) acrylate, polytetramethylene glycol (n=3～16) two (methyl) acrylate, poly-(1-methyl butyleneglycol) (n=5～20) two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, hydroxy new pentane acid neopentyl glycol two (methyl) acrylate, two senses (methyl) acrylate such as tristane dihydroxymethyl two (methyl) acrylate etc.

It should be noted that, the described EO modification in above-mentioned refers to oxyethane modification, and n represents the repeat number of epoxy alkane unit.

As (C) composition, can only use a kind in above-claimed cpd, also can be used in combination two or more.

As (C) composition, in above-claimed cpd, preferably the photoelastic coefficient 1 of homopolymer is lower than the compound of (A) composition, the compound that more preferably photoelastic coefficient 1 of homopolymer is negative value.

As the concrete example of this compound, particularly preferably (methyl) isobornyl acrylate, (methyl) tert-butyl acrylate, N-(methyl) acryloyl morpholine and NVP.

As the ratio of (C) composition, suitably set according to target, as long as the amount that can not make the flexibility of gained cured article reduce, but preferably with respect to (A) composition and (B) total amount 100 weight parts of composition be 1～100 % by weight, 1～80 % by weight more preferably.

(D) composition

(D) composition is Photoepolymerizationinitiater initiater.

(D) composition is the composition coordinating in the situation that using ultraviolet ray and visible ray as active energy beam.In the situation that using electron rays as active energy beam, be not necessary to coordinate (D) composition, but in order to improve solidified nature, also can coordinate as required a small amount of (D) composition.

As (D) composition, can enumerate:

Benzil dimethyl ketal, benzil, bitter almond oil camphor, bitter almond oil camphor ethyl ether, bitter almond oil camphor isopropyl ether, bitter almond oil camphor isobutyl ether, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone, oligomeric [2-hydroxy-2-methyl-1-[4-1-(methyl ethylene) phenyl] acetone, 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl propionyl) benzyl] phenyl }-2-methylpropane-1-ketone, 2-methyl isophthalic acid-[4-(methylthio group)] phenyl]-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholine-4-base-phenyl) butane-1-ketone, Adeka Optomer N-1414 ((strain) ADEKA system), phenyl glyoxalic acid methylester, EAQ, the aromatic ketone compounds such as phenanthrenequione,

Benzophenone, 2 methyl benzophenone, 3-methyldiphenyl ketone, 4-methyldiphenyl ketone, 2, 4, 6-tri-methyl benzophenone, 4-phenyl benzophenone, 4-(methylbenzene sulfenyl) phenyl methane, methyl-2-benzophenone, 1-[4-(4-benzoylphenyl sulfanilyl radical) phenyl]-2-methyl-2-(4-aminomethyl phenyl alkylsulfonyl) propane-1-ketone, 4, 4 '-bis-(dimethylamino) benzophenone, 4, 4 '-bis-(diethylamino) benzophenone, N, N '-tetramethyl--4, 4 '-diaminobenzophenone, N, N '-tetraethyl--4, the benzophenone compounds such as 4 '-diaminobenzophenone and 4-methoxyl group-4 '-dimethylamino benzophenone,

Two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, ethyl (2,4,6-trimethylbenzoyl) phenylphosphite ester and two (2,6-dimethoxy benzoyl)-2,4, the acylphosphine oxide compounds such as 4-tri-methyl-amyl phosphine oxide;

Thioxanthone, CTX, 2,4-diethyl thioxanthone, isopropyl thioxanthone, the chloro-4-propyl group of 1-thioxanthone, 3-[3,4-dimethyl-9-oxo-9H-thioxanthone-2-yl] oxygen base]-2-hydroxypropyl-N, N, the thioxanthone compounds such as N-trimethyl ammonium chloride and fluorine thioxanthone;

The acridones compounds such as dihydroketoacridine, 10-butyl-2-chloro-acridine ketone;

1-[4-(thiophenyl) phenyl] 1,2-acetyl caproyl 2-(O-benzoyl oxime) and 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl] the oxime ester class such as ethyl ketone 1-(O-acetyl oxime);

2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dimer, 2-(Chloro-O-Phenyl)-4,5-bis-(m-methoxyphenyl) imidazoles dimer, 2-(adjacent fluorophenyl)-4,5-phenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenyl-imidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenyl-imidazole dimer, 2,4-bis-(p-methoxyphenyl)-5-phenylimidazole dimer and 2-(2,4-Dimethoxyphenyl)-4,5-diphenyl-imidazole dimer etc. 2,4,5-triarylimidazoles dimer; And

The acridine derivatives such as two (9, the 9 '-acridyl) heptane of 9-phenylacridine and 1,7-etc.

These compounds can use a kind or be used in combination two or more.

As the mixing ratio of (D) composition, with respect to (A) composition and (B) total amount 100 weight parts of composition, be preferably 0.01～10 % by weight, 0.1～5 % by weight more preferably; In the time comprising above-mentioned (C) composition, with respect to (A) composition, (B) composition and (C) total amount 100 weight parts of composition, be preferably 0.01～10 % by weight, 0.1～5 % by weight more preferably.

By making the mixing ratio of (D) composition more than 0.01 % by weight, can utilize appropriate ultraviolet ray or visible light quantity that composition is solidified, thereby can boost productivity, on the other hand, by making the mixing ratio of (D) composition below 10 % by weight, can make cured article there is excellent weathering resistance and the transparency.

(E) composition

The objects such as the screening characteristics for improvement to base material, it is organic solvent that composition of the present invention preferably comprises (E) composition.

As the concrete example of (E) composition, can enumerate:

The varsols such as normal hexane, benzene,toluene,xylene, ethylbenzene and hexanaphthene;

Methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, isopropylcarbinol, 2-methyl cellosolve, cellosolvo, 2-(methoxymethoxy) ethanol, 2-isopropoxide ethanol, butoxy ethanol, 2-isopentyloxy ethanol, 2-hexyloxy ethanol, 2-phenoxyethyl alcohol, 2-BOE, furfuryl alcohol, tetrahydrofurfuryl alcohol, Diethylene Glycol, diethylene glycol monomethyl ether, TC, Diethylene Glycol single-butyl ether, 1-methoxy-2-propanol, the alcoholic solvents such as 1-oxyethyl group-2-propyl alcohol and propylene glycol monomethyl ether,

The ether solvents such as tetrahydrofuran (THF), diox, ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethyl ether, ethylene glycol bisthioglycolate butyl ether, two (2-methoxy ethyl) ether, two (2-ethoxyethyl group) ether and two (2-butoxyethyl group) ether;

The ketones solvents such as acetone, methylethylketone, methyl n-propyl ketone, metacetone, butyl methyl ketone, methyl iso-butyl ketone (MIBK), Methyl amyl ketone, diη-propyl ketone, diisobutyl ketone, sym.-diisopropylideneacetone, isophorone, cyclopentanone, pimelinketone and methylcyclohexanone;

The esters solvents such as ethyl acetate, butylacetate, isobutyl acetate, methyl glycol acetic ester, propylene glycol monomethyl ether, cellosolve acetate;

The non-proton property polar solvents such as DMF, N,N-dimethylacetamide, methyl-sulphoxide, METHYLPYRROLIDONE, gamma-butyrolactone.

As (E) composition, can use one kind or two or more in above-claimed cpd.

As organic solvent, can add separately, also can the organic solvent using in the manufacture of (A) composition not separated and directly be used.

As the ratio of (E) composition, suitably set, but in composition, be preferably 10～90 % by weight, 40～80 % by weight more preferably.

stopper is or/and antioxidant

In composition of the present invention, add stopper or/and when antioxidant, can make the storage stability of composition of the present invention improve, therefore preferably.

As stopper, preferably quinhydrones, hydroquinone monomethyl ether, 2,6 di tert butyl 4 methyl phenol and various phenol are antioxidant, and also can add sulphur is that secondary antioxidant, phosphorus are secondary antioxidant etc.

Or/and total mixing ratio of antioxidant, with respect to (A) composition and (B) total amount 100 weight parts of composition, be preferably 0.001～3 % by weight, 0.01～0.5 % by weight more preferably as these stoppers; In the time comprising above-mentioned (C) composition, with respect to (A) composition, (B) composition and (C) total amount 100 weight parts of composition, be preferably 0.001～3 % by weight, 0.01～0.5 % by weight more preferably.

photostabilization activator

In composition of the present invention, can add the photostabilization such as UV light absorber, photostabilizer activator.

As UV light absorber, can enumerate:

The benzotriazole cpds such as 2-(2 '-hydroxy-5-methyl base phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-3 '-tertiary butyl-5 '-aminomethyl phenyl) benzotriazole;

The triaizine compounds such as two (2,4-3,5-dimethylphenyl)-6-(the different octyloxyphenyl of the 2-hydroxyl-4-) s-triazine of 2,4-;

2,4 dihydroxyl benzophenone, ESCALOL 567,2-hydroxyl-4-methoxyl group-4 '-methyldiphenyl ketone, 2,2 '-dihydroxyl-4-methoxy benzophenone, 2,4,4 '-trihydroxybenzophenone, 2,2 ', 4,4 '-tetrahydroxybenzophenone, 2,3,4,4 '-tetrahydroxybenzophenone, 2,3 ', 4,4 '-tetrahydroxybenzophenone or 2,2 '-dihydroxyl-4, the benzophenone cpds such as 4 '-dimethoxy-benzophenone etc.

As light stability agent, can enumerate: N, N '-bis-(2,2,6,6-tetramethyl--4-piperidyl)-N, N '-diformyl hexamethylene-diamine, two (1,2,2,6,6-pentamethyl--4-piperidyl)-2-(3,5-di-tert-butyl-4-hydroxyl benzyl)-2-n-butylmalonic acid ester, two (1,2,2,6,6-pentamethyl--4-piperidyl) the low molecular weight hindered amine compound such as sebate; N, N '-bis-(2,2,6,6-tetramethyl--4-piperidyl)-N, the hindered amine light stabilizers such as high molecular hindered amine compound such as N '-diformyl hexamethylene-diamine, two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate.

As the mixing ratio of photostabilization activator, with respect to (A) composition and (B) total amount 100 weight parts of composition, be preferably 0～5 % by weight, 0～1 % by weight more preferably; In the time comprising above-mentioned (C) composition, with respect to (A) composition, (B) composition and (C) total amount 100 weight parts of composition, be preferably 0～5 % by weight, 0～1 % by weight more preferably.

4. using method

Composition of the present invention can adopt various using method according to the film formed object of optics.

Particularly, can enumerate: composition is coated on to base material and irradiates active energy beam and make its curing method; By composition be coated on base material and with the laminating of other base material after, further irradiate active energy beam and make its curing method; Composition is injected and has the molding box (Japanese original text: type frame) of recess, and irradiate active energy beam and make its curing method etc.

As base material, can use strippable base material and not there is any base material in the base material (below also referred to as " non-release property base material ") of release property.

As strippable base material, can enumerate: passed through the film of demoulding processing, the surperficial untreated film with separability and metal (being also referred to as below " release materials ") etc.

As release materials, can enumerate: silicone-treated polyethylene terephthalate film, surperficial untreated polyethylene terephthalate film, surperficial untreated cyclo-olefin-polymer films and surperficial untreated OPP film (polypropylene) etc.

For the mist degree of the cured article of composition of the present invention is suppressed at below 1.0%, preferably use surperficial untreated polyethylene terephthalate film, surperficial untreated OPP film (polypropylene).

For the blooming being obtained by composition of the present invention, in order to make it reach low haze or to give surface smoothness to it, preferably use surfaceness (center line average roughness) Ra be base material below 150nm as strippable base material, the base material that more preferably Ra is 1～100nm.In addition, as mist degree, be preferably below 3.0%.In addition, mist degree is preferably more than 0.01%.

As the concrete example of this base material, can enumerate surperficial untreated polyethylene terephthalate film, surperficial untreated OPP film (polypropylene) etc.

It should be noted that, the described surface roughness Ra in the present invention refers to: the mean roughness of measuring the concavo-convex of film surface and calculating.

As non-release property base material, can enumerate the various plastics except above-mentioned, can enumerate: the cellulose ethanoate resins such as polyvinyl alcohol, cellulose triacetate and secondary cellulose acetate, acrylic resin, polyester, polycarbonate, polyarylester, polyethersulfone, cyclic polyolefin resin taking cyclic olefins such as norbornylenes as monomer etc.

In the time of coating composition of the present invention, for the generation that makes gained blooming become the defects such as sneaking into of foreign matter prevented, space is prevented, the film of optics physical properties excellent, as composition, preferably use the composition obtaining through refining after material composition stirring/mixing.

As the process for purification of composition, the method that composition is filtered is comparatively easy, therefore preferably.As the method for filtering, can enumerate pressure filtration etc.

Filtering accuracy is preferably below 10 μ m, more preferably below 5 μ m.Filtering accuracy is more little more preferred, but filtering accuracy is when too small, easily makes the exchange frequency of filter stoppage, strainer increase, productivity reduces, and therefore preferably under it, is limited to 0.1 μ m.

As coating method, suitably set according to target, can enumerate the method that utilization known rod painting in the past, applicator (applicator), scraper, knife coater, comma coating machine (comma coater), contrary roll-coater, mould painting machine, lip formula coating machine (lip coater), intaglio plate coating machine and miniature intaglio plate coating machine etc. apply.

As active energy beam, can enumerate electron rays, ultraviolet ray and visible ray etc.In these active energy beams, be never must coordinate Photoepolymerizationinitiater initiater, the thermotolerance of cured article and the aspect of excellent in light-resistance are considered, more preferably electron rays.

For the illuminate condition such as irradiation dose, exposure intensity of active energy beam, suitably set according to used composition, base material and object etc.

5. blooming

Composition of the present invention can be preferred for the manufacture of blooming.

Below, blooming is described.

It should be noted that, below carried out part explanation based on Fig. 1 and Fig. 2.

the manufacture method of 5-1. blooming

As the manufacture method of blooming, according to ordinary method, for example, can after composition being coated to base material, manufacture blooming to its irradiation active energy beam.

Fig. 1 is the schematic diagram that shows an example of the preferable production process of the blooming being made up of release materials/cured article.

In Fig. 1, (1) represents release materials.

In the situation that composition is no-solvent type (Fig. 1: F1), composition is coated on to release materials (Fig. 1: (1)).In the situation that composition comprises organic solvent etc. (Fig. 1: F2), composition is coated on to release materials (Fig. 1: (1)) afterwards, it is dried so that the evaporations such as organic solvent (Fig. 1: 1-1).

By the sheet material irradiation active energy beam forming form composition layer (2) in release materials, the blooming that can obtain being formed by release materials/cured article.With regard to the irradiation of active energy beam, conventionally irradiate from composition layer side, but also can irradiate from release materials side.

During as base material (1), can manufacture the blooming being formed by release materials/cured article in above-mentioned middle use release materials.

As the coating amount of composition of the present invention, suitably select according to used purposes, but preferably so that the thickness after dry organic solvent etc. reaches the mode of 5～200 μ m applies, more preferably so that the thickness after dry organic solvent etc. reaches the mode of 10～100 μ m applies.

In the situation that composition comprises organic solvent etc., after coating, heat and be dried, thereby making the evaporations such as organic solvent.

As heating and drying means, can adopt and make it by possessing the method in the stove of heating unit, or can also be by blowing to implement,

Heating and drying conditions are according to used organic solvent etc. and suitably setting can be enumerated the method for the temperature that is heated to 40～150 DEG C etc.

As heating and dried composition, preferably make the ratio of organic solvent reach below 1 % by weight.

The illuminate condition such as irradiation dose, exposure intensity of active energy beam is suitably set according to used composition, base material and object etc.

Fig. 2 is the schematic diagram that shows an example of the preferable production process of the blooming being made up of release materials/cured article/release materials.

In Fig. 2, (1), (3), (4) represent release materials.

In the situation that composition is no-solvent type (Fig. 2: F1), composition is coated on to release materials (Fig. 2: (1)).In the situation that composition comprises organic solvent etc. (Fig. 2: F2), composition is coated on to release materials (Fig. 2: (1)) afterwards, it is dried so that the evaporations such as organic solvent (Fig. 2: 2-1).By it being irradiated active energy beam or irradiating active energy beam lamination release materials (4) afterwards, can be formed successively the blooming that release materials, cured article and release materials form after release materials (3) being laminated on composition layer (2).

In above-mentioned Fig. 1 and 2, record be to use release materials as the example of base material, also can manufacture blooming with non-release property base material.

For example, also can replace with non-release property base material the release materials of (1) in Fig. 1, and similarly irradiate active energy beam and it is solidified with above-mentioned, thereby manufacture the blooming that formed by non-release property base material/cured article.

In addition, also can use non-release property base material as the arbitrary release materials in (1), (3) and (4) in Fig. 2, and utilize method same as described above to irradiate active energy beam and it is solidified, thereby manufacture by blooming that release materials/cured article/non-release property base material forms or by blooming that non-release property base material/cured article/non-release property base material forms.

As the concrete example of this embodiment, can enumerate: use polaroid as non-release property base material, coating composition also irradiates active energy beam, thus on polaroid the direct method etc. of formation protective membrane.

In addition, manufacturing lens in the situation that, can enumerate: use overlay as non-release property base material, after coating composition, on this film laminating as the metal die of release materials, and the method etc. of irradiating active energy beam from overlay side.

In addition, cited in above-mentioned example is coating composition and manufacture the example of blooming on base material, but in the case of manufacturing the blooming that thickness is large, also composition injection can be there is to the molding box of specific recess etc., and similarly irradiate active energy beam so that composition solidifies with above-mentioned, thereby manufacture blooming.

the purposes of 5-2. blooming

The blooming being formed by composition of the present invention can be applicable to various optical applications, more specifically, can enumerate polaroid protective film, prismatic lens support membrane and light guiding film etc. for the polarization plates of liquid crystal indicator etc.In addition, as purposes in addition, can enumerate the lens of Fresnel lens and biconvex lens etc. etc., biconvex lens can also further be used in bore hole 3D indicating meter.

Below, the polarization plates that has used the polaroid protective film (below also referred to as " protective membrane ") being formed by composition of the present invention is described.

polarization plates

Polarization plates has the formation at the folded protective membrane of at least one surface layer of polaroid.

As polarization plates, can be by direct coating composition of the present invention make it be solidified to form protective membrane manufacture on polaroid, also can be by by polaroid and protective membrane is bonding manufactures.

As polaroid, as long as there is the function that optionally sees through the rectilinearly polarized light of a direction from natural light, can use various materials.

For example, can enumerate: make iodine be adsorbed in polyvinyl alcohol film and iodine class polarization film that orientation forms occurs, make dichroic dye be adsorbed in polyvinyl alcohol film and dye class polarization film, the coating dichroic dye that orientation forms occur and make application type polaroid that its orientation and immobilization form etc.These iodine class polarization films, dye class polarization film and application type polaroid have from natural light and optionally see through the rectilinearly polarized light of a direction and absorb the function of the rectilinearly polarized light of other direction, are therefore called as absorption-type polaroid.In these polaroids, preferably use visual excellent absorption-type polaroid.The thickness of absorption-type polaroid is preferably 5～40 μ m.

Polarization plates of the present invention is the polarization plates forming as protective membrane at the folded blooming of the present invention of at least one surface layer of polaroid, and it is undertaken bonding by caking agent.

Can consider that it uses any caking agent separately cementability in the situation that for the caking agent of bonding polaroid and protective membrane.

As caking agent, specifically can enumerate polyvinyl alcohol water class caking agent, solvent based caking agent, hot melt class caking agent and solvent-free class caking agent etc., can preferably use the active energy ray curable caking agent of solvent-free class.

As active energy ray curable caking agent, can enumerate: light cationic curing type caking agent, optical free radical curing caking agent and be used in combination light cationic curing and commixed type caking agent that optical free radical is curing.

As light cationic curing type caking agent, can enumerate: the caking agent that comprises the cation photocuring such as epoxy compounds and oxetane compound compound and cationic photopolymerization initiator etc.

As optical free radical curing caking agent, can enumerate: the caking agent that comprises the optical free radical solidified nature compounds such as (methyl) acrylate, vinyl ether, vinyl compound and optical free radical polymerization starter etc.

As commixed type caking agent, can enumerate: the caking agent that comprises above-mentioned smooth cation-curable compound, optical free radical solidified nature compound, light cationic polymerization initiators and optical free radical polymerization starter etc.

Have protective membrane on the two sides of polaroid, most preferably there is protective membrane of the present invention on two sides.But also can use protective membrane of the present invention and use the protective membrane (below also referred to as " other protective membrane ") except protective membrane of the present invention at another side in one side as required.

As other protective membrane, for example can enumerate: the cellulose ethanoate resin molding of cellulose triacetate, secondary cellulose acetate and so on; Acrylic resin film; Polyester resin film; Cyclic polyolefin resin film using the cyclic olefin of norbornylene and so on as monomer etc.In addition, in the case of these protective membranes are used as the protective membrane of indicating meter side, can be also the dephased film of tool.

Embodiment

Below, enumerate embodiment and comparative example the present invention is carried out to more specific detail.It should be noted that, described " part " in following represents weight part.

zero Production Example A1(manufacture of (A) composition)

In the 500mL reaction vessel that is equipped with stirrer, thermometer, condenser, under room temperature (25 DEG C, lower with), add as the IPDI145.9g of isocyanic ester, as the dibutyl tin laurate 0.07g of catalyzer, in the nitrogen atmosphere that comprises 5 capacity % oxygen, limit is stirred limit to them and is heated to liquid temperature and reaches 70 DEG C.

So that reaching 75 DEG C of following modes, interior temperature drips polycarbonate diol (Asahi Kasei Chemicals (strain) Duranol T-5651 processed, the number-average molecular weight 1 as alcoholic solution, 000) 43.0g, 1, the mixing solutions of 4-butyleneglycol 33.5g and methylethylketone (below also referred to as " MEK ") 65.0g, then, at 80 DEG C of interior temperature, make reaction carry out 2 hours.

Thereafter, so that reaching 75 DEG C of following modes, interior temperature drips vinylformic acid 2-hydroxy methacrylate (below also referred to as " HEA ") 57.6g, as 2 of stopper, 6-di-tert-butyl-4-methy phenol (below also referred to as " BHT ") 0.28g, the mixing solutions of MEK5.0g and dibutyl tin laurate 0.07g, then make reaction carry out 3 hours, utilize infrared absorption spectrum device (the FT-IR Spectrum100 processed of Perkin Elmer company) to measure spectrum, confirm that isocyanate group is completely consumed, obtain the MEK solution (solids component 80%) that comprises urethane acrylate (hereinafter referred to as " UA-1 ").

Utilize GPC (solvent: tetrahydrofuran (THF), chromatographic column: the HSPgel HR processed MB-L of Waters company) to measure the polystyrene conversion weight-average molecular weight (below also referred to as Mw) of UA-1, result is 2,300.

Measured photoelastic coefficient 1 according to aftermentioned method, result is 12.3 × 10 ^-12pa ^-1.

zero Production Example A2(manufacture of (A) composition)

The IPDI as isocyanic ester in Production Example A1 is set as to 127.8g, as alcoholic solution, has used 37.6g Duranol T5651, three ring [5.2.1.0 ^2,6] mixing solutions of decane dimethanol (TCDDM processed of Oxcea company) 64.1g and MEK65.0g, and HEA is set as to 50.5g, in addition, carry out identical operation with Production Example A1, obtained the MEK solution (solids component 80%) that comprises urethane acrylate (hereinafter referred to as " UA-2 ").

Mw to gained UA-2 and photoelastic coefficient 1 have carried out the mensuration identical with Production Example A1, and result Mw is 2,300, photoelastic coefficient 1 is 9.7 × 10 ^-12pa ^-1.

zero Production Example A3(manufacture of (A) composition)

The IPDI as isocyanic ester in Production Example A1 is set as to 151.4g, as alcoholic solution, use polycaprolactonetriol (Daisel chemical industry Co., Ltd's system) Plaxcel303, number-average molecular weight 300) 18.3g, 20.4g Duranol T5651,1, the mixing solutions of 4-butyleneglycol 28.2g and MEK65.0g, and HEA is set as to 61.6g, in addition, carry out identical operation with Production Example A1, obtained the MEK solution (solids component 80%) that comprises urethane acrylate (hereinafter referred to as " UA-3 ").

Mw to gained UA-3 and photoelastic coefficient 1 have carried out the mensuration identical with Production Example A1, and result Mw is 2,400, photoelastic coefficient 1 is 13.5 × 10 ^-12pa ^-1.

zero Production Example A4(manufacture of (A) composition)

The IPDI as isocyanic ester in Production Example A1 is set as to 148.8g, as alcoholic solution, use polyester glycol (carboxylate, the number-average molecular weight 500 of DIC (strain) Exp4358 processed, hexanodioic acid and ethylene glycol) 42.1g, 1, the mixing solutions of 4-butyleneglycol 30.4g and MEK65.0g, and HEA is set as to 58.7g, in addition, carry out identical operation with Production Example A1, obtained the MEK solution (solids component 80%) that comprises urethane acrylate (hereinafter referred to as " UA-4 ").

Mw to gained UA-4 and photoelastic coefficient 1 have carried out the mensuration identical with Production Example A1, and result Mw is 1,900, photoelastic coefficient 1 is 12.6 × 10 ^-12pa ^-1.

zero Production Example A5(manufacture of (A) composition)

As the isocyanic ester in Production Example A1, use the mixing solutions of IPDI99.6g and MEK50.0g, as alcohol, use the spiroglycol (hydroxyl value: 369mgKOH/g, P-Mn:304) (Mitsubishi Gas Chemical (strain) SPG processed) 74.4g and MEK (for after adding as the SPG of powder, the part that is attached to reaction vessel being washed) 25.5g, as hydroxy acryl acid ester, 1 mole of affixture of 6-caprolactone (FA1DDM processed of Daicel Co., Ltd.) 95.6g of vinylformic acid 2-hydroxy methacrylate and the mixing solutions of MEK5.0g are used, in addition, carry out identical operation with Production Example A1, obtain the MEK solution (solids component 80%) that comprises urethane acrylate (hereinafter referred to as " UA-5 ").

Mw to gained UA-5 and photoelastic coefficient 1 have carried out the mensuration identical with Production Example A1, and result Mw is 2,400, photoelastic coefficient 1 is 11.6 × 10 ^-12pa ^-1.

zero Production Example A6(manufacture of (A) composition)

The IPDI as isocyanic ester in Production Example A1 is set as to 134g, as alcoholic solution, use 1, the mixing solutions of 4-butyleneglycol 34.2g and MEK65.0g, as hydroxy acryl acid ester, use FA1DDM104.8g, in addition, carry out identical operation with Production Example A1, obtained the MEK solution (solids component 80%) that comprises urethane acrylate (hereinafter referred to as " UA-6 ").

Mw to gained UA-6 and photoelastic coefficient 1 have carried out the mensuration identical with Production Example A1, and result Mw is 2,200, photoelastic coefficient 1 is 17.5 × 10 ^-12pa ^-1.

zero Production Example A ' 1(manufacture of the urethane acrylate except (A) composition)

In the 500mL reaction vessel that is equipped with stirrer, thermometer, condenser, under room temperature, add as the IPDI196.0g of isocyanic ester, as the dibutyl tin laurate 0.035g of catalyzer, in the nitrogen atmosphere that comprises 5 capacity % oxygen, limit is stirred limit to them and is heated to liquid temperature and reaches 70 DEG C.

Drip the Duranol T5651 of 49.5g as alcohol so that interior temperature reaches 75 DEG C of following modes, then, at 80 DEG C of interior temperature, reaction is carried out 2 hours.

, so that interior temperature reach 75 DEG C following modes drip HEA104.5g and BHT0.09g after, reaction is carried out 3 hours, obtained urethane acrylate (hereinafter referred to as " UA ' 1 ") thereafter.

Mw to gained UA ' 1 and photoelastic coefficient 1 have carried out the mensuration identical with Production Example A1, and result Mw is 4,400, photoelastic coefficient 1 is 153 × 10 ^-12pa ^-1.

zero Production Example B1(manufacture of (B) composition)

In the 500mL reaction vessel that is equipped with stirrer, thermometer, condenser, add methyl methacrylate (below also referred to as " MMA ") 20.0g, N-acryloyl morpholine (below also referred to as " ACMO ") 20.0g, methyl iso-butyl ketone (MIBK) (below also referred to as " MIBK ") 200g, at room temperature make its uniform dissolution.

Stir the content of flask on limit, limit is warming up to 92 DEG C by interior temperature in nitrogen atmosphere, after interior temperature is constant, with 4 hours supply with MMA80.0g, with 3 hours supply ACMO80.0g, on the other hand, with within 5 hours, supplying with continuously respectively the polymerization starter solution that comprises V-65 (with the pure pharmaceutical worker's industry of light (strain) system 2,2 '-azo is two-2,4-methyl pentane nitrile) 10g and MIBK40 part.

After supply finishes continuously, interior temperature is held in to 92 DEG C and has carried out slaking in 3 hours, result has obtained comprising the solution (solids component 47%) of the polymkeric substance (hereinafter referred to as " LP-1 ") with negative photoelastic coefficient 2.

The Mw of gained LP-1 has been carried out to the mensuration identical with Production Example A1, and result Mw is 10,000.In addition, by the following method the photoelastic coefficient 2 of LP-1 is measured, result is-5.0 × 10 ^-12pa ^-1.

In addition, for the photoelastic coefficient 2 of (B) composition, used urethane acrylate is added (B) composition and obtains blooming with arbitrary proportion, and the photoelastic coefficient value at 23 DEG C is measured to obtained blooming, make rectilinear coordinate graph by its addition and photoelastic coefficient, calculate the photoelastic coefficient value when being extrapolated to addition and being 100% by this rectilinear coordinate graph, and record this value.

(1) embodiment 1～12 and comparative example 1～7 (manufacture of composition)

Composition shown in aftermentioned table 1 is dropped into stainless steel container made with the ratio shown in table 1, and limit heating edge utilizes magnetic stirrer to evenly, obtains composition.

[table 1]

Abbreviation in table 1 represents following implication.

LP-2: polymethylmethacrylate resinoid, Mitsubishi Rayon (strain) Dainal BR-87 (solids component: 100%, Mw:25,000, acid number: 10.5mgKOH/g, photoelastic coefficient 2:-6 × 10 ^-12pa ^-1)

LP-3:N-vinyl-2-pyrrolidone/vinyl acetate copolymer, ISP Japan (strain) PVP/VA S-630 processed (solids component: 100%, Mw:45,000, photoelastic coefficient 2:-9 × 10 ^-12pa ^-1)

Dc1173:2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, BASF JAPAN (strain) DAROCUR-1173 processed

(2) embodiment F 1～F10 and Comparative Example F 1～F6 (manufacturing blooming based on electron(beam)curing)

The mode of utilizing applicator that the composition obtaining in embodiment 1～10 and comparative example 1～6 is reached to 40 μ m with the thickness after dry 10 minutes at 80 DEG C is coated on the film " Lumirror50-T60 " (surperficial untreated polyethylene terephthalate film, thick 50 μ m, hereinafter referred to as " Lumirror ") of Toray (strain) manufacture of wide 300mm × long 300mm.

Thereafter, after the Lumirror of wide 300mm × long 300mm is laminated to composition layer, utilize electron beam irradiation device that (strain) NHV Corporation manufactures to carry out electron rays irradiation under acceleration voltage 200kV, irradiation dose 50kGy (being adjusted according to electron rays electric current and transfer rate), condition below oxygen concn 300ppm, obtained blooming.

After solidifying, peel off from Lumirror, and for postponing and the evaluation of thickness direction retardation in photoelastic coefficient 1 described later, face.

(3) embodiment F 11～F12 and comparative example 7 (manufacturing blooming based on ultraviolet curing)

The mode of utilizing applicator that the ultraviolet-curable composition obtaining in embodiment 11～12 and comparative example 7 is reached to 40 μ m with the thickness after dry 10 minutes at 80 DEG C is coated on the Lumirror of wide 300mm × long 300mm.

Thereafter, after the Lumirror of wide 300mm × long 300mm is laminated to composition layer, (exposure intensity of high voltage mercury lamp, lamp height 12cm, 365nm is 400mW/cm to the conveyor type UV irradiation equipment of utilizing Eyegraphics (strain) to manufacture ²(measured value of the UV POWER processed PUCK of Fusion UV Systems Japan (strain) company)) adjust line speed, having carried out accumulative total light quantity is 1,000mJ/cm ²uviolizing, obtained ultraviolet hardening blooming.

After solidifying, peel off from Lumirror, and for evaluation described later.

(photoelastic coefficient 1)

The blooming obtaining in embodiment and comparative example is cut into 15mm × 60mm, phase difference value in face while using automatic double refraction instrument (KOBRA-WR, prince's instrumentation machine (strain) system) to be at room temperature determined at respectively to change 5 tension force σ in the scope of 0N～10N, and obtain photoelastic coefficient 1 by the slope of the near linear of making according to the following formula.Result is as shown in table 2.

Δn＝C·σ

(in formula, Δ n represents that stress birefringence rate, σ represent that tension force, C represent photoelastic coefficient 1.)

In addition, for the photoelastic coefficient 1 of the cured article of (A) composition, utilize and manufacture method identical in blooming with above-mentioned based on electron(beam)curing, only make (A) composition curing and made film, and carried out mensuration same as described above.

(in face, postponing and thickness direction retardation)

For the blooming obtaining in embodiment and comparative example, use measuring difference of phases device (prince's instrumentation machine (strain) KOBRA-21ADH processed) to measure interior (being also called below " 0 ° of Re " and " 40 ° of Re ") and the thickness direction retardation (below also referred to as " Rth ") of postponing of faces positive and oblique 40 °.These results are as shown in table 2.

[table 2]

Embodiment F 1～F12 is the blooming being obtained by the composition of the embodiment 1～12 as composition of the present invention, and the photoelastic coefficient 1 that their photoelastic coefficient 1 is less than the TAC that is in the past used as polaroid protective film is 13 × 10 ^-12pa ^-1, and there is not the hidden danger of light leak and whiting.In addition, thickness direction retardation is less than TAC (the i.e. 30～40nm of 40 μ Rth m) is the film of field angle excellent.

On the other hand, Comparative Example F 1～F5 does not comprise (B) composition, and therefore photoelastic coefficient 1 or thickness direction retardation are large, cannot reduce the two simultaneously.In addition, although Comparative Example F 6～F7 comprises (B) composition, the photoelastic coefficient 1 of UA-5 monomer is large, therefore cannot fully reduce photoelastic coefficient 1.

zero Production Example B2(containing the manufacture of carboxyl prepolymer)

In the 1L reaction vessel that is equipped with stirrer, thermometer, condenser, add methyl methacrylate (below also referred to as " MMA ") 52.0g, 2-hydroxyethyl methacrylate (below also referred to as " HEMA ") 16.0g, methacrylic acid (below also referred to as " MAA ") 12.0g, 3-thiohydracrylic acid (below also referred to as " MPA ") 3.2g, methyl iso-butyl ketone (MIBK) (below also referred to as " MIBK ") 480g, make its at room temperature uniform dissolution.

Stir the content of flask on limit, limit is warming up to 92 DEG C by interior temperature in nitrogen atmosphere, after interior temperature is constant, with the mixed solution 748.8g that adds MMA468.0g, HEMA144.0, MAA108.0, MPA28.8g for 5 hours, on the other hand, added and comprise 2 continuously respectively with 5.5 hours, 2 '-azo two-2, the polymerization starter solution of 4-methyl pentane nitrile (with the pure pharmaceutical worker's industry of light (strain) V-65 processed, below also referred to as " V-65 ") 6.4g and MEK80g.

After continuous adding finishes, interior temperature is held in to 92 DEG C and has carried out slaking in 2 hours, obtained the solution (solids component 62%) containing carboxyl prepolymer (hereinafter referred to as " LP-4 ").

Mn, Mw, photoelastic coefficient 2 to gained LP-4 have carried out the mensuration identical with Production Example B1, and result Mn is 3,200, Mw is 5,800, photoelastic coefficient 2 is 0.2 × 10 ^-12pa ^-1.

These results are as shown in table 3.It should be noted that, the numeral of recording in table 3 is to be the ratios of 100 % by weight while converting according to the ratio of used whole monomers, and has omitted the organic solvent that uses and the record of ratio thereof.

zero Production Example B3(containing the manufacture of carboxyl prepolymer)

Except having carried out like that change according to record in table 3 by the raw material using in Production Example B2, carry out same operation with Production Example B2, obtained having the solution (solids component 62%) containing carboxyl prepolymer (hereinafter referred to as " LP-5 ") of negative photoelastic coefficient 2.

Mn, Mw, photoelastic coefficient 2 to gained LP-5 have carried out the mensuration identical with Production Example B1, and result Mn is 4,400, Mw is 11,000, photoelastic coefficient 2 is-2.0 × 10 ^-12pa ^-1.These results are as shown in table 3.

zero Production Example B4(containing the manufacture of terminal carboxyl(group) polymkeric substance)

In the 1L reaction vessel that is equipped with stirrer, thermometer, condenser, add MMA400.0g, MPA5.8g, MIBK640.0g, and make its at room temperature uniform dissolution.

Stir the content of flask on limit, limit is warming up to 92 DEG C by interior temperature in nitrogen atmosphere, after interior temperature is constant, with 3 hours interpolations MMA400.0g, MPA8.64g, on the other hand, with 4 hours continuously add comprise 1.3g V-65 and 32g MEK polymerization starter solution (1), with 2 hours continuously interpolation comprise 5.2g V-65 and 128.0g MEK polymerization starter solution (2).

After continuous adding finishes, interior temperature is held in to 92 DEG C and has carried out slaking in 2 hours, obtained having the solution (solids component 51%) containing terminal carboxyl(group) polymkeric substance (hereinafter referred to as " LP-6 ") of negative photoelastic coefficient 2.

Mn, Mw, photoelastic coefficient 2 to gained LP-6 have carried out the mensuration identical with Production Example B1, and result Mn is 6,000, Mw is 12,000, photoelastic coefficient 2 is-4.0 × 10 ^-12pa ^-1.These results are as shown in table 3.

[table 3]

zero Production Example B5(manufacture of (B) composition)

In the 1L reaction vessel that is equipped with stirrer, thermometer, condenser, add 350.0g LP-4 (solids component 62%), be warming up to after 92 DEG C, snare drum enters 5% oxygen-nitrogen mixture limit and stirs 1 hour with 180rpm.Thereafter, disposable adding as the BHT0.11g of stopper, DBTDL0.05g, 2-acryloxy ethyl isocyanate (clear and electrician's (strain) Calends AOI processed as catalyzer, below also referred to as " AOI ") 43.0g, and carried out stirring for 4 hours.

The isocyanate group confirming in solution by infrared measure disappears, and shows that this urethane reaction finishes.Obtain thus the solution (solids component 64%) of (B) composition (hereinafter referred to as " ULP-1 ").

Mn, Mw, photoelastic coefficient 2 to gained ULP-1 have carried out the mensuration identical with Production Example B1.In addition, calculated the f value of ULP-1 according to formula (3).

The result of Mn, Mw, f value, unsaturated group importing position and the photoelastic coefficient 2 of ULP-1 is as shown in table 4.

It should be noted that, the numeral of recording in table 4 is to be the ratios of 100 % by weight while converting according to the ratio of the whole monomers that use in prepolymer manufacture, and has omitted the solvent and the ratio thereof that use.

zero Production Example B6～16(manufacture of (B) composition)

Except kind and the ratio of the monomer that uses when manufacturing prepolymer in Production Example B5 having been carried out like that change and having changed the kind and ratio of the compound using in addition reaction according to what record in table 4 and table 5, carry out same operation with Production Example B5, obtained the solution (solids component 51～64%) of (B) composition.

Mn, Mw, f value and photoelastic coefficient 2 to gained ULP-2～12 are measured according to the method same with Production Example B6.These results are imported to position together with unsaturated group and charge to table 4 and table 5.

It should be noted that, in Production Example B11 and B14, the acid number that uses autotitrator (COM-900, flat natural pond industry (strain) system) to confirm in reaction soln disappears, and shows that carboxyl finishes with reacting of epoxy group(ing).

[table 4]

[table 5]

F in table 4 and table 5 is the average ethylenically unsaturated group number in every 1 molecule.

It should be noted that, the abbreviation (comprising the material title of above-mentioned definition) in table 3～5 is as follows.

MMA: methyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

MAA: methacrylic acid

MA: methyl acrylate

GMA: glycidyl methacrylate

ACMO: acryloyl morpholine

V-65:2,2 '-azo is two-2,4-methyl pentane nitrile

MPA:3-thiohydracrylic acid

MTG:2-mercaptoethanol

DM: lauryl mercaptan

AOI:2-acryloxy ethyl isocyanate

AA: vinylformic acid

MOI:2-methacryloxyethyl isocyanic ester

DBTDL: dibutyl tin laurate

TBAB: Tetrabutyl amonium bromide

BHT:2,6-di-tert-butyl-4-methy phenol

(4) embodiment U1～embodiment U20 and comparative example U1～comparative example U2 (manufacture of composition)

Composition shown in aftermentioned table 6～9 is dropped in stainless steel container made with the ratio shown in table 6～9, and limit heating edge utilizes magnetic stirrer to evenly, obtains composition.

[table 6]

[table 7]

M309 in table 7 represents Viscoat 295 ((strain) Aronics M-309 processed is synthesized in East Asia).

[table 8]

[table 9]

(5) embodiment UF1～UF20 and comparative example UF1 and UF2 (manufacturing blooming based on electron(beam)curing)

The mode of utilizing applicator that the composition obtaining in embodiment U1～U20 and comparative example U1～U2 is reached to 40 μ m with the thickness after dry 10 minutes at 120 DEG C is coated on the film " Lumirror50-T60 " (surperficial untreated polyethylene terephthalate film, thick 50 μ m, hereinafter referred to as " Lumirror ") of Toray (strain) manufacture of wide 300mm × long 300mm.

Thereafter, after the Lumirror of wide 300mm × long 300mm is laminated to composition layer, utilize electron beam irradiation device that (strain) NHV Corporation manufactures to carry out electron rays irradiation under acceleration voltage 200kV, irradiation dose 150kGy (being adjusted according to electron rays electric current and transfer rate), condition below oxygen concn 300ppm, obtained blooming.

After solidifying, peel off from Lumirror, and postpone and thickness direction retardation in utilized method evaluation same as described above photoelastic coefficient 1, face.In addition, by the following method cutting and resistance to bending are evaluated.

(cutting)

For the flexibility of the film to made is evaluated, the cutting according to following standard when cutting with cutting knife is evaluated.These results are as shown in table 10.

Zero: the state that can cut smoothly

△: fairness is slightly not enough

×: the state that when cutting, section cracks

(resistance to bending)

For the flexibility of the film to made is evaluated, according to following standard to by cut into 15mm × 150mm 180 ° of film bendings time patience evaluate.These results are as shown in table 10.

Zero: do not rupture through 3 bendings

△: fracture has occurred through 1～2 bending

×: there is fracture through 1 bending

[table 10]

Embodiment UF1～UF17 is the blooming being obtained by the composition of the embodiment U1～U17 as composition of the present invention, and the photoelastic coefficient 1 that their photoelastic coefficient 1 is less than the TAC that is in the past used as polaroid protective film is 13 × 10 ^-12pa ^-1, and there is not the hidden danger of light leak and whiting.In addition, thickness direction retardation is less than TAC (the i.e. 30～40nm of 40 μ Rth m) is the film of field angle excellent.In addition, its flexibility is also excellent.

On the other hand, although embodiment UF18～UF20 is to be the blooming that the composition (embodiment U18～U20) of (B) that photoelastic coefficient 1 polymkeric substance low or that have a negative value does not have ethylenically unsaturated group ' composition is manufactured by comprising, although itself and embodiment U1～U17 similarly have excellent photoelastic coefficient 1 and postpone, all lack flexibility.

Comparative example UF1 is that its photoelastic coefficient 1 and thickness direction retardation are large, cannot reduce the two simultaneously by the blooming that composition (comparative example U1) containing (B) composition is not manufactured.Comparative example UF2 is the blooming of being manufactured by the composition that has used the urethane acrylate different from (A) composition (comparative example U2), and its photoelastic coefficient 1 is large.

zero Production Example PL1(manufacture of polaroid)

Make the polyvinyl alcohol film of thick 80 μ m swelling in the water-bath of 30 DEG C after, in the iodine aqueous solution of 5 % by weight (weight ratio: iodine/potassiumiodide=1/10), dye.Then, be impregnated in the aqueous solution that comprises 3 % by weight boric acid and 2 % by weight potassiumiodides, then in the aqueous solution that comprises 4 % by weight boric acid and 3 % by weight potassiumiodides of 55 DEG C, after uniaxial extension to 5.5 times, impregnated in the potassium iodide aqueous solution of 5 % by weight., in the baking oven of 70 DEG C carry out 1 minute be dried, obtained the polaroid (hereinafter referred to as polaroid P) of thick 30 μ m thereafter.

To gained polaroid P, utilize the spectrophotometer ((strain) island Feng makes made UV-2200) with ahrens prism to measure degree of polarization and monomer transmitance, result is respectively 99.99% and 43.1%.

zero Production Example V1(manufacture of ultraviolet hardening caking agent)

By 50 parts of dihydroxyphenyl propane diglycidyl ether (Japan Epoxy Resin (strain) jER807 processed), 20 parts of tetrahydrofurfuryl acrylates (Osaka organic chemistry industry (strain) THF-A processed), 30 parts of vinylformic acid 4-hydroxyl butyl esters (Japan changes into (strain) 4-HBA processed), 4 parts of iodine (4-aminomethyl phenyl) [4-(2-methyl-propyl) phenyl] the phosphofluoric acid esters (BASF JAPAN (strain) IRGACURE250 processed) of Photoepolymerizationinitiater initiater (below also referred to as " light trigger "), 2, in 1 part of input stainless steel container made of 4-diethyl thioxanthone (Japanese chemical drug (strain) Kayacure DETX-s processed), and utilize magnetic stirrer to even, obtain ultraviolet hardening caking agent (hereinafter referred to as caking agent UVX1).

(6) embodiment P1, embodiment P2 and comparative example P1 (manufacture of polarization plates)

Use the blooming obtaining in embodiment F 3 and embodiment F 5 and Comparative Example F 6 as polaroid protective film; after the two sides of polaroid P is with 5 μ m thickness coating adhesive UVX1 the blooming of fitting, (exposure intensity of high voltage mercury lamp, lamp height 15cm, 365nm is 370mW/cm to the conveyor type UV irradiation equipment of utilizing Eyegraphics (strain) to manufacture ²(measured value of the UV POWER processed PUCK of Fusion UV Systems Japan (strain) company)) adjust line speed, having carried out accumulative total light quantity is 220mJ/cm ²uviolizing, obtained polarization plates (wide 100mm × long 100mm).

It should be noted that, for random polarization sheet protective membrane, all do not carry out corona treatment.

(mensuration of degree of polarization and monomer transmitance)

For the polarization plates obtaining in embodiment and comparative example, utilize the spectrophotometer ((strain) island Feng makes made UV-2200) with ahrens prism to measure degree of polarization and monomer transmitance.These results are as shown in table 11.

(cementability of polaroid protective film and polaroid)

For the polaroid protective film of the polarization plates obtaining in embodiment and comparative example and the cementability of polaroid P, according to following standard evaluation reverse and state when the two is twisted off manually applying.These results are as shown in table 11.

Zero: polaroid and polaroid protective film are integrated and do not peel off.

×: between polaroid and polaroid protective film, confirm and peeled off.

(humidity resistance of polarization plates)

After the polarization plates obtaining in embodiment and comparative example is placed 120 hours in the constant temperature and humidity cabinet of 60 DEG C of 90%RH, have or not distortion to carry out visual valuation according to following standard to sample.These results are as shown in table 11.

Zero: do not observe distortion.

×: observe distortion.

[table 11]

Embodiment P1 and P2 are the polarization plates having used as the blooming obtaining in the embodiment F 3 of composition of the present invention and F5, and it has kept the performance of polaroid P, and cementability and humidity resistance are good.

On the other hand, comparative example P1 is the polarization plates that has used the blooming obtaining in Comparative Example F 6, and it has kept the performance of polaroid P, and cementability is good, but humidity resistance reduces.

(7) embodiment P3～embodiment P12 (manufacture of polarization plates)

The blooming obtaining in using embodiment F 1, F2, F4 and F6～F12, as polaroid protective film, has been made respectively polarization plates according to the force method same with embodiment P1, and humidity resistance has been evaluated.

The random polarization plate of embodiment P3～P12 all demonstrates good humidity resistance.

zero Production Example V2(manufacture of ultraviolet hardening caking agent)

By 40 parts of dihydroxyphenyl propane diglycidyl ether (Japan Epoxy Resin (strain) jER807 processed), 20 parts of tetrahydrofurfuryl acrylates (Osaka organic chemistry industry (strain) THF-A processed), 30 parts of vinylformic acid 4-hydroxyl butyl esters (Japan changes into (strain) 4-HBA processed), 10 parts of the modification two of isocyanuric acid oxyethane and triacrylates ((strain) Aronics M-313 processed is synthesized in East Asia), light trigger is 6 parts of the 50 % by weight carbonate propanediol ester solutions (SAN-APRO CPI-100P processed) of phenylbenzene-4-(thiophenyl) phenyl sulfonium phosphofluoric acid ester, in 1 part of input stainless steel container made of 1-hydroxycyclohexylphenylketone (BASF Japan (strain) Irgacure184 processed), and utilize magnetic stirrer to even, obtain ultraviolet hardening caking agent (hereinafter referred to as caking agent UVX2).

(8) embodiment UP1, embodiment UP2 and comparative example UP1 (manufacture of polarization plates)

Use the blooming obtaining in embodiment UF7, embodiment UF10 and comparative example UF2 as polaroid protective film; and use UVX2 as caking agent; in addition, obtained polarization plates (wide 100mm × long 100mm) according to the method same with embodiment P1.

For the polarization plates obtaining in embodiment and comparative example; utilize the method identical with above-described embodiment P1 to measure degree of polarization and monomer transmitance, and utilize the cementability of method same as described above to polaroid protective film and polaroid and the humidity resistance of polarization plates to evaluate.These results are as shown in table 12.

[table 12]

Embodiment UP1 and UP2 are the polarization plates having used as the blooming obtaining in the embodiment UF7 of composition of the present invention and UF10, and it has kept the performance of polaroid P, and cementability and humidity resistance are good, are effective as protective film for polarizing plate.

On the other hand, comparative example UP1 is the polarization plates that has used the blooming obtaining in comparative example UF2, and it has kept the performance of polaroid P, and cementability is good, but humidity resistance reduces.

(9) embodiment UP3～embodiment UP20 (manufacture of polarization plates)

The blooming obtaining in using embodiment UF1～UF6, UF8, UF9 and UF11～UF20, as polaroid protective film, has been made respectively polarization plates according to the method same with embodiment UP1, and humidity resistance has been evaluated.

The random polarization plate of embodiment UP3～UP20 all demonstrates good humidity resistance.

Utilizability in industry

Blooming of the present invention forms the manufacture applicable to blooming with active energy ray-curable composition.

In addition, describing in detail as above-mentioned, blooming of the present invention is applicable to polaroid protective film purposes.

Claims

1. a blooming formation active energy ray-curable composition, it comprises carbamate (methyl) acrylate (A) and polymkeric substance (B),

The following photoelastic coefficient 1 of the cured article of described carbamate (methyl) acrylate (A) is 30 × 10 ^-12pa ^-1below,

The following photoelastic coefficient 2 of described polymkeric substance (B) has 5 × 10 ^-12pa ^-1following value, and described polymkeric substance (B) is polymkeric substance except (A) composition,

The following photoelastic coefficient 1 of the cured article of said composition is 10 × 10 ^-12pa ^-1below,

In the time measuring with the thickness of 40 μ m, the interior delay of face positive and oblique 40 ° of cured article and the delay of thickness direction are below 5nm,

Wherein, photoelastic coefficient 1 is illustrated in the photoelastic coefficient at 23 DEG C,

Photoelastic coefficient 2 represents following value: used (A) composition is added (B) composition and obtains blooming with arbitrary proportion, and obtained blooming is determined to the photoelastic coefficient value at 23 DEG C, make rectilinear coordinate graph by its addition and photoelastic coefficient, and photoelastic coefficient value when being extrapolated to addition and being 100% by this rectilinear coordinate graph.

2. blooming formation active energy ray-curable composition according to claim 1, wherein, described (A) composition is the compound without aromatic series base.

3. blooming formation active energy ray-curable composition according to claim 1 and 2; wherein; described (A) composition is that to have 2 above (methyl) acryls and weight-average molecular weight be 1,000～15,000 oligopolymer.

4. according to the blooming formation active energy ray-curable composition described in any one in claim 1～3, wherein, described (A) composition is the reactant of polyvalent alcohol, organic multiple isocyanate and hydroxyl (methyl) acrylate.

5. blooming formation active energy ray-curable composition according to claim 4, wherein,

In described (A) composition,

Polyvalent alcohol is aliphatic diol or alicyclic diol or polycarbonate diol or polyester glycol and the aliphatic diol of carbonatoms 2～12 or the combination of alicyclic diol of carbonatoms 2～12,

Organic multiple isocyanate is without xanthochromia type organic diisocyanate.

6. blooming formation active energy ray-curable composition according to claim 4, wherein,

In described (A) composition,

Polyvalent alcohol is that number-average molecular weight is more than 62 and lower than aliphatic diol or the alicyclic diol of 500 carbonatoms 2～12,

Organic multiple isocyanate is without xanthochromia type organic diisocyanate,

Hydroxyl (methyl) acrylate is the caprolactone affixture of hydroxyl (methyl) acrylate.

7. according to the blooming formation active energy ray-curable composition described in any one in claim 1～6, wherein, described (B) composition is homopolymer or the multipolymer with the monomer of (methyl) acryl.

8. blooming formation active energy ray-curable composition according to claim 7, wherein, described (B) composition is the multipolymer with the monomer of (methyl) acryl, and this multipolymer has amide structure or carboxyl.

9. according to the blooming formation active energy ray-curable composition described in any one in claim 1～6, wherein, described (B) composition is NVP multipolymer.

10. according to the blooming formation active energy ray-curable composition described in any one in claim 1～9, wherein, described (B) composition is the polymkeric substance with ethylenically unsaturated group.

11. blooming formation active energy ray-curable compositions according to claim 10, wherein, the ethylenically unsaturated group in described (B) composition is (methyl) acryl.

12. according to the blooming formation active energy ray-curable composition described in claim 11 or 12, wherein, described (B) composition be selected from following polymkeric substance more than a kind:

On the polymkeric substance that contains carboxyl, addition has the compound of epoxy group(ing) and ethylenically unsaturated group and the polymkeric substance that obtains;

On the polymkeric substance that contains carboxyl and/or the polymkeric substance that contains hydroxyl, addition has the compound of isocyanate group and ethylenically unsaturated group and the polymkeric substance that obtains; And

On the polymkeric substance that contains epoxy group(ing), addition has the compound of carboxyl and ethylenically unsaturated group and the polymkeric substance that obtains.

13. blooming formation active energy ray-curable compositions according to claim 12; wherein, the polymkeric substance that contains the polymkeric substance of carboxyl, the polymkeric substance that contains hydroxyl described in or contain epoxy group(ing) is the multipolymer with the compound of (methyl) acryl.

14. according to the blooming formation active energy ray-curable composition described in claim 12 or 13, wherein, described in contain carboxyl polymkeric substance or the polymkeric substance that contains hydroxyl be respectively the polymkeric substance that polymkeric substance that end contains carboxyl or end contain hydroxyl.

15. according to the blooming formation active energy ray-curable composition described in any one in claim 1～14, wherein, taking (A) composition and (B) total amount of composition as benchmark, comprise (A) composition 10～80 % by weight and (B) composition 20～90 % by weight.

16. according to the blooming formation active energy ray-curable composition described in any one in claim 1～15, and it is blooming formation electronics ray-curable composition.

17. 1 kinds of bloomings, its cured article by the composition described in any one in claim 1～15 is formed as membranaceous or sheet and obtains.

18. 1 kinds of polaroid protective films, it comprises the blooming described in claim 17.

The manufacture method of 19. 1 kinds of bloomings, it comprises:

On flat substrates, be coated with the composition described in any one in claim 1～15, then irradiate active energy beam from applicator surface side or flat substrates side.

The manufacture method of 20. bloomings according to claim 19, wherein, flat substrates is strippable base material.

The manufacture method of 21. 1 kinds of bloomings, it comprises:

On flat substrates, be coated with the composition described in any one in claim 1～15, and at the applicator surface of composition other flat substrates of fitting, then irradiate active energy beam from any side of described flat substrates.

The manufacture method of 22. bloomings according to claim 21, wherein, any one in flat substrates or both are strippable base materials.

23. 1 kinds of polarization plates, it is that wherein, this polaroid is adhered to this polaroid protective film across bond layer in the polarization plates of the polaroid protective film described in the folded requirement 18 of having the right of at least one surface layer of the polaroid being formed by polyvinyl alcohol resin.