CN101675083B - Resin composition for optical use and resin material for optical use using the same - Google Patents

Abstract

Disclosed are a resin composition for optical use and a resin material for optical use, which are excellent in transparency, while having adequate adhesiveness and impact absorption. The resin composition for optical use and the resin material for optical use are low in skin irritation and thus easily handled. In addition, since the resin composition and the resin material do not erode constitutional materials of a panel for an image display device, they are suitably used for image display devices. Specifically disclosed is a resin composition for optical use containing a (meth)acrylic acid derivative polymer (A), a monofunctional (meth)acrylic acid derivative monomer (B) and a di- or higher functional (meth)acrylic acid derivative (C). In this resin composition for optical use, the monomer (B) contains a (meth)acrylic acid monomer (B1) represented by the general formula (1) below and at least one substance (B2) selected from the group consisting of polyalkyleneoxyalkyl ether (meth)acrylates having 4 or more repeating units and polyalkyleneoxy (meth)acrylates having 4 or more repeating units. [chemical formula 1] CH2=CHCO(OClH2l)mOCnH2n+1 (1) (In the formula, l represents an integer of 2-4; m represents 0 or 1; and n represents an integer of 8-18.

Description

Optical resin compsn and the resin material for optical use that uses it

Technical field

The present invention relates to the guard block of a kind of pictorial display with panel.

Background technology

As representational image display panel, can enumerate out the liquid crystal image display device.The liquid crystal image display unit is made up of liquid crystal cells and the optical thin films such as polaroid that are attached to its two outside surfaces, liquid crystal cells be through between a pair of glass substrate that is pre-formed transparency electrode and pattern of pixels etc. from the teeth outwards with the thickness about about 1mm, Jie is by about several microns gap filling liquid crystal and seal and make.The display unit that constitutes like this is that parts are used in impaired demonstration that approach and easy.Therefore, particularly in purposes such as mobile phone, game machine, digital camera and on-vehicle parts, generally front surface Jie in display unit is provided with transparent front panel (protection panel) by certain space.

In addition, in the present large-scale image liquid crystal display device, be provided with polaroid at the front surface of liquid crystal panel.Anti-dazzle (AG) processing is carried out on the surface of polaroid, improves visuality through the reflection of light in the front surface that reduces display unit.Under the situation of large-scale display unit,, parts such as front panel are not set in addition generally, make liquid crystal panel totally reach external member totally to have shock-resistance but they are constituted in order to improve the impact absorbency of device.Problem in this large-scale image liquid crystal display device is: handle through AG, image is shown by fuzzy (ooze and spread and sink in); Liquid crystal panel generation deflection when contacting, image disorder with the surface of display unit; Handle owing to carry out AG, the dirt on surface is difficult to come off, on the other hand, if injure easily when brute force scrapes.In addition, be accompanied by the maximization of liquid crystal panel from now on, the shock-resistance of liquid crystal panel self reduces, and thinking can the generation problem on the shock-resistance of display unit.

In view of above-mentioned situation, consider to have implemented the front panel that anti-reflex treated (AR) is handled the front surface setting of liquid crystal panel, attempt to eliminate and handle the shortcoming of bringing by AG.But, there is air in front between plate and the liquid crystal panel, when promptly having the space, consider reduction that has picture quality loss of transmission, that cause by dual reflection etc.Therefore, proposed with the technology (with reference to patent documentation 1,2,3 and 4) with the space landfill between front panel and the liquid crystal panel such as resin.

When being used for TV, according to the regulation of UL specification or electron beam tube logos etc., following situation can not appear in display unit: parts disperse when the impulse withstand test that steel ball falls with image display device (indicating meter), and perhaps steel ball connects parts.Now, in the glass cathode ray tube (CRT) of extensively popularizing,, need thicker sheet glass is set, have the overall weight of CRT and become heavy tendency in order to satisfy previous specification.Therefore, as the means that do not add plate glass and give the anti-dustability of display unit, proposed in the range upon range of technology (with reference to patent documentation 5 and 6) of glass pane surface with synthetic resins protective membrane of self reparation property.

In addition; In the Plasmia indicating panel (PDP) that gets most of the attention in recent years as an example of flat-panel screens (FPD); In order to prevent the breakage of panel part, being situated between at PDP front surface (visible surface one side) is provided with the front panel of glass about thick 3mm etc. by the space about 1～5mm.But, be accompanied by the maximization of PDP, because the area of front panel also becomes greatly, have the overall weight of PDP and become heavy tendency.Therefore, in order to prevent the breakage of image display device (indicating meter), proposed at the range upon range of specific resin of display surface, or the light filter layer of range upon range of specific resin be stacked in the technology (with reference to patent documentation 7,8,9 and 10) of display surface.

Patent documentation 1: japanese kokai publication hei 05-011239 communique

Patent documentation 2: japanese kokai publication hei 03-204616 communique

Patent documentation 3: japanese kokai publication hei 06-59253 communique

Patent documentation 4: TOHKEMY 2004-125868 communique

Patent documentation 5: japanese kokai publication hei 06-333515 communique

Patent documentation 6: japanese kokai publication hei 06-333517 communique

Patent documentation 7: TOHKEMY 2004-58376 communique

Patent documentation 8: TOHKEMY 2005-107199 communique

Patent documentation 9: TOHKEMY 2004-263084 communique

Patent documentation 10: TOHKEMY 2007-9115 communique

Summary of the invention

As stated, reported that with the protection image display device be the various technology of purpose, but when they are applicable to large-scale liquid crystal image display unit, can not obtain gratifying result, needed to do further exploitation.In further detail, in above-mentioned document 1, though filled oil in the space, the sealing that is used for anti-heads is difficult.In addition, oil possibly encroached on the material of liquid crystal panel, and then the plate cracking possibility that the time has oil leakage to go out in front, hopes improvement.The unsaturated polyester that uses in the above-mentioned in addition document 2 owing to dye yellow easily, therefore preferably is not applicable to indicating meter.

The siloxanes that uses in the above-mentioned document 3 is because sealing force is little, therefore for the fixing tackiness agent that needs to use other.So not only manufacturing process becomes numerous and diverse, and since with the bonding force of tackiness agent a little less than, can peel off, have the possibility of bubble entering when impacting so machine applied.The polymkeric substance of the Acrylic Acid Monomer that uses in the above-mentioned document 4 has the weak tendency of bonding force.Therefore, if small-sized machine then need not use other tackiness agent, but for the front panel that keeps giant display then need use other tackiness agent, it is numerous and diverse that manufacturing process becomes.Raw material owing to polymkeric substance only is made up of monomer in addition, so viscosity is low, and has the big tendency of cure shrinkage change, is difficult to make equably large-area film.

In addition, in the above-mentioned document 5,6, through realizing anti-dustability at range upon range of synthetic resins protective membrane with self reparation property on glass, but they do not have the function that prevents glass breakage concurrently.

And in the above-mentioned document 7,8, do not have the special composition of investigating about the resin that uses, make the means of resin performance cementability, the transparency indeterminate.Particularly in above-mentioned document 7, the moisture-proof safety of resin is not investigated, when the resin of the composition that in embodiment, specifically illustrates was applicable to indicating meter, resin just produced white casse in the short period of time in humidity test.In the above-mentioned document 8, the resin shown in concrete contains vinylformic acid among the embodiment, and resin also produces white casse in humidity test for a long time.In addition, also produce following problem: the metallic corrosion that contacts when resin material makes humidity test.And above-mentioned document 7,8 is not studied from the viewpoint that realizes good impact absorbency fully.In the above-mentioned document 8, the thickness of the shock-resistant layer that is made up of resin is 0.2～1mm, but does not openly improve impact absorbency through increasing its thickness.

In the above-mentioned document 9, humidity resistance is investigated, but seen, shock-resistance is significantly improved from the raw material composition of disclosed resin.In addition, the thickness of the resin layer among the embodiment is 1mm, thinks to be difficult to obtain better impact absorbency.In addition, disclosed resin is an also soft resin after solidifying among the embodiment of above-mentioned document 9.Therefore, when the thickness that makes the front surface wave filter increased, the surface hardness of wave filter reduced, and the possibility of scuff resistance generation problem is high.Disclosed material in the above-mentioned document 10, though the transparency and impact absorbency during moisture absorption are all good, the skin irritation of material is high, should be noted that during use.

In view of above-mentioned situation; First purpose of the present invention provides a kind of optical resin compsn of the purposes that is applicable to image display device and the optical resin material that uses it; The said optical resin compsn transparency is good, have appropriateness bounding force and the required impact absorbency of protection image display device; On the other hand, skin irritation is low, use is easy, and does not encroach on the constituent material of device used for image display panel.In addition, second purpose of the present invention provides the optical resin compsn of the good purposes that is applicable to image display device of moisture-proof safety and the resin sheet for optical that uses it.

Optical resin compsn of the present invention is characterised in that it contains: (A) (methyl) acrylic acid series derivative polymer, (B) 1 functional (methyl) acrylic acid series derivatives monomer and (C) 2 officials can above (methyl) acrylic acid series verivate; Above-mentioned (B) 1 functional (methyl) acrylic acid series derivatives monomer contains: (B1) (methyl) acrylic monomer of representing of formula at least a,

CH ₂＝CHCO(OC _lH _2l) _mOC _nH _2n+1 (1)

(in the formula; 1 is 2～4 integer; M is 0 or 1, and n is 8～18 integer) and (B2) to be selected from by number of repeat unit be that polyalkylene oxide base alkyl oxide (methyl) propenoate and number of repeat unit more than 4 is at least a in the group that constitutes of polyalkylene oxide base (methyl) propenoate more than 4.

Here, above-mentioned (B) 1 functional (methyl) acrylic acid series derivatives monomer preferably contains (methyl) alkyl acrylate at least.(methyl) alkyl acrylate preferably has branched structure.(methyl) alkyl acrylate as having branched structure preferably contains 2-EHA.

In addition, as above-mentioned (B) 1 functional (methyl) acrylic acid series derivatives monomer, preferably contain polyalkylene oxide base alkyl oxide (methyl) propenoate at least.Polyalkylene oxide base alkyl oxide (methyl) propenoate preferably contains nine (terepthaloyl moietie) monomethyl ether methacrylic ester.

It is 4～18 alkyl acrylate and the multipolymer with propenoate of hydroxyl that above-mentioned (A) (methyl) acrylic acid series derivative polymer is preferably carbonatoms.(A) (methyl) acrylic acid series derivative polymer for example is preferably the multipolymer of 2-EHA and vinylformic acid 2-hydroxy methacrylate.Above-mentioned (A) (methyl) acrylic acid series derivative polymer preferably has 100,000～700,000 weight-average molecular weight.

Optical resin compsn involved in the present invention preferably further contains (D) polymerization starter.

(D) polymerization starter is preferably Photoepolymerizationinitiater initiater.Photoepolymerizationinitiater initiater preferably contains and is selected from by (d1) Alpha-hydroxy alkyl phenones based compound, (d2) acylphosphine oxide based compound, (d3) oligomeric (2-hydroxy-2-methyl-1-(4-(1-methyl ethylene) phenyl) acetone), and (d4) at least a in the group that mixture constituted of hydroxyl-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetic acid base-oxyethyl group]-ethyl ester and hydroxyl-phenyl-acetic acid 2-[2-hydroxyl-oxyethyl group]-ethyl ester.

Optical resin material of the present invention is characterised in that, is made up of the cured article of above-mentioned optical resin compsn of the present invention.Optical resin material preferably has the shape of sheet or film.

In addition; The application require simultaneously same applicant the patented claim 2007-161439 of Japan number of on June 19th, 2007 application, in the patented claim 2008-100191 of Japan number right of priority of application on April 8th, 2008; Through specification sheets, as the part of this explanation and charge to the present invention with reference to them.

Optical resin compsn of the present invention and the resin material for optical use that constitutes by its cured article; Because skin irritation is low; The transparency, impact absorbency is good, therefore can be adapted at using in the purposes of image display device and device used for image display spectral filter.For example, when optical resin compsn of the present invention and resin material are used as the transparent resin layer of image display device, can in image display device, realize good moisture-proof safety and impact absorbency.

Description of drawings

Fig. 1 is the side cut away view that schematically shows the formation example of liquid crystal indicator in the past.

Fig. 2 is the side cut away view that schematically shows the formation example of liquid crystal indicator in the past.

Fig. 3 is the side cut away view that schematically shows the formation example of liquid crystal indicator of the present invention.

Fig. 4 is the side cut away view that schematically shows the formation example of liquid crystal indicator of the present invention.

Fig. 5 is the side cut away view that schematically shows the formation example of liquid crystal indicator of the present invention.

Fig. 6 is the side cut away view that schematically shows the formation example of liquid crystal indicator of the present invention.

Embodiment

Below, the present invention is elaborated.First mode of the present invention relates to a kind of optical resin compsn; It is characterized in that, contain: (A) (methyl) acrylic acid series derivative polymer, specific (B) 1 functional (methyl) acrylic acid series derivatives monomer and (C) 2 officials can above (methyl) acrylic acid series verivate.In optical resin compsn of the present invention; As stated can be with the polymkeric substance of mentioned component (A), use as the composition (B) of diluting monomer with as composition (C) combination of linking agent; Through improving their consistency, improve the solvability of component of polymer.Also can obtain good resin combination of the transparency and their cured article when therefore, using high molecular weight polymers.In addition, contain the resin combination of high molecular weight polymers with higher concentration, approach the good parts of impact absorbency though can realize thickness through preparation and use.In addition, in the optical resin compsn of the present invention,, can be shaped, be difficult for producing bubble, and make film or sheet easily with thickness without solvent comes the letdown resin compsn through the diluted polymer composition that becomes to assign to certain monomers.

Below, to the composition (A) that constitutes optical resin compsn of the present invention～(C) describe.

Composition (A):

(A) (methyl) acrylic acid series derivative polymer that uses among the present invention contain at least through block polymerization, solution polymerization, suspension polymerization and letex polymerization etc. in the past known method make and have the polymkeric substance that the monomeric compound polymerization of 1 (methyl) polymerizing acrylic acid property unsaturated link(age) obtains at intramolecularly more than a kind or 2 kinds.As long as in the scope that can obtain effect of the present invention; Also can use following polymkeric substance: as monomeric compound; And be used in other monomeric compounds that intramolecularly has (methyl) polymerizing acrylic acid property unsaturated link(age) more than 2, the polymkeric substance that the copolymerization through these compounds obtains.(A) (methyl) acrylic acid series derivative polymer can also be following polymkeric substance: except above-mentioned (methyl) acrylic monomer compound, append other the monomeric compound with polymerizability unsaturated link(age), make their copolymerizations and the polymkeric substance that obtains.

(A) at the intramolecularly of (methyl) acrylic acid series derivative polymer, be purpose with the binding property that improves with sheet glass, preferably give polar group in advance.As example, can enumerate: hydroxyl, carboxyl, cyanic acid, glycidyl etc. the effective polar group of fusible raising.The importing of these polar groups for example can be reached with the copolymerization of (methyl) acrylic monomer compound through making the monomeric compound with polar group.Through in polymkeric substance, importing hydroxyl isopolarity group, can make resin combination have appropriate polarity, the white casse in the time of might preventing moisture absorption.In addition, when making film or sheet, can make them demonstrate high adhesion by this resin combination.This have fusible or a thin film component, can not use caking agent and fit with the surface of device such as display panel.

(methyl) acrylic monomer compound for constituting above-mentioned (A) (methyl) acrylic acid series derivative polymer comprises vinylformic acid and methylacrylic acid, their verivate.The object lesson of monomeric compound that has 1 (methyl) polymerizing acrylic acid property unsaturated link(age) at intramolecularly is as follows:

Vinylformic acid, methylacrylic acid, acrylic amide,

Carbonatomss such as (methyl) methyl acrylate, (methyl) n-butyl acrylate, (methyl) NSC 20949, (methyl) 2-EHA, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) vinylformic acid n-octyl, (methyl) vinylformic acid bay alcohol ester, (methyl) stearyl acrylate alcohol ester are (methyl) alkyl acrylate of 4～18

(methyl) vinylformic acid aralkyl esters such as (methyl) benzyl acrylate,

(methyl) alkoxyalkyl acrylates such as (methyl) vinylformic acid butoxy ethyl ester,

(methyl) vinylformic acid N, (methyl) acrylic-amino alkyl esters such as N-dimethylamino ethyl ester,

(methyl) propenoate of (methyl) propenoate of (methyl) propenoate of diethylene glycol ethyl ether, (methyl) propenoate of triglycol butyl ether, Tetraglycol 99 monomethyl ether, the polyalkylene glycol alkyl oxides such as (methyl) propenoate of dipropylene glycol methyl ether,

(methyl) propenoate of polyalkylene glycol aryl ethers such as (methyl) propenoate of hexaethylene glycol phenyl ether,

(methyl) cyclohexyl acrylate, (methyl) vinylformic acid two pentamethylene esters, (methyl) IBOA, (methyl) vinylformic acid methoxy ring trialkenyl in last of the ten Heavenly stems ester etc. have (methyl) propenoate of ester ring type base,

(methyl) vinylformic acid fluorinated alkyl esters such as (methyl) vinylformic acid 17 fluorine esters in the last of the ten Heavenly stems,

(methyl) propenoate of (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, triglycol, (methyl) propenoate of eight Ucar 35, (methyl) vinylformic acid glyceryl ester etc. have (methyl) propenoate of hydroxyl

(methyl) vinylformic acid glycidyl esters etc. has (methyl) propenoate of epoxypropyl,

Poly glycol monomethyl ether (methyl) propenoate such as Tetraglycol 99 monomethyl ether (methyl) propenoate, hexaethylene glycol monomethyl ether (methyl) propenoate, eight glycol monomethyl ether (methyl) propenoate, nine glycol methyl ether (methyl) propenoate,

W 166 monomethyl ether (methyl) propenoate such as seven propylene glycol monomethyl ethers (methyl) propenoate,

Polyoxyethylene glycol ether (methyl) propenoate such as Tetraglycol 99 ether (methyl) propenoate,

Tetraglycol 99 (methyl) propenoate, hexaethylene glycol (methyl) propenoate, eight Ucar 35 (methyl) propenoate etc.

In addition, methacrylic ester and propenoate are represented in the record of " (methyl) propenoate " in this specification sheets.For example TEB 3K and methyl acrylate are represented in the record of " (methyl) methyl acrylate ".

In above-mentioned monomeric compound, in order to show impact absorbency, from reducing viewpoints such as second-order transition temperature, reduction skin irritation and material are more cheap, preferred carbonatoms is (methyl) alkyl acrylate of 4～18.More preferably they and intramolecularly further had (methyl) propenoate and the usefulness of polar group.Not special the qualification, but, can enumerate following situation as preferred a kind of embodiment of the present invention: with 2-EHA and 2-hydroxy acrylate and usefulness, the interpolymer that uses them is as (A) (methyl) acrylic acid series derivative polymer composition.Not special qualification of ratio with monomeric compound of polar group, but with the weight of the total monomer compound that uses as benchmark, the ratio of preferred 15～30 weight %.Have the ratio of monomeric compound of polar group when too small, produce the tendency of white casse when having moisture absorption.On the other hand, when its ratio was excessive, have the tendency that produces following unfavorable condition: the dimensional change during moisture absorption was big, exposed, peeled off from the use position etc.

When and when being used in intramolecularly and having the monomeric compound of above-mentioned (methyl) the polymerizing acrylic acid property unsaturated link(age) more than 2; Compound does not limit as long as have (methyl) the acrylic acid unsaturated link(age) position that helps polyreaction more than 2 at intramolecularly especially.The object lesson of this monomeric compound is as follows:

Diacrylate 1,4-butanediol ester, diacrylate 1,6-pinakon ester, diacrylate 1, diacrylate alkylidene diol esters such as 9-nonanediol ester,

Polyalkylene glycol such as polyethyleneglycol diacrylate, polypropyleneglycol diacrylate diacrylate,

Triacrylates such as Viscoat 295, ethoxyquin Viscoat 295,

Tetraacrylate such as ethoxyquin tetramethylol methane tetraacrylate, two (TriMethylolPropane(TMP)) tetraacrylate, tetramethylol methane tetraacrylate,

Dipentaerythritol acrylate etc.

Excessively use when intramolecularly has the monomeric compound of 2 above polymerizability unsaturated link(age)s, gelation takes place when synthesizing (methyl) acrylic acid series derivative polymer through their polymerization.Therefore, when and during with above-mentioned monomeric compound, be benchmark with the gross weight of the monomeric compound that uses as the formation raw material of polymkeric substance, its ratio is preferably below the 0.3 weight %.

Among the present invention, during the polymkeric substance of prepared composition (A) can with other monomeric compound of above-mentioned (methyl) acrylic monomer compound and usefulness, get final product not special the qualification so long as intramolecularly has the compound of polymerizability unsaturated link(age).As object lesson, can enumerate: polymerizable compounds such as vinyl cyanide, vinylbenzene, vinyl-acetic ester, ethene, propylene.

The weight-average molecular weight of (A) (methyl) acrylic acid series derivative polymer that the polymerization through above-mentioned various monomeric compounds obtains is preferably 100,000～700, and 000, more preferably 150,000～400,000, further be preferably 200,000～350,000.

When the weight-average molecular weight of component of polymer was too small, resin layer broke easily or is out of shape when being hit.On the other hand, when weight-average molecular weight was excessive, it is too high that viscosity becomes, and when the liquor charging of molten resin, needs high pressure.In addition, because bubble is difficult to remove, therefore has the tendency of residual bubble in the cured article.In addition, " weight-average molecular weight " expression of putting down in writing in this specification sheets uses the lubber-line of polystyrene standard to measure the value that obtains through GPC.

The use level of (A) (methyl) acrylic acid series derivative polymer in the resin material for optical use of the present invention is 100 o'clock in mentioned component (A), (B) and total use level (C), is preferably the scope of 15～50 weight parts, more preferably the scope of 15～40 weight parts.When the use level of the component of polymer of above-mentioned (A) is very few, produce the problem of mechanical characteristics aspect, have the tendency of the impact absorbency reduction of resin material for optical use.Cure shrinkage becomes big in addition, also is being easy to generate problem aspect the flatness of the film of sheet of making or film.On the other hand, when use level was too much, the viscosity of resin combination was too high, made sheet or film and became difficult.

Composition (B):

(B) 1 functional (methyl) the acrylic acid series derivatives monomer that uses among the present invention is characterised in that; By at least a in the low propenoate of (B1) alkyl chain length and polarity and (B2) the high and at least a formation of number of repeat unit in the propenoate more than 4 of polarity, in resin combination, work as thinner.More specifically; It is characterized in that; The monomer of above-mentioned (B) by in the propenoate of (B1) following formula (1) expression at least a with (B2) constitute, wherein (B2) is for being selected from by number of repeat unit at least a in the group of the formation of polyalkylene oxide base (methyl) propenoate more than 4 of polyalkylene oxide base alkyl oxide (methyl) propenoate 4 or more and number of repeat unit.

The propenoate composition of above-mentioned (B1) is represented by following formula (1).

CH ₂＝CHCO(OC _lH _2l) _mOC _nH _2n+1 (1)

(in the formula, l is 2～4 integer, and m is 0 or 1, and n is 8～18 integer)

Object lesson as the compound of above-mentioned (B1); Can enumerate (methyl) alkyl acrylates such as (methyl) 2-EHA, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) vinylformic acid n-octyl, (methyl) vinylformic acid bay alcohol ester, (methyl) stearyl acrylate alcohol ester of m=0 in the above-mentioned formula (1), (methyl) vinylformic acid aralkyl esters such as (methyl) vinylformic acid benzyl ester etc.In addition, as the object lesson of the compound of m=1, can enumerate vinylformic acid ethylhexyl oxygen base ethyl ester.Do not have special qualification, but, be preferably (methyl) alkyl acrylate from the aspect of cost aspect, yellowing resistance.

And then, in (methyl) alkyl acrylate, the aspect low from viscosity, that usability is good, preferred intramolecularly has the compound of branched structure.In addition, about the acryliccompound of above-mentioned (B1), skin irritation is big after a little while at carbonatoms, should be noted that when therefore using.On the other hand, when carbonatoms was excessive, viscosity uprised, and became solid-like in addition easily, had the bad tendency of usability.Therefore, in above-mentioned formula (1), the carbonatoms of preferred alkyl chain " n " is 8～18.

As the object lesson of this compound, can enumerate: 2-EHA, Isooctyl acrylate monomer, isodecyl acrylate, vinylformic acid isooctadecanol ester are preferably 2-EHA, vinylformic acid isooctadecanol ester.

Number of repeat unit in above-mentioned (B2) is meant following compound at polyalkylene oxide base alkyl oxide (methyl) propenoate more than 4: have number of repeat unit such as terepthaloyl moietie, Ucar 35 at the glycol position more than 4; Have the alkyl oxide position of methyl, ethyl etc. at an one of which end, have (methyl) propenoate position at another end.Also can use the above-claimed cpd of number of repeat unit less than 4, but because their skin irritations play macula greatly, easily, so use should be noted that the time.Object lesson as preferred compound; Can enumerate: poly glycol monomethyl ether (methyl) propenoate such as Tetraglycol 99 monomethyl ether (methyl) propenoate, hexaethylene glycol monomethyl ether (methyl) propenoate, eight glycol monomethyl ether (methyl) propenoate, nine glycol monomethyl ether (methyl) propenoate; W 166 monomethyl ether (methyl) propenoate such as seven propylene glycol monomethyl ethers (methyl) propenoate, polyoxyethylene glycol ether (methyl) propenoate such as Tetraglycol 99 ether (methyl) propenoate etc.

On the other hand; Number of repeat unit in above-mentioned (B2) is meant following compound at polyalkylene oxide base (methyl) propenoate more than 4: have number of repeat unit such as terepthaloyl moietie, Ucar 35 at the glycol position more than 4; Have hydroxyl sites at an one of which end, have (methyl) propenoate position at another end.Also can use the above-claimed cpd of number of repeat unit less than 4, but because their skin irritation plays macula greatly, easily, so should be noted that during use.As the object lesson of preferred compound, can enumerate: Tetraglycol 99 (methyl) propenoate, hexaethylene glycol (methyl) propenoate, eight Ucar 35 (methyl) propenoate etc.

As stated, as the compound that (B2) uses, from the viewpoint of skin irritation, the preferred repeat units number is more than 4.Do not have special qualification, but in an embodiment of the invention, as (B2) composition, being 9 nine glycol monomethyl ether metacrylic acid esters with number of repeat unit is fit to as the polyethylene glycol monomethyl ethermethacrylic acid esters of principal constituent.The trade(brand)name " FA-400M " that this methacrylic ester can be used as Hitachi Chemical Co., Ltd.'s manufacturing obtains easily.In addition, when repeating unit is excessive, when for example number of repeat unit is 23 compound,, be difficult to use owing to form solid at normal temperatures.If even with using behind this compound heating and melting, owing to when temperature reduces, also generating white casse, so be not preferred.Thus, preferably use at normal temperatures compound in the present invention as liquid state.

As stated; Not only use (methyl) acrylic monomer composition of (B1); Also use the compound that has the aklylene glycol base with (A) good (B2) of component of polymer consistency as diluting monomer, can not damage the transparency of resin combination thus, and can adjust bounding force easily.In addition, owing to do not contain low-molecular-weight (methyl) propenoate that contains hydroxyl, therefore can suppress the skin irritation of resin combination as diluting monomer.

The use level of the composition (B) in the optical resin compsn of the present invention is 100 o'clock with the use level of all the components that constitutes resin combination, is preferably the scope of 40～70 weight parts, more preferably the scope of 40～60 weight parts.The tendency that when use level of mentioned component (B) was very few, the viscosity with resin combination was too high, make sheet or film difficulty.On the other hand, when use level is too much, possibly have problems aspect the mechanical characteristics of sheet of making or film.In addition, compsn when not making moisture absorption and cured article thereof generate white casse, (B1) in the composition (B): ratio (B2) is preferably suitably adjusted 90: 10～60: 40 scope in.

(C) 2 officials that use among the present invention can be meant the compound that can become linking agent by above (methyl) acrylic acid series verivate.Concrete is meant: have the reactive unsaturated link(age) more than 2 at intramolecularly, at least one in these reactive unsaturated link(age)s is the compound of (methyl) acryl.Promptly; In the compound that uses as (C) composition among the present invention; Except containing (methyl) acryl, can also be to contain other free-radical polymerised group such as vinyl, styryl and allyl group as the compound of reactive unsaturated link(age) as the reactive unsaturated link(age).In addition, above-claimed cpd also can be the compound that intramolecularly contains functional groups such as hydroxyl.

Though not special the qualification; But, can enumerate out: (C1) (methyl) acrylic acid series verivate of low-molecular-weight (methyl) acrylic acid series derivatives monomer, (C2) middle molecular weight or (C3) (methyl) acrylic acid series verivate of higher molecular weight as the compound that can be used as mentioned component (C) among the present invention.Below they are described.

Object lesson as above (methyl) acrylic acid series derivatives monomer of operable among the present invention (C1) low-molecular-weight 2 officials ability; Can enumerate: diacrylate 1; 4-butanediol ester, diacrylate 1; 6-pinakon ester, diacrylate 1; Diacrylate alkylidene diol esters such as 9-nonanediol ester, polyalkylene glycol diacrylates such as polyethyleneglycol diacrylate, polypropyleneglycol diacrylate, triacrylates such as Viscoat 295, ethoxyquin Viscoat 295; Tetraacrylate such as ethoxyquin tetramethylol methane tetraacrylate, two (TriMethylolPropane(TMP)) tetraacrylate, tetramethylol methane tetraacrylate, dipentaerythritol acrylate etc.Low from skin irritation, adjust the aspect of degree of crosslinking easily, more preferably the polyalkylene glycol diacrylate is preferably polypropyleneglycol diacrylate especially.

(methyl) acrylic acid series verivate of molecular weight is that molecular weight is more than 1000 and the compound of less than 4000 degree in operable among the present invention (C2).The concrete compound that can enumerate general formula (a)～(g) expression shown in following.These compounds can use separately or combination use more than 2 kinds.

The diacrylate ester cpds of the alkylene oxide adducts of the dihydroxyphenyl propane of formula (a) expression and the compound that the acryl in these compounds is replaced as methacryloyl.

(wherein, in the formula (a), R representes ethylidene or propylidene, and m and n represent 1～20 integer respectively independently.)

The epoxychloropropane modified thing of the dihydroxyphenyl propane of formula (b) expression and acrylic acid addition carboxylate and the compound that the acryl in these compounds is replaced as methacryloyl.

(wherein, in the formula (b), m and n represent 1～10 integer respectively independently.)

The diacrylate ester cpds of the alkylene oxide adducts of the phosphoric acid of formula (c) expression and the compound that the acryl in these compounds is replaced as methacryloyl.

(wherein, in the formula (c), R representes ethylidene or propylidene, and m and n represent 1～20 integer respectively independently.)

Formula (d)

(wherein, in the formula (d), m and n represent 1～10 integer respectively independently.) table chlorine (epichlorine) modifier and acrylic acid addition carboxylate and the compound that the acryl in these compounds is replaced as methacryloyl of phthalic acid of expression.

1 of formula (e) expression, the table chlorine modifier of 6-pinakon and acrylic acid addition carboxylate (having 2 acryls in a part) and the compound that the acryl in these compounds is replaced as methacryloyl.

(wherein, in the formula (e), m and n represent 1～20 integer respectively independently.)

The triacrylate compound of the alkylene oxide adducts of the phosphoric acid of formula (f) expression and the compound that the acryl in these compounds is replaced as methacryloyl.

(wherein, in the formula (f), R representes ethylidene or propylidene, and 3 m represent 1～20 integer respectively independently.)

The triacrylate compound of the alkylene oxide adducts of the TriMethylolPropane(TMP) of formula (g) expression and the compound that the acryl in these compounds is replaced as methacryloyl.

(wherein, in the formula (g), R representes ethylidene or propylidene, m, m ' and m " represent 1～20 integer respectively independently.)

2 officials of operable among the present invention (C3) higher molecular weight can preferably have 4,000～20,000 weight-average molecular weight by above (methyl) acrylic acid series verivate, more preferably 8,000～16,000 weight-average molecular weight.When the molecular weight of these verivates is too small, has the tendency that cured article becomes fragile easily.On the other hand, when molecular weight is excessive, has too high, the difficult tendency of making sheet of viscosity of resin combination.Though not special the qualification can above (methyl) acrylic acid series verivate as 2 officials of higher molecular weight,, be preferably with aklylene glycol as raw material and derived compounds from the viewpoint of consistency.

Below, the object lesson of expression composition (C3).

(1) two of diol compound (methyl) propenoate: for example can obtain through following reaction: polyalkylene glycol such as polyoxyethylene glycol, W 166, polytetramethylene glycol and acrylic or methacrylic acid, 2-(methyl) acryloxy ethyl succsinic acid, 2-(methyl) acryloxy ethyl six hydrogen phthalandiones etc. have the reaction of (methyl) propenoate of carboxyl; Above-mentioned glycol and methylacrylic acid 2-isocyanato ethyl (trade(brand)name Karenz " MOI ", clear and electrician's manufacturing) or vinylformic acid 2-isocyanato ethyl (trade(brand)name Karenz " AOI ", clear and electrician's manufacturing) etc. have the reaction of (methyl) propenoate of NCO; Perhaps above-mentioned glycol and Racemic glycidol (methyl) propenoate etc. have the reaction of (methyl) propenoate of glycidyl.

(2) two of epoxy resin (methyl) propenoate: for example can obtain through following reaction: the diglycidylether etc. with polyalkylene glycol positions such as polyoxyethylene glycol, W 166, polytetramethylene glycols intramolecularly have 2 epoxy group(ing) epoxy resin and acrylic or methacrylic acid, have (methyl) propenoate of carboxyl or have the reaction of (methyl) propenoate of hydroxyl.The object lesson of (methyl) propenoate with hydroxyl is as follows: vinylformic acid 2-hydroxy methacrylate; Vinylformic acid 2-hydroxy propyl ester; Vinylformic acid 3-hydroxy propyl ester; Vinylformic acid 4-hydroxyl butyl ester; The polyoxyethylene glycol mono acrylic ester; The W 166 mono acrylic ester; Ethylene glycol and 1,2-propylene glycol segmented copolymer mono acrylic ester; Terepthaloyl moietie-tetramethylene glycol multipolymer mono acrylic ester; Caprolactone modification mono acrylic ester (trade(brand)name " Plaxel FA " series; DAICEL KCC makes); Pentaerythritol triacrylate etc. (methyl) acrylic acid derivative; And 2-hydroxyethyl methacrylate; Methylacrylic acid 2-hydroxy propyl ester; Methylacrylic acid 3-hydroxy propyl ester; Methylacrylic acid 4-hydroxyl butyl ester; Polyethylene glycol monomethacrylate; Polypropylene glycol monomethacrylate; Ethylene glycol and 1,2-propylene glycol segmented copolymer monomethacrylates; Terepthaloyl moietie-tetramethylene glycol multipolymer monomethacrylates; Caprolactone modification monomethacrylates (trade(brand)name " Plaxel FM " series; DAICEL KCC makes); Methacrylic acid derivatives such as pentaerythritol acrylate trimethyl etc.

As additive method; Also can be: the compound reaction that further has epoxy group(ing) through (methyl) propenoate that makes vinylformic acid, methylacrylic acid, has (methyl) propenoate of carboxyl or have a hydroxyl with end; Thereby obtain (methyl) propenoate of epoxy resin, wherein terminal compound with epoxy group(ing) is that the reaction through above-mentioned polyalkylene glycol and excessive epoxy resin (intramolecularly has 2 epoxy group(ing)) obtains.

Two (methyl) propenoate of (3) two terminal polyester for hydroxyl: for example can obtain through the reaction of polyester polyol and saturated acid, polyvalent alcohol.As the object lesson of saturated acid, can enumerate: aliphatic dicarboxylic acids such as nonane diacid, hexanodioic acid, sebacic acid.As the object lesson of polyvalent alcohol, can enumerate terepthaloyl moietie, Ucar 35, glycol ether, dipropylene glycol, butyleneglycol, polyoxyethylene glycol, W 166 etc.Through this polyester polyol and vinylformic acid, methylacrylic acid, have (methyl) propenoate of carboxyl or have (methyl) propenoate of glycidyl or have the reaction of (methyl) propenoate of NCO, thereby obtain two (methyl) propenoate of polyester.

As additive method; Also can be: make saturated acid and polyol reaction make the polyester poly carboxylic acid; These carboxylic acids with have (methyl) propenoate of hydroxyl or have (methyl) propenoate of NCO or have Racemic glycidol (methyl) acrylate reactions, thereby obtain two (methyl) propenoate of polyester.

(4) two of urethane (methyl) propenoate: for example urethane can obtain through the reaction of polyol compound and multicomponent isocyanate compound.Object lesson as polyvalent alcohol; Can enumerate: Ucar 35, tetramethylene glycol, 1; 4-butyleneglycol, 1; 5-pentanediol, 1,6-pinakon, NSC 6366,1,4 cyclohexane dimethanol, 2-methyl isophthalic acid; 8-ethohexadiol, 1; 9-nonanediol, 3-methyl isophthalic acid, gather 1, the propylene oxide adduct of 2-butyleneglycol, W 166, polytetramethylene glycol, ethylene glycol and 1,2-propylene glycol segmented copolymer, terepthaloyl moietie-tetramethylene glycol multipolymer, methyl pentanediol modification polytetramethylene glycol, propylene glycol modified polytetramethylene glycol, dihydroxyphenyl propane, the propylene oxide adduct of Hydrogenated Bisphenol A 99, the propylene oxide adduct of Bisphenol F, the propylene oxide adduct of A Hydrogenated Bisphenol A F etc. at the 5-pentanediol.Object lesson as the multicomponent isocyanate compound; Can enumerate: vulcabond such as the diphenylmethanediisocyanate of the toluene support vulcabond of toluene support vulcabond, XDI, diphenylmethanediisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, tetramethylxylene diisocyanate, isophorone diisocyanate, hydrogenation, the XDI of hydrogenation, hydrogenation, norbornylene vulcabond, and then the urea-modified body of the polymkeric substance of these vulcabond or vulcabond, biuret modified body etc.

Through handle the urethane that constitutes as stated with the polyvalent alcohol of excess quantity; Obtain the compound that end has hydroxyl; Make resulting end have compound and vinylformic acid, the methylacrylic acid of hydroxyl, (methyl) propenoate or Racemic glycidol (methyl) propenoate etc. and have (methyl) propenoate of glycidyl or have (methyl) acrylate reactions of NCO, can obtain two (methyl) propenoate of urethane with carboxyl.

(5) compound that urethane is obtained with the compound reaction with hydroxyl and reactive unsaturated link(age): as the polyvalent alcohol of the raw material of urethane and multicomponent isocyanate compound such as previous explanation, these polyvalent alcohols and multicomponent isocyanate can use separately or more than 2 kinds and use separately.

Through handle the urethane that constitutes as stated with the multicomponent isocyanate of excess quantity; Obtain the compound that end has NCO; Make compound that resulting end has a NCO and have the compound of hydroxyl and reactive unsaturated link(age) or have (methyl) acrylate reactions of carboxyl, can obtain the urethane that end has reactive unsaturated link(age).

As the object lesson of compound, can enumerate: (methyl) acrylic acid derivatives such as vinylformic acid 2-hydroxy methacrylate, vinylformic acid 2-hydroxy propyl ester, vinylformic acid 3-hydroxy propyl ester, vinylformic acid 4-hydroxyl butyl ester, polyoxyethylene glycol mono acrylic ester, W 166 mono acrylic ester, ethylene glycol and 1,2-propylene glycol segmented copolymer mono acrylic ester, terepthaloyl moietie-tetramethylene glycol multipolymer mono acrylic ester, caprolactone modification mono acrylic ester (trade(brand)name " Plaxel FA " series, DAICEL KCC make), pentaerythritol triacrylate with hydroxyl and reactive unsaturated link(age); 2-hydroxyethyl methacrylate; Methylacrylic acid 2-hydroxy propyl ester; Methylacrylic acid 3-hydroxy propyl ester; Methylacrylic acid 4-hydroxyl butyl ester; Polyethylene glycol monomethacrylate; Polypropylene glycol monomethacrylate; Ethylene glycol and 1,2-propylene glycol segmented copolymer monomethacrylates; Terepthaloyl moietie-tetramethylene glycol multipolymer monomethacrylates; Caprolactone modification monomethacrylates (trade(brand)name " Plaxel FM " series; DAICEL KCC makes); Methacrylic acid derivatives such as pentaerythritol acrylate trimethyl etc.These compounds can use separately or also use more than 2 kinds.

Above the synthetic of (methyl) acrylic acid derivative can carry out through known polymerization methods such as block polymerization, solution polymerization, suspension polymerization and letex polymerizations the 2 officials ability of above-mentioned (C3) higher molecular weight.

From the viewpoint of the obdurability relevant with the cured article of resin combination, composition (C) preferably uses the acrylic acid series verivate of above-mentioned (C3) at least.(methyl) acrylic acid series verivate suitable with (C3) can use separately or combination use more than 2 kinds.Though not special the qualification, as composition (C3), in above-mentioned (1)～(5) in the compound of explanation, preferably two (methyl) propenoate of the urethane explained of conduct (4) and (5), the urethane that end has reactive unsaturated link(age).Wherein, preferably reactive unsaturated link(age) is the urethane based on (methyl) acryl.More specifically, the compound that constitutes by W 166 or polytetramethylene glycol of the diol component of urethane preferably.Especially preferably use following urethane: the diol component of urethane is W 166 or polytetramethylene glycol, and the vulcabond composition is the urethane of isophorone diisocyanate.

In the optical resin compsn of the present invention; When the consistency of (methyl) acrylic acid series verivate that (A) 2 officials of the higher molecular weight of (methyl) acrylic acid series derivative polymer and composition (C3) can be above is low; Following situation is arranged: the use level of composition (C3) increases, and then generates white casse in the cured article.But, among the present invention,, can improve the consistency with polymkeric substance through using with the composition (C3) of aklylene glycol as raw material, can not rely on the amount of composition (C3) and keep the transparency of resin combination and cured article thereof.In addition, (methyl) acrylic acid series verivate through using (C3) at least is as composition (C), even when it cooperates more amount, also can prevent the fragilityization of cured article and the remarkable reduction of bounding force.Therefore, owing to allow the increase of the use level of (C3) in the resin combination, the variation of the characteristic of the cured article that the error in the time of therefore can suppressing owing to cooperation causes.

The use level of (C) (methyl) acrylic acid derivative in the resin material for optical use of the present invention as 100 o'clock, is preferably the scope of 1～40 weight part with the use level of total composition of constituting resin combination.When the use level of the composition in the resin combination (C) is very few, has the tendency that cured article is difficult to keep shape.On the other hand, when use level is too much, the making of too high and the sheet tendency that difficulty and bounding force become too small that becomes that becomes of the viscosity with resin combination.And the tendency that the cured article with resin combination becomes fragile, the mechanical characteristics aspect is easy to generate problem.

In the optical resin compsn of the present invention, preferably, also further contain (D) polymerization starter except mentioned component (A), (B) with (C).But the polymerization starter of composition among the present invention (D) is also nonessential.For optical resin compsn of the present invention, when shining that for example electron rays is implemented its polyreaction, can not use polymerization starter yet and carry out polyreaction.Therefore, suitable being used in of polymerization starter do not use polymerization starter just can't carry out the situation of polyreaction among the present invention.Operable polymerization starter can be any one in Photoepolymerizationinitiater initiater and the thermal polymerization among the present invention, also can both and usefulness.

As stated, when resin combination of the present invention is for example shone electron rays, even do not use polymerization starter also can carry out polyreaction sometimes.That is, be used to make resin combination solidified polyreaction of the present invention, irradiation that can be through active energy ray, heat or the curing of they and usefulness implemented.In addition, " active energy ray " is meant ultraviolet ray, electron rays, α line, β line, γ line etc.Use in (methyl) acrylic acid series derivative polymer of composition (A) that above-mentioned curing also can be in compound resin composition.But,, therefore have the situation that is difficult to heat resin combination owing to reasons such as the high thermal resistance of the polaroid that uses in the liquid crystal panel are low.At this moment, optical resin compsn of the present invention is coated with original state or casting, heating are difficult, therefore preferred the use can the polymeric Photoepolymerizationinitiater initiater through light.

When polymerization starter was very few, polyreaction can not be carried out well, and the curing of resin combination is insufficient, and on the contrary, when polymerization starter was too much, polymerization starter was residual in a large number, caused possibly having problems aspect optical characteristics, the mechanical characteristics.Therefore, the use level of polymerization starter as 100, is preferably the scope of 0.01～5 weight part with composition (A), (B), (C) and total use level (D), the more preferably scope of 0.01～3 weight part, the scope of preferred especially 0.03～2 weight part.When particularly using Photoepolymerizationinitiater initiater, with respect to above-mentioned total use level 100, the scope of preferred 0.1～5 weight part, the more preferably scope of 0.3～3 weight part, the scope of preferred especially 0.5～2 weight part.When using thermal polymerization, with respect to above-mentioned total use level 100, the scope of preferred 0.01～1 weight part, the more preferably scope of 0.01～0.5 weight part.

And, with Photoepolymerizationinitiater initiater and thermal polymerization and time spent, preferred suitably adjustment in above-mentioned scope respectively.More preferably adjust usage quantity separately according to curing process.For example, carry out working fastening, lead when solidifying through thermopolymerization afterwards through photopolymerization, preferably will more a spot of Photoepolymerizationinitiater initiater and thermal polymerization and usefulness.Concrete, as 100, be that 0.1～0.5 weight part and thermal polymerization are the ratio use of 0.1～1.0 weight part with composition (A), (B), (C) and total use level (D) preferably with Photoepolymerizationinitiater initiater.As other examples, through photopolymerization make solidify most ofly finish, through thermopolymerization make a minimum part be difficult to photocuring partly solidified the time, from the viewpoint of storage stability, preferably use the thermal polymerization of less amount.Concrete, with respect to above-mentioned total use level 100, be that 0.5～5 weight part and thermal polymerization are the ratio use of 0.01～0.2 weight part preferably with Photoepolymerizationinitiater initiater.

The Photoepolymerizationinitiater initiater that uses among the present invention can be selected from known compounds such as benzophenone, anthraquinone class, bitter almond oil camphor class, sulfonium salt, diazonium salt, salt.These Photoepolymerizationinitiater initiaters are particularly high to ultraviolet sensitivity to light.

Object lesson as the operable compound of Photoepolymerizationinitiater initiater is as follows.

UVNUL MS-40, N, N '-tetramethyl--4,4 '-diaminobenzophenone (Michler's keton), N; N-tetraethyl--4,4 '-diaminobenzophenone, 4-methoxyl group-4 '-dimethylamino UVNUL MS-40, Alpha-hydroxy isobutyl-benzophenone, 2-ethyl-anthraquinone, tertiary butyl anthraquinone, 1,4-dimethyl-anthraquinone, 1-chloroanthraquinone, 2; 3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 1,2-benzo anthraquinone, 2-phenyl anthraquinone, 1,4-naphthoquinones, 9; 10-phenanthrenequione, thioxanthone, 2-chloro thioxanthone, 1-hydroxycyclohexylphenylketone, 2; 2-dimethoxy-1,2-diphenylethane-1-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-aromatic ketone compounds such as 1-ketone

Bitter almond oil camphor compounds such as bitter almond oil camphor, methylbenzene acyloin, ethylbenzene acyloin,

Benzoin ether compounds such as benzoin methyl ether, bitter almond oil camphor ethyl ether, bitter almond oil camphor isobutyl ether, bitter almond oil camphor phenyl ether,

Benzil, 2, the diester compound of 2-diethoxy phenyl methyl ketone, benzyl dimethyl ketal, β-(acridine-9-yl) vinylformic acid etc.,

9-phenylacridine, 9-pyridyl acridine, 1, acridine compounds such as 7-two acridyl heptane,

2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dipolymer, 2-(Chloro-O-Phenyl)-4,5-two (m-methoxyphenyl) imidazole dimer, 2-(adjacent fluorophenyl)-4; 5-diphenyl-imidazole dipolymer, 2-(o-methoxyphenyl)-4,5-diphenyl-imidazole dipolymer, 2-(p-methoxyphenyl)-4,5-diphenyl-imidazole dipolymer, 2; 4-two (p-methoxyphenyl) 5-phenylimidazole dipolymer, 2-(2, the 4-Dimethoxyphenyl)-4,5-diphenyl-imidazole dipolymer, 2-(to the methyl mercapto phenyl)-4; 2 of 5-diphenyl-imidazole dipolymer etc.; 4,5-triarylimidazoles dipolymer

2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-1-butanone, 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholino-1-propane, two (2; 4,6-trimethylbenzoyl)-phenyl phosphine oxide, oligomeric (2-hydroxy-2-methyl-1-(4-(1-methyl ethylene) phenyl) acetone) etc.

Among the present invention, as Photoepolymerizationinitiater initiater and formerly the compound of example can use separately or more than 2 kinds combination use, preferably select suitable compound according to purpose.For example, painted in order not make resin combination, the preferred use separately or the compound below the combination use more than 2 kinds.

The Alpha-hydroxy alkyl phenones based compound of 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 etc.,

Two (2,4, the 6-trimethylbenzoyl)-phenyl phosphine oxides, two (2,6-dimethoxy benzoyl-)-2,4,4-trimethylammonium-amyl group phosphine oxide, 2,4, the acylphosphine oxide based compound of 6-trimethylbenzoyl-diphenyl phosphine oxide etc.,

Oligomeric (2-hydroxy-2-methyl-1-(4-(1-methyl ethylene) phenyl) acetone),

The mixture of hydroxyl-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetic acid base-oxyethyl group]-ethyl ester and hydroxyl-phenyl-acetic acid 2-[2-hydroxyl-oxyethyl group]-ethyl ester.

In order to make thick sheet, at least as Photoepolymerizationinitiater initiater, preferred use two (2; 4,6-trimethylbenzoyl)-phenyl phosphine oxide, two (2,6-dimethoxy benzoyl-)-2; 4; 4-trimethylammonium-amyl group phosphine oxide, 2,4, the acylphosphine oxide based compound of 6-trimethylbenzoyl-diphenyl phosphine oxide etc.

In order to reduce the foul smell of sheet, preferably use at least a in the mixture of oligomeric (2-hydroxy-2-methyl-1-(4-(1-methyl ethylene) phenyl) acetone) and hydroxyl-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetic acid base-oxyethyl group]-ethyl ester and hydroxyl-phenyl-acetic acid 2-[2-hydroxyl-oxyethyl group]-ethyl ester.

Hinder in order to reduce the polymerization that causes by oxygen, preferably use the mixture of hydroxyl-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetic acid base-oxyethyl group]-ethyl ester and hydroxyl-phenyl-acetic acid 2-[2-hydroxyl-oxyethyl group]-ethyl ester.

The aforementioned hot polymerization starter is meant the initiator that produces radical through heat; Concrete; Can enumerate: benzoyl peroxide, TBPB tertiary butyl perbenzoate, cumene hydroperoxide, di-isopropyl peroxydicarbonate, peroxy dicarbonate di-n-propyl ester, peroxy dicarbonate two (2-ethoxyethyl group) ester, new peroxide tert-butyl caprate, the peroxo-PIVALIC ACID CRUDE (25) tert-butyl ester, (3; 5,5-trimethyl acetyl base) organo-peroxide such as superoxide, dipropyl acyl peroxide, diacetyl peroxide, two (dodecyl) superoxide.In addition, can enumerate: 2,2 '-Diisopropyl azodicarboxylate, 2; 2 '-azo two (2-methylbutyronitrile), 1,1 '-azo two (hexanaphthene-1-carbonyl), 2,2 '-azo two (2; The 4-methyl pentane nitrile), 2,2 '-azo two (2,4-dimethyl--4-methoxyl group valeronitrile), dimethyl-2; 2 '-azo two (2 Methylpropionic acid ester), 4; 4 '-azo two (4-cyanopentanoic acid), 2,2 '-azo two (2-hydroxymethyl propionitrile), 2,2 '-azo two azo based compounds such as [2-(2-tetrahydroglyoxaline-2-yl) propane].

When in optical resin compsn of the present invention, using thermal polymerization, they preferably have and are preferably 40～80 ℃, more preferably 40～65 ℃, are preferably 10 hours half life temperatures of 50～65 ℃ especially." 10 hours half life temperatures " be meant, the temperature when half of thermal polymerization decomposed in 10 hours.Half life temperature was crossed when hanging down in 10 hours, had the tendency of the storage stability reduction of resin combination.On the other hand, when half life temperature was too high in 10 hours, need therefore have the possibility that following problem takes place in heat during owing to curing reaction: the deterioration in characteristics of liquid crystal or polaroid, the display characteristic of liquid-crystal display worsened.When using the higher thermal polymerization of 10 hours half life temperatures, guarantee the storage stability of resin combination easily, but because reactive the reduction, so they need more addition.On the contrary, under the situation of the low thermal polymerization of 10 hours half life temperatures, the polyreaction of resin combination when suppressing keeping, preferably more a spot of addition.

In addition, in the optical resin compsn of the present invention, also can be as required, and with other polymerizable compound conduct and above-mentioned various compositions (A), (B), (C) and (D) different resinous principle.With suitable polymerizable compound, can improve the shape-holding property of optical resin composition through also.For example, can be also with the polymerizable compound that has 1 unsaturated link(age) in vinyl cyanide, vinylbenzene, vinyl acetate, ethene, the propylene equimolecular.At this moment, in order to obtain effect desired among the present invention, and the use level of the polymerizable compound of usefulness, be preferably below the 90 overall weight % of compsn, more preferably below the 50 weight %, further be preferably below the 20 weight %.In addition, also can and have the polyunsaturated compounds of 2 above unsaturated link(age)s, when the use level of this compound is too much, have the bounding force of resin combination and the tendency that shock-resistance reduces with intramolecularly.Therefore, when also using polyunsaturated compounds among the present invention, its use level totally is preferably below the 20 weight % with respect to compsn.

And then optical resin compsn of the present invention also can contain various stablizers as required.As operable stablizer among the present invention; For example, can enumerate: with the storage stability that improves resin combination be the stoppers such as p methoxy phenol that use of purpose, the oxidation inhibitors such as triphenylphosphine that use for the thermotolerance of the cured article that improves resin combination, in order to improve HALS that weathering resistance uses etc.Also can multiple combination of stabilizers be used.Other as long as in the scope that can obtain effect of the present invention, also can use well-known additive.

The of the present invention the 2nd mode relates to the resin material for optical use that the cured article by the optical resin compsn constitutes.Resin material for optical use of the present invention can obtain through following method: the optical resin compsn is being kept using common coating machine to be coated with into required thickness or cast molding under original state; Be cured reaction afterwards, process cured article and obtain.Curing reaction can use the thermopolymerization method.In addition, also can be cured reaction through applying luminous energies such as UV, EB.Also can and use these curings.

Resin material for optical use of the present invention is not special to be limited, and preferably makes with sheet or membranaceous shape.The sheet or the film that resin combination are solidified and make have binding property.Therefore, do not use tackiness agent or caking agent, can these resin material for optical use that is called as sheet or film be fitted in glass, other base materials etc. yet and go up use.

Because optical resin compsn of the present invention can not encroached on the material that uses in the image display devices such as liquid crystal indicator, PDP and had the good transparency, therefore can be suitable as towards the resin material for optical use of various display unit and use.In addition, the cured article by optical resin compsn of the present invention obtains owing to contain high molecular weight polymers, therefore has the hardness of appropriateness, and impact is difficult to take place viscous deformation.So,, can improve their impact absorbency through increasing the thickness of resin material for optical use.Therefore, in the example preferred embodiment of the present invention, above-mentioned resin material for optical use is used as the impact absorbing layer in image display device and the device used for image display spectral filter.

During as the impact absorbing layer of image display device, the second-order transition temperature of the cured article of resin combination (Tg) is preferably below 0 ℃ with resin material for optical use.When the second-order transition temperature of cured article surpassed 0 ℃, the impact absorbing layer hardening was ftractureed because of impact easily.Tg more preferably-20～-60 ℃.In addition, when resin material for optical use was applicable to image display device, its visible light transsmissivity was preferably more than 80%.

In order to make impact absorbing layer by optical resin compsn of the present invention; Resin combination is coated pictorial display with after making film on the surface of panel or image display device or the base material of spectral filter etc., make it to solidify at light such as its coated face irradiation ultraviolet radiation or electron rays isoradial and get final product.In addition; When making spectral filter, for example, behind coating optical resin compsn system film of the present invention on the functional layers such as the base material of spectral filter or antireflection film layer; And then base material, functional layer or the resist of spectral filter is range upon range of, shine radioactive rays then and make it to solidify and get final product.

Pictorial display with the surface of panel or image display device on coating resin compsn when resin material layer is set, preferably implement the system film to make its thickness be 0.1mm～3mm.If consider impact absorbency, then resin material layer more preferably has the above thickness of 0.2mm.When particularly thinking the intensifying impact absorptivity, the thickness of preferred resin material is more than 1.3mm.Do not have special qualification, but, preferably use common coating machine to be coated with in order to process desired thickness.

In addition,, also can make the sheet or the film of self-support type in advance, use them then through the curing reaction of optical resin compsn as resin material for optical use of the present invention.When making this resin material for optical use, can use methods such as cast molding.In addition, the curing reaction of resin combination can be through heating, perhaps carrying out through light such as irradiation ultraviolet radiation, electron rays isoradial.When resin material for optical use of the present invention was configured as sheet or the film of self-support type, its thickness was preferably 0.1mm～3mm.If consider not also to be applicable to the situation of image display device with transparency protected substrate and with resin material for optical use as impact absorbing layer, then more preferably it is configured as the thickness more than the 0.2mm.When particularly need to strengthen impact absorbency, the above thickness of preferred 1.3mm.On the other hand, and when using transparent protection plate, preferably process the thickness below the 0.5mm, especially preferably process below the 0.2mm.The resin material for optical use that is configured as the shape of this or film can be directly range upon range of on the surface of panel or image display device or spectral filter etc. at pictorial display, perhaps carries out range upon range of through tackiness agent or caking agent.

When carrying out the curing reaction of optical resin compsn of the present invention,, the polymeric of obstruction situation is arranged then if there is oxygen through light such as irradiation ultraviolet radiations.In this case, preferably block oxygen with the surface of transparent film or transparent glass covering solidified resin layer.In addition, also can block oxygen through under inertness atmosphere, carrying out polymerization.When being difficult to, can reduce the influence of oxygen through the addition that increases polymerization starter with these method blocking-up oxygen.As the polymerization starter that at this moment uses, the mixture of preferred hydroxyl-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetic acid base-oxyethyl group]-ethyl ester and hydroxyl-phenyl-acetic acid 2-[2-hydroxyl-oxyethyl group]-ethyl ester.As UV irradiation equipment, not special the qualification can be used well-known UV irradiation equipments such as vane-type, conveyor type.In addition, as the light source that uviolizing is used, can be Cooper-Hewitt lamp, middle medium pressure mercury lamp, high pressure mercury vapour lamp, metal halide lamp etc., LED lamp etc., preferably use high pressure mercury vapour lamp or metal halide etc.

As the example of the image display device that can be suitable for optical resin compsn of the present invention or resin material for optical use, can enumerate: plasma display (PDP), liquid-crystal display (LCD), cathode ray tube (CRT), field-emitter display (FED), OLED display, Electronic Paper etc.When in these image display devices, being suitable for resin material for optical use of the present invention, as required, also can make up with functional layers such as anti-reflection layer, stain-proofing layer, pigmentary layer and hard coats.For example; Also can be used for image display device with following multilayer structure making appropriate, said multilayer structure making is: on base material films such as polyvinylidene film, polyester film with functional layer system films such as anti-reflection layer, stain-proofing layer, pigmentary layer and hard coat or range upon range of and multilayer structure making that obtain.

Here, as functional layer and the anti-reflection layer of example,, can use on transparent substrates such as transparent plastic film with known reflection and prevent that method from handling and the layer that obtains as long as have reflectivity to visible light in the preventing property of reflection below 5%.

Stain-proofing layer is used to prevent to adhere to dirt on the surface and uses, and can be made up of well-known material.Do not have special qualification, but in order to reduce surface tension, stain-proofing layer is made up of fluorine-type resin or siloxane resin etc. preferably.

Pigmentary layer is in order to reduce not light, to improve purity of color and use, and when the purity of color of the light that is sent in panel by pictorial display such as liquid crystal panels is hanged down, is effective.The pigment of the light that absorbs unwanted zone is dissolved in the resin, it is made film or range upon range of on base material films such as polyvinylidene film, polyester film, perhaps through above-mentioned pigment is formed with methods such as tackiness agent mix.

Hard coat uses in order to improve surface hardness.Hard coat can form through following method: vinyl resins such as urethane acrylate or epoxy acrylate, epoxy resin etc. are made film or range upon range of formation on base material films such as polyvinylidene film.Same, in order to improve surface hardness, also can use glass, acrylic board, polycarbonate etc. plate, or on these plates with hard coat system film or range upon range of and plate that obtain.

Optical resin compsn or above-mentioned resin material for optical use among the present invention are not limited to above-mentioned functional layers such as anti-reflection layer, also can use with having functional layer of required appropriate combination.Functional layer can be in a surperficial laminated of transparent substrate, also can be on the two sides laminated.In addition, can on the two sides of transparent substrate, distinguish the different layer of range upon range of function, perhaps also can be at the identical layer of its two sides laminated function.In addition, the lamination order of functional layer, not special the qualification can suitably be changed.But, when multilayered structure is processed in optical resin compsn of the present invention or resin material for optical use and functional layer combination, preferably these compsns or material and pictorial display with the surface of panel or image display device near and range upon range of.

Optical resin compsn of the present invention or resin material for optical use also can use with the polaroid combination.At this moment, optical resin compsn of the present invention or resin material for optical use can be layered in visible surface one side of polaroid, also can be layered in its opposition side.When they are layered in visible surface one side of polaroid, visible surface one side also can further range upon range of anti-reflection layer, functional layer such as stain-proofing layer, hard coat.In addition, when between polaroid and liquid crystal cells, using these resin combinations or resin material, also can be in the range upon range of various functional layers of visible surface one side of polaroid.Bonding coat can be set between each layer as required, use roll laminating machine or thin slice rigging machine to carry out range upon range of.

Through optical resin compsn of the present invention or resin material for optical use are layered in the multilayer structure making that obtains on the various functional layers; Use roll laminating machine or thin slice rigging machine, can be easily and pictorial display with the front surface of panel or image display device or the front panel or the transparency protected baseplate-laminating of device used for image display.At this moment, preferred multilayer structure making more near visible surface, be configured in the appropriate location of pictorial display with the panel front surface.The special preferred disposition of multilayer structure making is between pictorial display is with panel and front panel or transparency protected substrate.

Below, to the use of resin material for optical use of the present invention in image display device, be that the situation of liquid crystal indicator is enumerated more specifically as an example and explained with the image display device.

Be assembled in the liquid crystal display in the liquid crystal indicator, not special the qualification can be made up of well-known liquid crystal material in this technical field.In addition, can be divided into several types of TN, STN, VA, IPS etc. according to the control method of liquid crystal material, but also can be to use the liquid crystal display of any control method among the present invention.

Fig. 1 and Fig. 2 are the sectional views of an example that schematically shows the structure of liquid crystal indicator in the past.Liquid crystal indicator shown in Fig. 1 by liquid crystal display 10, be attached to polaroid 20 and 22 on its two sides, being situated between to be configured in as the transparency protected substrate 40 of polaroid 20 upper surfaces of the visible side of display unit and the back light system 50 that is arranged on the lower surface of polaroid 22 by space 30 constitutes.Liquid crystal display 10 is structures of in 2 sheet glass (not having accompanying drawing), enclosing liquid crystal material, attaches polaroid 20 and 22 at each glass surface.Back light system 50 is made up of lighting means such as reflection means such as reflector and lamps typically.In addition, liquid crystal indicator shown in Figure 2 except not being provided with the transparency protected substrate at the upper surface (front surface) as the polaroid 20 of the visible side of display unit, constitutes with liquid crystal indicator shown in Figure 1 equally.

On the other hand, be suitable for the liquid crystal indicator that resin material for optical use of the present invention constitutes, it is characterized in that possessing the transparent resin layer that constitutes by resin material for optical use.Fig. 3～Fig. 6 is the constructed profile of an example that schematically shows the structure of liquid crystal indicator of the present invention.Liquid crystal indicator shown in Figure 3 corresponding to liquid crystal indicator in the past shown in Figure 1, exists transparent resin layer 32 to replace space 30 (Fig. 1).That is, liquid crystal indicator shown in Figure 3 by liquid crystal display 10, the back light system 50 that is attached to polaroid 20 and 22 on its two sides, is arranged on transparent resin layer 32 as the upper surface of the polaroid 20 of the visible side of display unit, is arranged on the transparency protected substrate 40 on its surface and is arranged on the lower surface of polaroid 22 constitutes.Have the liquid crystal indicator of this formation and compare with liquid crystal indicator in the past, the combination through transparent protection plate and transparent resin layer improves shock-resistance, therefore is difficult for breaking.In addition, even have the advantage that also is difficult to generate display dot under the situation on the surface that is squeezed in device.In addition; Same, in the structure of plasma display, fill resin combination of the present invention between plate and the plasma display device in front, when making it to solidify; The picture quality that can suppress to be caused by the dual reflection of visible in the plasma display reduces, and also can improve contrast gradient in addition.

As shown in Figure 4, also can be to liquid crystal indicator shown in Figure 3 structure with the order transposing of transparent resin layer 32 and polaroid 20.At this moment, for transparency protected substrate and polaroid are attached, also can use tackiness agent etc.Like Fig. 3 and shown in Figure 4, have at upper surface under the situation of liquid crystal indicator of transparency protected substrate 40, as required, also can be in functional layers such as the surperficial range upon range of anti-reflection layer of transparency protected substrate, stain-proofing layer, hard coats.In addition as other structure, as required, also can be in functional layers such as the surperficial range upon range of anti-reflection layer of polaroid 20, stain-proofing layer, hard coats.

Liquid crystal indicator can not be provided with transparency protected substrate 40 yet and constitutes in Fig. 3 and formation shown in Figure 4.For example, liquid crystal indicator shown in Figure 5 is made up of liquid crystal display 10, the transparent resin layer 32 that is arranged on its upper surface and polaroid 20, the polaroid 22 and the back light system 50 that are arranged on below the liquid crystal display.Polaroid 20 is up front the time like this, as required, and also can be in functional layers such as the surperficial laminated anti-reflection layer of polaroid 20, stain-proofing layer, hard coats.Liquid crystal indicator also can be as shown in Figure 6, to liquid crystal indicator shown in Figure 5 with the transposing of the order of transparent resin layer 32 and polaroid 20 and constitute.Thus, transparent resin layer 32 is up front the time, as required, and also can be in functional layers such as the surperficial laminated anti-reflection layer of transparent resin layer 32, stain-proofing layer, hard coats.Do not have special qualification, but preferably hard coat is set at least.

In addition, the front panel that uses in the transparency protected substrate of liquid crystal indicator and other the display unit can be that optics is used transparency carrier.Concrete, can enumerate: inorganics plates such as sheet glass, quartz plate, resin boards such as acrylic board, polycarbonate plate, thick resin sheets such as polyester chips.Plate such as preferred glass, acrylic, more preferably sheet glass when needing high surface hardness.Also can prevent on the surface of these transparency protected substrates or front panel reflection, antifouling, processing such as be coated with firmly.This surface treatment can be to a surface of front panel or transparency protected substrate, or the two sides is implemented.Transparency protected substrate or front panel also can use its multi-disc combination.

The polaroid that uses in the liquid crystal indicator can be a normally used polaroid in this technical field.The surface of these polaroids also can prevent reflection, antifouling, processing such as be coated with firmly.This surface treatment can be to a surface of polaroid, perhaps to its two sides enforcement.

More than, the liquid crystal indicator that possesses the transparent resin layer that is made up of resin material for optical use of the present invention is specified.But optical resin compsn of the present invention and resin material are not limited in liquid crystal indicator, use, and also are applicable to other image display device such as plasma display.In addition, resin material for optical use of the present invention not only can be used as the formation element of image display device, and can be used as and have the layer combination of required function and the multilayer structure making of the spectral filter made etc. uses.

For example, spectral filter can be through making in functional layers such as substrate laminated anti-reflection layer, electromagnetic shielding layer, near-infrared shielding layers such as glass, acrylic, polycarbonate and resin material for optical use of the present invention.

The electromagnetic shielding layer so long as the visible light transsmissivity be more than 60% and have electromagnetic shielding property and get final product, can constitute equally with well-known electromagnetic shielding layer.For example, can use the net made through nesa coating, conducting fibre net, conductive ink etc.The viewpoint of, high electromagnetic shielding property transparent from height, most preferred metal system net.Metal system net can obtain through following method: any in transparent substrates such as polyester film and conductive metal paper tinsels such as Copper Foil, aluminium foil or they on both coating adhesive both applyings are carried out range upon range of, through chemical etching process the conductive metal paper tinsel is carried out etching and processing then and obtains.As the conductive metal paper tinsel that uses, from guaranteeing the stopping property aspect, preferred surface is the tinsel of uneven surface, and the uneven surface that on transparent substrate, makes this conductive metal paper tinsel carries out range upon range of towards the layer of caking agent.Preferably: behind above-mentioned etch process making metal system net; At the online coating resin of this metal system; Especially preferably being coated under the irradiation of ultraviolet ray, electron rays isoradial can the solidified resin; Make resin solidification through irradiation ultraviolet radiation, electron rays isoradial, the layer of the caking agent that uneven surface is transferred carries out planarization, processes transparent.Also can use resin combination of the present invention as the resin that on wire netting, is coated with.

In addition, anti-reflection layer also can use following anti-reflection layer so long as the display of visually luminous reflectance factor gets final product in the preventing property of reflection below 5%: the layer of on transparent transparent substrates such as plastics film, having implemented to be used to prevent the well-known processing of reflecting.And the near-infrared shielding layer can be made up of the resin that is dispersed with imonium salt near-infrared-absorbing materials such as (imonium salt) or near-infrared shielding material.The near-infrared shielding layer also can be layered on the transparent transparent substrates such as plastics film.In optical resin compsn of the present invention, also can make near-infrared-absorbing material or near-infrared shielding dispersion of materials such as imonium salt, use as resin with near-infrared shielding function.In addition, also can and use by this resin making sheet.

In the spectral filter, and functional layers such as the whole above-mentioned electromagnetic shielding layer of nonessential use, anti-reflection layer, near-infrared shielding layer, also can use according to the layer of the range upon range of suitable necessity of purposes.For example, having electromagnetic wave shielding or near-infrared shielding layer is adapted at using in the plasma display as the spectral filter of functional layer.Functional layer can be layered on the surface of transparent substrate, also can be on the two sides of transparent substrate laminated.In addition, can on the two sides of transparent substrate, distinguish the different layer of range upon range of function, perhaps also can be at the identical layer of its two sides laminated function.When constituting this multilayer structure making, preferably make the layer that contains optical resin compsn of the present invention or optical resin material at outermost layer.In addition, the lamination order of functional layer is not special to be limited, and can suitably change.Range upon range of bonding coat, use roll laminating machine or the thin slice rigging machine of can between each layer, being provided with of functional layer carries out.Further use roll laminating machine or thin slice rigging machine, the spectral filter of making thus is fitted on the position of regulation of image display device.The position of fitting is different because of the formation of image display device, for example, and can be at pictorial display with the front surface of panel, the front panel of image display device.At this moment; Through making the layer that contains optical resin compsn of the present invention or resin material for optical use for outermost layer, also can not use tackiness agent and multilayer structure makings such as spectral filter are fitted on the front panel of pictorial display with the front surface of panel, image display device.

Embodiment

Below, being described in detail the present invention through embodiment, scope of the present invention is not limited to these embodiment.In addition, below the term " weight-average molecular weight " of record is through being that the GPC of solvent is measured with THF, utilizes the lubber-line of polystyrene standard to convert and the value confirmed this measured value.

(embodiment 1)

1, the preparation of multipolymer

In reaction vessel with cooling tube, TM, whipping appts, addition funnel and nitrogen injection tube; As the initial stage monomer; Weighing 2-EHA 84.0g, vinylformic acid 2-hydroxy methacrylate 36.0g and mibk 150.0g; Air quantity with 100ml/min carries out nitrogen replacement, is heated to 70 ℃ through 15 minutes from normal temperature simultaneously.Afterwards, on one side holding temperature is at 70 ℃, weighing 2-EHA 21.0g and vinylformic acid 2-hydroxy methacrylate 9.0g dissolve lauroyl peroxide 0.6g therein as appending monomer on one side, and preparation solution dripped this solution through 60 minutes.After dripping end, further carry out 2 hours reaction.Remove mibk through distillation from the reaction mixture that obtains, obtain the multipolymer (weight-average molecular weight 250,000) of 2-EHA and vinylformic acid 2-hydroxy methacrylate.

2, the preparation of urethane acrylate

Then; In reaction vessel with cooling tube, TM, whipping appts, addition funnel and air injection tube; Weighing W 166 (molecular weight 2000) 180g, vinylformic acid 2-hydroxy methacrylate 2.33g, as the p methoxy phenol 0.5g of stopper with as the dibutyl tin laurate 0.05g of catalyzer, be warming up to 70 ℃ while flow into air.Afterwards, holding temperature evenly drips isophorone diisocyanate 22.2g at 70～75 ℃ while stir through 2 hours, reacts.After dripping end, continue reaction after about 5 hours, carry out the result that IR measures, confirm the disappearance of isocyanic ester.Finish reaction at this time point, obtain following urethane acrylate (weight-average molecular weight 16000): have the repeating unit that derives from W 166 and isophorone diisocyanate, have the polymerizability unsaturated link(age) at two ends.

3, optical resin preparation of compositions

Compound below the difference weighing:

(A) the multipolymer 24.88g of preparation in above-mentioned 1

(B1) 2-EHA (2EHA) 27.85g

(B2) polyethylene glycol monomethyl ethermethacrylic acid esters 11.94g

(Hitachi Chemical Co., Ltd.'s system, trade(brand)name " FA-400M ", number of repeat unit 9 are main)

(C) urethane acrylate (UA1) 34.83g of preparation in above-mentioned 2

(D) 1-hydroxyl-cyclohexyl-phenyl-ketone 0.50g

(Ciba Japan Co., Ltd. system, trade(brand)name " Irgacure-184 "),

Add in the reaction vessel, use stirrer (Three-One Motor) under room temperature (25 ℃), to mix 30 minutes, prepare the optical resin compsn thus.

4, the evaluation of optical resin compsn

Optical resin compsn to previous preparation carries out rabbit eye irritation test (Draize test), and by irritating degree such as its pII value evaluating skin maculas, the result is that skin irritation is low, and macula etc. does not take place during use.In addition, the Draize test is an object with 3 rabbits, according to its MV of benchmark evaluation of OECD guide No.404.The pII value is with 0～8 numeric representation, and this value is low more, and the expression thorn is intense low.

In addition; Make the optical resin compsn of previous preparation flow into wide for 100mm, depth be 100mm, deeply in 0.5mm framed; Behind ultraviolet perviousness glass covering framed top; Use UV irradiation equipment compsn to be solidified, make sheet thus with cumulative exposure amount 3000mJ irradiation ultraviolet radiation.Sheet is transparent.Then, the sheet of making is carried out the various tests shown in following, estimate its characteristic.Evaluation result is shown in table 1.

(total light transmittance)

To the sheet of making, measure total light transmittance through using aberration turbidity measurement device COH-300A (Japanese electric look Industrial Co., Ltd system), estimate the transparency.

(ΔYI)

To the sheet of making, use aberration turbidity measurement device COH-300A (Japanese electric look Industrial Co., Ltd system) to measure YI (Yellowness Index).As shown in the formula said, the difference of placing the YI that measures after 500 hours with the YI at initial stage with in 85 ℃ high temperature groove is as Δ YI.YI is more little for Δ, and the expression thermotolerance is good more, painted few more under the high temperature.

Δ YI=(YI after 500 hours)-(YI at initial stage)

(shock-resistance)

The shock-resistance test is implemented through following method: the front surface glass of on a surface of the sheet of making, fitting; And then the thick 0.7mm that on another face, fits with liquid crystal panel in normally used glassy phase with glass, in front surface glass one side the steel ball of 510g is fallen afterwards.With 5cm, 8cm, 10cm, 12cm, 15cm, change from the height at the center of front surface glass to steel ball with the scale of 5cm steel ball is fallen later on, carry out the whether damaged judgement of front surface glass.Shock strength is calculated based on following formula.

Shock strength=steel ball heavy (Kg) * high (m) * 9.8 (m/s ²)

For example, when high 5cm falls, be 0.51 * 0.05 * 9.8=0.25J.

(moisture-proof safety)

The sheet of making is put into 60 ℃, the high temperature and humidity test groove of 90%RH carried out fuchsin(e)test in 50 hours, afterwards the cosmetic variation through the visual observation sheet.With not seeing white casse in the sheet after the fuchsin(e)test, keeping transparent be judged as " good state ".

(embodiment 2)

Compound below the difference weighing:

(A) the multipolymer 47.50g of preparation among the embodiment 1

(B1) 2-EHA (2EHA) 33.26g

(B2) polyethylene glycol monomethyl ethermethacrylic acid esters 14.24g

(Hitachi Chemical Co., Ltd.'s system, trade(brand)name " FA-400M ", number of repeat unit 9 are main)

(C) polypropyleneglycol diacrylate (PPGDA) 5.00g

(D) 1-hydroxyl-cyclohexyl-phenyl-ketone 0.51g

(Ciba Japan Co., Ltd. system, trade(brand)name " Irgacure-184 "),

Add in the reaction vessel, use stirrer (Three-One Motor) under room temperature (25 ℃), to mix 30 minutes, prepare the optical resin compsn thus.

To the optical resin compsn that obtains, carry out the Draize test equally with embodiment 1, the result is that skin irritation is low, and macula etc. does not take place during use.In addition; Make the optical resin compsn flow into wide for 100mm, depth be 100mm, deeply in 0.5mm framed; Behind ultraviolet perviousness glass covering framed top, use UV irradiation equipment compsn to be solidified with cumulative exposure amount 3000mJ irradiation ultraviolet radiation, make sheet thus.Sheet is transparent.Then, the sheet to making carries out various tests equally with embodiment 1, estimates its characteristic.Evaluation result is shown in table 1.

(embodiment 3)

Compound below the difference weighing:

(A) the multipolymer 45.12g of embodiment 1

(B1) vinylformic acid isooctadecanol ester (ISA) 38.90g

(B2) polyethylene glycol monomethyl ethermethacrylic acid esters 11.67g

(Hitachi Chemical Co., Ltd.'s system, trade(brand)name " FA-400M ", number of repeat unit 9 are main)

(C) polypropyleneglycol diacrylate (PPGDA) 3.89g

(D) 1-hydroxyl-cyclohexyl-phenyl-ketone 0.43g

(Ciba Japan Co., Ltd. system, trade(brand)name " Irgacure-184 "),

Add in the reaction vessel, use stirrer (Three-One Motor) under room temperature (25 ℃), to mix 30 minutes, prepare the optical resin compsn thus.

To the optical resin compsn that obtains, carry out the Draize test equally with embodiment 1, the result is that skin irritation is low, and macula etc. does not take place during use.In addition; Make the optical resin compsn flow into wide for 100mm, depth be 100mm, deeply in 0.5mm framed; Behind ultraviolet perviousness glass covering framed top, use UV irradiation equipment compsn to be solidified with cumulative exposure amount 2000mJ irradiation ultraviolet radiation, make sheet thus.Sheet is transparent.Then, the sheet to making carries out various tests equally with embodiment 1, estimates its characteristic.Evaluation result is shown in table 1.

(embodiment 4)

1, the preparation of urethane acrylate

In reaction vessel with cooling tube, TM, whipping appts, addition funnel and air injection tube; Add polytetramethylene glycol (molecular weight 850) 520.80g, glycol ether 1.06g, unsaturated fatty acids hydroxyalkyl acrylate modification 6-caprolactone (Plaxel FA2D:DAICEL chemical industry Co., Ltd.; Trade(brand)name) 275.20g, as the p methoxy phenol 0.5g of stopper with as the dibutyl tin laurate 0.3g of catalyzer, be warming up to 70 ℃.Afterwards, holding temperature evenly drips isophorone diisocyanate 222g at 70～75 ℃ while stir through 2 hours, reacts.After dripping end, continue reaction after about 5 hours,, confirm the disappearance of isocyanic ester according to carrying out the result that IR measures.Finish reaction at this time point, obtain weight-average molecular weight and be 7000 urethane acrylate.

2, optical resin preparation of compositions

Compound below the difference weighing:

(A) the multipolymer 47.00g of preparation among the embodiment 1

(B1) 2-EHA (2EHA) 33.25g

(B2) polyethylene glycol monomethyl ethermethacrylic acid esters 14.25g

(Hitachi Chemical Co., Ltd.'s system, trade(brand)name " FA-400M ", number of repeat unit 9 are main)

(C) urethane acrylate (UA2) 5.00g of preparation in above-mentioned 1

(D) 1-hydroxyl-cyclohexyl-phenyl-ketone 0.50g

(Ciba Japan Co., Ltd. system, trade(brand)name " Irgacure-184 "),

Add in the reaction vessel, use stirrer (Three-One Motor) under room temperature (25 ℃), to mix 30 minutes, prepare the optical resin compsn thus.

To the optical resin compsn that obtains, carry out the Draize test equally with embodiment 1, the result is that skin irritation is low, and macula etc. does not take place during use.In addition; Make the optical resin compsn flow into wide for 100mm, depth be 100mm, deeply in 0.5mm framed; Behind ultraviolet perviousness glass covering framed top, use UV irradiation equipment compsn to be solidified with cumulative exposure amount 3000mJ irradiation ultraviolet radiation, make sheet thus.Sheet is transparent.Then, the sheet to making carries out various tests equally with embodiment 1, estimates its characteristic.Evaluation result is shown in table 1.

(embodiment 5)

Compound below the difference weighing:

(A) the multipolymer 47.50g of embodiment 1

(B1) tridecyl acrylate (TDA) 33.25g

(B2) polyethylene glycol monomethyl ethermethacrylic acid esters 14.25g

(Hitachi Chemical Co., Ltd.'s system, trade(brand)name " FA-400M ", number of repeat unit 9 are main)

(C) polypropyleneglycol diacrylate (PPGDA) 5.00g

(D) 1-hydroxyl-cyclohexyl-phenyl-ketone 0.49g

(Ciba Japan Co., Ltd. system, trade(brand)name " Irgacure-184 "),

Add in the reaction vessel, use stirrer (Three-One Motor) under room temperature (25 ℃), to mix 30 minutes, prepare the optical resin compsn thus.

To the optical resin compsn that obtains, carry out the Draize test equally with embodiment 1, the result is that skin irritation is low, and macula etc. does not take place during use.In addition; Make the optical resin compsn flow into wide for 100mm, depth be 100mm, deeply in 0.5mm framed; Behind ultraviolet perviousness glass covering framed top, use UV irradiation equipment compsn to be solidified with cumulative exposure amount 2000mJ irradiation ultraviolet radiation, make sheet thus.Sheet is transparent.Then, the sheet to making carries out various tests equally with embodiment 1, estimates its characteristic.Evaluation result is shown in table 1.

(embodiment 6)

Compound below the difference weighing:

(A) the multipolymer 48.51g of embodiment 1

(B1) 2-EHA (2EHA) 29.10g

(B2) poly glycol monomethyl ether propenoate 19.40g

(Xin Zhong village chemical industry Co., Ltd. system, trade(brand)name " NK ester AM-90G ")

(C) polypropyleneglycol diacrylate (PPGDA) 3.00g

(D) 1-hydroxyl-cyclohexyl-phenyl-ketone 0.52g

(Ciba Japan Co., Ltd. system, trade(brand)name " Irgacure-184 "),

Add in the reaction vessel, use stirrer (Three-One Motor) under room temperature (25 ℃), to mix 30 minutes, prepare the optical resin compsn thus.

To the optical resin compsn that obtains, carry out the Draize test equally with embodiment 1, the result is that skin irritation is low, and macula etc. does not take place during use.In addition; Make the optical resin compsn flow into wide for 100mm, depth be 100mm, deeply in 0.5mm framed; Behind ultraviolet perviousness glass covering framed top, use UV irradiation equipment compsn to be solidified with cumulative exposure amount 1300mJ irradiation ultraviolet radiation, make sheet thus.Sheet is transparent.Then, the sheet to making carries out various tests equally with embodiment 1, estimates its characteristic.Evaluation result is shown in table 2.

(embodiment 7)

Compound below the difference weighing:

(A) the multipolymer 48.99g of embodiment 1

(B1) vinylformic acid isooctadecanol ester (ISA) 29.41g

(B2) W 166 mono acrylic ester 19.60g

(Japan Oil Co's system, trade(brand)name " Block レ Application マ one AP-400 ")

(C) polypropyleneglycol diacrylate (PPGDA) 1.99g

(D) 1-hydroxyl-cyclohexyl-phenyl-ketone 0.49g

(Ciba Japan Co., Ltd. system, trade(brand)name " Irgacure-184 "),

Add in the reaction vessel, use stirrer (Three-One Motor) under room temperature (25 ℃), to mix 30 minutes, prepare the optical resin compsn thus.

To the optical resin compsn that obtains, carry out the Draize test equally with embodiment 1, the result is that skin irritation is low, and macula etc. does not take place during use.In addition; Make the optical resin compsn flow into wide for 100mm, depth be 100mm, deeply in 0.5mm framed; Behind ultraviolet perviousness glass covering framed top, use UV irradiation equipment compsn to be solidified with cumulative exposure amount 1300mJ irradiation ultraviolet radiation, make sheet thus.Sheet is transparent.Then, the sheet to making carries out various tests equally with embodiment 1, estimates its characteristic.Evaluation result is shown in table 2.

(embodiment 8)

Compound below the difference weighing:

(A) the multipolymer 47.48g of preparation among the embodiment 1

(B1) 2-EHA (2EHA) 18.33g

(B1) 2-ethylhexyl glycol ether propenoate 18.34g

(Kyoeisha Chemical Co., Ltd.'s system, trade(brand)name " ラ イ ト ア Network リ レ one ト EHDG-AT ")

(B2) polyethylene glycol monomethyl ethermethacrylic acid esters 8.35g

(Hitachi Chemical Co., Ltd.'s system, trade(brand)name " FA-400M ", number of repeat unit 9 are main)

(C) polypropyleneglycol diacrylate (PPGDA) 5.00g

(D) 1-hydroxyl-cyclohexyl-phenyl-ketone 0.50g

(Ciba Japan Co., Ltd. system, trade(brand)name " Irgacure-184 "),

Add in the reaction vessel, use stirrer (Three-One Motor) under room temperature (25 ℃), to mix 30 minutes, prepare the optical resin compsn thus.

To the optical resin compsn that obtains, carry out the Draize test equally with embodiment 1, the result is that skin irritation is low, and macula etc. does not take place during use.In addition, make the optical resin compsn flow into wide for 100mm, depth be 100mm, deeply in 0.5mm framed, cover framed top with ultraviolet perviousness glass after, heating made compsn curing in 3 hours in 70 ℃ air-supply stove, made sheet thus.Sheet is transparent.Then, the sheet to making carries out various tests equally with embodiment 1, estimates its characteristic.Evaluation result is shown in table 2.

(embodiment 9)

Compound below the difference weighing:

(A) the multipolymer 47.49g of preparation among the embodiment 1

(B1) 2-EHA (2EHA) 33.25g

(B2) polyethylene glycol monomethyl ethermethacrylic acid esters 14.26g

(Hitachi Chemical Co., Ltd.'s system, trade(brand)name " FA-400M ", number of repeat unit 9 are main)

(C) polypropyleneglycol diacrylate (PPGDA) 5.00g

(D) dilauroyl peroxide (LPO) 0.40g

Add in the reaction vessel, use stirrer (Three-One Motor) under room temperature (25 ℃), to mix 30 minutes, prepare the optical resin compsn thus.

To the optical resin compsn that obtains, carry out the Draize test equally with embodiment 1, the result is that skin irritation is low, and macula etc. does not take place during use.In addition, make the optical resin compsn flow into wide for 100mm, depth be 100mm, deeply in 0.5mm framed, cover framed top with ultraviolet perviousness glass after, heating made compsn curing in 3 hours in 70 ℃ air-supply stove, made sheet thus.Sheet is transparent.Then, the sheet to making carries out various tests equally with embodiment 1, estimates its characteristic.Evaluation result is shown in table 2.

(comparative example 1)

Compound below the difference weighing:

(A) the multipolymer 47.50g of preparation among the embodiment 1

(B1) 2-EHA (2EHA) 47.50g

(C) 1,6 hexanediol diacrylate (1,6-HxA) 5.00g

(D) 1-hydroxyl-cyclohexyl-phenyl-ketone 0.50g

(Ciba Japan Co., Ltd. system, trade(brand)name " Irgacure-184 "),

Add in the reaction vessel, use stirrer (Three-One Motor) under room temperature (25 ℃), to mix 30 minutes, prepare the optical resin compsn thus.

To the optical resin compsn that obtains, carry out the Draize test equally with embodiment 1, the result is that skin irritation is low, and macula etc. does not take place during use.In addition; Make the optical resin compsn flow into wide for 100mm, depth be 100mm, deeply in 0.5mm framed; Behind ultraviolet perviousness glass covering framed top, use the ultraviolet ray of UV irradiation equipment irradiation 2000mJ that compsn is solidified, make sheet thus.Sheet generation white casse, transparent poor.Then, the sheet to making carries out various tests equally with embodiment 1, estimates its characteristic.Evaluation result is shown in table 3.

(comparative example 2)

Compound below the difference weighing:

(A) the multipolymer 47.50g of preparation among the embodiment 1

(B2) polyethylene glycol monomethyl ethermethacrylic acid esters 47.50g

(Hitachi Chemical Co., Ltd.'s system, trade(brand)name " FA-400M ", number of repeat unit 9 are main)

(C) 1,6 hexanediol diacrylate (1,6-HxA) 5.00g

(D) 1-hydroxyl-cyclohexyl-phenyl-ketone 0.50g

(Ciba Japan Co., Ltd. system, trade(brand)name " Irgacure-184 "),

Add in the reaction vessel, use stirrer (Three-One Motor) under room temperature (25 ℃), to mix 30 minutes, prepare the optical resin compsn thus.

To the optical resin compsn that obtains, carry out the Draize test equally with embodiment 1, the result is that skin irritation is low, and macula etc. does not take place during use.In addition; Make the optical resin compsn flow into wide for 100mm, depth be 100mm, deeply in 0.5mm framed; Behind ultraviolet perviousness glass covering framed top, use the ultraviolet ray of UV irradiation equipment irradiation 5000mJ that compsn is solidified, make sheet thus.Sheet generation white casse, transparent poor.Then, the sheet to making carries out various tests equally with embodiment 1, estimates its characteristic.Evaluation result is shown in table 3.

(comparative example 3)

Compound below the difference weighing:

(A) the multipolymer 47.50g of preparation among the embodiment 1

(B1) 2-EHA (2EHA) 33.25g

(B2 ') vinylformic acid 2-hydroxy methacrylate (HEA) 14.25g

(C) 1,6 hexanediol diacrylate (1,6-HxA) 5.00g

(D) 1-hydroxyl-cyclohexyl-phenyl-ketone 0.50g

(Ciba Japan Co., Ltd. system, trade(brand)name " Irgacure-184 "),

Add in the reaction vessel, use stirrer (Three-One Motor) under room temperature (25 ℃), to mix 30 minutes, prepare the optical resin compsn thus.

To the optical resin compsn that obtains, carry out the Draize test equally with embodiment 1, the result is that skin irritation is high, and macula takes place during use.In addition; Make the optical resin compsn flow into wide for 100mm, depth be 100mm, deeply in 0.5mm framed; Behind ultraviolet perviousness glass covering framed top, use the ultraviolet ray of UV irradiation equipment irradiation 2000mJ that compsn is solidified, make sheet thus.Sheet is transparent.Then, the sheet to making carries out various tests equally with embodiment 1, estimates its characteristic.Evaluation result is shown in table 3.

(comparative example 4)

Compound below the difference weighing:

(A) the multipolymer 47.50g of preparation among the embodiment 1

(B1) 2-EHA (2EHA) 47.50g

(C) polypropyleneglycol diacrylate (PPGDA) 5.00g

(D) 1-hydroxyl-cyclohexyl-phenyl-ketone 0.50g

(Ciba Japan Co., Ltd. system, trade(brand)name " Irgacure-184 "),

Add in the reaction vessel, use stirrer (Three-One Motor) under room temperature (25 ℃), to mix 30 minutes, prepare the optical resin compsn thus.

To the optical resin compsn that obtains, carry out the Draize test equally with embodiment 1, the result is that skin irritation is low, and macula etc. does not take place during use.In addition; Make the optical resin compsn flow into wide for 100mm, depth be 100mm, deeply in 0.5mm framed; Behind ultraviolet perviousness glass covering framed top, use the ultraviolet ray of UV irradiation equipment irradiation 2000mJ that compsn is solidified, make sheet thus.Sheet generation white casse, transparent poor.Then, the sheet to making carries out various tests equally with embodiment 1, estimates its characteristic.Evaluation result is shown in table 3.

(comparative example 5)

Compound below the difference weighing:

(A) the multipolymer 24.88g of preparation among the embodiment 1

(B1) 2-EHA (2EHA) 27.85g

(B2 ') vinylformic acid 2-hydroxy methacrylate (HEA) 11.94g

(C) urethane acrylate (UA1) 34.83g of preparation among the embodiment 1

(D) 1-hydroxyl-cyclohexyl-phenyl-ketone 0.50g

(Ciba Japan Co., Ltd. system, trade(brand)name " Irgacure-184 "),

Add in the reaction vessel, use stirrer (Three-One Motor) under room temperature (25 ℃), to mix 30 minutes, prepare the optical resin compsn thus.

To the optical resin compsn that obtains, carry out the Draize test equally with embodiment 1, the result is that skin irritation is high, and macula takes place during use.In addition; Make the optical resin compsn flow into wide for 100mm, depth be 100mm, deeply in 0.5mm framed; Behind ultraviolet perviousness glass covering framed top, use the ultraviolet ray of UV irradiation equipment irradiation 2000mJ that compsn is solidified, make sheet thus.Sheet is transparent.Then, the sheet to making carries out various tests equally with embodiment 1, estimates its characteristic.Evaluation result is shown in table 3.

(comparative example 6)

Compound below the difference weighing:

(A) the multipolymer 47.00g of preparation among the embodiment 1

(B1) 2-EHA (2EHA) 33.25g

(B2 ') vinylformic acid 2-hydroxy methacrylate (HEA) 14.25g

(C) urethane acrylate (UA2) 5.00g of preparation in above-mentioned 1

(D) 1-hydroxyl-cyclohexyl-phenyl-ketone 0.50g

(Ciba Japan Co., Ltd. system, trade(brand)name " Irgacure-184 "),

Add in the reaction vessel, use stirrer (Three-One Motor) under room temperature (25 ℃), to mix 30 minutes, prepare the optical resin compsn thus.

To the optical resin compsn that obtains, carry out the Draize test equally with embodiment 1, the result is that skin irritation is high, and macula takes place during use.In addition; Make the optical resin compsn flow into wide for 100mm, depth be 100mm, deeply in 0.5mm framed; Behind ultraviolet perviousness glass covering framed top, use the ultraviolet ray of UV irradiation equipment irradiation 2000mJ that compsn is solidified, make sheet thus.Sheet is transparent.Then, the sheet to making carries out various tests equally with embodiment 1, estimates its characteristic.Evaluation result is shown in table 3.

About the above embodiments 1～9 and comparative example 1～6, the main composition and the various evaluation result of optical resin compsn is shown in table 1～3.In addition, "-" expression undetermined in each table.In addition, be illustrated in about the evaluation " G " of moisture-proof safety and do not see white casse in the sheet, sheet is kept the transparency, is in good state.

Table 1

Table 2

Table 3

(embodiment 10)

Present embodiment relates to the making and the evaluation of the liquid crystal indicator that possesses the transparent resin layer that is formed by optical resin compsn of the present invention.The making of liquid crystal indicator is carried out according to following order.At first, in order to form transparent resin layer, lip-deep on 4 limits of the polaroid that AG handled at the liquid crystal display that is attached at 32 inches at diagonal angle in advance attaches the band of thick 0.5mm, wide 5mm respectively, forms framed thus.Then, in this is framed, flow into the optical resin compsn of preparation among the embodiment 2, the soda glass plate of its surface with 32 inches at diagonal angle, thick 2.8mm covered with the mode that does not get into bubble.In addition, the soda glass plate uses the sheet glass that is pre-formed anti-reflection layer on its surface.Then, use the conveyor-type UV irradiation equipment adopted metal halide lamp, with cumulative exposure amount 2000mJ irradiation ultraviolet radiation, resin combination is solidified, form transparent resin layer thus from the top of the anti-reflection layer on soda glass plate surface.As stated, transparent resin layer, soda glass plate and anti-reflection layer on the surface of liquid crystal display, have been stacked gradually.

Then, the liquid crystal display that had before obtained is installed in the basket with back light system and driving circuit, makes liquid crystal indicator.Performance to the liquid crystal indicator made is studied, and the result is the variable color that does not take place by the painted transparent resin layer that causes of resin material, unconfirmedly on the interface of transparent resin layer and sheet glass bad phenomenon such as peels off, floats.In addition, the image deterioration that liquid crystal indicator is not caused by dual reflection is not seen the deterioration in image quality that the deflection by panel causes yet when contacting with apparatus surface.

(comparative example 7)

Use the resin of comparative example 1, likewise be produced on the liquid crystal indicator that has stacked gradually transparent resin layer, soda glass plate and anti-reflection layer on the surface of liquid crystal display with embodiment 10.In the liquid crystal indicator of making, transparent resin layer generation white casse produces the bad phenomenons of picture quality such as display image turns white, brightness reduction.

Can know by above explanation, not violate in the spirit and scope of the present invention that can in wide scope, constitute various embodiment, the present invention is limited in the scope of claim, not restricted by its specific embodiment.

Claims (14)

1. an optical resin compsn is characterized in that, this optical resin compsn contains:

(A) (methyl) acrylic acid series derivative polymer,

(B) 1 functional (methyl) acrylic acid series derivatives monomer and

(C) above (methyl) acrylic acid series verivate of 2 officials ability;

Said (B) 1 functional (methyl) acrylic acid series derivatives monomer contains: (B1) at least a monomer in (methyl) acrylic monomer of formula (1) expression and (B2) to be selected from by number of repeat unit be that polyalkylene oxide base alkyl oxide (methyl) propenoate and number of repeat unit 4 or more is at least a monomer that normal temperature in the group that constitutes of polyalkylene oxide base (methyl) propenoate 4 or more descends the compound that is liquid state;

CH ₂＝CHCO(OC _lH _2l) _mOC _nH _2n+1 (1)

In the formula, l is 2～4 integer, and m is 0 or 1, and n is 8～18 integer.

2. optical resin compsn according to claim 1, wherein said (B) 1 functional (methyl) acrylic acid series derivatives monomer contains (methyl) alkyl acrylate at least.

3. optical resin compsn according to claim 1, wherein said (B) 1 functional (methyl) acrylic acid series derivatives monomer contains polyalkylene oxide base alkyl oxide (methyl) propenoate at least.

4. optical resin compsn according to claim 2, wherein said (methyl) alkyl acrylate has branched structure.

5. optical resin compsn according to claim 3, wherein said polyalkylene oxide base alkyl oxide (methyl) propenoate comprises nine glycol monomethyl ether metacrylic acid esters.

6. optical resin compsn according to claim 4, wherein said (methyl) alkyl acrylate with branched structure comprises 2-EHA.

7. according to each described optical resin compsn in the claim 1～6, wherein said (A) (methyl) acrylic acid series derivative polymer is that carbonatoms is 4～18 alkyl acrylate and the multipolymer with propenoate of hydroxyl.

8. optical resin compsn according to claim 7, wherein said (A) (methyl) acrylic acid series derivative polymer is the multipolymer of 2-EHA and vinylformic acid 2-hydroxy methacrylate.

9. according to each described optical resin compsn in the claim 1～6, it further contains (D) polymerization starter.

10. optical resin compsn according to claim 9, wherein said (D) polymerization starter is a Photoepolymerizationinitiater initiater.

11. optical resin compsn according to claim 10, wherein said Photoepolymerizationinitiater initiater contain at least a material that is selected from the group that is made up of following substances:

(d1) Alpha-hydroxy alkyl phenones based compound,

(d2) the acylphosphine oxide based compound,

(d3) oligomeric (2-hydroxy-2-methyl-1-(4-(1-methyl ethylene) phenyl) acetone), and

(d4) mixture of hydroxyl-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetic acid base-oxyethyl group]-ethyl ester and hydroxyl-phenyl-acetic acid 2-[2-hydroxyl-oxyethyl group]-ethyl ester.

12. according to each described optical resin compsn in the claim 1～6, wherein said (A) (methyl) acrylic acid series derivative polymer has 100000～700000 weight-average molecular weight.

13. a resin material for optical use, it obtains through each described optical resin compsn in the claim 1～6 is solidified.

14. resin material for optical use according to claim 13, it has sheet or membranaceous shape.

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