CN100582131C - Fumaric diester copolymer - Google Patents
Fumaric diester copolymer Download PDFInfo
- Publication number
- CN100582131C CN100582131C CN200610005177A CN200610005177A CN100582131C CN 100582131 C CN100582131 C CN 100582131C CN 200610005177 A CN200610005177 A CN 200610005177A CN 200610005177 A CN200610005177 A CN 200610005177A CN 100582131 C CN100582131 C CN 100582131C
- Authority
- CN
- China
- Prior art keywords
- film
- methyl
- daip
- display optical
- optical film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
A novel fumaric diester copolymer suitable for used in an optical material having excellent heat resistance and transparency is provided. The fumaric diester copolymer comprises a specific fumaric diester residue, and at least one (meth)acrylic ester residue unit selected from a specific (meth)acrylic ester residue unit having an oxetanyl group and a specific (meth)acrylic ester residue unit having a tetrahydrofurfuryl group, and has a number average molecular weight of from 1,000 to 500,000.
Description
Technical field
The present invention relates to novel dimethyl ester polymkeric substance, in more detail, relate to the thermotolerance with excellence, the novel Daip of the transparency.
Background technology
Known homopolymer or the multipolymer that is obtained by dimethyl ester demonstrates the thermotolerance higher than general thermoplastic ethylene's base polymer, is the more excellent resin of the transparency.For example, even the homopolymer that is obtained by fumaric acid diisopropyl ester or fumaric acid two cyclohexyls is not showing softening temperature and second-order transition temperature yet more than 200 ℃ or 200 ℃, be expected to become the material that can be used in the transparent resin of various uses at optical field.(for example, with reference to patent documentation 1 or non-patent literature 1)
[patent documentation 1] JP-B-5-40281 communique (Theterm " JP-B " as used herein meansan " examined Japanese patent publication ")
[non-patent literature 1] big Tianjin grand row work, following material,, Vol.2, No.12 in 2002 are issued, (the 70th～74 page)
But, in patent documentation 1 or the non-patent literature 1 record contain dimethyl ester residue unit and have (methyl) acrylate residue unit of epoxypropyl (オ キ セ タ ニ Le) and/or have the unitary multipolymer of (methyl) acrylate residue of tetrahydrofurfuryl (テ ト ラ ヒ De ロ Off Le Off リ Le).
Summary of the invention
Therefore, the object of the present invention is to provide the thermotolerance with excellence, the novel Daip of the transparency.
Present inventors are for solving the novel Daip that found that of above-mentioned problem further investigation, so that finished the present invention.
That is, main points of the present invention are following (1)～(14)
(1) a kind of Daip, it is characterized in that, this Daip contain the dimethyl ester residue unit of useful following general formula (1) expression and unitary at least 1 (methyl) acrylate of (methyl) acrylate residue residue of representing with (methyl) acrylate residue unit with epoxypropyl of following general formula (2) expression and with following general formula (3) with tetrahydrofurfuryl unitary, its number-average molecular weight is 1000～500000
(R here,
1And R
2Separately independently, the expression carbonatoms is that 1～6 straight chain shape alkyl, branch-like alkyl or carbonatoms are 3～6 cyclic alkyl.)
(R here,
3Expression hydrogen, methyl, R
4Expression hydrogen, carbonatoms are 1～4 straight chain shape alkyl, branch-like alkyl, n=1 or 2.)
(R here,
5Expression hydrogen, methyl, R
6Expression hydrogen, carbonatoms are 1～4 straight chain shape alkyl, branch-like alkyl.)；
(2) according to the Daip of above-mentioned (1) record, it is characterized in that dimethyl ester residue unit is fumaric acid diisopropyl ester residue unit;
(3) Daip of putting down in writing according to above-mentioned (1), it is characterized in that (methyl) acrylate residue unit is vinylformic acid-3-ethyl-3-epoxypropyl methyl ester residue, methacrylic acid-3-ethyl-3-epoxypropyl methyl ester residue, tetrahydrofurfuryl acrylate residue, tetrahydrofurfuryl methacrylate residue;
(4) the crosslinked body of a kind of dimethyl ester is characterized in that, the Daip of any record in above-mentioned (1)～(3) is crosslinked and obtain;
(5) a kind of film, this film contain the crosslinked body of the Daip of record in above-mentioned (4);
(6) a kind of display optical film is characterized in that, this display optical film is, contains the film of above-mentioned (5) record, and thickness is 10～700 μ m, and the gel fraction by the insoluble composition measurement of tetrahydrofuran (THF) is the cross linking membrane more than 10% or 10%;
(7) according to the display optical film of above-mentioned (6) record, it is characterized in that the total light transmittance of this blooming is more than 85% or 85%, the light penetration under 400nm is more than 80% or 80%, and the mist value is below 2% or 2%;
(8) display optical film of putting down in writing according to above-mentioned (6) or (7), it is characterized in that, the thickness deviation of this blooming is 10 μ m or below the 10 μ m, and the phase differential of measuring from the front of film is 10nm or below the 10nm, and the phase differential deviation in the face is 5nm or below the 5nm;
According to the display optical film of any record in above-mentioned (6)～(8), it is characterized in that (9) this blooming is the one or more layers of gas-barrier layer of lamination and constituting at least;
According to the display optical film of any record in above-mentioned (6)～(9), it is characterized in that (10) this blooming is the one or more layers of hard coat of lamination and constituting at least;
(11) a kind of polaroid protective film is characterized in that, this polarizing plate protective film contains the display optical film of any record in above-mentioned (6)～(10);
(12) a kind of phase retardation film is characterized in that, this phase retardation film contains the display optical film of any record in above-mentioned (6)～(10);
(13) a kind of touch panel film is characterized in that, this touch panel film contains the display optical film of any record in above-mentioned (6)～(10);
(14) a kind of flat-panel monitor film substrate is characterized in that, this flat-panel monitor contains the display optical film of any record in above-mentioned (6)～(10) with the film substrate;
(15) a kind of liquid-crystal display plastic film substrate is characterized in that, this liquid-crystal display contains the display optical film of any record in above-mentioned (6)～(10) with the plastic film substrate.
Description of drawings
Fig. 1 is that the Daip that obtained by embodiment 1 is at CDCl
3In
1The H-NMR spectrogram.
Fig. 2 is that the Daip that obtained by embodiment 3 is at CDCl
3In
1The H-NMR spectrogram.
Embodiment
Below, explain the present invention.
Daip of the present invention be contain the dimethyl ester residue unit of useful certain formula (1) expression and (methyl) acrylate residue unit of representing with (methyl) acrylate residue unit with epoxypropyl of certain formula (2) expression and with certain formula (3) with tetrahydrofurfuryl in the unitary multipolymer of at least one (methyl) acrylate residue.Here, with the R in the dimethyl ester residue unit of general formula (1) expression
1And R
2Independent separately, the expression carbonatoms is that 1～6 straight chain shape alkyl, branch-like alkyl or carbonatoms are 3～6 cyclic alkyl, it as carbonatoms 1～6 straight chain shape alkyl, can enumerate, for example, methyl, ethyl, propyl group, normal-butyl, amyl group, hexyl etc., it as carbonatoms 1～6 branch-like alkyl, can enumerate, for example, sec.-propyl, isobutyl-, sec-butyl, the tertiary butyl etc., it as carbonatoms 3～6 cyclic alkyl, can enumerate, for example, cyclopropyl, cyclobutyl, cyclohexyl etc.Wherein, from the viewpoint of the Daip excellent heat resistance that obtains, preferred sec.-propyl, the tertiary butyl, cyclohexyl etc., preferred especially sec.-propyl.
And, as concrete dimethyl ester residue unit with general formula (1) expression, can enumerate, for example, dimethyl fumarate residue, DEF residue, fumaric acid dipropyl residue, di n butyl fumarate residue, fumaric acid diamyl ester residue, fumaric acid dihexyl residue, fumaric acid diisopropyl ester residue, fumaric acid diisobutyl ester residue, fumaric acid di-secondary butyl ester residue, fumaric acid di tert butyl carbonate residue, fumaric acid two ring propyl ester residues, fumaric acid two ring butyl ester residues, fumaric acid two cyclohexyl residues etc.Wherein, preferred fumaric acid diisopropyl ester residue, fumaric acid di tert butyl carbonate residue, fumaric acid two cyclohexyl residues etc., preferred especially fumaric acid diisopropyl ester residue.
In the Daip of the present invention with the R in (methyl) acrylate residue unit with epoxypropyl of general formula (2) expression
3Be hydrogen, methyl, R
4For hydrogen, carbonatoms are 1～4 straight chain shape alkyl, branch-like alkyl, n is 1 or 2.As R
4In carbonatoms be that 1～4 straight chain shape alkyl can be enumerated, for example, methyl, ethyl, propyl group, normal-butyl etc. are 1～4 branch-like alkyl as carbonatoms, can enumerate, for example, sec.-propyl, isobutyl-, sec-butyl, the tertiary butyl etc.
Also have, as concrete (methyl) acrylate residue unit with epoxypropyl with general formula (2) expression, can enumerate, for example, vinylformic acid-3-epoxypropyl methyl ester residue, vinylformic acid-3-methyl-3-epoxypropyl methyl ester residue, vinylformic acid-3-ethyl-3-epoxypropyl methyl ester residue, vinylformic acid-3-propyl group-3-epoxypropyl methyl ester residue, vinylformic acid-3-normal-butyl-3-epoxypropyl methyl ester residue, vinylformic acid-3-sec.-propyl-3-epoxypropyl methyl ester residue, vinylformic acid-3-isobutyl--3-epoxypropyl methyl ester residue, vinylformic acid-3-sec-butyl-3-epoxypropyl methyl ester residue, vinylformic acid-3-the tertiary butyl-3-epoxypropyl methyl ester residue, vinylformic acid-3-epoxypropyl ethyl ester residue, vinylformic acid-3-methyl-3-epoxypropyl ethyl ester residue, vinylformic acid-3-ethyl-3-epoxypropyl ethyl ester residue, vinylformic acid-3-propyl group-3-epoxypropyl ethyl ester residue, vinylformic acid-3-normal-butyl-3-epoxypropyl ethyl ester residue, vinylformic acid-3-sec.-propyl-3-epoxypropyl ethyl ester residue, vinylformic acid-3-isobutyl--3-epoxypropyl ethyl ester residue, vinylformic acid-3-sec-butyl-3-epoxypropyl ethyl ester residue, vinylformic acid-3-the tertiary butyl-3-epoxypropyl ethyl ester residue, methacrylic acid-3-epoxypropyl methyl ester residue, methacrylic acid-3-methyl-3-epoxypropyl methyl ester residue, methacrylic acid-3-ethyl-3-epoxypropyl methyl ester residue, methacrylic acid-3-propyl group-3-epoxypropyl methyl ester residue, methacrylic acid-3-normal-butyl-3-epoxypropyl methyl ester residue, methacrylic acid-3-sec.-propyl-3-epoxypropyl methyl esters residue, methacrylic acid-3-isobutyl--3-epoxypropyl methyl ester residue, methacrylic acid-3-sec-butyl-3-epoxypropyl methyl ester residue, methacrylic acid-3-the tertiary butyl-3-epoxypropyl methyl ester residue, methacrylic acid-3-epoxypropyl ethyl ester residue, methacrylic acid-3-methyl-3-epoxypropyl ethyl ester residue, methacrylic acid-3-ethyl-3-epoxypropyl ethyl ester residue, methacrylic acid-3-propyl group-3-epoxypropyl ethyl ester residue, methacrylic acid-3-normal-butyl-3-epoxypropyl ethyl ester residue, methacrylic acid-3-sec.-propyl-3-epoxypropyl ethyl ester residue, methacrylic acid-3-isobutyl--3-epoxypropyl ethyl ester residue, methacrylic acid-3-sec-butyl-3-epoxypropyl ethyl ester residue, methacrylic acid-3-the tertiary butyl-3-epoxypropyl ethyl ester residue etc.
In addition, the unitary R of (methyl) acrylate residue in the Daip of the present invention with tetrahydrofurfuryl with general formula (3) expression
5Be hydrogen, methyl, R
6For hydrogen, carbonatoms 1～4 straight chain shape alkyl, branch-like alkyl.As R
6In carbonatoms be 1～4 straight chain shape alkyl, can enumerate, for example, methyl, ethyl, propyl group, normal-butyl etc. are 1～4 branch-like alkyl as carbonatoms, can enumerate, for example, sec.-propyl, isobutyl-, sec-butyl, the tertiary butyl etc.
And, (methyl) acrylate residue unit as the concrete tetrahydrofurfuryl of using general formula (3) expression, can enumerate, for example, tetrahydrofurfuryl acrylate residue, vinylformic acid-2-methyl tetrahydrochysene chaff ester residue, acrylic acid-2-ethyl tetrahydrochysene chaff ester residue, vinylformic acid-2-propyl group tetrahydrochysene chaff ester residue, vinylformic acid-2-normal-butyl tetrahydrochysene chaff ester residue, vinylformic acid-2-sec.-propyl tetrahydrochysene chaff ester residue, vinylformic acid-2-isobutyl-tetrahydrochysene chaff ester residue, vinylformic acid-2-sec-butyl tetrahydrochysene chaff ester residue, vinylformic acid-2-tertiary butyl tetrahydrochysene chaff ester residue, the tetrahydrofurfuryl methacrylate residue, methacrylic acid-2-methyl tetrahydrochysene chaff ester residue, methacrylic acid-2-ethyl tetrahydrochysene chaff ester residue, methacrylic acid-2-propyl group tetrahydrochysene chaff ester residue, methacrylic acid-2-normal-butyl tetrahydrochysene chaff ester residue, methacrylic acid-2-sec.-propyl tetrahydrochysene chaff ester residue, methacrylic acid-2-isobutyl-tetrahydrochysene chaff ester residue, methacrylic acid-2-sec-butyl tetrahydrochysene chaff ester residue, methacrylic acid-2-tertiary butyl tetrahydrochysene chaff ester residue etc.
And, in these (methyl) acrylate residue unit, from obtaining the viewpoint of thermotolerance, Daip that the transparency is excellent, preferably use vinylformic acid-3-ethyl-3-epoxypropyl methyl esters residue, methacrylic acid-3-ethyl-3-epoxypropyl methyl esters residue, tetrahydrofurfuryl acrylate residue, tetrahydrofurfuryl methacrylate residue.
Dimethyl ester residue unit in the Daip of the present invention with general formula (1) expression, with at least one (methyl) in (methyl) acrylate residue unit of representing with (methyl) acrylate residue unit with epoxypropyl of general formula (2) expression with general formula (3) with tetrahydrofurfuryl as long as the unitary blending ratio of acrylate residue can obtain Daip of the present invention, any blending ratio can, wherein, from obtaining thermotolerance, the viewpoint of the Daip that the transparency is excellent, preferred dimethyl ester residue unit is 50～99 moles of %, at least one (methyl) acrylate residue unit that has (methyl) acrylate residue unit of epoxypropyl and have in (methyl) acrylate residue unit of tetrahydrofurfuryl is 50～1 moles of %, and preferred especially dimethyl ester residue unit is 80～99 moles of %, at least one (methyl) acrylate residue unit that has (methyl) acrylate residue unit of epoxypropyl and have in (methyl) acrylate residue unit of tetrahydrofurfuryl is 20～1 moles of %.
Number-average molecular weight with the Daip of the present invention that passes through polystyrene conversion of gel permeation chromatography is 1000～500000, preferred 10000～100000.During number-average molecular weight less than 1000, the intensity of Daip is insufficient.On the other hand, number-average molecular weight surpasses at 500000 o'clock, the viscosity height of Daip, and operability worsens.
Manufacture method as Daip of the present invention, as long as can obtain containing the dimethyl ester residue unit of useful general formula (1) expression, with the unitary Daip of at least one (methyl) acrylate residue in (methyl) acrylate residue unit of representing with (methyl) acrylate residue unit with epoxypropyl of general formula (2) expression and with general formula (3) with tetrahydrofurfuryl, can use any manufacture method, wherein, from the viewpoint that can easily make, preferred use will contain the dimethyl ester of useful following general formula (4) expression, carry out free-radical polymerized method with (methyl) acrylate of representing with following general formula (5) and with at least 1 (methyl) acrylate in (methyl) acrylate of following general formula (6) expression with tetrahydrofurfuryl with epoxypropyl.
(R here,
7And R
8Separately independently, the expression carbonatoms is that 1～6 straight chain shape alkyl, branch-like alkyl or carbonatoms are 3～6 cyclic alkyl.)
(R here,
9Expression hydrogen, methyl, R
10Expression hydrogen, carbonatoms are 1～4 straight chain shape alkyl, branch-like alkyl, p=1 or 2.)
(R here,
11Expression hydrogen, methyl, R
12Expression hydrogen, carbonatoms are 1～4 straight chain shape alkyl, branch-like alkyl.)
R in the dimethyl ester of using general formula (4) expression that uses in the manufacture method of Daip of the present invention
7And R
8Independent separately, the expression carbonatoms is that 1～6 straight chain shape alkyl, branch-like alkyl or carbonatoms are 3～6 cyclic alkyl, it as carbonatoms 1～6 straight chain shape alkyl, can enumerate, for example, methyl, ethyl, propyl group, normal-butyl, amyl group, hexyl etc., it as carbonatoms 1～6 branch-like alkyl, can enumerate, for example, sec.-propyl, isobutyl-, sec-butyl, the tertiary butyl etc., it as carbonatoms 3～6 cyclic alkyl, can enumerate, for example, cyclopropyl, cyclobutyl, cyclohexyl etc.Wherein, the viewpoint of calm facile Daip, preferred sec.-propyl, the tertiary butyl, cyclohexyl etc., preferred especially sec.-propyl.
And, as concrete dimethyl ester with general formula (4) expression, can enumerate, for example, dimethyl fumarate, DEF, fumaric acid dipropyl, di n butyl fumarate, fumaric acid diamyl ester, fumaric acid dihexyl, fumaric acid diisopropyl ester, fumaric acid diisobutyl ester, fumaric acid di-secondary butyl ester, fumaric acid di tert butyl carbonate, fumaric acid two ring propyl ester, fumaric acid two ring butyl esters, fumaric acid two cyclohexyls etc.Wherein, preferred fumaric acid diisopropyl ester, fumaric acid di tert butyl carbonate, fumaric acid two cyclohexyls etc., preferred especially fumaric acid diisopropyl ester.
Use in the manufacture method of Daip of the present invention with the R in (methyl) acrylate of general formula (5) expression with epoxypropyl
9Be hydrogen, methyl, R
10For hydrogen, carbonatoms are 1～4 straight chain shape alkyl, branch-like alkyl, p is 1 or 2.As R
10In carbonatoms be that 1～4 straight chain shape alkyl can be enumerated, for example, methyl, ethyl, propyl group, normal-butyl etc. are 1～4 branch-like alkyl as carbonatoms, can enumerate, for example, sec.-propyl, isobutyl-, sec-butyl, the tertiary butyl etc.
And, as concrete (methyl) acrylate with epoxypropyl with general formula (5) expression, can enumerate, for example, vinylformic acid-3-epoxypropyl methyl ester, vinylformic acid-3-methyl-3-epoxypropyl methyl esters, vinylformic acid-3-ethyl-3-epoxypropyl methyl esters, vinylformic acid-3-propyl group-3-epoxypropyl methyl esters, vinylformic acid-3-normal-butyl-3-epoxypropyl methyl ester, vinylformic acid-3-sec.-propyl-3-epoxypropyl methyl ester, vinylformic acid-3-isobutyl--3-epoxypropyl methyl ester, vinylformic acid-3-sec-butyl-3-epoxypropyl methyl ester, vinylformic acid-3-the tertiary butyl-3-epoxypropyl methyl ester, vinylformic acid-3-epoxypropyl ethyl ester, vinylformic acid-3-methyl-3-epoxypropyl ethyl ester, vinylformic acid-3-ethyl-3-epoxypropyl ethyl ester, vinylformic acid-3-propyl group-3-epoxypropyl ethyl ester, vinylformic acid-3-normal-butyl-3-epoxypropyl ethyl ester, vinylformic acid-3-sec.-propyl-3-epoxypropyl ethyl ester, vinylformic acid-3-isobutyl--3-epoxypropyl ethyl ester, vinylformic acid-3-sec-butyl-3-epoxypropyl ethyl ester, vinylformic acid-3-the tertiary butyl-3-epoxypropyl ethyl ester, methacrylic acid-3-epoxypropyl methyl ester, methacrylic acid-3-methyl-3-epoxypropyl methyl ester, methacrylic acid-3-ethyl-3-epoxypropyl methyl ester, methacrylic acid-3-propyl group-3-epoxypropyl methyl ester, methacrylic acid-3-normal-butyl-3-epoxypropyl methyl ester, methacrylic acid-3-sec.-propyl-3-epoxypropyl methyl ester, methacrylic acid-3-isobutyl--3-epoxypropyl methyl ester, methacrylic acid-3-stretches butyl-3-epoxypropyl methyl ester, methacrylic acid-3-the tertiary butyl-3-epoxypropyl methyl ester, methacrylic acid-3-epoxypropyl ethyl ester, methacrylic acid-3-methyl-3-epoxypropyl ethyl ester, methacrylic acid-3-ethyl-3-epoxypropyl ethyl ester, methacrylic acid-3-propyl group-3-epoxypropyl ethyl ester, methacrylic acid-3-normal-butyl-3-epoxypropyl ethyl ester, methacrylic acid-3-sec.-propyl-3-epoxypropyl ethyl ester, methacrylic acid-3-isobutyl--3-epoxypropyl ethyl ester, methacrylic acid-3-sec-butyl-3-epoxypropyl ethyl ester, methacrylic acid-3-the tertiary butyl-3-epoxypropyl ethyl ester etc.Wherein, preferably use vinylformic acid-3-ethyl-3-epoxypropyl methyl ester, methacrylic acid-3-ethyl-3-epoxypropyl methyl ester.
In addition, the R that uses in the manufacture method of Daip of the present invention with (methyl) acrylate of general formula (6) expression with tetrahydrofurfuryl
11Be hydrogen, methyl, R
12For hydrogen, carbonatoms 1～4 straight chain shape alkyl, branch-like alkyl.As R
12In carbonatoms be 1～4 straight chain shape alkyl, can enumerate, for example, methyl, ethyl, propyl group, normal-butyl etc. are 1～4 branch-like alkyl as carbonatoms, can enumerate, for example, sec.-propyl, isobutyl-, sec-butyl, the tertiary butyl etc.
And, as concrete (methyl) acrylate with tetrahydrofurfuryl with general formula (6) expression, can enumerate, for example, tetrahydrofurfuryl acrylate, vinylformic acid-2-methyl tetrahydrochysene chaff ester, acrylic acid-2-ethyl tetrahydrochysene chaff ester, vinylformic acid-2-propyl group tetrahydrochysene chaff ester, vinylformic acid-2-normal-butyl tetrahydrochysene chaff ester, vinylformic acid-2-sec.-propyl tetrahydrochysene chaff ester, vinylformic acid-2-isobutyl-tetrahydrochysene chaff ester, vinylformic acid-2-sec-butyl tetrahydrochysene chaff ester, vinylformic acid-2-tertiary butyl tetrahydrochysene chaff ester, tetrahydrofurfuryl methacrylate, methacrylic acid-2-methyl tetrahydrochysene chaff ester, methacrylic acid-2-ethyl tetrahydrochysene chaff ester, methacrylic acid-2-propyl group tetrahydrochysene chaff ester, methacrylic acid-2-normal-butyl tetrahydrochysene chaff ester, methacrylic acid-2-sec.-propyl tetrahydrochysene chaff ester, methacrylic acid-2-isobutyl-tetrahydrochysene chaff ester, methacrylic acid-2-sec-butyl tetrahydrochysene chaff ester, methacrylic acid-2-tertiary butyl tetrahydrochysene chaff ester etc.Wherein, preferably use tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate.
As by will be with the dimethyl ester of following general formula (4) expression, carry out free-radical polymerized method when making Daip of the present invention with at least 1 (methyl) acrylate in (methyl) acrylate of representing with (methyl) acrylate with epoxypropyl of following general formula (5) expression and with following general formula (6) with tetrahydrofurfuryl, have no particular limits, can be with known free-radical polymerized method manufacturing, can enumerate, for example, in aqueous medium, use the suspension copolymerization method of suspension agent, emulsion copolymerization method, use the solution copolymerization method of organic solvents such as toluene, do not use the bulk copolymerization method of solvent etc.
As carrying out free-radical polymerized fashionable polymerization starter, can enumerate, for example, benzoyl peroxide, lauroyl peroxide, peroxidation decoyl, acetyl peroxide, ditertiary butyl peroxide, tertiary butyl cumyl peroxide, dicumyl peroxide, peroxide acetic acid butyl ester, peroxidized t-butyl perbenzoate, the tertiary butyl are crossed butyl trimethylacetic acid ester organo-peroxides such as (tert-Block チ Le パ one Block チ Le ピ バ レ one ト); 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (2-butyronitrile), 2,2 '-Diisopropyl azodicarboxylate, dimethyl-2, the two isobutyrates, 1 of 2 '-azo, the two azo-initiators such as (hexanaphthenes-1-nitrile) of 1 '-azo.
As carrying out the fashionable operable solvent of radical polymerization, have no particular limits, can enumerate, for example, aromatic series kind solvents such as benzene,toluene,xylene; Alcoholic solvents such as methyl alcohol, ethanol, propyl alcohol, butanols; Hexanaphthene; Diox; Tetrahydrofuran (THF); Acetone; Methylethylketone; Dimethyl formamide; Iso Butyl Acetate, water etc. also can use their mixed solvent.
Carry out the polymerization temperature when free-radical polymerized, can look the decomposition temperature of polymerization starter and suitably set, preferably carry out usually 40～150 ℃ scope.
In Daip of the present invention, in the scope that does not depart from purpose of the present invention, can also contain other monomer residue unit, as other monomer residue unit, can enumerate, for example, alkene residues such as ethene residue, propylene residues, 1-butylene base residue; Alkyl-acrylates residues such as methyl acrylate residue, ethyl propenoate residue, butyl acrylate residue; Alkyl methacrylate residues such as methyl methacrylate residue, Jia Jibingxisuanyizhi residue, butyl methacrylate residue; Vinyl aromatic hydrocarbon residues such as vinylbenzene residue, alpha-methyl styrene residue; Vinyl carboxylates class residues such as vinyl acetate residue, propionate residue, trimethylacetic acid vinyl acetate residue; Vinyl ethers residues such as methylvinylether residue, ethyl vinyl ether residue, butyl vinyl ether residue; N-substituted maleimide residues such as N-methyl maleimide residue, N-cyclohexyl maleimide residue, N-phenylmaleimide residue; The vinyl cyanide residue; Methacrylonitrile residue etc.
Daip of the present invention is from the excellent more viewpoint of dimensional stability, resistance, preferably make crosslinked body Daip is crosslinked and the Daip that obtains, especially preferably make the crosslinked body of Daip that the epoxypropyl in the Daip and at least one open loop in the tetrahydrofurfuryl are obtained.Method when making crosslinked body, as long as can obtain the crosslinked body of Daip, then can use any method, wherein, the viewpoint of the crosslinked body that is easy to get is calmly preferably added after the crosslinking accelerator in Daip, make the method for the crosslinked body of Daip by rayed, for example, can use, carry out rayed at the state that Daip and crosslinking accelerator is dissolved in solvent and make the method for crosslinked body; Formed body is made in the fusion in solvent with Daip and crosslinking accelerator, for example makes after the film, carries out rayed and makes method of crosslinked body etc.
The crosslinking accelerator that uses when making crosslinked body, so long as crosslinking accelerator gets final product, have no particular limits, can use known substances, can enumerate, for example, aromatic series diazonium salts such as phenyl diazonium hexafluoro-antimonic acid (acid of Off エ ニ Le ジ ア ゾ ニ ウ system ヘ キ サ Off Le オ ロ ア Application チ モ Application), phenyl diazonium phosphofluoric acid, phenyl diazonium Tetrafluoroboric acid; Aromatic series salt compounded of iodine such as phenylbenzene iodine hexafluoro-antimonic acid, phenylbenzene iodine phosphofluoric acid, phenylbenzene iodine Tetrafluoroboric acid; Aromatic series sulfonium salts such as triphenylsulfonium hexafluoro-antimonic acid, triphenyl phosphofluoric acid, triphenylsulfonium Tetrafluoroboric acid; (2,4-cyclopentadiene-1-yl) [(1-methylethyl) benzene]-iron complex compound; Adjacent nitrobenzyl silyl ether-aluminium coordination compound etc.The addition of the crosslinking accelerator of this moment is with respect to the preferred 0.1～10g of 100g Daip, preferred especially 0.2～5g.
The light that uses when making crosslinked body has no particular limits, can enumerate, for example, mercuryvapour lamp, metal halide lamp, Excimer lamp etc.
Daip of the present invention is the novel Daip with thermotolerance, transparency, can be used in various formed materials such as film, sheet, injection moulding product.
In addition, Daip of the present invention is crosslinked and the crosslinked body Daip that obtains can be used in various formed materials such as film, sheet, moulding product, wherein, preferably be used in film, more preferably be used in blooming, especially preferably be used in display optical film.
By the display optical film that the crosslinked body with the crosslinked Daip that obtains of Daip forms, preferred 10～700 μ m of thickness, preferred especially 50～500 μ m are more preferably the scope of 100～300 μ m.
In addition, display optical film is more preferably more than 30% or 30%, more than preferred especially 50% or 50% by more than the gel fraction of the insoluble composition measurement of tetrahydrofuran (THF) preferred 10% or 10%.In addition, said here gel fraction is to represent as the index of the degree of crosslinking of display optical film.
As the manufacture method of display optical film, as long as can obtain display optical film, can use any method, can enumerate, for example, and by with Daip membranization of the present invention, the method that the crosslinked membranization of this film is made; Daip of the present invention is made manufacture method of cross linking membrane etc. after crosslinked, wherein, from the viewpoint of display optical film that can the quality bills of materials excellence, preferably by with Daip membranization of the present invention, the method that the crosslinked membranization of this film is made.
As method with Daip system of the present invention membranization, can use as methods such as the common extrusion by melting of making the method for film and being known, solution casting (キ ヤ ス ト) methods, wherein, from obtaining the film that particularly optical characteristics, thermotolerance, surface property etc. are excellent, the viewpoint of display optical film, preferably by the solution casting manufactured.
Here, so-called solution casting method is to obtain the method for film after resin solution (being commonly referred to rubber cement) curtain coating is on support substrate by the heating evaporation solvent.As the method for curtain coating, can use, for example, T pattern method, scraper plate method, rod are coated with method, rolling method, scraper coating method etc., industrial the most commonly used be that rubber cement is extruded method into band shape or tubular continuously on support substrate from mould.In addition, as the support substrate that uses glass substrate, stainless steel or iron plate plastic bases such as metal substrate, polyethylene terephthalate such as (Off エ ロ タ イ プ) etc. are for example arranged.Industrial, for making the blooming of superficiality, optics uniformity height excellence continuously, the preferred metal substrate that the surface is carried out mirror polish processing that uses.
In addition,, can enumerate, for example, carry out crosslinked method by electron rays, light and/or heat about the method for crosslinked membranization.
As carrying out crosslinked method, can use normally used electron beam irradiation device by electron rays.And, excellent more for making crosslinked reaction efficiency at this moment, the preferred for example crosslinking coagents such as polyfunctional vinyl compound such as three vinylformic acid TriMethylolPropane(TMP)s, triallyl cyanurate that use.In addition, when adopting electron rays crosslinked, the preferred 5～500kGy of the exposure intensity of electron rays, preferred especially 10～100kGy.From the excellent especially viewpoint of cross-linking efficiency, adopt the crosslinked display optical film that can obtain excellent heat resistance of this electron rays.
As carrying out crosslinked method by light, can enumerate, for example,,, can enumerate the method that heats merely as carry out crosslinked method by heat with the method as light source such as mercuryvapour lamp, metal halide lamp, Excimer lamp.
In addition, from crosslinked, the efficient crosslinked possibility that becomes more equably, and obtain the display optical film of excellent quality, preferably when crosslinked membranization, use crosslinking accelerator, as crosslinking accelerator, can enumerate, for example, aromatic series diazonium salts such as phenyl diazonium hexafluoro-antimonic acid, phenyl diazonium phosphofluoric acid, phenyl diazonium Tetrafluoroboric acid; Aromatic series salt compounded of iodine such as phenylbenzene iodine hexafluoro-antimonic acid, phenylbenzene iodine phosphofluoric acid, phenylbenzene iodine Tetrafluoroboric acid; Aromatic series sulfonium salts such as triphenylsulfonium hexafluoro-antimonic acid, triphenyl phosphofluoric acid, triphenylsulfonium Tetrafluoroboric acid; 1-benzyl-2-cyanopyridine hexafluoro-antimonic acid, 1-benzyl-2-cyanopyridine phosphofluoric acid, 1-benzyl-aromatic series ammonium salts such as 2-cyanopyridine Tetrafluoroboric acid; Aromatic series microcosmic salts such as ethyl triphenyl phosphorus tetrafluoro metaantimmonic acid; (2,4-cyclopentadiene-1-yl) [(1-methylethyl) benzene]-iron complex compound; Adjacent nitrobenzyl silyl ether-aluminium coordination compound etc.The addition of the crosslinking accelerator of this moment is with respect to preferred 0.1～10 weight part of 100 weight part Daips, preferred especially 0.2～5 weight part.
Make from the transparency, the quality viewpoint of excellent display optical film especially, more than the total light transmittance of display optical film preferred 85% or 85%, more than preferred especially 90% or 90%.In addition, more than the light transmission rate preferred 80% or 80% to the light of 400nm, be more preferably more than 85% or 85%, more than preferred especially 90% or 90%.In addition, below the mist value preferred 2% or 2%, below preferred especially 1% or 1%.
From the viewpoint of the display optical film that makes the display quality excellence, display optical film is from the positive preferred 10nm of phase differential that measures of film or below the 10nm, preferred especially 5nm or below the 5nm.The preferred 5nm of phase differential deviation in the face or below the 5nm, preferred especially 3nm or below the 3nm.The preferred homogeneous of film thickness, preferred 10 μ m of thickness deviation or below the 10 μ m are more preferably 5 μ m or below the 5 μ m, preferred especially 3 μ m or below the 3 μ m.
Because the deterioration of the indicating meter that moisture under atmospheric environment or oxidation cause, display optical film is the one or more layers of gas-barrier layer of lamination at least preferably in order to prevent.Can enumerate as this gas-barrier layer, for example, inorganic layers such as silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, tantalum oxide, aluminium film; Organic film such as polyvinyl alcohol, polyolefine, particularly, from make optical characteristics, gas barrier property, for the display optical film of the meticulous very important excellent in dimensional stability of demonstration of height, preferred inorganic layer, preferred especially silicon oxide, silicon nitride, silicon oxynitride.In addition, the thickness of gas-barrier layer, at the preferred 1～1000nm of the occasion of mineral membrane, preferred especially 10～300nm.In the occasion of organic layer, preferred 0.1～100 μ m, preferred especially 1～50 μ m.These gas-barrier layers can be with organic layer and inorganic layer laminationization, multiple stratification.Gas-barrier layer can pass through known method such as evaporation, sputter, PECVD, CatCVD, coating or lamination and form.
With the superficiality that improves film, traumatic resistance, resistance when TFT forms is purpose, and display optical film preferably has one or more layers of hard coat at least.Can enumerate as this hard coat, for example, contain the layer of silicon resinoid, acrylic resin, silicon Acrylote resinoid, ultraviolet curing resin, the hard coating agent of polyurethanes, these can use one or more.Wherein, from the viewpoint of the display optical film that makes the transparency, traumatic resistance, resistance excellence, preferably with the hard coat that forms by the ultraviolet hardening coating agent.As the ultraviolet hardening coating agent, can enumerate, for example, ultraviolet hardening urethane acrylate, ultraviolet hardening epoxy acrylate, ultraviolet hardening (gathering) ester acrylate, ultraviolet hardening trimethylene oxide etc.Preferred 0.1～100 μ m of the thickness of hard coat, more preferred 1～50 μ m, preferred especially 2～20 μ m.
In addition, display optical film can carry out the primary coat processing between this display optical film and gas-barrier layer and/or hard coat.
For improving thermostability or light stability, display optical film can also contain oxidation inhibitor, photostabilizer.As this oxidation inhibitor, can enumerate, for example, Hinered phenols antioxidant, Phosphorus oxidation inhibitor, sulfur type antioxidant, lactone oxidation inhibitor, amine antioxidants, azanol kind antioxidant, vitamin-E kind antioxidant, other oxidation inhibitor.In addition,, can enumerate as this photostabilizer, for example, hindered amine light stabilizer etc.These oxidation inhibitor, photostabilizer can use separately separately, also can distinguish simultaneously and use.
In addition, be purpose with deterioration of preventing liquid crystalline cpd etc., display optical film can also contain UV light absorber, as this UV light absorber, can optionally add UV light absorber such as benzotriazole, benzophenone, triazine, benzoic ether.These UV light absorber also can be a kind of or plant more than be used in combination.
Have again, in the scope that does not exceed purport of the present invention, display optical film can also add other polymkeric substance, tensio-active agent, polymer electrolyte, electroconductibility coordination compound, mineral filler, pigment, dyestuff, antistatic agent, anti, lubricant etc.
Display optical film can be used as polaroid protective film, phase retardation film, touch panel film, flat-panel monitor film substrate, liquid-crystal display plastic film substrate use.
As polaroid protective film, for the polaroid that for example contains polyvinyl alcohol iodine class, for protecting its surface, can be on its two sides or one side this display optical film of fitting use.
As phase retardation film, can carry out unidirectional or two-way stretch is processed and made to this display optical film.As drawing process, can enumerate, known uniaxial extension method, for example, adopt tenter machine tensile method, by the rolling press calendering tensile method, between roller tensile method, unsupported width unilateral stretching method, Fixed width unilateral stretching method etc., as the two-way stretch method, can enumerate, for example, by tenter machine tensile method, two-way stretch method in turn, the method for two-way stretch simultaneously etc.
Can be used as the film use that formation is touched the face panel display as the touch panel film.Its using method has no particular limits, for example, in the occasion of impedance type touch panel, can be by on this display optical film, forming nesa coating, as upper electrode substrate or lower electrode substrate and use.
Because excellent heat resistance, display optical film can also use with the plastic film substrate with film substrate, particularly liquid-crystal display as flat-panel monitor.On this film substrate, form colour filter and can use known methods such as photolithography, print process, electrodip process.Form TFT and can use known technology on this film substrate, for example, the method for record is implemented among the S.I.D.O 3Digest p-992 (2003).
The present invention can provide the thermotolerance with excellence, the novel Daip of the transparency.
Based on embodiment the present invention is described, but the present invention is not subjected to the qualification of these embodiment.Below, the evaluating and measuring method of the Daip that obtains by embodiment is shown.In addition, short of explanation, the reagent of use adopts commercially available product.
～number-average molecular weight～
Using gel permeation chromatography (GPC) device (eastern ソ one manufacturing, HLC-802A), is solvent with the chloroform, measures down at 40 ℃, is converted by standard vinylbenzene and tries to achieve.
The composition of～Daip～
Use nuclear magnetic resonance measuring device (NEC manufacturing, trade(brand)name JNM-GX270), by the proton magnetic resonance (PMR) beam split (
1H-NMR) spectroscopic analysis is tried to achieve.
The evaluation method of～the transparency～
For carrying out the evaluation of the transparency, use tetrahydrofuran (THF) as solvent, making thickness with solution casting method is the sheet of 300 μ m, measures total light transmittance and mist value with mist value instrument (trade(brand)name NDH2000 is made in Japanese electric look industry).
～stable on heating evaluation method～
The thermotolerance of Daip keeps the sheet that is used in transparency evaluation 1 hour in 150 ℃ baking oven, has or not variable color, distortion by visual judgement.Judgment standard is, situation that do not have the good situation of variable color, distortion to be designated as zero, to find variable color, distortion is designated as *.
The thermotolerance of cross linking membrane kept 1 hour in 220 ℃ baking oven, and visual judgement has or not variable color, distortion.Judgment standard is, situation that do not have the good situation of variable color, distortion to be designated as zero, to find variable color, distortion is designated as *.
The mensuration of～gel fraction～
Measure the weight of cross linking membrane,, measure the weight of solute with Soxhlet extraction method (solvent: tetrahydrofuran (THF), backflow in 3 hours) extraction solute.Deduct solute weight from cross linking membrane weight, obtain the weight of insolubles, gel fraction is obtained according to following formula.
Gel fraction (%)=nonsoluble weight/cross linking membrane weight * 100
The mensuration of～amount of phase difference～
Use Sai Nameng (セ Na Le モ Application) polarizing microscope (Senarmont interferometric method) of compensating prism by record in the polarizing microscope the ABC of (the abundant work in grain room, ア グ ネ technology セ Application タ one edition, the 5th chapter, pp78～82 (2001)) of macromolecular material carries out the mensuration of phase differential.
The evaluation method of～dimensional stability～
Mark mark everywhere on the film 100mm that uses is square in transparency evaluation, film is clipped between sheet glass, by 4 interval of precision coordinate instrumentation calibration note.Then, in 220 ℃ baking oven, kept 1 hour.Afterwards the film that takes out and be cooled to room temperature from baking oven is measured 4 interval once more, try to achieve the size changing rate of heating front and back.
Size * 100 before size changing rate (%)=(size before the heating-heating back size)/heating
The mensuration of～surface hardness～
Surface hardness is measured the cut pencil hardness according to JIS K5600-5-4 (1996).
Embodiment 1
In 4 mouthfuls of flasks of the 500mL that has stirrer, cooling tube, nitrogen ingress pipe and thermometer, add polyvinyl alcohol (molecular weight 2000, saponification deg 80%) 0.4g, distilled water 260g, fumaric acid diisopropyl ester 122g (0.609 mole), vinylformic acid-3-ethyl-3-epoxypropyl methyl ester 18g (0.106 mole) and as the peroxidation trimethylacetic acid tert-butyl ester 0.8g (0.005 mole) of polymerization starter, after carrying out 1 hour nitrogen gas foaming, stir with 550rpm on the limit, the limit kept 24 hours down at 50 ℃, carried out free-radical polymerized thus.After copolyreaction finishes, filter the polymkeric substance in the flask, by obtain multipolymer (yield: 53%) with distilled water and methanol cleaning.By
1The mensuration of H-NMR (Fig. 1), the multipolymer that obtains are the Daips of fumaric acid diisopropyl ester residue unit/vinylformic acid-3-ethyl-3-epoxypropyl methyl ester residue unit=86/14 (mole %).In addition, the number-average molecular weight of Daip is 81000.
Thermotolerance, the transparency to the Daip that obtains are estimated.The results are shown in table 1.
Embodiment 2
In 4 mouthfuls of flasks of the 500mL that has stirrer, cooling tube, nitrogen ingress pipe and thermometer, add polyvinyl alcohol (molecular weight 2000, saponification deg 80%) 0.4g, distilled water 260g, fumaric acid diisopropyl ester 137.5g (0.687 mole), vinylformic acid-3-ethyl-3-epoxypropyl methyl ester 2.5g (0.015 mole) and as the peroxidation trimethylacetic acid tert-butyl ester 0.8g (0.005 mole) of polymerization starter, after carrying out 1 hour nitrogen gas foaming, stir with 550rpm on the limit, the limit kept 24 hours down at 50 ℃, carried out free-radical polymerized thus.After copolyreaction finishes, filter the polymkeric substance in the flask, by obtain multipolymer (yield: 82%) with distilled water and methanol cleaning.By
1H-NMR measures, and the multipolymer that obtains is the Daip of fumaric acid diisopropyl ester residue unit/vinylformic acid-3-ethyl-3-epoxypropyl methyl esters residue unit=96/4 (mole %).In addition, the number-average molecular weight of Daip is 47000.
The Daip that obtains is estimated similarly to Example 1.The results are shown in table 1.
In 4 mouthfuls of flasks of the 500mL that has stirrer, cooling tube, nitrogen ingress pipe and thermometer, add polyvinyl alcohol (molecular weight 2000, saponification deg 80%) 0.4g, distilled water 260g, fumaric acid diisopropyl ester 134g (0.669 mole), tetrahydrofurfuryl acrylate 6g (0.038 mole) and as the peroxidation trimethylacetic acid tert-butyl ester 1.1g (0.006 mole) of polymerization starter, after carrying out 1 hour nitrogen gas foaming, stir with 550rpm on the limit, the limit kept 24 hours down at 50 ℃, carried out free-radical polymerized thus.After copolyreaction finishes, filter the polymkeric substance in the flask, by obtain multipolymer (yield: 60%) with distilled water and methanol cleaning.By
1H-NMR measures (Fig. 2), and the multipolymer that obtains is the Daip of fumaric acid diisopropyl ester residue unit/tetrahydrofurfuryl acrylate residue unit=95/5 (mole %).In addition, the number-average molecular weight of Daip is 40000.
The Daip that obtains is estimated similarly to Example 1.The results are shown in table 1.
Embodiment 4
In 4 mouthfuls of flasks of the 500mL that has stirrer, cooling tube, nitrogen ingress pipe and thermometer, add polyvinyl alcohol (molecular weight 2000, saponification deg 80%) 0.4g, distilled water 260g, fumaric acid diisopropyl ester 103g (0.514 mole), tetrahydrofurfuryl acrylate 37g (0.212 mole) and as the peroxidation trimethylacetic acid tert-butyl ester 0.8g (0.005 mole) of polymerization starter, after carrying out 1 hour nitrogen gas foaming, stir with 550rpm on the limit, the limit kept 24 hours down at 50 ℃, carried out free-radical polymerized thus.After copolyreaction finishes, filter the polymkeric substance in the flask, by obtain multipolymer (yield: 65%) with distilled water and methanol cleaning.By
1H-NMR measures, and the multipolymer that obtains is the Daip of fumaric acid diisopropyl ester residue unit/tetrahydrofurfuryl acrylate residue unit=64/36 (mole %).In addition, the number-average molecular weight of Daip is 50000.
The Daip that obtains is estimated similarly to Example 1.The results are shown in table 1.
Embodiment 5
In 4 mouthfuls of flasks of the 500mL that has stirrer, cooling tube, nitrogen ingress pipe and thermometer, add polyvinyl alcohol (molecular weight 2000, saponification deg 80%) 0.4g, distilled water 260g, fumaric acid diisopropyl ester 115g (0.574 mole), methacrylic acid-3-ethyl-3-epoxypropyl methyl ester 25g (0.136 mole) and as the peroxidation trimethylacetic acid tert-butyl ester 0.8g (0.005 mole) of polymerization starter, after carrying out 1 hour nitrogen gas foaming, stir with 550rpm on the limit, the limit kept 24 hours down at 50 ℃, carried out free-radical polymerized thus.After copolyreaction finishes, filter the polymkeric substance in the flask, by obtain multipolymer (yield: 55%) with distilled water and methanol cleaning.By
1H-NMR measures, and the multipolymer that obtains is the Daip of fumaric acid diisopropyl ester residue unit/methacrylic acid-3-ethyl-3-epoxypropyl methyl ester residue unit=80/20 (mole %).In addition, the number-average molecular weight of Daip is 120000.
The Daip that obtains is estimated similarly to Example 1.The results are shown in table 1.
In 4 mouthfuls of flasks of the 500mL that has stirrer, cooling tube, nitrogen ingress pipe and thermometer, add polyvinyl alcohol (molecular weight 2000, saponification deg 80%) 0.4g, distilled water 260g, fumaric acid diisopropyl ester 130g (0.649 mole), tetrahydrofurfuryl methacrylate 10g (0.059 mole) and as the peroxidation trimethylacetic acid tert-butyl ester 0.8g (0.005 mole) of polymerization starter, after carrying out 1 hour nitrogen gas foaming, stir with 550rpm on the limit, the limit kept 24 hours down at 50 ℃, carried out free-radical polymerized thus.After copolyreaction finishes, filter the polymkeric substance in the flask, by obtain multipolymer (yield: 60%) with distilled water and methanol cleaning.By
1H-NMR measures, and the multipolymer that obtains is the Daip of fumaric acid diisopropyl ester residue unit/tetrahydrofurfuryl acrylate residue unit=90/10 (mole %).In addition, the number-average molecular weight of Daip is 50000.
The Daip that obtains is estimated similarly to Example 1.The results are shown in table 1.
Table 1
Embodiment 7～12
After Daip 30g that embodiment 1～6 is obtained and phenylbenzene iodine phosphofluoric acid 0.5g are dissolved in the tetrahydrofuran (THF), obtain the sheet of 300 μ m by solution casting method.To 10 minutes mercuryvapour lamps of this sheet irradiation.Results verification arrives, because the film that obtains is insoluble to tetrahydrofuran (THF) or toluene equal solvent, is the crosslinked body that contains Daip therefore.And, the transparency of the crosslinked body that obtains is estimated.The results are shown in table 2.In addition, in thermotolerance was similarly to Example 1 estimated, any crosslinked body was not all found variable color, distortion, was good.
Table 2
Embodiment 13
With respect to Daip 100 weight parts that obtain by embodiment 1, mix phenylbenzene iodine phosphofluoric acid 1.5 weight parts, tetrahydrofuran (THF) 400 weight parts, make the solution of 20 weight %.In this solution, add tetramethylolmethane four (3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester) 0.35 weight part, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphate 1.05 weight parts again, make solution.
With excellent coating machine with the solution casting that obtains on the polyethylene terephthalate film, then, under 100 ℃, add the heat extraction solvent, make thickness 140 μ m thus, thickness deviation is the Daip film of 2 μ m.
To 10 minutes light of this film irradiation, carry out crosslinkedly with mercuryvapour lamp, obtain cross linking membrane.
The cross linking membrane thickness that obtains is 140 μ m, and gel fraction is 60%.Measure total light transmittance, the light penetration under the 400nm wavelength, mist value, phase differential and phase differential deviation.In addition, measure the size changing rate of thermotolerance evaluation and 220 ℃ of heating front and back.It the results are shown in table 3.
The cross linking membrane that obtains is suitable for display optical film.
Embodiment 14
With respect to Daip 100 weight parts that obtain by embodiment 3, mix phenylbenzene iodine phosphofluoric acid 1.5 weight parts, tetrahydrofuran (THF) 400 weight parts, make the solution of 20 weight %.In this solution, add tetramethylolmethane four (3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester) 0.35 weight part, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphate 1.05 weight parts again, make solution.
By T pattern method with the solution casting that obtains on the support of solution casting device, 40 ℃, 80 ℃, 120 ℃ respectively dry 1 hour down, make wide 300mm, thickness 60 μ m, thickness deviation is the Daip film of 1 μ m.
To 10 minutes light of this film irradiation, carry out crosslinkedly with mercuryvapour lamp, obtain cross linking membrane.
The cross linking membrane thickness that obtains is 60 μ m, and gel fraction is 30%.Measure total light transmittance, the light penetration under the 400nm wavelength, mist value, phase differential and phase differential deviation.In addition, measure the size changing rate of thermotolerance evaluation and 220 ℃ of heating front and back.It the results are shown in table 3.
The cross linking membrane that obtains is suitable for display optical film.
Table 3
| Total light transmittance (%) | Light penetration during 400nm (%) | Mist value (%) | Phase differential (nm) | Phase differential deviation (nm) | Outward appearance after 220 ℃ of heating | Size changing rate (%) | |
| Embodiment 13 | 93 | 91 | 0.4 | 0 | 0 | ○ | 0.007 |
| Embodiment 14 | 93 | 91 | 0.4 | 0 | 0 | ○ | 0.005 |
Embodiment 15～17 (formation of gas-barrier layer)
The cross linking membrane that embodiment 13 is obtained is the silicon nitride layer (embodiment 15) of 100nm by sputtering at film two sides formation thickness under the following conditions.Similarly, formed the film of silicon oxide layer (embodiment 16), silicon oxynitride layer (embodiment 17) being produced on the two sides.
System film temperature: room temperature, background pressure: 1*10
-7Torr, sputtering pressure: 0.6Pa (Ar:80SCCM, N
2: 20SCCM), apply voltage: RF magnetic control 500w.
The measurement result of the size changing rate of the mist value of the display optical film that obtains, Water Vapour Permeability and 220 ℃ of heating front and back is shown in table 4.
Table 4
| Mist value (%) | Water Vapour Permeability (g/m 2/day) | Outward appearance after 220 ℃ of heating | Size changing rate (%) | Gas-barrier layer | |
| Embodiment 13 | 0.4 | 50 | ○ | 0.007 | Do not have |
| Embodiment 15 | 0.9 | ＜0.1 | ○ | 0.002 | Silicon nitride |
| Embodiment 16 | 0.6 | ＜0.1 | ○ | 0.004 | Silicon oxide |
| Embodiment 17 | 0.7 | ＜0.1 | ○ | 0.002 | Silicon oxynitride |
Embodiment 18 (formation of hard coat)
The two sides of the cross linking membrane of the 140 μ m that obtain in embodiment 13 is contained ultraviolet hardening urethane acrylate 75 weight parts with coater with the coating of the thickness of 4 μ m, 1,6-hexylene glycol acrylate 10 weight parts, isobornyl acrylate 10 weight parts, light trigger (make by チ バ ス ペ シ ヤ Le テ イ one ケ ミ カ Le, trade(brand)name ダ ロ キ ユ ア 1173) 3.5 weight parts, oxidation inhibitor (make by チ バ ス ペ シ ヤ Le テ イ one ケ ミ カ Le, trade(brand)name Irganox1010) 1.4 weight parts, the ultraviolet-curing resin composition of silicon class flow agent 0.1 weight part, carry out rayed with high pressure mercury vapour lamp, make film with hard coat.
Optical characteristics and surface hardness to the film that obtains are estimated.The results are shown in table 5.
Embodiment 19 (formation of hard coat)
Contain ultraviolet hardening epoxy acrylate 60 weight parts with coater with the coating of the thickness of 4 μ m on the film that in embodiment 15, obtains with silicon nitride film, 1,6-hexylene glycol acrylate 20 weight parts, isobornyl acrylate 15 weight parts, light trigger (make by チ バ ス ペ シ ヤ Le テ イ one ケ ミ カ Le, trade(brand)name ダ ロ キ ユ ア 1173) 3.5 weight parts, oxidation inhibitor (make by チ バ ス ペ シ ヤ Le テ イ one ケ ミ カ Le, trade(brand)name Irganox1010) 1.4 weight parts, the ultraviolet-curing resin composition of silicon class flow agent 0.1 weight part carries out rayed with high pressure mercury vapour lamp.Optical characteristics and surface hardness to the display optical film that obtains are estimated.The results are shown in table 5.
Table 5
| Gas-barrier layer | Hard coat | Mist value (%) | Surface hardness | Outward appearance after 220 ℃ of heating | |
| Embodiment 13 | Do not have | Do not have | 0.4 | HB | ○ |
| Embodiment 18 | Do not have | Have | 0.5 | 2H | ○ |
| Embodiment 19 | Have | Have | 0.9 | 3H | ○ |
Embodiment 20 (making of polarizing plate protective film)
By method similarly to Example 14, making thickness is that 60 μ m, thickness deviation are the cross linking membrane of 2 μ m.
With the vinyl acetic monomer solution of excellent coating method how pure and mild isocyanic ester of coated polyester on the one side of this film, be fitted in the two sides of polyvinyl alcohol iodine polaroid, carry out thermal treatment in 1 hour at 120 ℃.The film of fitting can not peeled off from polaroid owing to heating, can be used as polaroid protective film and uses.
Embodiment 21 (making of phase retardation film)
The cross linking membrane that embodiment 13 is obtained be cut into 5cm square after, use biaxial orientation stretching machine (this makings of well is made), under 180 ℃ condition, stretch the making film.The thickness of the film that obtains is 80 μ m, and phase differential is 10nm, is the cross linking membrane that is suitable for phase retardation film.
Embodiment 22 (making of touch panel film)
At lamination that embodiment 15 obtains on the film of gas-barrier layer, form nesa coating (ITO film) with following method, make film.The film total light transmittance that obtains is 93%, the mist value is 0.4%, has again, owing to demonstrate sputter temperature (200 ℃) or the above thermotolerance of this temperature when forming the ITO film, therefore is suitable for the touch panel film.
The film forming condition of nesa coating: system film temperature: 200 ℃, background pressure (バ Star Network グ ラ Application De pressure): 1*10
-7Torr, sputtering pressure: 0.6Pa (Ar:80SCCM, O
2: 20SCCM), apply voltage: RF magnetic control 500W.
Embodiment 23 (making of plastic film substrate)
On the film that in embodiment 19, obtains, ELD (ITO film) (sputter temperature: 200 ℃) is set by sputter process with gas-barrier layer and hard coat.Then, on the ITO layer,, under 180 ℃, carry out carrying out friction treatment after the baking in 1 hour by the spin application alignment film of polyimide.On the film substrate of making like this, scatter partition (ス ペ one サ one), vertically fix 2 with sealing agent with frictional direction up and down.After the sealant cures, inject liquid crystal, use epoxy sealing, make liquid crystal cells by vacuum.The polaroid (day eastern electrician's system, trade(brand)name NPF) of fitting up and down in the unit is estimated display characteristic.White shows and black display can homogeneous and agonic demonstration.In addition, the liquid crystal display device of these making is soft and has flexible, is suitable for the liquid-crystal display plastic base.
Though the present invention discloses as above with preferred embodiment; right its is not in order to limit the present invention; as those of ordinary skills; without departing from the spirit and scope of the invention; certainly can do various changes and retouching, so protection scope of the present invention is as the criterion when looking appended the claim person of defining.
Claims (15)
1. Daip that is used for display optical film, it is characterized in that, this Daip contain the dimethyl ester residue unit of useful following general formula (1) expression and (methyl) acrylate residue unit of representing with (methyl) acrylate residue unit with epoxypropyl of following general formula (2) expression and with following general formula (3) with tetrahydrofurfuryl at least 1 (methyl) acrylate residue unit, and number-average molecular weight is 1000～500000
Here, R
1And R
2Independent separately, the expression carbonatoms is that 1～6 straight chain shape alkyl, branch-like alkyl or carbonatoms are 3～6 cyclic alkyl,
Here, R
3Expression hydrogen or methyl; R
4Expression hydrogen, carbonatoms are 1～4 straight chain shape alkyl or branch-like alkyl; N=1 or 2,
Here, R
5Expression hydrogen or methyl; R
6Expression hydrogen, carbonatoms are 1～4 straight chain shape alkyl or branch-like alkyl.
2. according to the Daip that is used for display optical film of claim 1 record, it is characterized in that dimethyl ester residue unit is fumaric acid diisopropyl ester residue unit.
3. according to the Daip that is used for display optical film of claim 1 record, it is characterized in that (methyl) acrylate residue unit is vinylformic acid-3-ethyl-3-epoxypropyl methyl ester residue, methacrylic acid-3-ethyl-3-epoxypropyl methyl ester residue, tetrahydrofurfuryl acrylate residue or tetrahydrofurfuryl methacrylate residue.
4. the crosslinked body of a Daip is characterized in that, the Daip that is used for display optical film of claim 1 record is crosslinked and obtain.
5. film, this film contain the crosslinked body of the Daip of record in the claim 4.
6. a display optical film is characterized in that, this display optical film is, contains the film of claim 5 record, and thickness is 10～700 μ m, and the gel fraction by the insoluble composition measurement of tetrahydrofuran (THF) is the cross linking membrane more than 10%.
7. according to the display optical film of claim 6 record, it is characterized in that the total light transmittance of this blooming is more than 85%, the light penetration under 400nm is more than 80%, and the mist value is below 2%.
8. according to the display optical film of claim 6 record, it is characterized in that the thickness deviation of this blooming is below the 10 μ m, the phase differential of measuring from the front of film is below the 10nm, and the phase differential deviation in the face is below the 5nm.
9. according to the display optical film of claim 6 record, it is characterized in that this blooming is the above gas-barrier layer of lamination one deck and constituting at least.
10. according to the display optical film of claim 6 record, it is characterized in that this blooming is the above hard coat of lamination one deck and constituting at least.
11. a polaroid protective film is characterized in that this polarizing plate protective film contains the display optical film of claim 6.
12. a phase retardation film is characterized in that this phase retardation film contains the display optical film of claim 6.
13. a touch panel film is characterized in that this touch panel film contains the display optical film of claim 6.
14. a flat-panel monitor film substrate is characterized in that this flat-panel monitor contains the display optical film of claim 6 with the film substrate.
15. a liquid-crystal display plastic film substrate is characterized in that this liquid-crystal display contains the display optical film of claim 6 with the plastic film substrate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005006535A JP4529696B2 (en) | 2005-01-13 | 2005-01-13 | Fumaric acid diester copolymer |
| JP006535/05 | 2005-01-13 | ||
| JP069359/05 | 2005-03-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1814639A CN1814639A (en) | 2006-08-09 |
| CN100582131C true CN100582131C (en) | 2010-01-20 |
Family
ID=36799946
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200610005177A Active CN100582131C (en) | 2005-01-13 | 2006-01-13 | Fumaric diester copolymer |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4529696B2 (en) |
| CN (1) | CN100582131C (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4697098B2 (en) * | 2006-09-05 | 2011-06-08 | 東ソー株式会社 | Retardation film |
| EP1898252B1 (en) | 2006-09-05 | 2014-04-30 | Tosoh Corporation | Optical compensation film stack and stretched retardation film |
| JP5028974B2 (en) * | 2006-11-27 | 2012-09-19 | 東ソー株式会社 | POLYMER PARTICLE AND METHOD FOR PRODUCING POLYMER PARTICLE |
| JP5327269B2 (en) * | 2011-04-27 | 2013-10-30 | 日本ゼオン株式会社 | Method for producing long optical compensation film |
| JP5387647B2 (en) * | 2011-10-11 | 2014-01-15 | 東ソー株式会社 | Retardation film |
| JP5920085B2 (en) * | 2012-07-20 | 2016-05-18 | 東ソー株式会社 | Diisopropyl fumarate-cinnamate copolymer and retardation film using the same |
| JP5983300B2 (en) * | 2012-10-22 | 2016-08-31 | 東ソー株式会社 | Diisopropyl fumarate-cinnamic acid copolymer and retardation film using the same |
| US9321870B2 (en) | 2012-07-20 | 2016-04-26 | Tosoh Corporation | Diisopropyl fumarate-cinnamic acid derivative copolymer and retardation film using the same |
| US9512284B2 (en) | 2012-11-28 | 2016-12-06 | Tosoh Corporation | Fumaric acid diester-cinnamic acid ester-based copolymer, production method thereof and film using the same |
| JP6557965B2 (en) * | 2013-12-03 | 2019-08-14 | 東ソー株式会社 | Resin solution for transparent insulating film and method for producing transparent insulating film |
| WO2018105561A1 (en) | 2016-12-07 | 2018-06-14 | 東ソー株式会社 | Copolymer and optical film using same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4051194A (en) * | 1974-11-11 | 1977-09-27 | Dainippon Ink And Chemicals, Inc. | Thermosetting resin composition for powder paint comprising of a (I) polymer consisting of β-methylglycidyl (meth)acrylate, styrene, unsaturated dialkyl ester, alkylacrylate and (II) saturated aliphatic dibasic acid |
| US5266434A (en) * | 1989-12-12 | 1993-11-30 | Mitsui Toatsu Chemicals, Incorporated | Electrophotographic toner composition |
| US5416180A (en) * | 1992-11-11 | 1995-05-16 | Menicon Co., Ltd. | Soft ocular lens material |
| CN1367185A (en) * | 2001-01-24 | 2002-09-04 | Tdk株式会社 | Cross-linked low medium electrical property high polymer material and film, base plate and electronic part using the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6272710A (en) * | 1985-09-26 | 1987-04-03 | Nippon Oil & Fats Co Ltd | Production of acrylic acid ester polymer composite |
| JPH0511220A (en) * | 1991-07-04 | 1993-01-19 | Nippon Oil & Fats Co Ltd | High oxygen permeability contact lens |
| JP3612349B2 (en) * | 1994-06-24 | 2005-01-19 | 株式会社日本コンタクトレンズ | Materials used as contact lenses or intraocular lenses |
-
2005
- 2005-01-13 JP JP2005006535A patent/JP4529696B2/en active Active
-
2006
- 2006-01-13 CN CN200610005177A patent/CN100582131C/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4051194A (en) * | 1974-11-11 | 1977-09-27 | Dainippon Ink And Chemicals, Inc. | Thermosetting resin composition for powder paint comprising of a (I) polymer consisting of β-methylglycidyl (meth)acrylate, styrene, unsaturated dialkyl ester, alkylacrylate and (II) saturated aliphatic dibasic acid |
| US5266434A (en) * | 1989-12-12 | 1993-11-30 | Mitsui Toatsu Chemicals, Incorporated | Electrophotographic toner composition |
| US5416180A (en) * | 1992-11-11 | 1995-05-16 | Menicon Co., Ltd. | Soft ocular lens material |
| CN1367185A (en) * | 2001-01-24 | 2002-09-04 | Tdk株式会社 | Cross-linked low medium electrical property high polymer material and film, base plate and electronic part using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006193616A (en) | 2006-07-27 |
| JP4529696B2 (en) | 2010-08-25 |
| CN1814639A (en) | 2006-08-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100582131C (en) | Fumaric diester copolymer | |
| US7160587B2 (en) | Plastic substrate for display and display element | |
| US10526430B2 (en) | Methacrylic resin or methacrylic resin composition | |
| EP2998328B1 (en) | Film | |
| EP2998355B1 (en) | Methacrylic resin composition and molded body thereof | |
| JP5291919B2 (en) | Protective film for polarizing plate used for display surface or film for image display device front plate | |
| US20090197020A1 (en) | Optical film and information technology apparatus comprising the same | |
| CN105264002A (en) | Resin composition, optical compensation film employing same, and production method for same | |
| JP5028961B2 (en) | Copolymer and optical film made of the copolymer | |
| US7759451B2 (en) | Fumaric diester copolymer | |
| JP2006249318A (en) | Optical film for display | |
| WO2021235393A1 (en) | Methacrylic copolymer for reverse wavelength dispersive retardation film, composition, film, method for manufacturing film, and laminate | |
| KR101475565B1 (en) | Optical film exhibiting excellent blocking property for ultraviolet rays and polarizing plate comprising the same | |
| JP2006162748A (en) | Polarizer protection film and polarizing plate | |
| KR102072883B1 (en) | Optical films, polarizing plate and liquid crystal display apparatus and method for manufacturing same | |
| CN105419207B (en) | Thermoplastic resin film | |
| Agarwal et al. | Photoelastic birefringence of copolymers with non-planar structure | |
| JP4918761B2 (en) | Method for producing transparent film | |
| KR20180129674A (en) | Resin laminate with curved shape | |
| KR102201543B1 (en) | Adhesive composition and polarizing plate comprising adhesive layer formed by using the same | |
| JP6914694B2 (en) | Stretched film | |
| JP2006299029A (en) | Transparent resin composition and transparent film | |
| KR101565629B1 (en) | Resin composition for optical film and optical film using the same | |
| JP2021050291A (en) | Resin composition and optical film based on the same | |
| JP2021031573A (en) | Resin composition and film comprising the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |