CN102337004A - Resin composition, transparent composite substrate and substrate for display element - Google Patents
Resin composition, transparent composite substrate and substrate for display element Download PDFInfo
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- CN102337004A CN102337004A CN2011101766315A CN201110176631A CN102337004A CN 102337004 A CN102337004 A CN 102337004A CN 2011101766315 A CN2011101766315 A CN 2011101766315A CN 201110176631 A CN201110176631 A CN 201110176631A CN 102337004 A CN102337004 A CN 102337004A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
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Abstract
The invention provides a resin composition, a transparent composite substrate and a substrate for display an element, wherein for the resin composition, the resin composition is cured to work as a composite substrate, and when reliability tests such as humid heat treatment of the composite substrate is performed, the transparent composite substrate capable of inhibiting optical anisotropy deterioration caused by interior stress is provided. The resin composition is the resin composition capable of manufacturing a transparent composite substrate after being cured to work as the composite substrate, and comprising epoxy resins, glass filling materials, and hindered phenol system anti-oxidants. In addition, glass fiber cloth is preferably selected as the glass filling materials. What's more, preferably, the hindered phenol system anti-oxidants and phosphor system anti-oxidants are together used.
Description
Technical field
The present invention relates to resin combination, transparent composite base plate and display element substrate.
Background technology
As the substrate (display element substrate), filter substrate and the used for solar batteries substrate that in the display element of liquid crystal display device or organic EL display element etc., use, widespread use sheet glass.Yet that sheet glass exists is frangible, can't be crooked, be not suitable for problem such as lightweight, based on these reasons,, study the substrate that constitutes by plastic material in recent years as the substitute material of sheet glass always.
For example; In patent documentation 1,2, record a kind of used for liquid crystal display element transparent resin substrate, this used for liquid crystal display element transparent resin substrate is by to containing that epoxy resin, acid anhydrides are that the composition epoxy resin of solidifying agent and curing catalysts is cured and the cured article that obtains constitutes.Yet these linear expansivitys that in the past replaced the plastic material that sheet glass uses are greater than sheet glass.Therefore, when particularly being used in the active matrix display element substrate, the warpage of substrate taking place in its manufacturing process or follow the problem of the wiring broken string of this warpage.Therefore, be difficult to use on these purposes.
Therefore, in order to reduce linear expansivity, in resin material, cooperate mineral filler such as glass powder or spun glass and carry out compoundization of material.But,, therefore, damage the transparency of matrix material through the light of resin material on the interface of resin material and mineral filler scattering takes place because the specific refractory power of resin material and mineral filler is different.
In order to address the above problem, a kind of photopermeability composition epoxy resin is disclosed at patent documentation 3, this photopermeability composition epoxy resin is by constituting with the packing material that the epoxy resin that is cured through acid anhydrides has an identical specific refractory power in fact.In such resin combination, through controlling the refringence between epoxy resin and the packing material less, thereby attempt to realize the transparence of matrix material.
In above-mentioned matrix material, even the transparency is improved, but based on matrix material institute inherent structure, the optical anisotropy of microcosmic takes place.Specifically; Because the thermal expansivity between resin material and the filler (packing material) is different, therefore, on both interfaces, produce small internal stress; Follow this internal stress to produce the orientation of resin material molecule, thereby cause optically anisotropic generation.Such optical anisotropy comes phase differential for the light belt that sees through matrix material, so, when for example adopting matrix material to make the display element substrate, be difficult to carry out distinct demonstration.Particularly in recent years, the development that becomes more meticulous of display pixel is rapid, so the optical anisotropy in the matrix material becomes important characteristic more.
For example, as far as the display element substrate, be under the harsh and unforgiving environments of so-called wet heat treatment, to carry out reliability test, require to have the weather resistance that can withstand this harsh and unforgiving environments.Yet, because the situation that the reliability test optical anisotropy worsens becomes problem.
Prior art
Patent documentation 1: japanese kokai publication hei 6-337408 communique
Patent documentation 2: japanese kokai publication hei 7-120740 communique
Patent documentation 3: japanese kokai publication hei 4-236217 communique
Summary of the invention
The objective of the invention is to; The transparent composite base plate and the display element substrate that a kind of resin combination are provided and adopt this resin combination to make; Wherein, As far as above-mentioned resin combination, it is solidified the back when carrying out reliability test such as wet heat treatment as composite base plate and to this composite base plate, the transparent composite base plate that can provide the optical anisotropy that can suppress to cause to worsen because of internal stress.
Above-mentioned purpose realizes through the present invention of following (1)～(12).
(1) a kind of resin combination is the resin combination that is used to make transparent composite base plate, it is characterized in that, containing epoxy resin, glass filler and hindered phenol is inhibitor.
(2) like above-mentioned (1) described resin combination, wherein, said hindered phenol is that the content of inhibitor is 0.01 quality %～5 quality %.
(3) like above-mentioned (1) or (2) described resin combination, wherein, said hindered phenol is that inhibitor is that fusing point is the inhibitor more than 100 ℃.
(4) like each described resin combination in above-mentioned (1)～(3), wherein, said hindered phenol is that inhibitor is the inhibitor that has the neopentane structure in the molecular structure.
(5) like each described resin combination in above-mentioned (1)～(4), wherein, be inhibitor with respect to the hindered phenol of 100 mass parts, also contain the phosphorous antioxidant of 30～300 mass parts.
(6) like each described resin combination in above-mentioned (1)～(5), wherein, said epoxy resin contains alicyclic epoxy resin and Racemic glycidol type epoxy resin.
(7) like above-mentioned (6) described resin combination, wherein, said alicyclic epoxy resin contains by the alicyclic epoxy resin of following chemical formula (1) expression with by in the alicyclic epoxy resin of following chemical formula (2) expression at least one,
In above-mentioned formula (2) ,-X-representes-O-,-S-,-SO-,-SO
2-,-CH
2-,-CH (CH
3)-or-C (CH
3)
2-.
(8) like above-mentioned (6) or (7) described resin combination, wherein, with respect to the said alicyclic epoxy resin of 100 mass parts, the content of said Racemic glycidol type epoxy resin is 0.5～10 mass parts.
(9) like each described resin combination in above-mentioned (1)～(8), wherein, said glass filler is a glasscloth.
(10) like each described resin combination in above-mentioned (1)～(9), wherein, when said resin combination heats one minute under 300 ℃ temperature, inhibitor or its decompose composition as gas detect in fact less than.
(11) a kind of transparent composite base plate is characterized in that, by the cured article formation of each described resin combination in above-mentioned (1)～(10).
(12) a kind of display element substrate is characterized in that, has above-mentioned (11) described transparent composite base plate.
According to the present invention, can obtain a kind of resin combination, this resin combination can reduce the optical anisotropy that produces because of internal stress when making it be solidified to form composite base plate, the transparent composite base plate that can replace glass substrate can be provided thus.
Transparent composite base plate for using at the display element substrate requires this transparent composite base plate must have long-term reliability, need in reliability test, not have the deterioration or the less transparent composite base plate of characteristic degradation of characteristic.According to the present invention, even can obtain in reliability test, the transparent composite base plate that optically anisotropic deterioration is less, and optical anisotropy is less and color shows distinct display element substrate.
Description of drawings
It is the evaluation result (mass spectrum) of the monomeric degassing of inhibitor that Fig. 1 (a) is illustrated in the hindered phenol that uses among the embodiment 7;
Fig. 1 (b) expression is by the evaluation result (mass spectrum) of the degassing of embodiment 7 resulting transparent composite base plates.
The explanation of Reference numeral
The A peak
Embodiment
Below, according to preferred implementation shown in the drawings, resin combination of the present invention, transparent composite base plate and display element substrate are elaborated.
Resin combination of the present invention is the resin combination that is used to make transparent complex through moulding, curing, is to contain the resin combination that epoxy resin, glass filler and hindered phenol are inhibitor.
In addition, transparent composite base plate of the present invention is that above-mentioned resin combination is shaped to tabular film, and solidifies the substrate that forms, and is the little transparent composite base plate of optical anisotropy.
In addition, display element substrate of the present invention has above-mentioned transparent composite base plate, and its optical anisotropy is less and can realize distinct demonstration.
< resin combination >
At first, resin combination of the present invention is described.
Resin combination of the present invention is to contain the compsn that epoxy resin, glass filler and hindered phenol are inhibitor.
(epoxy resin)
As using at epoxy resin of the present invention; For example can enumerate bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin or these epoxy resin hydrogenate, have the Dicyclopentadiene (DCPD) skeleton epoxy resin, have the triglycidyl isocyanurate skeleton epoxy resin, have a shape (cardo, カ Le De) epoxy resin of skeleton, the epoxy resin with polysiloxane structure, ester ring type polyfunctional epoxy resin, have the hydrogenation biphenyl backbone alicyclic epoxy resin, have the alicyclic epoxy resin of Hydrogenated Bisphenol A 99 skeleton etc., can use one or more the mixture in these epoxy resin.
In addition, though above-mentioned epoxy resin roughly divide into: comprise glycidyl and ehter bond the Racemic glycidol ether type epoxy, comprise glycidyl and ester bond glycidyl ester type epoxy resin, comprise the Racemic glycidol type epoxy resin of glycidyl and amino glycidyl amine type epoxy resin etc.; And ester ring type epoxy group(ing), but in the present invention, especially preferably use intramolecularly to have the alicyclic epoxy resin of two above epoxy cyclohexane rings with ester ring type epoxy group(ing).
In addition, preferred especially the use by the hydrogenation biphenyl type ester ring type epoxy construction of following chemical formula (1) expression or the ester ring type epoxy construction of representing by following chemical formula (2).
In above-mentioned formula (2) ,-X-representes-O-,-S-,-SO-,-SO
2-,-CH
2-,-CH (CH
3)-or-C (CH
3)
2-.
Such alicyclic epoxy resin solidified nature at low temperatures is excellent, therefore can be cured processing at low temperatures.Thus, need not during curing resin combination is reached a high temperature, therefore,, also can suppress the variation of temperature amount even make resin combination return to room temperature thereafter.Its result in the transparent composite base plate that obtains adopting resin combination of the present invention, can suppress to follow temperature variation and the thermal stresses that produces, and can suppress optical anisotropy.
In addition; Linear expansivity after the curing of alicyclic epoxy resin is low as stated; Therefore; Contain the resin combination of this alicyclic epoxy resin and the transparent composite base plate that obtains for employing, the almost nil temperature of the interfacial stress on glass filler and epoxy resin interface approaches room temperature.Therefore, the resin combination of the application of the invention can access the little transparent composite base plate of above-mentioned interfacial stress, and this transparent composite base plate becomes the little substrate of optical anisotropy.And, because linear expansivity is low, therefore can prevent the distortion of transparent composite base plate generation warpage or bending etc.
In addition, therefore the transparency of these alicyclic epoxy resins and excellent heat resistance, help to realize photopermeability excellence and the high transparent composite base plate of thermotolerance.
In addition, in resin combination of the present invention,, preferred also with alicyclic epoxy resin and Racemic glycidol type epoxy resin as epoxy resin.Thus, when guaranteeing photopermeability, improve the intermiscibility between epoxy resin and the inhibitor.Its result can access the low transparent composite base plate of photopermeability height and optical anisotropy.In addition, the intermiscibility between epoxy resin and the inhibitor is improved, its result, and the volatility of inhibitor is inhibited, and can also improve the thermotolerance of transparent composite base plate.
At this moment, with respect to the alicyclic epoxy resin of 100 mass parts, the addition of Racemic glycidol type epoxy resin is preferably about 0.1～10 mass parts, more preferably about 1～5 mass parts.Thus, when can highly guarantee photopermeability, also can highly suppress optical anisotropy.
In addition, in employed Racemic glycidol type epoxy resin, the also preferred Racemic glycidol type epoxy resin that uses with a shape (cardo) structure.Promptly; Use through in alicyclic epoxy resin, adding Racemic glycidol type epoxy resin with shape structure; Can contain a lot of aromatic nucleus thus from two aryl fluorene skeletons; Therefore the optically anisotropic while that can suppress transparent composite base plate, can further improve the transparency and thermotolerance.
As Racemic glycidol type epoxy resin, for example, can enumerate On-Court (オ Application コ one ト) EX series (Nagase Industrial Co., Ltd.'s manufacturing), OGSOL (オ グ ソ one Le) (manufacturing of Osaka aerochemistry Co., Ltd.) etc. with this axle shape structure.
(solidifying agent)
Resin combination of the present invention can also contain curing agent for epoxy resin.As this solidifying agent, linking agent, the positively charged ion that can enumerate acid anhydrides, fatty amine etc. are that solidifying agent, negatively charged ion are solidifying agent etc., can use one or more the mixture in these solidifying agent.
In these solidifying agent, especially preferably using positively charged ion is solidifying agent.Through using positively charged ion is solidifying agent, can under lower temperature, make epoxy resin cure, therefore, need not during curing resin combination is reached a high temperature, and can suppress thus to follow temperature variation and the thermal stresses that produces.Its result can obtain the low transparent composite base plate of optical anisotropy.
In addition, be solidifying agent through using positively charged ion, can access the higher transparent composite base plate of thermotolerance (for example, second-order transition temperature).Its reason is considered to, and is solidifying agent through using positively charged ion, the cause that the cross-linking density of epoxy resin cured product is uprised.
As above-mentioned positively charged ion is solidifying agent, can enumerate the solidifying agent that discharges the material that causes cationoid polymerisation through heating, for example salt cation solidifying agent or aluminum chelate cation solidifying agent; And discharge the solidifying agent of the material that causes cationoid polymerisation through active energy ray, for example the salt cation is a solidifying agent etc.Wherein, preferred hot positively charged ion is a solidifying agent.Thus, can access more excellent in curing thing of thermotolerance.
As a thermal cationic curing agents include, for example aromatic sulfonium salts, aromatic iodine-salt, ammonium salt, aluminum chelate, boron trifluoride amine complexes.Specifically,, can enumerate the SI-60L, SI-80L, the SI-100L that make by three new chemical industry Co., Ltd. as the aromatic series sulfonium salt, and hexafluoro antimonates such as SP-66 that makes by Asahi Denka Kogyo K. K and SP-77; As aluminum chelate, can enumerate methyl aceto acetate diisopropoxy aluminium, tri ethylacetoacetate aluminium etc.; As the boron trifluoride amine complex, can enumerate boron trifluoride mono aminoethane complex compound, boron trifluoride imidazol complex, boron trifluoride piperidines complex compound etc.
On the other hand, crop light positively charged ion is a solidifying agent, for example can enumerate the SP170 that made by Asahi Denka Kogyo K. K etc.
For such positively charged ion is that the content of solidifying agent does not have special qualification; For example; When the epoxy resin that uses shown in above-mentioned chemical formula (1); With respect to the epoxy resin of 100 mass parts, positively charged ion is that the content of solidifying agent is preferably about 0.1～5 mass parts, about preferred especially 0.5～3 mass parts.If content is lower than above-mentioned lower value, the situation that solidified nature reduces then appears sometimes, if content surpasses above-mentioned higher limit, the situation that transparent composite base plate becomes fragile then appears sometimes.
When carrying out photocuring, as required also can be also with sensitizer, acid proliferation generator etc., to promote curing reaction.
(glass filler)
Glass filler be by inorganic be the filler (packing material) that formed fiber of glass material or particle etc. constitute.
Specifically; Can enumerate glasscloth, glass filament, glass chopped strand, granulated glass sphere, sheet glass, glass powder, milled glass (milled glass) of woven fiber glass, glass non-woven fabrics etc. etc.; Wherein, Consider from the effect that improves the linear expansivity that reduces transparent composite base plate, preferably use glass filament and glasscloth, more preferably use glasscloth.
Crop is inorganic to be glass material; For example can enumerate the glass of E glass, C glass, A glass, S glass, T glass, D glass, NE glass, quartz, low-k, the glass of high-k etc.; Wherein, Preferred use E glass, S glass, T glass, the NE glass that basic metal isoiony impurity is less and obtain easily, particularly, use more preferably that average coefficient of linear expansion is S glass below the 5ppm or T glass under 30 ℃～250 ℃ temperature.
For the content of glass filler, preferably it accounts for 1～90 quality % in transparent composite sheet, and more preferably 10～80 quality % further are preferably 30～70 quality %.When the content of glass filler during, moulding easily, can obtain the effect of the reduction polar expansion that compoundization bring in this scope.The content of glass filler is many if this is, the homogeneity of the amount of resin of per unit volume is improved, and the cause of the homogeneity of stress raising.If these homogeneities are improved, then the bending of transparent composite base plate is just little.
In addition, the diameter of preferred glass long filament and glasscloth is below the 100nm.For such glass filament and glasscloth, no matter the refringence between these glass fillers and the epoxy resin how much, all is difficult to produce scattering on the interface, therefore transparent composite base plate is transparent higher.
On the other hand, when diameter surpasses 100nm, preferably to consider the refringence between glass filler and the epoxy resin.At this moment, for the glass material that constitutes glass filament and glasscloth, preferably using specific refractory power is 1.4～1.6 material, and more preferably using specific refractory power is 1.5～1.55 material.Thus, can access the transparent composite base plate that has high photopermeability in wide wavelength region may.
On the other hand, for the median size of glass chopped strand, granulated glass sphere, sheet glass, glass powder, milled glass etc., below the also preferred 100nm, more preferably below the 80nm.
(inhibitor)
As hindered phenol is inhibitor, for example can enumerate BHT, 2,2 '-methylene-bis (4-methyl-6 tert.-butyl phenol), tetramethylolmethane four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], 3,3 '-3 "; 5,5 ' 5 "-six tertiary butyls-α, α ', α "-(mesitylene-2,4; 6-three bases) three p-cresol, octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester, 1,3,5-three ((the 4-tertiary butyl-3-hydroxyl-2,6-xylyl) methyl)-1; 3,5-triazine-2,4,6-(1H, 3H; 5H)-triketone, 1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-1,3; 5-triazine-2,4,6-(1H, 3H, 5H)-triketone, diethylammonium two [(3; Two (1, the 1-the dimethyl ethyl)-4-hydroxy phenyls of 5-) methyl] phosphonic acids calcium, two (2,2 '-dihydroxyl-3,3 '-di-t-butyl-5,5 '-3,5-dimethylphenyl) ethane, N; N '-hexane-1, the hindered phenol of two (3-(3,5 di-t-butyl)-4-hydroxy phenyl) propionic acid amides of 6-two base etc. is an inhibitor, can use these hindered phenols is one or more the mixture in the inhibitor.
Specifically, can enumerate IRGANOX (イ Le ガ ノ Star Network ス) 1330, IRGANOX 1010, IRGANOX 1076, IRGANOX 3114 (above) by the manufacturing of Ciba Specialty Chemicals Co., Ltd.; SUMILIZER (ス ミ ラ イ ザ one) BHT, SUMILIZER BP-101 (above) by Sumitomo Chemical Co's manufacturing; YOSHINOX (ヨ シ ノ Star Network ス) BHT, YOSHINOX250, TOMINOX (ト ミ ノ Star Network ス) SS, TOMINOX TT, YOSHINOX 314, GSY-242 (above) by the API manufactured; ADK STAB (ア デ カ ス タ Block) AO-50, Mark AO-50, ADK STAB AO-60, ADK STAB AO-20 etc. (above) by the manufacturing of ADEKA Co., Ltd..
The content that preferred hindered phenol is an inhibitor is the 0.01 quality %～5 quality % of resin combination, more preferably greater than 0.01 quality % and less than 5 quality %, further is preferably about 0.1 quality %～3 quality %.Be within the above-mentioned scope through the content that makes inhibitor, can access the low transparent composite base plate of optical anisotropy, and can access the little transparent composite base plate of optically anisotropic deterioration in reliability test.
Though through adding such hindered phenol is that inhibitor suppresses reason that optical anisotropy in the transparent composite base plate worsens and indeterminate; But as one of its reason; Can enumerate: the interaction between hindered phenol position and the epoxy resin; The effect of eliminating or protecting is played at the position that becomes epoxy resin deterioration initial point, suppressed the deterioration of epoxy resin thus.In addition, because the chemicalstability at hindered phenol position is higher, can strengthens optical stability through increasing the ratio of hindered phenol position in transparent composite base plate, thinking thus, promptly can suppress optically anisotropic deterioration.Its result can obtain the low transparent composite base plate of optical anisotropy, and can obtain the also little transparent composite base plate of optically anisotropic deterioration in reliability test.
In addition, be inhibitor for hindered phenol, preferably its fusing point is more than 100 ℃, more preferably more than 110 ℃.If fusing point is within the above-mentioned scope,, resin combination can prevent that then inhibitor from volatilizing when solidifying.That is, residual really when resin combination solidifies have inhibitor, so can improve above-mentioned optical stability.Its result, the hindered phenol that has above-mentioned fusing point through use is an inhibitor, can access optical anisotropy low and in reliability test the repressed transparent composite base plate of optically anisotropic significance (sensible change).
In addition, preferred hindered phenol is that the weight-average molecular weight of inhibitor is 200～2000, more preferably 500～1500, further be preferably 1000～1400.Be within the above-mentioned scope if hindered phenol is the weight-average molecular weight of inhibitor, when then the volatility of inhibitor is inhibited, can guarantee intermiscibility epoxy resin.Such hindered phenol is an inhibitor, and is residual even the reliability test of process as the wet heat treatment also can continue, and can realize suppressing the transparent composite base plate of optically anisotropic deterioration thus.
And preferred hindered phenol is that inhibitor has neopentane structure or isocyanurate structure in molecular structure.No matter these structures still all show more roomy structure in the plane on solid, therefore, most binding sites (for example hydroxyl) exist according to the mode of extensive distribution.Therefore, the hindered phenol with these structures is that inhibitor combines the probability of (interaction) high with epoxy resin, and hindered phenol is that inhibitor can be kept the bonding state with epoxy resin for a long time reliably.Its result when resin combination solidifies, can prevent that hindered phenol from being the phenomenon that inhibitor volatilizees, the thermotolerance of transparent composite base plate descends.
Preferred above-mentioned neopentane structure is comprised in the position beyond the hindered phenol, makes the effect of this structure and effect more remarkable thus.
In addition, be inhibitor as the hindered phenol that comprises the neopentane structure in the molecular structure, can enumerate by the inhibitor shown in the following chemical formula (3) (for example, IRGANOX 1010 etc.).
And then, be inhibitor as the hindered phenol that comprises isocyanurate structure in the molecular structure, can enumerate by the inhibitor shown in the following chemical formula (4) (for example, ADK STAB AO-20 etc.).
In addition, also can contain other inhibitor except hindered phenol is inhibitor in the resin combination of the present invention.As other inhibitor, the phenol that can enumerate except that hindered phenol is inhibitor is that inhibitor, phosphorous antioxidant and sulphur are inhibitor etc.
As the phenol except that hindered phenol is inhibitor is inhibitor, for example can enumerate a substituting group being positioned at the position of clamping hydroxyl by substituted half hindered phenol of institutes such as methyl be oxidation inhibitor, two substituting groups clamping hydroxyl are inhibitor by substituted low (the less hindered type) phenol that is obstructed of institutes such as methyl all.These inhibitors are that the mode of the addition of inhibitor is added according to being less than hindered phenol.
As phosphorous antioxidant; For example can enumerate three decyl phosphorous acid esters, phenylbenzene decyl phosphorous acid ester, four (2, the 4-di-tert-butyl-phenyl) (1, the 1-xenyl]-4; 4 '-two basic bis-phosphites, two [2; Two (1, the 1-the dimethyl ethyl)-6-aminomethyl phenyls of 4-] phosphorous acid ethyl ester, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites etc.Can use a kind of in these inhibitors or use two or more mixtures.
Specifically, can enumerate GSY-P101, ト ミ ホ ス 202 (trade(brand)names) (above) by the API manufactured; Mark2112, ADK STAB PEP-36, ADK STAB PEP-24, ADK STABPEP-45, ADK STAB HP-10 (above) by the manufacturing of ADEKA Co., Ltd.; SUMILIZERGP (making) etc. by Sumitomo Chemical Co.
Wherein, through and be inhibitor and phosphorous antioxidant with hindered phenol, can bring into play the effect that they multiply each other, the optically anisotropic more remarkable effect that prevents the oxidation of epoxy resin thus and suppress transparent composite base plate.Its reason is considered to, because that hindered phenol is the antioxidation mechanism of inhibitor and phosphorous antioxidant is different, so both work independently of each other, and then the effect that multiplies each other of generation.
As sulphur is inhibitor, can enumerate the two stearyl alcohol esters of Tyox B, thio-2 acid etc., can use one or more the mixture in these inhibitors.
Specifically, can enumerate DLTP ヨ シ ト ミ (trade mark), LMTP ヨ シ ト ミ, DSTP ヨ シ ト ミ, DTTP ヨ シ ト ミ (above) by the API manufactured; ADK STAB AO-23 (above) by the manufacturing of ADEKA Co., Ltd.; SUMILIZER TPL, SUMILIZER TPM, SUMILIZER TPS, SUMILIZER TL, SUMILIZER TP-D etc. (above) by Sumitomo Chemical Co's manufacturing.
Hindered phenol with respect to 100 mass parts is an inhibitor, and the addition of preferred this inhibitor (particularly phosphorous antioxidant) except hindered phenol is inhibitor is about 30～300 mass parts, more preferably about 50～200 mass parts.Thus, be inhibitor and inhibitor in addition for hindered phenol, the effect that they are brought into play separately can not buried, and then can bring the effect that multiplies each other.
Resin combination of the present invention within the scope of not damaging its characteristic, also can contain the oligopolymer or the monomer of thermoplastic resin or thermosetting resin as required, perhaps coupling agent etc.Wherein, when using these oligopolymer or monomer, the suitable ratio of components of setting is so that the whole specific refractory power and the specific refractory power of glass filler match.
And then resin combination of the present invention within the scope of not damaging its characteristic, also can contain UV light absorber, dyestuff, pigment, other filler etc. as required.
Resin combination of the present invention is that inhibitor etc. obtains through mixing above-mentioned epoxy resin, glass filler, hindered phenol.
In addition, resin combination of the present invention, preferably heating one minute time the under 300 ℃ temperature, inhibitor or its decompose composition as gas detect in fact less than.As stated, because this resin combination can suppress the volatilization of inhibitor when solidifying, therefore, and as far as resulting cured article, the low and transparent height of its optical anisotropy.
In addition, gas detection adopts gas chromatograph or gas chromatography mass analyser.Wherein, when adopting the gas chromatography mass analyser, can from chromatogram (Chromatogram), can directly obtain mass spectrum, the evaluation ratio of gaseous constituent is easier to, thereby preferred.That is, do not detect inhibitor or its decomposition composition, can judge the volatilization whether inhibitor has taken place thus through on mass spectrum, estimating.
In addition, so-called " inhibitor or its decompose composition as gas detect in fact less than ", be meant the situation that for example in mass spectrum, can't identify the existence at peak.
< transparent composite base plate and display element substrate >
Transparent composite base plate of the present invention is that the cured article by resin combination of the present invention constitutes.That is, transparent composite base plate of the present invention is to be shaped to tabularly through the resin combination with the invention described above, and its curing is formed.
As forming method, the forming method that can enumerate forming method, pour into a mould after resin combination is dissolved in solvent to shaping mould casting.In addition, when with glasscloth when the glass filler, can enumerate the composition except glass filler in the resin combination impregnated in glasscloth, and as the forming method of the resin combination of tabular moulding.
For the condition of cure of resin combination, preferred Heating temperature is about 150～300 ℃, be about 0.5～10 hour heat-up time, and more preferably Heating temperature is about 170～250 ℃, be about 1～5 hour heat-up time.
Transparent composite base plate of the present invention for example be applicable to used for liquid crystal display element substrate, organic EL with substrate, colour filter with substrate, Electronic Paper with in substrate, used for solar batteries substrate and touch panel the various transparency carriers with substrate etc.
Mean thickness to transparent composite base plate does not have special qualification, but about preferred 40～200 μ m, more preferably about 50～100 μ m.
In addition, the preferred average coefficient of linear expansion of transparent composite base plate of the present invention under 30 ℃～150 ℃ temperature is below the 40ppm, more preferably below the 20ppm, further is preferably below the 10ppm.For example, when this transparent composite sheet is used when active matrix display element is used substrate, if surpass this higher limit, the problems such as broken string of warpage or aluminium wiring might take place in its manufacturing process then.
Transparent composite base plate of the present invention is applicable to that above-mentioned various display element is with transparency carrier (display element substrate).
At this moment, the total light transmittance of display element substrate under wavelength 400nm is more than 80%, more preferably more than 85%, further is preferably more than 88%.If the total light transmittance under the wavelength 400nm is lower than lower value, then the display performance in the display element might be insufficient.
In addition, when transparent composite base plate of the present invention is applicable to the display element substrate, resin coating also can be set in the both sides of substrate to improve surface smoothing property.As the resin that in coating, uses, for example, preferably have excellent thermotolerance, the transparency, resistance to chemical reagents, specifically, the preferred use resin identical with the epoxy resin that in transparent composite base plate, uses.In addition, the mean thickness of coating is preferably about 0.1～30 μ m, more preferably about 0.5～30 μ m.
And then, when transparent composite base plate of the present invention is applicable to the display element substrate, also the damping of shocks layer can be set, in order to suppress from the impact of outside breakage to substrate.As the formation of impact plies, can enumerate at least the formation that a side at transparent composite base plate is provided with smooth layer and the damping of shocks layer is set on this smooth layer; Or the damping of shocks side is set and the formation of smooth layer is set on this damping of shocks layer in a side of transparent composite base plate at least.That is, the damping of shocks layer can be set on a plurality of layers optional position.
In addition, though the shock-resistance of display element substrate of the present invention in fall sphere test originally just is higher than glass substrate, through above-mentioned damping of shocks layer is set, shock-resistance is further enhanced.
As stated, resin combination of the present invention, transparent composite base plate and display element substrate are illustrated, but the present invention is not limited thereto, for example in transparent composite base plate and display element substrate, also can adds and constitute thing arbitrarily.
Embodiment
Next, specific embodiment of the present invention is described.
1, the manufacturing of transparent composite base plate
(embodiment 1)
At first; According to the ratio shown in the table 1; To hydrogenation biphenyl type alicyclic epoxy resin with following chemical formula (1) structure (E-BP, the Tg that are made by Daisel chemical industry Co., Ltd:＞250 ℃), bisphenol-A epoxy resin (YX-8000 that is made by japan epoxy resin Co., Ltd., Tg:103 ℃), aromatic matte is that hot cation curing agent (SI-100L that made by three new chemistry) is that inhibitor (IRGANOX 1010, weight-average molecular weight by the manufacturing of Ciba Specialty Chemicals Co., Ltd. are 1178) mixes with hindered phenol, prepares resin material thus.
Then, make resulting resin material be impregnated into T glass be woven fiber glass (thickness be 95 μ m, specific refractory power be 1.52, by day east spin Co., Ltd. and make) in and carry out deaeration.Prepare resin combination thus.Two sheet glass with handling through the demoulding are clamped the above-mentioned woven fiber glass that floods resin material (resin combination); And in the heating of 80 ℃ temperature after 2 hours; 250 ℃ temperature reheat 2 hours, obtaining thickness thus was the transparent composite base plate of 97 μ m (content of glass filler is 63 quality %).
(embodiment 2～22)
Except the composition with resin combination changes to the composition shown in table 1 and the table 2, through obtaining transparent composite base plate respectively with embodiment 1 identical method.
In addition; The alicyclic epoxy resin that in embodiment 20 and embodiment 21, uses (by the EHPE3150 of Daisel chemical industry Co., Ltd's manufacturing); Be 2; 1 of two (the hydroxymethyl)-1-butanols of 2-, 2-epoxy group(ing)-4-(2-epoxy ethyl) hexanaphthene affixture (molecular weight is 2234), its general formula is shown in the following formula (5).
In above-mentioned formula (5), R is an organic radical, and n is the integer more than 1.
In addition, the alicyclic epoxy resin that in embodiment 22, uses (by the E-DOA that Daisel chemical industry Co., Ltd makes, Tg:＞250 ℃) is the alicyclic epoxy resin with following chemical formula (2) structure, and wherein ,-X-is-CH (CH
3)-.
(embodiment 23)
Except using glass powder to replace woven fiber glass and this glass powder and resin material being mixed together and make the resin combination, through obtaining transparent composite base plate with embodiment 1 identical method.
(comparative example 1)
Except the use of omitting inhibitor, through obtaining transparent composite base plate with embodiment 1 identical method.
(comparative example 2)
Except the phosphorous antioxidant of amount shown in the use table 2 replaces hindered phenol is the inhibitor, through obtaining transparent composite base plate with embodiment 1 identical method.
(comparative example 3)
Except the low hindered phenol (less-hindered phenols) that uses amount shown in the table 2 be inhibitor to replace hindered phenol be the inhibitor, through obtaining transparent composite base plate with embodiment 1 identical method.
(comparative example 4)
Except using glass powder and this glass powder and resin material being mixed together and making the resin combination, through obtaining transparent composite base plate with comparative example 2 identical methods.
(comparative example 5)
Except using glass powder and this glass powder and resin material being mixed together and making the resin combination, through obtaining transparent composite base plate with comparative example 3 identical methods.
The fusing point of the hindered phenol system that in each embodiment and each comparative example, uses in addition, is for being described below.
·IRGANOX?1010：110～125℃
·ADK?STAB?AO-20：220℃
·SUMILIZER?BHT：69～73℃
·IRGANOX?1076：50～55℃
2. the evaluation of transparent composite base plate
2.1 optically anisotropic evaluation
Resulting transparent composite base plate is implemented following two stage wet heat treatment respectively.
< condition of first wet heat treatment >
Treatment temp: 85 ℃
Handle humidity: 85%RH
Treatment time: 1061 hours
< condition of second wet heat treatment >
Treatment temp: 85 ℃
Handle humidity: 85%RH
Treatment time: 3015 hours
Next, measure the optical anisotropy of the transparent composite base plate after the wet heat treatment respectively through following method.
Specify this measuring method: at first, observe through the transparent composite base plate after first wet heat treatment with orthogonal polarizing microscope.Then, fixedly the optical axis of polarizing microscope rotates transparent composite base plate under intensity of light source constant state, and the part or the whole base plate that are fixed in substrate become the brightest angle.Then, the observation of 2.4mm * 1.8mm is partly carried out image conversion (pixel count is 640 * 480) and with on its input minicomputer, converted thereof into the black white image that each pixel has 0～255 gray scale (gradation).Comprehensive income to black white image in the gray scale of each pixel, and with its optically anisotropic evaluation of estimate after as first wet heat treatment.
Then, the transparent composite base plate that uses in first wet heat treatment is used for wet heat treatment once more, and handles to the accumulated process time always and reach the above-mentioned second wet heat treatment condition.Then, adopt method same as described above, obtain black white image.Comprehensive income to black white image in the gray scale of each pixel, and with its optically anisotropic evaluation of estimate after as second wet heat treatment.
Evaluation result with 2.1 is illustrated in the table 1,2.
Can know clearly that from table 1,2 optical anisotropy of the transparent composite base plate that obtains through each embodiment is all less than the optical anisotropy of the transparent composite base plate that obtains through each comparative example.
2.2 the degassing is estimated
Adopt the chromatography of gases spectrometry mass that the degassing of the transparent composite base plate of gained is estimated.Wherein, estimating environment is 1 minute environment of heating under 300 ℃ temperature.
Its result, in the transparent composite base plate that obtains through each embodiment, not observing from hindered phenol is the volatilization of antioxidant composition.
It is the evaluation result (mass spectrum) of the monomeric degassing of inhibitor that Fig. 1 (a) is illustrated in the hindered phenol that uses among the embodiment 7; Fig. 1 (b) expression is by the evaluation result (mass spectrum) of the degassing of embodiment 7 resulting transparent composite base plates.
Clearly can know from Fig. 1 (a); For for the hindered phenol that uses among the embodiment 7 is inhibitor, it volatilizees through 300 ℃ heating under free state, and on mass spectrum, can be used as peak A and detect; With respect to this; Can know clearly that from Fig. 1 (b) the transparent composite base plate that obtains through embodiment 7 is not even detect peak A yet after 300 ℃ temperature heating.Can confirm thus; In the transparent composite base plate that obtains through embodiment 7, epoxy resin and hindered phenol are that inhibitor interacts, even under free state, take place in the evaporable high temperature; Also can suppress the volatilization of inhibitor, thereby it is residual that inhibitor is continued.
On the other hand, in the transparent composite base plate that obtains through each comparative example, confirmed volatilization from antioxidant composition.Thus, can confirm that inhibitor is overflowed through heating in these transparent composite base plates.In addition, think because the effusion of inhibitor has increased the weight of the deterioration of characteristics such as optical anisotropy.
Claims (12)
1. a resin combination is the resin combination that is used to make transparent composite base plate, it is characterized in that, containing epoxy resin, glass filler and hindered phenol is inhibitor.
2. resin combination as claimed in claim 1, wherein, said hindered phenol is that the content of inhibitor is 0.01 quality %～5 quality %.
3. according to claim 1 or claim 2 resin combination, wherein, said hindered phenol is that the fusing point of inhibitor is more than 100 ℃.
4. like each described resin combination in the claim 1～3, wherein, said hindered phenol is that inhibitor has the neopentane structure in molecular structure.
5. like each described resin combination in the claim 1～4, it is characterized in that, is inhibitor with respect to the hindered phenol of 100 mass parts, also contains the phosphorous antioxidant of 30～300 mass parts.
6. like each described resin combination in the claim 1～5, wherein, said epoxy resin comprises alicyclic epoxy resin and Racemic glycidol type epoxy resin.
7. resin combination as claimed in claim 6, wherein, said alicyclic epoxy resin contains by the alicyclic epoxy resin of following chemical formula (1) expression with by in the alicyclic epoxy resin of following chemical formula (2) expression at least one,
In above-mentioned formula (2) ,-X-representes-O-,-S-,-SO-,-SO
2-,-CH
2-,-CH (CH
3)-or-C (CH
3)
2-.
8. like claim 6 or 7 described resin combinations, wherein, with respect to the said alicyclic epoxy resin of 100 mass parts, the content of said Racemic glycidol type epoxy resin is 0.5～10 mass parts.
9. like each described resin combination in the claim 1～8, wherein, said glass filler is a glasscloth.
10. like each described resin combination in the claim 1～9, wherein, when said resin combination heats one minute under 300 ℃ temperature, said inhibitor or its decompose composition as gas detect in fact less than.
11. a transparent composite base plate is characterized in that, is made up of the cured article of each described resin combination in the claim 1～10.
12. a display element substrate is characterized in that, has the described transparent composite base plate of claim 11.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010145609 | 2010-06-25 | ||
| JP2010-145609 | 2010-06-25 | ||
| JP2011124139A JP2012025935A (en) | 2010-06-25 | 2011-06-02 | Resin composition, transparent composite substrate, and display element substrate |
| JP2011-124139 | 2011-06-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102337004A true CN102337004A (en) | 2012-02-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011101766315A Pending CN102337004A (en) | 2010-06-25 | 2011-06-22 | Resin composition, transparent composite substrate and substrate for display element |
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| Country | Link |
|---|---|
| KR (1) | KR20120000518A (en) |
| CN (1) | CN102337004A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104932148A (en) * | 2015-06-30 | 2015-09-23 | 厦门天马微电子有限公司 | Composite substrate, liquid crystal display screen, and manufacturing method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101010408A (en) * | 2004-08-31 | 2007-08-01 | 昭和电工株式会社 | Light-emitting body, lighting device and display device using the same |
| CN101522749A (en) * | 2006-10-11 | 2009-09-02 | 住友电木株式会社 | Transparent composite sheet |
-
2011
- 2011-06-22 CN CN2011101766315A patent/CN102337004A/en active Pending
- 2011-06-23 KR KR1020110061278A patent/KR20120000518A/en not_active Application Discontinuation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101010408A (en) * | 2004-08-31 | 2007-08-01 | 昭和电工株式会社 | Light-emitting body, lighting device and display device using the same |
| CN101522749A (en) * | 2006-10-11 | 2009-09-02 | 住友电木株式会社 | Transparent composite sheet |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104932148A (en) * | 2015-06-30 | 2015-09-23 | 厦门天马微电子有限公司 | Composite substrate, liquid crystal display screen, and manufacturing method |
| US10082703B2 (en) | 2015-06-30 | 2018-09-25 | Xiamen Tianma Micro-Electronics Co., Ltd. | Composite substrate and methods for fabricating the same, and liquid crystal display panel |
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|---|---|
| KR20120000518A (en) | 2012-01-02 |
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