CN102189728A - Laminated body film - Google Patents
Laminated body film Download PDFInfo
- Publication number
- CN102189728A CN102189728A CN201110065395XA CN201110065395A CN102189728A CN 102189728 A CN102189728 A CN 102189728A CN 201110065395X A CN201110065395X A CN 201110065395XA CN 201110065395 A CN201110065395 A CN 201110065395A CN 102189728 A CN102189728 A CN 102189728A
- Authority
- CN
- China
- Prior art keywords
- film
- group
- cage
- sio
- type silsesquioxane
- 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.)
- Granted
Links
- XYAOFRLIRVNNOP-UHFFFAOYSA-N CCC[NH+](CI)[IH-] Chemical compound CCC[NH+](CI)[IH-] XYAOFRLIRVNNOP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a laminated body film having excellent transparency, heat resistance and impact resistance, and formed by laminating a second layer of curable resin composite with cage type polyhedral oligomeric silsesquioxane curable organic silicon copolymer, including a structural unit represented by a general formula of Y-[Z-(O1/2-R22SiO1/2)a-(R3SiO3/2)k-(O1/2)b]1-Z-Y, on a first layer of curable resin composite including cage type polyhedral oligomeric silsesquioxane resin represented by (RSiO3/2)n; the first layer has excellent transparency, heat resistance and low thermal expansibility, and the second layer has excellent transparency, heat resistance and impact resistance, so that the laminated body film integrates excellent transparency, heat resistance, impact resistance and low thermal expansibility.
Description
Technical field
The present invention relates to the duplexer film of the transparency, hear resistance and resistance to impact excellence and low heat expansion.
Background technology
Utilizing of characteristics such as the transparency of glass performance all the time, hear resistance, low heat expansion, chemical stability is developed, is widely used as the optical glass of lens, CD and display base plate etc. since ancient times, helps the development of industry.In recent years, in such industrial field,, carrying out the research that heavy glass slimming is utilized for the such requirement of the lightweight that adapts to member.But,, therefore in the lightweight of the slimming that utilizes member, make and add the institute of breaking man-hour and cause that product percent of pass is declined to become problem because glass has poor impact resistance, such shortcoming of breaking easily.In order to improve easy disruptiveness, it is the film substrate (patent documentation 1) of resin bed, flexibility and the excellent heat resistance of main component with the metal oxide polymers that contains organic group that motion has the surperficial stacked of glass substrate, but using not change still on the glass this respect in these gimmicks, the further raising of lightweight and processability is difficult.
But, in recent years, utilize have the such characteristic of lightweight, slimming, the processability released previously, be that the trend of instead of glass of the transparent plastic material of target receives publicity with the optical applications.As the excellent plastic material of the transparency, can illustration polymethyl methacrylate (PMMA), ester ring type polyolefin, epoxy resin, organic siliconresin etc.Wherein,, therefore be known as lucite, obtain many uses as LGP, the CD purposes of optical lens, LCD because PMMA, ester ring type polyolefin have the excellent especially transparency.Therefore but these materials are because heat distortion temperature is low, and it is difficult using in the manufacturing of the substrate for display device of following for example 150 ℃～thermal process more than 200 ℃, and the purposes of glass is restricted as an alternative.
Up to now, the inventor etc., in patent documentation 2 motion have relate to used the transparency, hear resistance is high and the invention of the plastic foil of the cage-type silsesquioxane resin of excellent in dimensional stability.But, this plastic foil, though thick film has sufficient impact strength, thin film may cause product percent of pass to descend often during fabrication sometimes because of operation causes small damage, therefore has the leeway of improvement.
The prior art document
Patent documentation
Patent documentation 1: the spy opens the 2004-50565 communique
Patent documentation 2: the spy opens the 2006-89685 communique
Summary of the invention
The problem that invention will solve
The object of the present invention is to provide the duplexer film of the transparency, hear resistance and resistance to impact excellence, low heat expansion.
Invention solves the means of problem
The inventor etc., in view of aforesaid prior art problems is concentrated on studies repeatedly, found that, by in hear resistance, the transparency, low heat expansion aspect excellence, but then for resistance to impact stacked hear resistance on the face of the one or both sides of the layer (internal layer) that needs are further improved, the transparency, the layer of resistance to impact excellence (skin), thus by utilizing outer field impact absorbing layer to remedy internal layer for breaking easily of impacting, seek the raising of easy disruptiveness, and, by suppress the high thermal expansion of outer field interior direction with internal layer, can obtain with hear resistance, the transparency, resistance to impact, the duplexer film of low heat expansion, so that finished the present invention.
Promptly, the present invention is the duplexer film, it is characterized in that its second layer that contains the hardening resin composition that contains cage-type silsesquioxane curing organic silicon copolymer of the construction unit with following general formula (5) expression by the ground floor upper strata stacked package at the hardening resin composition that comprises the cage-type silsesquioxane resin that contains following general formula (1) expression forms.
[RSiO
3/2]
n (1)
(wherein, R is for being selected from any the organo-functional group in following general formula (2), (3) or (4), n=8,10,12 or 14)
[changing 1]
(wherein, m is 1～3 integer, R
1Expression hydrogen atom or methyl)
Y-[Z-(O
1/2-R
2 2SiO
1/2)
a-(R
3SiO
3/2)
k-(O
1/2)
b]
1-Z-Y (5)
(wherein, R
2And R
3For vinyl, alkyl, phenyl, (methyl) acryloyl group, pi-allyl or have the group of oxirane ring, at R
2Or R
3In, each substituting group can be the same or different each other, the R that contains in 1 molecule
3In at least one be in vinyl, (methyl) acryloyl group, pi-allyl or the group any with oxirane ring.In addition, a and basic b are 0～3 number, satisfy the relation of 1≤a+b≤4, k represents 8～14 number, is under the situation of odd number at k, and a and b comprise 0 the even number and the combination of odd number, at k is under the situation of even number, and a and b are the combination that comprises 0 even number, and l represents 1～2000 number.And Z is the divalent group of following general formula (6) expression, and Y is for being selected from any the 1 valency group in following general formula (7)～(10).)
[changing 2]
(wherein, R
4For hydrogen atom, vinyl, alkyl, phenyl, (methyl) acryloyl group, pi-allyl or have the group of oxirane ring, R
4Can be the same or different each other, in addition, p represents 0～30 number.)
[(R
5O)R
6 2SiO
1/2]
c-[R
7SiO
3/2]
d-[O
1/2]- (7)
[R
5O
1/2]
e-[R
7SiO
3/2]
d-[O
1/2-R
6 2SiO
1/2]- (8)
(R
5O
1/2)- (9)
(R
5 3SiO
1/2)- (10)
(wherein, R
6And R
7For vinyl, alkyl, phenyl, (methyl) acryloyl group, pi-allyl or have the group of oxirane ring, R
6Or R
7In, each substituting group can be the same or different each other, R
5Be selected from hydrogen atom, methyl or ethyl, in addition, c and e are 0～3 number, and d is 8～14 number, is under the situation of odd number at d, and c and e are 0 or 2 respectively independently, are under the situation of even number at d, and c and e are respectively 1 or 3 independently.)
The effect of invention
According to duplexer film of the present invention, owing to the duplexer film that its second layer that contains the hardening resin composition of cage-type silsesquioxane curing organic silicon copolymer for single face or the stacked package of upper strata, two sides at the ground floor that comprises the hardening resin composition that contains the cage-type silsesquioxane resin forms, therefore can obtain the duplexer film of the transparency, hear resistance and resistance to impact excellence and low heat expansion.Such duplexer film; for example as used for liquid crystal display element substrate, colored filter with substrate, organic EL substrate for display device, Electronic Paper with substrate, TFT glass substitute material with the window material of the blooming purposes of the film of the transparency carrier of substrate, solar cell substrate etc., touch panel, band transparency electrode, LGP, diaphragm, light polarizing film, phase retardation film, lens etc., various transmit machine, dwelling house etc.; it utilizes scope to broaden, and the value on the industry is high.
The specific embodiment
Below, for duplexer film of the present invention, at length describe based on preferred implementation.
In the present invention, the ground floor of duplexer film (being also referred to as internal layer), use comprises the layer of the hardening resin composition of the cage-type silsesquioxane resin that contains following general formula (1) expression.
[RSiO
3/2]
n (1)
(wherein, R is for being selected from any the organo-functional group in following general formula (2), (3) or (4), n=8,10,12 or 14)
[changing 3]
(wherein, m is 1～3 integer, R
1Expression hydrogen atom or methyl)
The cage-type silsesquioxane resin that is used for the formation of ground floor; be preferably have the reactive functional groups that is included in the organo-functional group that has (methyl) acryloyl group, glycidyl or vinyl on all silicon atoms, molecular weight distribution and the controlled cage-type silsesquioxane resin of molecular structure; a part can be by replacements such as alkyl, phenyl; in addition, also can not the polyhedral structure of complete closed but the structure of a part of cracking.In addition, the mean molecule quantity of such cage-type silsesquioxane resin also is not particularly limited, and such cage-type silsesquioxane resin also can be oligomer.
The hardening resin composition that contains the cage-type silsesquioxane resin of the formation that is useful on ground floor, except cage-type silsesquioxane, also can be for being mixed with the hardening resin composition that has compatibility and reactive curable resin with this cage-type silsesquioxane resin.The hardening resin composition that contains such cage-type silsesquioxane resin is the resin combination that can solidify by heat treated, the resin combination that maybe can solidify by the irradiation active energy ray.
As having compatibility and reactive curable resin, for example can enumerate repeat number as construction unit and be reactive oligomer of about 2～20 polymer or low-molecular-weight, low viscous reactive monomer with the cage-type silsesquioxane resin.Particularly, as reactive oligomer, can the illustration epoxy acrylate, epoxidized oil acrylate, urethane acrylate, unsaturated polyester (UP), polyester acrylate, polyether acrylate, vinylacrylic acid ester, polyenoid/mercaptan, organic silicon acrylic ester, polybutadiene, polystyrene-based EMA etc.In addition, as reactive monomer, can illustration styrene, vinylacetate, the N-vinyl pyrrolidone, butyl acrylate, 2-EHA, the just own ester of acrylic acid, cyclohexyl acrylate, acrylic acid ester in the positive last of the ten Heavenly stems, isobornyl acrylate, two cyclopentene oxygen bases (ジ シ Network ロ ペ Application テ ニ ロ キ シ) ethyl propylene acid esters, the acrylic acid phenoxy ethyl, the monofunctional monomer of trifluoroethyl methacrylate etc., or two cyclopenta (ジ シ Network ロ ペ Application タ ニ Le) diacrylate, tripropylene glycol diacrylate, 1, the 6-hexanediyl ester, the bisphenol A diglycidyl ether diacrylate, tetraethylene glycol diacrylate, 3-hydroxypivalic acid neopentylglycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, the polyfunctional monomer of dipentaerythritol acrylate etc.
As having compatibility and reactive curable resin with the cage-type silsesquioxane resin, except that above illustrative curable resin, can use various reactive oligomers, monomer, these can be used alone, can also be two or more kinds in combination respectively.
The hardening resin composition that contains the cage-type silsesquioxane resin of the formation that is useful on ground floor can add various additives in the scope that does not depart from purpose of the present invention.As various additives, can illustration organic/inorganic filler, plasticizer, fire retardant, heat stabilizer, antioxidant, light stabilizer, ultra-violet absorber, lubricant, antistatic additive, releasing agent, blowing agent, nucleator, colouring agent, crosslinking agent, dispersing aid etc., but be not limited to these.
The hardening resin composition that contains the cage-type silsesquioxane resin of the formation that is useful on ground floor, need contain the cage-type silsesquioxane resin, the content of such cage-type silsesquioxane resin is preferably the above amount of 3 quality % that reaches, more preferably reaches amount in the scope of 5～50 quality %.Above-mentioned content is lower than down in limited time, as the duplexer film that obtains important hear resistance deficiency in the manufacturing process that follows hot worked substrate for display device etc.On the other hand, above-mentioned content surpasses above-mentioned going up in limited time, and the toughness that obtains the duplexer film is impaired, because the bad of the breakage of crackle, film etc. taken place easily on the surface in carrying.
At the hardening resin composition that contains the cage-type silsesquioxane resin of the formation that is used for ground floor, also can further contain polymerization initiator as required.As such polymerization initiator, so long as Photoepolymerizationinitiater initiater, thermal polymerization get final product, commercially available product can suit to select to use.As Photoepolymerizationinitiater initiater, for example can enumerate alkynes benzophenone (ァ Le キ Application Off ェ ノ Application) class, acylphosphine oxide class, two luxuriant titanium classes etc.As thermal polymerization, for example can enumerate ketone peroxide class, ketal peroxide class, hydroperoxide type, dialkyl peroxide class, diacyl peroxide class, peroxy dicarbonates, peroxyesters etc.
In the present invention, can also use appropriate solvent to wait as the viscosity adjustment of being cured property of diluent resin combination uses, but operation needs the time because the volatilization of solvent is removed, production efficiency descends, there is residual solvent etc. in the resin bed inside that obtains after the curing and causes degradation under the characteristic of formed film, therefore in the hardening resin composition of coating, the content of solvent is limited to below 5% is advisable, and more preferably, uses not solvent-laden composition to be advisable.In addition, such hardening resin composition does not produce volatile ingredient during preferred consolidation.
In the present invention in the second layer (being also referred to as skin) of duplexer film, use comprises the layer of hardening resin composition, the cage-type silsesquioxane that contains that this hardening resin composition contains the construction unit with following general formula (5) expression solidifies the organic silicon copolymer
Y-[Z-(O
1/2-R
2 2SiO
1/2)
a-(R
3SiO
3/2)
k-(O
1/2)
b]
1-Z-Y (5)
[wherein, R
2And R
3For vinyl, alkyl, phenyl, (methyl) acryloyl group, pi-allyl or have the group of oxirane ring, at R
2Or R
3In, each substituting group can be the same or different each other, the R that contains in 1 molecule
3In at least one be in vinyl, (methyl) acryloyl group, pi-allyl or the group any with oxirane ring.In addition, a and b are 0～3 number, satisfy the relation of 1≤a+b≤4, k represents 8～14 number, is under the situation of odd number at k, and a and b comprise 0 the even number and the combination of odd number, at k is under the situation of even number, and a and b are the combination that comprises 0 even number, and l represents 1～2000 number.And Z is the divalent group of following general formula (6) expression, and Y is for being selected from any the 1 valency group in following general formula (7)～(10).)
[changing 4]
(wherein, R
4For hydrogen atom, vinyl, alkyl, phenyl, (methyl) acryloyl group, pi-allyl or have the group of oxirane ring, R
4Can be the same or different each other, in addition, p represents 0～30 number.)
[(R
5O)R
6 2SiO
1/2]
c-[R
7SiO
3/2]
d-[O
1/2]- (7)
[R
5O
1/2]
e-[R
7SiO
3/2]
d-[O
1/2-R
6 2SiO
1/2]- (8)
(R
5O
1/2)- (9)
(R
5 3SiO
1/2)- (10)
(wherein, R
6And R
7For vinyl, alkyl, phenyl, (methyl) acryloyl group, pi-allyl or have the group of oxirane ring, R
6Or R
7In, each substituting group can be the same or different each other, R
5Be selected from hydrogen atom, methyl or ethyl, in addition, c and e are 0～3 number, and d is 8～14 number, is under the situation of odd number at d, and c and e are 0 or 2 respectively independently, are under the situation of even number at d, and c and e are respectively 1 or 3 independently.)
The cage-type silsesquioxane that contains that is used for the formation of the second layer solidifies the organic silicon copolymer, be preferably the controlled cage-type silsesquioxane that contains of molecular weight distribution and molecular structure and solidify the organic silicon copolymer, molecular weight distribution wide also can, in addition weight average molecular weight is to get final product more than 7000, be not particularly limited.
The hardening resin composition that is used for the formation of the second layer can contain cage-type silsesquioxane and solidifies the organic silicon copolymer, and contains the hardening resin composition that cage-type silsesquioxane curing organic silicon copolymer has compatibility and reactive curable resin with this for being mixed with.
As with contain cage-type silsesquioxane and solidify the organic silicon copolymer and have compatibility and reactive curable resin, for example can enumerate repeat number as construction unit and be reactive oligomer of about 2～20 polymer or low-molecular-weight, low viscous reactive monomer.Particularly, as reactive oligomer, can the illustration epoxy acrylate, epoxidized oil acrylate, urethane acrylate, unsaturated polyester (UP), polyester acrylate, polyether acrylate, vinylacrylic acid ester, polyenoid/mercaptan, organic silicon acrylic ester, polybutadiene, polystyrene-based EMA etc.In addition, as reactive monomer, can illustration styrene, vinylacetate, the N-vinyl pyrrolidone, butyl acrylate, 2-EHA, the just own ester of acrylic acid, cyclohexyl acrylate, acrylic acid ester in the positive last of the ten Heavenly stems, isobornyl acrylate, two cyclopentene oxygen base ethyl propylene acid esters, the acrylic acid phenoxy ethyl, the monofunctional monomer of trifluoroethyl methacrylate etc., or two cyclopenta diacrylate, tripropylene glycol diacrylate, 1, the 6-hexanediyl ester, the bisphenol A diglycidyl ether diacrylate, tetraethylene glycol diacrylate, 3-hydroxypivalic acid neopentylglycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, the polyfunctional monomer of dipentaerythritol acrylate etc.These can be used alone, can also be two or more kinds in combination respectively.
The hardening resin composition that is used for the formation of the second layer can add various additives in the scope that does not depart from purpose of the present invention.As various additives, can the illustration thermoplastic resin and heat cured elastomer, rubber, organic/inorganic filler, plasticizer, fire retardant, heat stabilizer, antioxidant, light stabilizer, ultra-violet absorber, lubricant, antistatic additive, releasing agent, blowing agent, nucleator, colouring agent, crosslinking agent, dispersing aid etc., but be not limited to these.
The content that cage-type silsesquioxane solidifies the organic silicon copolymer that contains at the hardening resin composition of the formation that is used for the second layer preferably, makes and is advisable more than the 3 weight %.Above-mentioned content is lower than down in limited time, in following the manufacturing process of hot worked substrate for display device, and important hear resistance deficiency.
At the hardening resin composition of the formation that is used for the second layer, as required, can further have polymerization initiator.As such polymerization initiator,, can suitably select to use commercially available product so long as Photoepolymerizationinitiater initiater, thermal polymerization get final product.As Photoepolymerizationinitiater initiater, for example can enumerate alkynes benzophenone class, acylphosphanes oxidation class, two luxuriant titanium classes etc.As thermal polymerization, for example can enumerate ketone peroxide class, ketal peroxide class, hydroperoxide type, dialkyl peroxide class, diacyl peroxide class, peroxy dicarbonates, peroxyesters etc.
In the present invention, can also use appropriate solvent to wait as the viscosity adjustment of being cured property of diluent resin combination uses,, the resin bed inside that operation needs the time because the volatilization of solvent is removed, production efficiency descends, obtain after solidifying causes degradation under the characteristic of formed film but existing residual solvent etc., therefore in the hardening resin composition of coating, the content of solvent is limited to below 5% and gets final product, more preferably, use not solvent-laden composition to be advisable.In addition, such hardening resin composition does not produce volatile ingredient during preferred consolidation.
Duplexer film of the present invention is preferably formed the duplexer film for the three-decker that comprises " second layer (skin)-ground floor (the internal layer)-second layer (skin) ".Compare with only comprising to be provided with as the duplexer film of the two-layer structure of outer field resin bed, can reduce warpage, distortion of film etc. at single face.In addition, 2 outer field hardening resin compositions can be formed by same composition, in the little scope of distortion of warpage, bending etc., also can make the hardening resin composition difference of each face.
The skin of duplexer film and the thickness ratio of internal layer (layer thickness in the outer layer thickness ÷) are to be advisable below 1.0 more than 0.01, more preferably, are to be advisable below 1.0 more than 0.025.Above-mentioned thickness ratio is lower than down in limited time, probably outerly becomes thin and effect, duplexer film that can not give full play to as the impact absorbing layer of outer field feature are damaged easily.On the other hand, above-mentioned thickness ratio surpass last in limited time, probably outer become blocked up and can not restrict the thermal expansion of direction in the face on top layer with internal layer, the dimensional stability of duplexer film worsens.And the crooked quantitative change of duplexer film is big, can not expect that the resistance to impact of internal layer improves.
For the thickness of duplexer film, need internal layer and outer field thickness ratio to satisfy above-mentioned scope, more preferably, the gross thickness of duplexer film is that 10～1000 μ m are advisable, more preferably, is that 50～200 μ m are advisable.The thickness of duplexer film is lower than down in limited time, and the thickness of duplexer film became thin, as the rigidity deficiency of duplexer film.In addition, the thickness of duplexer film surpasses last prescribing a time limit, and inner layer film just fully has the resistance to impact as film separately, so the intention of making layer stack structure diminishes.
For the transparency of duplexer film, the light penetration of duplexer film at wavelength 550nm place before the heating for example as described below is preferably more than 85%, is preferably more than 90% especially.And, be preferably more than 85% at the light penetration at wavelength 550nm place after 2 hours 150 ℃ of following heat treated, be preferably more than 90% especially.In the present invention, by the stacked second layer that demonstrates the light penetration of above-mentioned scope on the ground floor of the light penetration that demonstrates above-mentioned scope, can guarantee the aforesaid transparency.
Thermal coefficient of expansion for duplexer film of the present invention, because the thermal expansion of outer field interior direction is restricted by the internal layer of low heat expansion excellence, even therefore individual layer direction in face demonstrates identical thermal expansion behavior with thickness direction, by forming the duplexer film, the part of outer field thermal expansion partly shows as the increase of the thermal expansion of thickness direction, the thermal coefficient of expansion of duplexer film direction in face demonstrates different values with thickness direction, therefore, below the thermal coefficient of expansion of said duplexer film of the present invention, be meant the thermal coefficient of expansion of the thermal coefficient of expansion gained of under the state of duplexer film, obtaining direction in its face.
Linear expansion coefficient for direction in the face of duplexer film is preferably below the 80ppm/K, more preferably below the 60ppm/K.Linear expansion coefficient surpasses last prescribing a time limit, and under situation about using as materials such as base plate for displaying, touch panels, the poor of linear expansion coefficient with circumferential component in comprising the manufacturing process of thermal process becomes big, so the reliability deficiency.In addition, for the linear expansion coefficient of each layer that constitutes the duplexer film, uses the linear expansion coefficient of internal layer to be lower than 80ppm/K, outer field linear expansion coefficient of while is advisable as the duplexer more than the 80ppm/K.The linear expansion coefficient of internal layer is 80ppm/K when above, and the linear expansion coefficient of duplexer film uprises, and diminishes as the intention of the duplexer film production stepped construction of low heat expansion excellence.Outer field linear expansion coefficient is 80ppm/K when following, be the fully excellent film of low heat expansion as individual layer, so the intention of making layer stack structure diminishes.In addition, say, the thermal expansion of direction restricts outer field expansion by internal layer in the face of duplexer film, the linear expansion coefficient as the duplexer film can be suppressed at the value of internal layer, does not therefore stipulate the higher limit of outer field linear expansion coefficient.
For the elastic modelling quantity of duplexer film, need the elastic modelling quantity of outer field modular ratio internal layer little.Under the big situation of the elastic modelling quantity of outer field modular ratio internal layer, the amount of bow of duplexer film increases, and can not expect the raising of resistance to impact.In addition, I'm afraid that outer field linear expansion coefficient becomes overriding, as can not to suppress outer field interior direction coefficient of thermal expansion.
Production method for duplexer film of the present invention is not particularly limited, for example can enumerate and to solidify the two sides of the film that forms as the hardening resin composition that contains the cage-type silsesquioxane resin of internal layer, the method that coating is made the duplexer film as the outer field hardening resin composition that contains cage-type silsesquioxane curing organic silicon copolymer, in addition, can also enumerate with the hardening resin composition that contains the cage-type silsesquioxane resin that will sandwich as the film that the outer field hardening resin composition curing that contains cage-type silsesquioxane curing organic silicon copolymer forms as the liquid state of internal layer, make the method for duplexer film.And, can enumerate coating as the hardening resin composition of the liquid state of skin and internal layer and the method that is cured simultaneously; Or make the hardening resin composition that contains the cage-type silsesquioxane resin as internal layer is solidified the film form and will contain hardening resin composition that cage-type silsesquioxane solidifies the organic silicon copolymer and solidify the film hot pressing that forms and fetch the method that forms the duplexer film etc. as outer field.The manufacture method of preferred each layer excellence aspect adaptation for the adaptation that further makes each layer improves, also can be carried out the surface-active-treatment of Corona discharge Treatment, ultraviolet treatment with irradiation, plasma treatment etc. on the surface of for example film.
Embodiment
Below, be described in detail by embodiment and comparative example for duplexer film of the present invention and manufacture method thereof, but the present invention is not limited to following embodiment.
[synthesis example 1: the manufacturing of the curable resin that in forming ground floor (internal layer), uses]
The cage-type silsesquioxane resin that uses in forming inner layer material, it is synthetic as getting off to open the method for putting down in writing in the 2004-143449 communique by the spy.
In the reaction vessel that possesses mixer, dropping funel and thermometer, pack into as 2-propyl alcohol (IPA) 40ml of solvent, as 5% tetramethylammonium hydroxide aqueous solution (the TMAH aqueous solution) 3.1g of base catalyst.In dropping funel, add IPA 15ml and 3-methacryloxypropyl trimethoxy silane 12.7g, on one side the stirring reaction container on one side at room temperature with the IPA solution of 30 minutes dropping 3-methacryloxypropyl trimethoxy silane.The 3-methacryloxypropyl trimethoxy silane is slowly turning back to room temperature after dripping and finishing, and does not add thermal agitation 2 hours.Under reduced pressure remove I PA after the stirring, with toluene 50ml dissolving.
[synthesis example 2: the manufacturing of the curable resin that in forming the second layer (skin), uses]
The cage-type silsesquioxane that contains that uses in forming cladding material solidifies the organic silicon copolymer, and it is synthetic as getting off to open the method for putting down in writing in the 2009-227863 communique by the spy.
Pack in reaction vessel toluene 250ml and phenyl trichlorosilane 52.5g are cooled to 0 ℃.An amount of water that drips is stirred to hydrolysis and finishes.Hydrolysate is washed the back add 30% commercially available benzyltrimethylammonium hydroxide solution 8.3ml, this mixture was heated 4 hours at reflux temperature.To all cool off then, place about 96 hours.To cool off then through the slurry that obtains after this time once more reflux temperature heating 24 hours, filter, obtain octaphenyl silsesquioxane 37.5g with the form of powder of white.
Then, possess Dean Stark device (デ ィ Application ス タ one Network), and the reaction vessel of condenser pipe in add toluene 100ml, TMAH 0.123g (1.35mmol, with 25% the form 0.49g of methanol solution), above-mentioned octaphenyl silsesquioxane 20.3g (19.7mmol) and 3-methacryloxypropyl diethoxymethyl silane 5.12g (19.7mmol), heat 1 hour distillation for removing methanol down at 80 ℃, further be heated to 100 ℃, after 2 hours, return to room temperature, reaction is finished.The white powder of the octaphenyl silsesquioxane of reaction solution disappears, and can judge fully and react.
With reaction solution with in 10% aqueous citric acid solution and after, water cleans, and dewaters with anhydrous magnesium sulfate.Remove by filter anhydrous magnesium sulfate, concentrate, obtain the cage-type silsesquioxane 19.7g of water white viscous liquid thus with 78% yield.The cage-type silsesquioxane that obtains is measured by GPC and NMR structure is confirmed.And, under nitrogen atmosphere, in the reaction vessel that possesses dropping funel and condenser pipe, the toluene 15ml that packs into, the above-mentioned cage-type silsesquioxane 9.0g (7mmol) that obtains and TMAH 4mg (the form 153mg of 0.044mmol, methanol solution) with 2.5%.70 ℃ down on one side stirring reaction solution on one side from dropping funel with dripping silanol end dimethyl silicone polymer (DMS-S 12:Mn (number-average molecular weight)=400-700: 4.6g ァ ズ マ ッ Network ス Co., Ltd.) in 3 hours.Further stir after 3 hours cool to room temperature.
With reaction solution with in 10% aqueous citric acid solution and after, water cleans, and dewaters with anhydrous magnesium sulfate.Remove by filter anhydrous magnesium sulfate, concentrate, the cage-type silsesquioxane that contains that obtains water white viscous liquid thus solidifies organic silicon copolymer 1 2.5g.The result of the GPC that contains cage-type silsesquioxane curing organic silicon copolymer that mensuration obtains, weight average molecular weight (Mw)=14000.Measure the result of 1H-NMR in addition, be confirmed to be to contain the resin that cage-type silsesquioxane solidifies the organic silicon copolymer.
[embodiment 1]
The cage-type silsesquioxane that contains that synthesis example 2 is obtained solidifies the organic silicon copolymer: 30 weight portions, two cyclopenta diacrylates: 70 weight portions and as the 2-hydroxy-2-methyl propiophenone of Photoepolymerizationinitiater initiater: 1.5 weight portions mix, froth breaking, obtain liquid hardening resin composition.Then, on glass plate, use roll coater casting hardening resin composition so that reach thickness 15 μ m, and then, use the high-pressure mercury-vapor lamp of 80W/cm, with 2000mJ/cm from last stacked coated glass sheets
2The accumulated exposure amount it is solidified after, peel off the film that has solidified from glass, obtain the skin film of 2 regulation thickness.
Then, the cage-type silsesquioxane resin that synthesis example 1 is obtained: 20 weight portions, trimethylolpropane triacrylate: 25 weight portions, two cyclopenta diacrylates: 55 weight portions and as the 1-hydroxycyclohexylphenylketone of Photoepolymerizationinitiater initiater: 2.5 weight portions mix, froth breaking, obtain liquid hardening resin composition, use the hardening resin composition of the above-mentioned liquid state that obtains of roll coater casting so that reach thickness 50 μ m at above-mentioned 1 skin that obtains on film, carry out crimping with another sheet skin with film from it, use the high-pressure mercury-vapor lamp of 80W/cm, with 2000mJ/cm
2The accumulated exposure amount make its curing, 15 μ m)-inner layer material (thickness: 50 μ m)-cladding material (thickness: the duplexer film of] 3-tier architecture 15 μ m) comprised [cladding material (thickness:.
[embodiment 2]
15 μ m)-internal layer (thickness: 80 μ m)-outer (thickness: the duplexer film of 3-tier architecture 15 μ m) casting thickness of internal layer is become 80 μ m, in addition, similarly to Example 1, obtain comprising skin (thickness:.
[embodiment 3]
25 μ m)-internal layer (thickness: 50 μ m)-outer (thickness: the duplexer film of 3-tier architecture 25 μ m) skin is become 25 μ m with the thickness of film, in addition, similarly to Example 1, obtain comprising skin (thickness:.
[embodiment 4]
The cage-type silsesquioxane resin that synthesis example 1 is obtained: 20 weight portions, trimethylolpropane triacrylate: 25 weight portions, two cyclopenta diacrylates: 55 weight portions and as the 1-hydroxycyclohexylphenylketone of Photoepolymerizationinitiater initiater: 2.5 weight portions mix, froth breaking, obtain liquid hardening resin composition.Then, on glass plate, use roll coater casting hardening resin composition so that reach thickness 50 μ m, and then, use the high-pressure mercury-vapor lamp of 80W/cm, with 2000mJ/cm from last stacked coated glass sheets
2The accumulated exposure amount it is solidified after, peel off the film that has solidified from glass, obtain the internal layer film of specific thickness.
Then, the cage-type silsesquioxane that contains that synthesis example 2 is obtained solidifies the organic silicon copolymer: 30 weight portions, two cyclopenta diacrylates: 70 weight portions and as the 2-hydroxy-2-methyl propiophenone of Photoepolymerizationinitiater initiater: 1.5 weight portions mix, froth breaking, obtain liquid hardening resin composition.Then, on glass plate, use roll coater casting hardening resin composition so that reach thickness 15 μ m, from the above-mentioned internal layer film of last covering, and then use roll coater to cast above-mentioned hardening resin composition so that reach thickness 15 μ m, cover glass thereon, use the high-pressure mercury-vapor lamp of 80W/cm, with 2000mJ/cm
2The accumulated exposure amount it is solidified after, peel off the film that has solidified from glass, 15 μ m)-internal layer (thickness: 50 μ m)-outer (thickness: the duplexer film of] 3-tier architecture 15 μ m) comprised [outer (thickness:.
[embodiment 5]
The cage-type silsesquioxane that contains that synthesis example 2 is obtained solidifies the organic silicon copolymer: 50 weight portions, two cyclopenta diacrylates: 50 weight portions and as the 2-hydroxy-2-methyl propiophenone of Photoepolymerizationinitiater initiater: 1.5 weight portions mix, froth breaking, obtain liquid hardening resin composition.Then, on glass plate, use roll coater casting hardening resin composition so that reach thickness 15 μ m, and then, use the high-pressure mercury-vapor lamp of 80W/cm, with 2000mJ/cm from last stacked coated glass sheets
2The accumulated exposure amount it is solidified after, peel off the film that has solidified from glass, obtain the skin film of 2 regulation thickness.
Then, the cage-type silsesquioxane resin that synthesis example 1 is obtained: 20 weight portions, trimethylolpropane triacrylate: 25 weight portions, two cyclopenta diacrylates: 55 weight portions and as the 1-hydroxycyclohexylphenylketone of Photoepolymerizationinitiater initiater: 2.5 weight portions mix, froth breaking, obtain liquid hardening resin composition, use the above-mentioned liquid curing resin combination that obtains of roll coater casting so that reach thickness 50 μ m at above-mentioned 1 skin that obtains on film, carry out crimping with the above-mentioned skin of another sheet with film from it, use the high-pressure mercury-vapor lamp of 80W/cm, with 2000mJ/cm
2The accumulated exposure amount make its curing, 15 μ m)-internal layer (thickness: 50 μ m)-outer (thickness: the duplexer film of] 3-tier architecture 15 μ m) comprised [outer (thickness:.
[comparative example 1]
The cage-type silsesquioxane resin that synthesis example 1 is obtained: 25 weight portions, trimethylolpropane triacrylate: 20 weight portions, two cyclopenta diacrylates: 55 weight portions and as the 1-hydroxycyclohexylphenylketone of Photoepolymerizationinitiater initiater: 2.5 weight portions mix, froth breaking, obtain liquid hardening resin composition.Then, on glass plate, use roll coater to cast, and then, use the high-pressure mercury-vapor lamp of 80W/cm, with 2000mJ/cm from last stacked coated glass sheets so that reach thickness 80 μ m
2The accumulated exposure amount it is solidified after, peel off the film that has solidified from glass, obtained forming the monofilm of specific thickness.
[comparative example 2]
The cage-type silsesquioxane that contains that synthesis example 2 is obtained solidifies the organic silicon copolymer: 30 weight portions, two cyclopenta diacrylates: 70 weight portions and as the 2-hydroxy-2-methyl propiophenone of Photoepolymerizationinitiater initiater: 1.5 weight portions mix, froth breaking, obtain liquid hardening resin composition.Then, on glass plate, use roll coater to cast, and then, use the high-pressure mercury-vapor lamp of 80W/cm, with 2000mJ/cm from last stacked coated glass sheets so that reach thickness 80 μ m
2The accumulated exposure amount it is solidified after, peel off the film that has solidified from glass, obtained forming the monofilm of specific thickness.
[comparative example 3]
The cage-type silsesquioxane that contains that synthesis example 2 is obtained solidifies the organic silicon copolymer: 50 weight portions, two cyclopenta diacrylates: 50 weight portions and as the 2-hydroxy-2-methyl propiophenone of Photoepolymerizationinitiater initiater: 1.5 weight portions mix, froth breaking, obtain liquid hardening resin composition.Then, on glass plate, use roll coater to cast, and then, use the high-pressure mercury-vapor lamp of 80W/cm, with 2000mJ/cm from last stacked coated glass sheets so that reach thickness 80 μ m
2The accumulated exposure amount it is solidified after, peel off the film that has solidified from glass, obtained forming the monofilm of specific thickness.
[comparative example 4]
Prepare PMMA (MR-200, レ ィ ョ Application society of the Mitsubishi make) sheet material of thickness 0.6mm.
To the embodiment of above-mentioned preparation and the film of comparative example, carry out following evaluation of physical property.Show the result in table 1.
[evaluation method: light penetration]
Use ultraviolet-uisible spectrophotometer (Hitachi makes the U4000 of manufacturing), for before the following heating, and each film after having heated 2 hours under 150 ℃, measure the light transmission rate spectrogram under the light of 400～800nm, be shown the transmitance of the light of wavelength 550nm as typical value.
[evaluation method: glass transition temperature]
In dynamic mechanical analysis (DMA) device, under the condition apart from 10mm, 16Hz between 5 ℃/min of programming rate, chuck, tan δ is reached the temperature of maximum as glass transition temperature.
[evaluation method: linear expansion coefficient]
In the tensile load pattern of thermo-mechanical analysis device (TMA), be determined under the condition of 5 ℃/min of programming rate variation from 50 ℃ to 150 ℃ thermal expansion amount.Need to prove, in comparative example 4, demonstrating rapid line swell increment more than 100 ℃, therefore, mensuration is from the variation of 50 ℃ to 90 ℃ thermal expansion amount.
[evaluation method: tensile modulus of elasticity]
Use cupping machine (RTE-1210 that ORIENTEC society makes), be determined at 25 ℃ of tensiles modulus of elasticity of each film down.At this moment, measuring under the condition apart from 50mm and draw speed 2mm/min between chuck.
[evaluation method: falling weight impact test]
The hammer (R=2.5mm) that carries out making more than 5 times 40g from the skin of highly vertically freely falling the duplexer film arbitrarily with the test on the face of film, the height during with this duplexer film destroy of the probability assessment more than 50%.
[table 1]
The rerum natura of the film that embodiment and comparative example obtain is as shown in table 1, in embodiment 1～5 and comparative example 1, is not observing clear and definite glass transition temperature below 300 ℃.Confirm by The above results, have the film that is equipped with hear resistance, resistance to impact and low heat expansion concurrently, in comparative example 1, compare with the duplexer film of embodiment, be the inadequate film of resistance to impact though have hear resistance with respect to having obtained in an embodiment.In addition, in comparative example 2 and 3, can only obtain the resistance to impact height but the inadequate film of low heat expansion.And in comparative example 4, in heat-resistance test, film deforms under 150 ℃ heating, increases at the high temperature field linear expansion coefficient more than 100 ℃ in addition, is the inadequate sheet material of hear resistance.
Claims (1)
1. duplexer film, it is characterized in that, it forms by the second layer that the ground floor upper strata stacked package at the hardening resin composition that comprises the cage-type silsesquioxane resin that contains following general formula (1) expression contains the hardening resin composition of cage-type silsesquioxane curing organic silicon copolymer, the described cage-type silsesquioxane that contains solidifies the construction unit that the organic silicon copolymer has following general formula (5) expression
[RSiO
3/2]
n (1)
Wherein, R is for being selected from any the organo-functional group in following general formula (2), (3) or (4), n=8,10,12 or 14;
Wherein, m is 1～3 integer, R
1Expression hydrogen atom or methyl;
Y-[Z-(O
1/2-R
2 2SiO
1/2)
a-(R
3SiO
3/2)
k-(O
1/2)
b]
1-Z-Y (5)
Wherein, R
2And R
3For vinyl, alkyl, phenyl, (methyl) acryloyl group, pi-allyl or have the group of oxirane ring, at R
2Or R
3In, each substituting group can be the same or different each other, the R that contains in 1 molecule
3In at least one be in vinyl, (methyl) acryloyl group, pi-allyl or the group any with oxirane ring, in addition, a and b are 0～3 number, satisfy the relation of 1≤a+b≤4, k represents 8～14 number, at k is under the situation of odd number, a and b comprise 0 the even number and the combination of odd number, at k is under the situation of even number, a and b are the combination that comprises 0 even number, and l represents 1～2000 number, and, Z is the divalent group of following general formula (6) expression, and Y is for being selected from any the 1 valency group in following general formula (7)～(10);
[changing 2]
Wherein, R
4For hydrogen atom, vinyl, alkyl, phenyl, (methyl) acryloyl group, pi-allyl or have the group of oxirane ring, R
4Can be the same or different each other, in addition, p represents 0～30 number;
[(R
5O)R
6 2SiO
1/2]
c-[R
7SiO
3/2]
d-[O
1/2]- (7)
[R
5O
1/2]
e-[R
7SiO
3/2]
d-[O
1/2-R
6 2SiO
1/2]- (8)
(R
5O
1/2)- (9)
(R
5 3SiO
1/2)- (10)
Wherein, R
6And R
7For vinyl, alkyl, phenyl, (methyl) acryloyl group, pi-allyl or have the group of oxirane ring, R
6Or R
7In, each substituting group can be the same or different each other, R
5Be selected from hydrogen atom, methyl or ethyl, in addition, c and e are 0～3 number, and d is 8～14 number, is under the situation of odd number at d, and c and e are 0 or 2 respectively independently, are under the situation of even number at d, and c and e are respectively 1 or 3 independently.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-062171 | 2010-03-18 | ||
| JP2010062171A JP5281607B2 (en) | 2010-03-18 | 2010-03-18 | Laminate film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102189728A true CN102189728A (en) | 2011-09-21 |
| CN102189728B CN102189728B (en) | 2014-11-12 |
Family
ID=44598994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110065395.XA Expired - Fee Related CN102189728B (en) | 2010-03-18 | 2011-03-18 | Laminated body film |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5281607B2 (en) |
| KR (1) | KR20110105338A (en) |
| CN (1) | CN102189728B (en) |
| TW (1) | TWI471219B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104732886A (en) * | 2013-12-24 | 2015-06-24 | 乐金显示有限公司 | Hard Coating Film And Display Device Using The Same |
| CN105273559A (en) * | 2014-06-30 | 2016-01-27 | 乐金显示有限公司 | Display device |
| CN109514954A (en) * | 2014-03-07 | 2019-03-26 | 株式会社可乐丽 | Laminated body |
| CN109923448A (en) * | 2016-12-28 | 2019-06-21 | 日本瑞翁株式会社 | Optical film and polarizing film |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5554724B2 (en) * | 2011-01-05 | 2014-07-23 | 新日鉄住金化学株式会社 | Gas barrier laminate film and method for producing the same |
| WO2013111990A1 (en) * | 2012-01-27 | 2013-08-01 | 제일모직 주식회사 | Laminate for window sheet, window sheet comprising same and display device comprising same |
| KR102047226B1 (en) * | 2013-01-25 | 2019-11-21 | 엘지디스플레이 주식회사 | Cover window for display device |
| KR101377472B1 (en) * | 2013-06-11 | 2014-03-26 | 주식회사 이솔 | Viewing window pannel of flip cover for movile phone and method for manufacturing the same |
| KR101611935B1 (en) * | 2014-04-23 | 2016-04-12 | (주)휴넷플러스 | Resin composition for trasparent plastic substrate |
| JPWO2022191328A1 (en) * | 2021-03-12 | 2022-09-15 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005104025A (en) * | 2003-09-30 | 2005-04-21 | Fuji Photo Film Co Ltd | Laminated film with gas barrier properties and image display element using this laminated film |
| JP2006095783A (en) * | 2004-09-29 | 2006-04-13 | Dainippon Printing Co Ltd | Transparent gas barrier film and substrate for display using it |
| JP2006123306A (en) * | 2004-10-28 | 2006-05-18 | Dainippon Printing Co Ltd | Gas barrier laminate |
| CN101104326A (en) * | 2006-07-13 | 2008-01-16 | 新日铁化学株式会社 | Thin film lamination body and manufacturing method thereof |
| JP2009227863A (en) * | 2008-03-24 | 2009-10-08 | Nippon Steel Chem Co Ltd | Cage structure-containing curable silicone copolymer, method for producing the same, curable resin composition using cage structure-containing curable silicone copolymer, and cured product thereof |
| JP2009226914A (en) * | 2007-08-24 | 2009-10-08 | Dainippon Printing Co Ltd | Gas barrier sheet, and manufacturing method of the gas barrier sheet |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4256756B2 (en) * | 2002-09-30 | 2009-04-22 | 新日鐵化学株式会社 | Method for producing cage-type silsesquioxane resin having functional group |
| JP4920513B2 (en) * | 2006-07-13 | 2012-04-18 | 新日鐵化学株式会社 | Film laminate and method for producing the same |
| JP4964748B2 (en) * | 2007-11-22 | 2012-07-04 | 新日鐵化学株式会社 | Method for producing transparent laminate film |
| JP2009221321A (en) * | 2008-03-14 | 2009-10-01 | Nippon Steel Chem Co Ltd | Method for producing laminate |
-
2010
- 2010-03-18 JP JP2010062171A patent/JP5281607B2/en not_active Expired - Fee Related
-
2011
- 2011-03-04 TW TW100107329A patent/TWI471219B/en not_active IP Right Cessation
- 2011-03-11 KR KR1020110021667A patent/KR20110105338A/en not_active Application Discontinuation
- 2011-03-18 CN CN201110065395.XA patent/CN102189728B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005104025A (en) * | 2003-09-30 | 2005-04-21 | Fuji Photo Film Co Ltd | Laminated film with gas barrier properties and image display element using this laminated film |
| JP2006095783A (en) * | 2004-09-29 | 2006-04-13 | Dainippon Printing Co Ltd | Transparent gas barrier film and substrate for display using it |
| JP2006123306A (en) * | 2004-10-28 | 2006-05-18 | Dainippon Printing Co Ltd | Gas barrier laminate |
| CN101104326A (en) * | 2006-07-13 | 2008-01-16 | 新日铁化学株式会社 | Thin film lamination body and manufacturing method thereof |
| JP2009226914A (en) * | 2007-08-24 | 2009-10-08 | Dainippon Printing Co Ltd | Gas barrier sheet, and manufacturing method of the gas barrier sheet |
| JP2009227863A (en) * | 2008-03-24 | 2009-10-08 | Nippon Steel Chem Co Ltd | Cage structure-containing curable silicone copolymer, method for producing the same, curable resin composition using cage structure-containing curable silicone copolymer, and cured product thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104732886A (en) * | 2013-12-24 | 2015-06-24 | 乐金显示有限公司 | Hard Coating Film And Display Device Using The Same |
| US10032795B2 (en) | 2013-12-24 | 2018-07-24 | Lg Display Co., Ltd. | Hard coating film and display device using the same |
| CN109514954A (en) * | 2014-03-07 | 2019-03-26 | 株式会社可乐丽 | Laminated body |
| CN105273559A (en) * | 2014-06-30 | 2016-01-27 | 乐金显示有限公司 | Display device |
| US10082606B2 (en) | 2014-06-30 | 2018-09-25 | Lg Display Co., Ltd. | Display device |
| US11099303B2 (en) | 2014-06-30 | 2021-08-24 | Lg Display Co., Ltd. | Display device |
| CN109923448A (en) * | 2016-12-28 | 2019-06-21 | 日本瑞翁株式会社 | Optical film and polarizing film |
| CN109923448B (en) * | 2016-12-28 | 2021-04-23 | 日本瑞翁株式会社 | Optical film and polarizing plate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5281607B2 (en) | 2013-09-04 |
| TWI471219B (en) | 2015-02-01 |
| KR20110105338A (en) | 2011-09-26 |
| JP2011194647A (en) | 2011-10-06 |
| TW201204549A (en) | 2012-02-01 |
| CN102189728B (en) | 2014-11-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102189728B (en) | Laminated body film | |
| CN102040903B (en) | Uv curable resin composition for hard coat, and hard coated film and hard coated moldings using the same | |
| CN104105598A (en) | Laminate for window sheet, window sheet comprising same and display device comprising same | |
| TWI606090B (en) | Hardenable composition, transparent heat-resistant material and use thereof | |
| JP5439717B2 (en) | Transparent conductive film | |
| CN102171265A (en) | Curable resin composition and paint, and plastic molded product produced by laminating the same | |
| TW201339247A (en) | Glass fiber composite resin substrate | |
| CN105732987B (en) | Organopolysiloxane compound containing isocyanate groups, method for producing same, adhesive, pressure-sensitive adhesive, and coating agent | |
| JP6414883B2 (en) | Resin composition for light diffusion film and light diffusion film | |
| JP2007182557A (en) | Impact resisting adhesive layer, method for producing the same and impact resisting adhesive laminated structure | |
| JP5315829B2 (en) | Curable hard coat agent composition | |
| JP2007171521A (en) | Liquid crystal display panel structure, its manufacturing method and display device | |
| CN103974826A (en) | Optical member, ultraviolet curable resin composition, and cured product | |
| CN102205679A (en) | Gas obstruction laminate film | |
| CN103314024A (en) | Resin molding, and laminate produced using same | |
| WO2014045856A1 (en) | Laminate and use thereof | |
| TWI516507B (en) | Thermocurable resin composition containing (meth) acrylate resin and cured article using the same | |
| JP2014031453A (en) | Ultraviolet-curable resin composition for optical laminate, cured product and optical laminate | |
| JP5730009B2 (en) | Laminated body | |
| JP5554724B2 (en) | Gas barrier laminate film and method for producing the same | |
| JP5205785B2 (en) | Transparent film | |
| JP5698566B2 (en) | Silicone resin composition and molded body thereof | |
| TWI660842B (en) | Laminate and display cover | |
| JP2017218477A (en) | Photocurable resin composition for curved surface coating, image display device and method for manufacturing the same | |
| TW201545871A (en) | A surface enhanced transparent substrate and method for manufacturing thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB02 | Change of applicant information |
Address after: Tokyo, Japan Applicant after: Nippon Steel Chemical Co. Address before: Tokyo, Japan Applicant before: Nippon Seel Chemical Co., Ltd. |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: NIPPON SEEL CHEMICAL CO., LTD. TO: NIPPON STEEL + SUMITOMO METAL CORPORATION |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141112 Termination date: 20160318 |