WO2015146676A1 - Film optique, film réfléchissant les infrarouges utilisant ce dernier et verre feuilleté - Google Patents

Film optique, film réfléchissant les infrarouges utilisant ce dernier et verre feuilleté Download PDF

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Publication number
WO2015146676A1
WO2015146676A1 PCT/JP2015/057712 JP2015057712W WO2015146676A1 WO 2015146676 A1 WO2015146676 A1 WO 2015146676A1 JP 2015057712 W JP2015057712 W JP 2015057712W WO 2015146676 A1 WO2015146676 A1 WO 2015146676A1
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refractive index
film
layer
optical film
index layer
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PCT/JP2015/057712
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English (en)
Japanese (ja)
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一仁 伊原
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コニカミノルタ株式会社
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Publication of WO2015146676A1 publication Critical patent/WO2015146676A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/26—Reflecting filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/28—Interference filters
    • G02B5/281—Interference filters designed for the infrared light
    • G02B5/282—Interference filters designed for the infrared light reflecting for infrared and transparent for visible light, e.g. heat reflectors, laser protection
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/28—Interference filters
    • G02B5/283—Interference filters designed for the ultraviolet

Definitions

  • the present invention relates to an optical film, an infrared reflecting film using the same, and a laminated glass. More specifically, an optical film having an optical functional layer on a support, having an appropriate heat shrinkability, excellent followability when bonded to curved glass, and having transparency, tear strength and elongation at break.
  • the present invention relates to an optical film excellent in temperature, an infrared reflecting film excellent in light resistance and adhesion using the optical film, and a laminated glass having excellent resistance to heat wrinkles.
  • Patent Document 1 discloses a heat-shielding film in which an infrared absorber is added to a hard coat layer.
  • a PET film polyethylene terephthalate film
  • TAC film triacetyl cellulose film
  • Patent Document 2 a technique for controlling infrared reflection by laminating about 400 high refractive index layers and low refractive index layers is disclosed, but since the multilayer is laminated, the stiffness of the film is strong, There are problems such as lack of followability when bonding to a glass curved surface, and the edge portion of the curved surface cannot be applied well. Moreover, since a base material is a PET film, light resistance is bad and there exists a problem of causing yellow discoloration with time.
  • the present invention has been made in view of the above-described problems and situations, and a solution to the problem is an optical film having an optical functional layer on a support, and the support has an appropriate heat shrinkability.
  • An optical film with excellent followability when bonded to curved glass and excellent in transparency, tear strength and elongation at break, excellent in infrared reflection film and heat wrinkle using it, excellent in light resistance and bonding properties It is to provide a laminated glass having high resistance.
  • the present inventor is an optical film having an optical functional layer on at least one surface of a film-like support in the process of examining the cause of the above-mentioned problem in order to solve the above-mentioned problem, and the support is It contains a specific cellulose derivative (A) and a polymer (B) having a soft segment, and the heat shrinkage rate at 150 ° C. for 30 minutes is within a specific range in one direction in the plane and in a direction perpendicular thereto. It is possible to obtain an optical film having moderate heat shrinkability, excellent followability when bonded to curved glass, and excellent transparency, tear strength, and elongation at break by the optical film adjusted to I found it.
  • An optical film having an optical functional layer on at least one surface of a film-like support comprising a cellulose derivative (A) containing no aromatic ring and a polymer (B) having a soft segment.
  • the heat shrinkage ratio after leaving the support to stand for 30 minutes in an environment of 150 ° C. is 1.0 to 5.0% in one direction in the plane and in the direction perpendicular thereto.
  • Item 4 The optical film according to any one of Items 1 to 3, wherein the polymer (B) is an aliphatic polyester or a polyalkylene oxide.
  • R 1 to R 6 each represent a substituent; i represents an integer of 0 to 2, j represents an integer of 0 to 10, k represents an integer of 3 to 10, a, b and c each represent a constituent ratio (molar ratio), and the sum of a, b and c is 1.) 6).
  • Item 1 to Item 5 wherein the cellulose derivative (A) is any one of triacetylcellulose, diacetylcellulose, cellulose acetate propionate, or a mixture of at least two of them.
  • the optical film as described in any one of.
  • the optical functional layer has a high refractive index layer containing a first water-soluble binder resin and first metal oxide particles, and a low refractive index containing a second water-soluble binder resin and second metal oxide particles.
  • the optical film according to any one of Items 1 to 9, wherein the optical film is a layer in which rate layers are alternately laminated to selectively reflect infrared rays.
  • a laminated glass comprising the infrared reflective film according to Item 11 sandwiched between two glass substrates.
  • an optical film having an optical functional layer on a support having an appropriate heat shrinkability, excellent followability when bonded to curved glass, and having transparency and tear strength And the optical film excellent in elongation at break, the infrared-reflective film excellent in light resistance using the same, and the laminated glass which has the tolerance outstanding in the heat wrinkle can be provided.
  • laminated glass is used for the windshield of automobiles.
  • a laminated glass with a heat ray reflective film also referred to as an infrared reflective film or a near infrared reflective film.
  • a laminated glass with a film interposed between them it is convenient to use a laminated glass with a film interposed between them to prevent scattering.
  • the film when the heat ray reflective film is later attached to the windshield or laminated glass, the film is likely to be wrinkled or peeled off at a portion with a high curvature.
  • the windshield has a particularly large area and a large amount of sunlight, and it is easy to raise the indoor temperature.However, the windshield has a high transmittance due to the driver's field of view and is subject to discoloration over time. There is a demand for film substrates that are transparent and have good light resistance.
  • triacetyl cellulose films that do not have an aromatic ring that absorbs ultraviolet rays are known to have high light resistance and high transparency. was there.
  • the TAC film has a problem that the tear strength is weaker than that of a PET film or the like, and the base material is torn during construction.
  • the base material needs to be easily shrunk to some extent in order to have curved surface followability, and a heat shrink base material is required. Since the TAC film is easily torn, it cannot be stretched at a high magnification and, therefore, has a problem that it cannot provide a desired heat shrinkability.
  • TAC has a rigid main chain structure.
  • a resin having a rigid main chain structure has low flexibility and low toughness.
  • the present inventor considered that the above-mentioned defects of the TAC film could be improved by separating and fusing the required functions.
  • highly compatible with another polymer could improve tearing strength and elongation at break while satisfying transparency and light resistance, and improve processability such as heat shrinkability.
  • the polymer (B) having a soft segment according to the present invention to TAC, which is a cellulose derivative (A) that does not contain an aromatic ring, the polymer having a rigid main chain of TAC and a soft segment can be converted into each other.
  • TAC which is a cellulose derivative (A) that does not contain an aromatic ring
  • the polymer having a rigid main chain of TAC and a soft segment can be converted into each other.
  • the craze (gap between polymer chains) generated when the film is pulled is stabilized
  • the polymer (B ) Functions as a rubber-like elastic body, contributes to the improvement of the flexibility and toughness of the film, and can greatly improve the ease of tearing of the TAC film.
  • the TAC film can be stretched at a high magnification by improving the flexibility and toughness of the film, it is presumed that appropriate heat shrinkability can be imparted.
  • the composition of the present invention has appropriate heat shrinkage, transparency, tear strength, and elongation at break. It is presumed that an optical film excellent in temperature, an infrared reflecting film excellent in light resistance and bonding properties using the optical film, and a laminated glass having excellent resistance to heat wrinkles can be provided.
  • Schematic sectional view showing an example of a configuration in which the optical film of the present invention having an optical reflective layer is applied to an infrared reflective film Schematic sectional view showing another example of a configuration in which the optical film of the present invention having an optical reflective layer is applied to an infrared reflective film
  • the optical film of the present invention is an optical film having an optical functional layer on at least one surface of a film-like support, and the support has a cellulose derivative (A) not containing an aromatic ring and a soft segment.
  • the heat shrinkage ratio after the polymer (B) is contained in a compatible state and the support is allowed to stand for 30 minutes in an environment of 150 ° C. is 1. It is characterized by being adjusted to be in the range of 0 to 5.0%.
  • the molecular weight of the polymer (B) is in the range of 4000 to 500,000, and the content of the polymer (B) is the cellulose derivative ( Within the range of 5 to 50% by mass with respect to the total mass of A) and the polymer (B), the flexibility and toughness are further improved and the tear strength is maintained without impairing the transparency of the optical film. Is preferable.
  • the polymer (B) is preferably an aliphatic polyester or polyalkylene oxide, and the polymer (B) is preferably an aliphatic polyester having a structure represented by the general formula (1).
  • the said cellulose derivative (A) is any of triacetylcellulose, diacetylcellulose, or cellulose acetate propionate, or its mixture, and an optical film. This is preferable because flexibility and toughness are further improved and tear strength is increased without impairing transparency.
  • the support used in the optical film of the present invention is stretched within a range of 1.0 to 5.0 times in the longitudinal direction and the width direction during film formation, so that the heat shrinkage rate is reduced. From the viewpoint of controlling within the target range, it is preferable.
  • the one direction in the plane and the direction perpendicular thereto are the longitudinal direction and the width direction during film formation, when processing the film in a roll shape, Since the film forming direction and the product length / width direction coincide with each other, it is preferable in production.
  • the optical functional layer according to the present invention preferably selectively transmits or shields light of a specific wavelength
  • the optical film of the present invention has the first water-soluble binder resin and the first optical functional layer as the optical functional layer.
  • An external reflection film is preferred.
  • the infrared reflective film is suitably provided in a laminated glass sandwiched between two glass substrates.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the optical film of the present invention is an optical film having an optical functional layer on at least one surface of a film-like support, and the support has a cellulose derivative (A) not containing an aromatic ring and a soft segment.
  • the heat shrinkage ratio after the polymer (B) is contained in a compatible state and the support is allowed to stand for 30 minutes in an environment of 150 ° C. is 1. It is characterized by being adjusted to be in the range of 0 to 5.0%, and with such a configuration, it has an appropriate heat shrinkability, has excellent followability when bonded to curved glass, and is transparent. An optical film excellent in tear strength and elongation at break can be obtained.
  • the optical film of the present invention is assumed to be used in an environment exposed to sunlight such as an infrared reflective film, it is preferable that the optical film has high resistance to ultraviolet rays. Therefore, it is preferable that the cellulose derivative (A) according to the present invention does not have a group having an ultraviolet absorbing ability, and is a cellulose derivative (A) having no aromatic ring in the main chain and the side chain.
  • the polymer (B) having a soft segment according to the present invention works as a compound imparting flexibility and toughness to a polymer having a rigid main chain such as TAC, from the viewpoint of improving the tear strength.
  • the weight average molecular weight is preferably in the range of 4000 to 500,000, and the content of the polymer (B) is 5 to 50 mass with respect to the total mass of the cellulose derivative (A) and the polymer (B). % Is preferable.
  • Entanglement of polymer chains increases, stabilizes crazes (gap between polymer chains) generated when the film is pulled, and polymer (B) functions as a rubber-like elastic body, improving the flexibility and toughness of the film It is presumed that the ease of tearing the TAC film can be greatly improved.
  • the thermal shrinkage rate after leaving the support used for the optical film in an environment of 150 ° C. for 30 minutes is 1.0 to 5 in both one direction in the plane and the direction perpendicular thereto. It is characterized by being adjusted to be within the range of 0.0%.
  • the heat shrinkage rate can be obtained by the following formula.
  • Thermal shrinkage (%) (L (23 ° C.) ⁇ L (150 ° C.)) / L (23 ° C.) ⁇ 100 L (23 ° C.): sample length when left for 1 day in an environment of 23 ° C. and 55% RH L (150 ° C.): after standing for 30 minutes in an environment of 150 ° C., 1 at 23 ° C. and 55% RH Sample length when allowed to stand for days In the support used in the optical film of the present invention, both the in-plane direction and the direction perpendicular thereto are measured by thermomechanical analysis of the support at 150 ° C.
  • the laminated vitrification step is carried out in the range of 100 to 150 ° C.
  • wrinkles and peeling occur due to the difference in thermal shrinkage between the intermediate film used for the laminated glass and the optical film provided with the support. May be damaged.
  • the interlayer film has high heat shrinkability, and when the support has a thermal shrinkage rate at 150 ° C. of less than 1.0%, the optical film cannot follow the thermal contraction of the interlayer film. The difference in the heat shrinkage rate may cause the optical film to bend and cause wrinkles.
  • the thermal contraction rate at 150 ° C. of the support is larger than 5.0%, a thermal contraction larger than the thermal contraction of the intermediate film occurs, so that a large tension acts between the optical film and the intermediate film. As a result, the optical film may break or some layers may peel off.
  • the heat shrinkage rate of the support is in the range of 1.0 to 5.0%, the heat shrinkage behavior similar to that of the intermediate film is exhibited, so that the appearance is good without causing wrinkles or peeling. Laminated glass can be obtained.
  • the thermal shrinkage rate measured by thermomechanical analysis of the support at 150 ° C. is in the range of 1.0 to 5.0%.
  • the tear strength of the support according to the present invention is determined according to JIS K 7128-2: 1998 (Plastics-Test method for tear strength of films and sheets-Part 2: Elmendorf tear method) This is determined by measuring the tear load in one direction in the film plane and in the direction perpendicular thereto by the Elmendorf tear method using a light load tear tester manufactured by Co., Ltd. The tear strength is measured under constant temperature and humidity conditions. In the present invention, the tear strength is measured under conditions of a temperature of 23 ° C. and 55% RH.
  • the tearing length and thickness of the sample are each under the same conditions.
  • one direction in a film surface and the direction orthogonal to it are the conveyance direction (MD direction) of a support body, and the direction (TD direction) orthogonal to it.
  • the tear strength of the support according to the present invention is preferably in the range of 100 to 350 mN, and more preferably in the range of 150 to 300 mN.
  • the elongation at break represents the maximum force (tensile strength) that can be sustained when the film is pulled and how much the film has stretched (tensile elongation).
  • the breaking elongation according to the present invention can be measured using a commercially available tensile tester using a sample film prepared to a thickness of 100 ⁇ m, for example.
  • An example of a specific method for measuring the elongation at break will be described below, but the present application is not limited to this.
  • ⁇ Measurement of elongation at break> After leaving the sample film in an environment of 23 ° C. and 55% RH for 24 hours, using a variable temperature tensile tester (for example, Shimadzu Autograph AGS-1000, manufactured by Shimadzu Corp.) Strength at a distance between chucks of 100 mm and a pulling speed of 300 mm / min in an environment of 23 ° C. and 55% RH, strength when the sample is cut (ruptured) (value obtained by dividing the tensile load value by the cross-sectional area of the test piece), And ask for elongation.
  • the breaking elongation is calculated by the following formula. In addition, five test pieces were prepared and measured for each of the film forming direction and the width direction, and the average value of the ten pieces was taken as the elongation at break.
  • Elongation at break (%) (L ⁇ Lo) / Lo ⁇ 100 Lo: sample length before test L: sample length at break
  • the break elongation of the support according to the present invention is preferably in the range of 60 to 200%, and in the range of 70 to 150%. It is more preferable.
  • the cellulose derivative (A) according to the present invention is characterized in that it is a cellulose derivative having no aromatic ring, that is, a non-aromatic cellulose derivative from the viewpoint of improving light resistance.
  • “having no aromatic ring” means not containing an aromatic hydrocarbon ring or a heteroaromatic ring
  • the cellulose derivative (A) according to the present invention has a non-aromatic main chain and side chain. It is composed of groups.
  • the cellulose derivative according to the present invention has a rigid main chain structure.
  • the “rigid main chain structure” means a structure in which the rotation of the main chain itself is suppressed, and includes a main structure including a ring structure. It refers to a main chain that has a large chain and steric hindrance and is difficult to rotate, a main chain that is highly sterically restricted, or a structure in which the rotation of the main chain is suppressed by hydrogen bonding or dipolar interaction.
  • Examples of the cellulose derivative (A) having no aromatic ring according to the present invention include cellulose ester or cellulose ether.
  • the cellulose derivative (A) at least a part of the hydrogen atoms of the 2-position, 3-position, and 6-position hydroxy groups of the ⁇ -glucose ring contained in cellulose is substituted with an aliphatic acyl group and / or an alkyl group. It is a thing.
  • cellulose ester examples include triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate.
  • cellulose ether examples include methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, allyl cellulose, hydroxyethyl methyl cellulose, hydroxyethyl ethyl cellulose, hydroxyethyl propyl cellulose, and hydroxyethyl allyl cellulose.
  • cellulose esters Preferred are cellulose esters, and more preferred are triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate and cellulose acetate butyrate. Among these, triacetyl cellulose is preferable from the viewpoint of moisture permeability at the time of water application and ease of processing.
  • the cellulose ester may contain a plurality of cellulose esters having different degrees of substitution in order to obtain desired characteristics.
  • the mixing ratio thereof can be in the range of 10:90 to 90:10 by mass ratio.
  • the cellulose used as the raw material for the cellulose derivative (A) is not particularly limited, and examples thereof include cotton linter, wood pulp, and kenaf. Moreover, the cellulose derivative (A) obtained from these can be used individually or in mixture at arbitrary ratios.
  • the film becomes brittle, and if the molecular weight is too high, the solubility in the solvent is poor and the solid content concentration of the resin solution is lowered, so that the amount of solvent used increases. It is not preferable in production.
  • the number average molecular weight Mn is preferably in the range of 20,000 ⁇ Mn ⁇ 300,000, and more preferably in the range of 40,000 ⁇ Mn ⁇ 200,000.
  • the weight average molecular weight (Mw) is preferably in the range of 80,000 to 1,000,000, more preferably in the range of 100,000 to 500,000, and in the range of 150,000 to 300,000. Is more preferable.
  • the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably in the range of 1.4 to 4.0, more preferably in the range of 1.5 to 3.5. .
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) of the cellulose ester can be measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • Triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, and cellulose acetate butyrate have an acyl group having 2 to 4 carbon atoms as a substituent, the degree of substitution of the acetyl group is X, and a propionyl group or a butyryl group.
  • substitution degree is Y, those satisfying the following formulas (I) and (II) are preferable.
  • the polymer (B) according to the present invention is characterized by being compatible with the cellulose derivative (A) by interaction and having a soft segment.
  • Whether the cellulose derivative (A) and the polymer (B) are compatible can be determined by, for example, the glass transition temperature Tg.
  • the two polymers when the two polymers have different glass transition temperatures, when the two polymers are mixed, there are two or more glass transition temperatures for each polymer because there is a glass transition temperature for each polymer. When they are compatible, the glass transition temperature specific to each polymer disappears and becomes one glass transition temperature, which is the glass transition temperature of the compatible polymer.
  • the glass transition temperature referred to here is a sample that has been conditioned for 24 hours in an atmosphere of 23 ° C. and 55% RH using a differential scanning calorimeter (DSC-7, manufactured by Perkin Elmer). It is measured at a heating rate of 20 ° C./min in an air current, and is defined as the midpoint glass transition temperature (Tmg) determined according to JIS K7121 (1987).
  • Examples of the interaction in the present invention include hydrogen bond, dipole-dipole interaction, intermolecular force, CH- ⁇ interaction, and the like.
  • Such a site capable of interaction is called an interaction point, and the interaction point may be included in the main chain, may be included in the side chain, and is included in the soft segment described later. It may be.
  • the polymer (B) has many interaction points per main chain and interacts with the cellulose derivative (A) multiple times. Since the number of possible states increases exponentially and entropy increases due to the possibility of multiple interactions, the free energy of the cast increases negatively, so that the system in which the cellulose derivative (A) and the polymer (B) interact with each other As a result of being greatly stabilized, high compatibility is possible.
  • the soft segment in the present invention refers to a linking group capable of imparting stretchability and rotation to the main chain, and specifically includes —O—, —COO—, OCOO—, —S—, — in the main chain.
  • a site containing a bond such as SOO—, —OSOO—, —OSiO—, —OSi— or an alkylene group.
  • the polymer (B) according to the present invention is preferably a polyalkylene oxide or a polyester, more preferably an aliphatic polyester or a polyalkylene oxide, and particularly preferably an aliphatic polyester.
  • the polyalkylene oxide that can be used as the polymer (B) according to the present invention is not particularly limited, and examples thereof include those containing ethylene oxide as one component, such as polyethylene oxide which is a homopolymer of ethylene oxide; Examples include copolymers with alkylene oxides. Examples of the other alkylene oxides include propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane, epichlorohydrin, epibromohydrin, trifluoromethylethylene oxide, cyclohexene oxide, styrene oxide, methyl glycidyl ether, and allyl.
  • Examples include glycidyl ether, phenyl glycidyl ether, glycidol, glycidyl acrylate, butadiene monooxide, and butadiene dioxide. Of these, polyethylene oxide and polypropylene oxide are preferable, and polyethylene oxide is more preferable.
  • the aliphatic polyester that can be used as the polymer (B) according to the present invention will be described.
  • the aliphatic polyester in the present invention is preferably a polyester obtained by a condensation reaction of an aliphatic polyhydric alcohol and an aliphatic polybasic acid, or an aliphatic polyester obtained by ring-opening polymerization of a cyclic ester.
  • an aliphatic polyester having a structure represented by the following general formula (1) is preferable.
  • R 1 to R 6 in the general formula (1) represent a substituent and may be substituted on the polymer (B) described later. Since the structure represented by the general formula (1) in the present invention contains a large number of linking groups such as —CO— and —O— which are soft segments, the substituents of R 1 to R 6 are intended for the present invention. Any substituent may be introduced as long as the effect is not hindered.
  • i represents an integer of 0 to 2
  • j represents an integer of 0 to 10
  • k represents an integer of 3 to 10.
  • i is preferably 0 to 1, and more preferably 1.
  • J in the general formula (1) is preferably 0 to 5, more preferably 1 to 4, and particularly preferably 3.
  • k is preferably 3 to 8, more preferably 3 to 5, and particularly preferably 3.
  • the substituent represented by R 1 to R 6 in the general formula (1) is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom, a methyl group or an ethyl group, and particularly preferably a hydrogen atom.
  • A, b, and c represent constituent ratios (molar ratio), and the sum of a, b, and c is 1.
  • Examples of the aliphatic polyester having the structure represented by the general formula (1) in the present invention include polyethylene adipate, polyethylene succinate, polybutylene adipate, polybutylene succinate, polybutylene succinate adipate, and the like. Polyethylene succinate, polybutylene succinate, and polybutylene succinate adipate are preferable.
  • Examples of the aliphatic polybasic acid used in the condensation reaction between the aliphatic polyhydric alcohol and the aliphatic polybasic acid (or an ester thereof) include succinic acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, Suberic acid, sebacic acid, azelaic acid, decanedicarboxylic acid, octadecanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid undecanedioic acid, dodecanedioic acid, and their anhydrides, or esters thereof are listed.
  • Examples of the alcohol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 3-methyl-1,5-pentanediol, 1,3-propanediol, 1,4-butanediol, , 9-nonangio Le, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexane dimethanol, polytetramethylene glycol 1,4-cyclohexane dimethanol, and the like.
  • polyoxyalkylene glycol as a part of the aliphatic polyhydric alcohol, and examples thereof include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, and copolymers thereof.
  • the aliphatic polyester elastomer can be used alone or in combination of two or more.
  • any of D-form, L-form, and racemate may be used, and the form may be any of solid, liquid, or aqueous solution.
  • the aliphatic polyhydric alcohol is ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 3-methyl- At least one selected from 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, polytetramethylene glycol 1,4-cyclohexanedimethanol,
  • the basic acid is at least one selected from succinic acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, and anhydrides thereof.
  • An aliphatic polybasic acid Door is preferable.
  • the aliphatic polyhydric alcohol is at least one selected from diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, and More preferably, the aliphatic polybasic acid is at least one aliphatic polybasic acid selected from succinic acid, oxalic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, and anhydrides thereof. preferable.
  • the total amount of the aliphatic polybasic acid (or its ester) component and the aliphatic polyhydric alcohol component may be initially mixed and reacted, or added in portions as the reaction proceeds. It doesn't matter.
  • the polycondensation reaction can be carried out by a common transesterification method or esterification method, or a combination of both. Further, if necessary, the degree of polymerization can be increased by applying pressure or reduced pressure in the reaction vessel.
  • Examples of the cyclic ester used in the method for ring-opening polymerization of a cyclic ester include ⁇ -propiolactone, ⁇ -methyl- ⁇ -propiolactone, ⁇ -valerolactone, and ⁇ -caprolactone. Of these, ⁇ -caprolactone is particularly preferred.
  • the ring-opening polymerization can be carried out by a method such as polymerization in a solvent or bulk polymerization using a known ring-opening polymerization catalyst.
  • the aliphatic polyester used in the present invention can be produced by a known method.
  • a general method of melt polymerization in which an esterification reaction and / or a transesterification reaction between the aliphatic dicarboxylic acid component and the aliphatic diol component is performed, followed by a polycondensation reaction under reduced pressure, although it can manufacture also by the well-known solution heating dehydration condensation method using a solvent, the method of manufacturing polyester by melt polymerization performed in the absence of a solvent from a viewpoint of economical efficiency or the simplicity of a manufacturing process is preferable.
  • the polycondensation reaction is preferably performed in the presence of a polymerization catalyst.
  • the addition timing of the polymerization catalyst is not particularly limited as long as it is before the polycondensation reaction, and it may be added when the raw materials are charged, or may be added at the start of pressure reduction.
  • the polymerization catalyst is generally a compound containing a group 1 to group 14 metal element excluding hydrogen and carbon in the periodic table.
  • Metals such as antimony, cadmium, manganese, iron, zirconium, vanadium, iridium, lanthanum, selenium, and organic metal compounds thereof, salts of organic acids, metal alkoxides, metal oxides, etc. It can also be used in combination with a promoter such as an acid.
  • These catalysts can be used singly or in combination of two or more, and the addition amount is preferably 0.1 mol or less, more preferably 0.8 mol or less, still more preferably with respect to 100 mol of all dicarboxylic acids. Is 0.6 mol or less.
  • the molecular weight can be increased using a chain extender.
  • chain extender include bifunctional or higher functional isocyanate compounds, epoxy compounds, aziridine compounds, oxazoline compounds, polyvalent metal compounds, polyfunctional acid anhydrides, phosphate esters, phosphites, and the like. Or you may combine 2 or more types.
  • a vertical reactor a batch reactor, a horizontal reactor, a twin screw extruder or the like is used, and it is preferable that the reaction is carried out in bulk or in solution.
  • the substituent that can be substituted on the polymer (B) in the present invention is not particularly limited, and examples thereof include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), alkyl groups (methyl group, ethyl group, n- Propyl group, isopropyl group, tert-butyl group, n-octyl group, 2-ethylhexyl group, etc.), cycloalkyl group (cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group etc.), alkenyl group (vinyl group, allyl group) Group), cycloalkenyl group (2-cyclopenten-1-yl, 2-cyclohexen-1-yl group, etc.), alkynyl group (ethynyl group, propargyl group, etc.), aryl group (phenyl group, p
  • the polymer (B) in the present invention is preferably composed of a non-aromatic component like the cellulose derivative (A). However, unlike the cellulose derivative (A), it may have an aromatic group and a heteroaromatic group. This is because the cellulose derivative (A) imparts heat resistance and UV resistance as a film, and the polymer (B) imparts flexibility and toughness. Therefore, the polymer (B) is slightly destroyed by ultraviolet rays. This is because the film performance is not greatly affected.
  • the aliphatic polyester according to the present invention has a weight average molecular weight of 4000 or more from the viewpoint of the rigidity and heat resistance of the resin.
  • the weight average molecular weight is a weight average molecular weight measured by gel permeation chromatography (GPC). More specifically, N-methylpyrrolidone is used as a solvent, a polystyrene gel is used, and the molecular weight is obtained using a conversion molecular weight calibration curve obtained in advance from a standard monodisperse polystyrene constituent curve.
  • GPC apparatus HLC-8220 GPC (manufactured by Tosoh Corporation) can be used.
  • the weight average molecular weight of the aliphatic polyester is preferably in the range of 4,000 to 500,000, and more preferably in the range of 30,000 to 400,000.
  • the stabilization energy when interacting with the cellulose derivative (A) is larger than the self-cohesive force of the polymer (B), and transparency, elongation at break and tear strength are increased. improves.
  • the cellulose derivative (A) and the polymer (B) in the present invention may be crosslinked by a covalent bond or may not be crosslinked. Further, the cellulose derivatives (A) and the polymers (B) may be crosslinked by covalent bonds, or may not be crosslinked.
  • aliphatic polyester As the aliphatic polyester according to the present invention, a commercially available product may be used.
  • PBS polybutylene succinate
  • PBSA polybutylene succinate adipate
  • the optical film of the present invention preferably contains an additive such as a sugar ester, a plasticizer, an antioxidant, a hydrolysis inhibitor, and fine particles.
  • the sugar ester is not particularly limited, but the compounds described in paragraphs [0130] to [0138] of JP2012-230154A are preferably used.
  • the plasticizer is not particularly limited, but is preferably a polycarboxylic acid ester plasticizer, a glycolate plasticizer, a phthalate ester plasticizer, a fatty acid ester plasticizer, a polyhydric alcohol ester plasticizer, or an ester plasticizer. Agent, acrylic plasticizer and the like.
  • the plasticizer content is preferably 0.5 to 30.0 mass% with respect to the cellulose derivative (A). If the content of the plasticizer is 30.0% by mass or less, bleeding out hardly occurs.
  • the antioxidant a known one can be used, and it may be a lactone compound, a sulfur compound, a phenol compound, a double bond compound, a hindered amine compound, a phosphorus compound, or the like.
  • lactone compound examples include Irgafos XP40 and Irgafos XP60 (BASF Japan Ltd.).
  • sulfur compound examples include Sumilizer TPL-R and Sumilizer TP-D (Sumitomo Chemical Co., Ltd.).
  • the phenolic compound preferably has a 2,6-dialkylphenol structure, and examples thereof include Irganox 1076, Irganox 1010 (BASF Japan Co., Ltd.), Adeka Stub AO-50 (Adeka).
  • double bond type compound examples include Sumilizer GM, Sumilizer GS (Sumitomo Chemical Co., Ltd.), and the like.
  • hindered amine compounds include Tinuvin 144 and Tinuvin 770 (BASF Japan Ltd.), ADK STAB LA-52 (ADEKA Corp.).
  • phosphorus compounds include Sumitizer GP (Sumitomo Chemical Co., Ltd.), ADK STAB PEP-24G, ADK STAB PEP-36 and ADK STAB 3010 (ADEKA), IRGAFOS P-EPQ (BASF Japan K.K.), GSY- P101 (Sakai Chemical Industry Co., Ltd.) can be mentioned.
  • the content of the antioxidant can be about 0.05 to 5% by mass, preferably 0.1 to 4% by mass, based on the total amount of the cellulose derivative (A) and the polymer (B).
  • hydrolysis inhibitor examples include carbodiimide compounds such as polycarbodiimide compounds and monocarbodiimide compounds.
  • carbodiimide compounds are preferable from the viewpoint of tear strength and breaking elongation, and monocarbodiimide compounds are preferable from the viewpoint of shear processability.
  • monocarbodiimide and polycarbodiimide together from the viewpoint of further improving the tear strength, breaking elongation, and shear processability.
  • Polycarbodiimide compounds include poly (4,4′-diphenylmethanecarbodiimide), poly (4,4′-dicyclohexylmethanecarbodiimide), poly (1,3,5-triisopropylbenzene) polycarbodiimide, poly (1,3,3). 5-triisopropylbenzene and 1,5-diisopropylbenzene) polycarbodiimide and the like, and examples of the monocarbodiimide compound include N, N′-di-2,6-diisopropylphenylcarbodiimide and the like.
  • the carbodiimide compounds may be used alone or in combination of two or more.
  • Poly (4,4'-dicyclohexylmethane carbodiimide) is obtained by converting carbodilite LA-1 (manufactured by Nisshinbo Chemical Co., Ltd.), poly (1,3,5-triisopropylbenzene) polycarbodiimide and poly (1,3,5-tri-imide).
  • polycarbodiimide is stavaxol P and stabaxol P-100 (manufactured by Rhein Chemie), and N, N'-di-2,6-diisopropylphenylcarbodiimide is stavaxol I (Rhein Chemie).
  • Rhein Chemie N, N'-di-2,6-diisopropylphenylcarbodiimide is stavaxol I (Rhein Chemie).
  • poly (4,4′-dicyclohexylmethanecarbodiimide) product name: Carbodilite LA-1, manufactured by Nisshinbo Chemical Co., Ltd.
  • Carbodilite LA-1 manufactured by Nisshinbo Chemical Co., Ltd.
  • the content of the hydrolysis inhibitor is 0.05 to 3 parts by mass with respect to 100 parts by mass of the total amount of the cellulose derivative (A) and the polymer (B) from the viewpoint of improving the transparency and shear processability of the optical film. Is preferable, 0.10 to 2 parts by mass is more preferable, and 0.2 to 1 part by mass is further preferable.
  • the optical film of the present invention may further contain fine particles (matting agent) as necessary in order to improve the slipperiness of the surface.
  • the fine particles may be inorganic fine particles or organic fine particles.
  • inorganic fine particles include silicon dioxide (silica), titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, Examples include magnesium silicate and calcium phosphate.
  • silicon dioxide and zirconium oxide are preferable, and silicon dioxide is more preferable in order to reduce the increase in haze of the obtained film.
  • Examples of the fine particles of silicon dioxide include Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600, NAX50 (manufactured by Nippon Aerosil Co., Ltd.), Seahoster KE-P10, KE-P30, KE-P50, KE-P100 (manufactured by Nippon Shokubai Co., Ltd.) and the like are included.
  • Aerosil R972V, NAX50, Seahoster KE-P30 and the like are particularly preferable because they reduce the coefficient of friction while keeping the turbidity of the resulting film low.
  • the average primary particle size of the fine particles is preferably in the range of 5 to 400 nm, more preferably in the range of 10 to 300 nm.
  • the fine particles may form secondary aggregates mainly having a particle size in the range of 0.05 to 0.30 ⁇ m. If the average particle size of the fine particles is in the range of 100 to 400 nm, they can exist as primary particles without agglomeration.
  • the content of the fine particles is preferably in the range of 0.01 to 1.00% by mass, and in the range of 0.05 to 0.50% by mass with respect to the total amount of the cellulose derivative (A) and the polymer (B). More preferably, it is within.
  • ⁇ Method for producing support containing cellulose derivative (A) and polymer (B) As a method for producing a support containing the cellulose derivative (A) and the polymer (B) according to the present invention (hereinafter also simply referred to as a support), the usual inflation method, T-die method, calendar method, cutting method Production methods such as the casting method, the casting method, the emulsion method, and the hot press method can be used. From the viewpoint of suppressing coloring, suppressing defects of foreign matter, and suppressing optical defects such as die lines, the film forming method is solution casting film forming. The method and the melt casting film forming method can be selected, and the solution casting film forming method is particularly preferable from the viewpoint of obtaining a uniform and smooth surface.
  • the support according to the present invention In the production of the support according to the present invention, at least the cellulose derivative (A), or the cellulose derivative (A) and the polymer (B), and if necessary, an additive or the like is dissolved in a solvent to prepare a dope and filtered.
  • the support according to the present invention preferably contains the cellulose derivative (A) in the solid content in the range of 60 to 95% by mass.
  • the organic solvent useful for forming the dope is cellulose derivative (A), or cellulose derivative (A) and polymer (B), and other additions. Any agent that dissolves the agent and the like can be used without limitation.
  • methylene chloride as a non-chlorinated organic solvent, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro- 2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane, etc.
  • methylene chloride, methyl acetate, ethyl acetate, and acetone can be preferably used as the main solvent. Particularly preferably
  • the dope preferably contains a linear or branched aliphatic alcohol having 1 to 4 carbon atoms in the range of 1 to 40% by mass.
  • a linear or branched aliphatic alcohol having 1 to 4 carbon atoms in the range of 1 to 40% by mass.
  • the proportion of alcohol in the dope increases, the web gels and peeling from the metal support is facilitated.
  • the proportion of alcohol is small, the cellulose derivative (A) in the non-chlorine organic solvent system and other
  • a method of forming a film using a dope having an alcohol concentration in the range of 0.5 to 15.0% by mass from the viewpoint of improving the flatness of the obtained support. Can be applied.
  • the cellulose derivative (A) and other compounds are dissolved in a total amount of 15 to 45% by mass in a solvent containing methylene chloride and a linear or branched aliphatic alcohol having 1 to 4 carbon atoms.
  • the dope composition is preferred.
  • linear or branched aliphatic alcohol having 1 to 4 carbon atoms examples include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, and tert-butanol. Methanol and ethanol are preferred because of the stability, boiling point of these inner dopes, and good drying properties.
  • a method carried out at normal pressure a method carried out below the boiling point of the main solvent, a method carried out under pressure above the boiling point of the main solvent, Various methods such as a method using a cooling dissolution method as described in JP-A-95544, JP-A-9-95557, or JP-A-9-95538, a method using a high pressure as described in JP-A-11-21379, etc.
  • a dissolution method can be used, a method in which pressure is applied at a temperature equal to or higher than the boiling point of the main solvent is particularly preferable.
  • the concentration of the cellulose derivative (A) in the dope is preferably in the range of 10 to 40% by mass.
  • the metal support in the casting process is preferably a mirror-finished surface, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used as the metal support.
  • the cast width can be in the range of 1 to 4 m, preferably in the range of 1.5 to 3 m, more preferably in the range of 2 to 2.8 m.
  • the surface temperature of the metal support in the casting step is set in the range of ⁇ 50 ° C. to the temperature at which the solvent boils and does not foam, more preferably in the range of ⁇ 30 to 0 ° C. A higher temperature is preferred because the web can be dried faster, but if it is too high, the web may foam or the flatness may deteriorate.
  • a preferable support temperature is appropriately determined at 0 to 100 ° C., and more preferably within a range of 5 to 30 ° C.
  • the method for controlling the temperature of the metal support is not particularly limited, and there are a method of blowing warm air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use warm water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short.
  • ⁇ Pressure dies that can adjust the slit shape of the die base and make the film thickness uniform are preferred.
  • the pressure die include a coat hanger die and a T die, and any of them is preferably used.
  • the surface of the metal support is a mirror surface. In order to increase the film forming speed, two or more pressure dies may be provided on the metal support, and the dope amount may be divided and laminated.
  • the web on the support after casting is preferably dried on the support in an atmosphere of 40 to 100 ° C. In order to maintain the atmosphere at 40 to 100 ° C., it is preferable to apply hot air at this temperature to the upper surface of the web or heat by means such as infrared rays.
  • Peeling process It is the process of peeling the web which the solvent evaporated on the metal support body in a peeling position.
  • the peeled web is sent to the next step as a film-like support.
  • the temperature at the peeling position on the metal support is preferably in the range of 10 to 40 ° C, more preferably in the range of 11 to 30 ° C.
  • the amount of residual solvent at the time of peeling of the web on the metal support at the time of peeling is preferably 50 to 120% by mass depending on the strength of drying conditions, the length of the metal support, and the like.
  • the amount of solvent is determined.
  • the residual solvent amount of the web is defined by the following formula (Z).
  • Residual solvent amount (%) (mass before web heat treatment ⁇ mass after web heat treatment) / (mass after web heat treatment) ⁇ 100 Note that the heat treatment for measuring the residual solvent amount represents performing heat treatment at 115 ° C. for 1 hour.
  • the drying step can be divided into a preliminary drying step and a main drying step.
  • the web obtained by peeling from the metal support is dried.
  • the web may be dried while being conveyed by a large number of rollers arranged above and below, or may be dried while being conveyed while fixing both ends of the web with clips like a tenter dryer. .
  • the means for drying the web is not particularly limited, and can be generally performed with hot air, infrared rays, a heating roller, microwave, or the like, but it is preferably performed with hot air in terms of simplicity.
  • the drying temperature in the web drying process is preferably a glass transition point of the film of ⁇ 5 ° C. or less, and it is effective to perform a heat treatment at a temperature of 100 ° C. or more for 10 minutes or more and 60 minutes or less. Drying is performed at a drying temperature in the range of 100 to 200 ° C, more preferably in the range of 110 to 160 ° C.
  • the support according to the present invention can be subjected to stretching treatment to control the orientation of molecules in the film, to improve the planarity and to control the heat shrinkage rate.
  • the support according to the present invention preferably extends in the casting direction (also referred to as the longitudinal direction or MD direction) and / or the width direction (also referred to as TD direction), and extends in both the MD direction and the TD direction. More preferably. Further, if necessary, the film may be stretched in an oblique direction with respect to the casting direction and in a direction perpendicular to the direction.
  • the stretching operation may be performed in multiple stages.
  • simultaneous biaxial stretching may be performed or may be performed stepwise.
  • stepwise means that, for example, stretching in different stretching directions can be sequentially performed, stretching in the same direction is divided into multiple stages, and stretching in different directions is added to any one of the stages. Is also possible.
  • stretching steps are possible: -Stretch in the casting direction-> Stretch in the width direction-> Stretch in the casting direction-> Stretch in the casting direction-Stretch in the width direction-> Stretch in the width direction-> Stretch in the casting direction-> Stretch in the casting direction
  • Simultaneous biaxial stretching includes stretching in one direction and contracting the other while relaxing the tension.
  • the residual solvent amount at the start of stretching is preferably in the range of 2 to 10% by mass.
  • the amount of the residual solvent is 2% by mass or more, the film thickness deviation is small and is preferable from the viewpoint of flatness, and if it is within 10% by mass, the unevenness of the surface is reduced and the flatness is improved.
  • the support according to the present invention is preferably stretched in a temperature range of (Tg + 15) to (Tg + 50) ° C. when the glass transition temperature is Tg.
  • Tg glass transition temperature
  • the stretching temperature is preferably in the range of (Tg + 20) to (Tg + 40) ° C.
  • the glass transition temperature Tg referred to here is a midpoint glass transition temperature (Tmg) measured at a rate of temperature increase of 20 ° C./min using a commercially available differential scanning calorimeter and determined according to JIS K7121 (1987). It is. A specific method for measuring the glass transition temperature Tg of the support is measured using a differential scanning calorimeter DSC220 manufactured by Seiko Instruments Inc. according to JIS K7121 (1987).
  • the support according to the present invention preferably stretches the web in the MD direction and the TD direction within a range of 1.0 to 5.0 times.
  • the stretching range is preferably 1.1 to 4.0 times the original width, and more preferably 1.2 to 3.0 times. If it is in the said range, the movement of the molecule
  • Stretching in the MD direction and TD direction may be stretched at different magnifications or may be stretched at the same magnification, but when stretched at the same magnification is used for bonding to a window glass or laminated glass. It is a preferred stretching method from the standpoint of ease of processing, because the film can have the same heat shrinkage ratio in the vertical and horizontal directions.
  • a low-speed roller group and a high-speed roller group may be provided, and a device that stretches the web in the MD direction by giving a peripheral speed difference to the roller may be used.
  • the stretching device include stretching by changing the interval between the clips or the pins with a clip tenter and a pin tenter, which can be selected and used as necessary.
  • the entire drying process or a part of the process as disclosed in Japanese Patent Application Laid-Open No. 62-46625 can be performed while holding the width ends of the web with clips or pins in the width direction.
  • a drying method (referred to as a tenter method), among them, a tenter method using clips and a pin tenter method using pins are preferably used.
  • Winding step This is a step of winding the support after the amount of residual solvent in the web is 2% by mass or less, and good dimensional stability is achieved by setting the amount of residual solvent to 0.4% by mass or less.
  • a support containing the cellulose derivative (A) can be obtained.
  • a generally used method may be used, and there are a constant torque method, a constant tension method, a taper tension method, a program tension control method with a constant internal stress, and the like.
  • the thickness of the support according to the present invention is preferably in the range of 30 to 200 ⁇ m, more preferably in the range of 30 to 150 ⁇ m, and still more preferably in the range of 35 to 100 ⁇ m. If the transparent resin film has a thickness of 30 ⁇ m or more, wrinkles and the like are less likely to occur during handling, and if the thickness is 200 ⁇ m or less, the handleability and transparency are excellent, and a thin film support is provided. Can do.
  • the support according to the present invention is preferably long, specifically, preferably about 100 to 10000 m, more preferably about 4000 to 6000 m in the form of a roll. It is done.
  • the width of the support is preferably 1 m or more, more preferably 1.4 m or more, and particularly preferably 1.4 to 3 m.
  • the visible light transmittance measured by JIS R3106 is preferably 60% or more, more preferably 70% or more, and further preferably 80% or more. It is.
  • the film for optical use is particularly preferably 90% or more.
  • the haze is preferably less than 1%, and more preferably less than 0.5%. By setting the haze to less than 1%, there is an advantage that the transparency of the film becomes higher and it becomes easier to use as a film for optical applications.
  • the support according to the present invention preferably has an equilibrium water content of 4% or less at 25 ° C. and a relative humidity of 60%, more preferably 3% or less.
  • the equilibrium moisture content By setting the equilibrium moisture content to 4% or less, the dimensions are less likely to change even if the temperature and humidity change.
  • the optical functional layer according to the present invention is not particularly limited as long as it has a function of controlling optical characteristics.
  • a layer for controlling reflectance and transmittance, a microlens, a microprism, a scattering layer, and the like examples include a layer that changes the direction of light or condenses light. Among them, it can be preferably used as an optical reflection layer that selectively transmits or blocks light of a specific wavelength.
  • a layer that selectively transmits or blocks light of a specific wavelength a layer that absorbs a specific wavelength by a dye or pigment, a layer that provides a metal thin film to reflect infrared light, a low refractive index layer, and a high refractive index
  • the layer include layers that are alternately stacked and reflect only light having a wavelength corresponding to the film thickness (an optical reflection layer using a multilayer film).
  • a high refractive index layer including the first water-soluble binder resin and the first metal oxide particles, and a low refractive index layer including the second water-soluble binder resin and the second metal oxide particles are alternately arranged. It is preferably applicable to a layer that selectively reflects light of a specific wavelength laminated on the substrate. In this method, the lower the interfacial mixing of the low refractive index layer and the high refractive index layer, the higher the interface reflection and the higher the reflectance. However, when the cellulose derivative (A) is used as a support, the solvent at the time of coating is changed.
  • the cellulose derivative (A) absorbs and the solvent can volatilize not only from the upper surface (air side) of the coating layer but also from the support side, the coating layer is quickly solidified, and the low refractive index layer and the high refractive index It is preferable to apply the cellulose derivative (A) to the support because the interfacial mixing of the layers is reduced and high reflectance is obtained. On the other hand, the layer structure is complicated and the influence of deterioration during storage is likely to occur. Therefore, it is very preferable to apply the support according to the present invention.
  • the optical reflection layer expresses a function of reflecting and blocking sunlight rays, for example, infrared components, and is composed of a plurality of refractive index layers having different refractive indexes. Specifically, a high refractive index layer and a low refractive index layer are laminated.
  • the optical reflection layer used in the present invention may have any structure including at least one laminate (unit) composed of a high refractive index layer and a low refractive index layer. It is preferable to have a configuration in which two or more of the above laminates composed of refractive index layers are laminated.
  • the uppermost layer and the lowermost layer of the optical reflection layer may be either a high refractive index layer or a low refractive index layer, but it is preferable that both the uppermost layer and the lowermost layer are low refractive index layers.
  • the uppermost layer is a low refractive index layer, the coating property is improved, and when the lowermost layer is a low refractive index layer, it is preferable from the viewpoint of improving adhesion.
  • an arbitrary refractive index layer of the optical reflection layer is a high refractive index layer or a low refractive index layer is determined by comparing the refractive index with an adjacent refractive index layer. Specifically, when a refractive index layer is used as a reference layer, if the refractive index layer adjacent to the reference layer has a lower refractive index than the reference layer, the reference layer is a high refractive index layer (the adjacent layer is a low refractive index layer). It is judged to be a rate layer.) On the other hand, if the refractive index of the adjacent layer is higher than that of the reference layer, it is determined that the reference layer is a low refractive index layer (the adjacent layer is a high refractive index layer).
  • the refractive index layer is a high refractive index layer or a low refractive index layer is a relative one determined by the relationship with the refractive index of the adjacent layer. Depending on the relationship, it can be a high refractive index layer or a low refractive index layer.
  • high refractive index layer component there are two components constituting the high refractive index layer (hereinafter also referred to as “high refractive index layer component”) and components constituting the low refractive index layer (hereinafter also referred to as “low refractive index layer component”).
  • low refractive index layer component a layer (mixed layer) containing the high refractive index layer component and the low refractive index layer component is mixed at the interface of the two layers.
  • a set of portions where the high refractive index layer component is 50% by mass or more is defined as a high refractive index layer
  • a set of portions where the low refractive index layer component exceeds 50% by mass is defined as a low refractive index layer.
  • the concentration profile of the metal oxide particles in the layer thickness direction in these laminated films can determine whether the mixed layer that can be formed is a high refractive index layer or a low refractive index layer.
  • the concentration profile of the metal oxide particles in the laminated film is sputtered at a rate of 0.5 nm / min using the XPS surface analyzer, etching from the surface to the depth direction, with the outermost surface being 0 nm. It can be observed by measuring the atomic composition ratio.
  • the metal oxide particles are not contained in the low refractive index component or the high refractive index component and are formed only from the water-soluble resin, similarly, in the concentration profile of the water-soluble resin, for example, It was confirmed that the mixed region was present by measuring the carbon concentration in the layer thickness direction, and further, its composition was measured by EDX (energy dispersive X-ray spectroscopy), and was etched by sputtering.
  • EDX energy dispersive X-ray spectroscopy
  • the XPS surface analyzer is not particularly limited, and any model can be used, but ESCALAB-200R manufactured by VG Scientific Fix Co. was used. Mg is used for the X-ray anode, and measurement is performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA).
  • the difference in refractive index between the adjacent low refractive index layer and high refractive index layer is 0.1 or more.
  • it is 0.3 or more, more preferably 0.35 or more, and particularly preferably more than 0.4.
  • the difference is preferably within the preferred range.
  • the refractive index layer constituting the uppermost layer or the lowermost layer of the optical reflection layer may have a configuration outside the above preferred range.
  • the number of refractive index layers of the optical reflection layer (units of high refractive index layer and low refractive index layer) is preferably 100 layers or less, that is, 50 units or less, and 40 layers (20 units). ) Or less, more preferably 20 layers (10 units) or less.
  • the refractive index ratio between the layers Since the reflection at the interface between adjacent layers depends on the refractive index ratio between the layers, the higher the refractive index ratio, the higher the reflectance.
  • n is the refractive index
  • d is the physical film thickness of the layer
  • n ⁇ d is the optical film thickness.
  • the reflectance in a specific wavelength region can be increased by the refractive index of each layer, the layer thickness of each layer, and the way of stacking each layer.
  • the optical reflection layer used in the present invention can be made into an ultraviolet reflection film, a visible light reflection film, or an infrared reflection film by changing a specific wavelength region for increasing the reflectance. That is, if the specific wavelength region for increasing the reflectance is set in the ultraviolet region, it becomes an ultraviolet reflecting film, if it is set in the visible light region, it becomes a visible light reflecting film, and if it is set in the near infrared region, it becomes an infrared reflecting film.
  • an infrared reflection film may be used.
  • the high refractive index layer contains the first water-soluble binder resin and the first metal oxide particles, and may contain a curing agent, other binder resin, a surfactant, and various additives as necessary. Good.
  • the refractive index of the high refractive index layer according to the present invention is preferably 1.80 to 2.50, more preferably 1.90 to 2.20.
  • the first water-soluble binder resin according to the present invention has a G2 glass filter (maximum pores of 40 to 50 ⁇ m) when dissolved in water at a concentration of 0.5% by mass at the temperature at which the water-soluble binder resin is most dissolved.
  • the mass of the insoluble matter that is filtered off when filtered in ()) is within 50 mass% of the added water-soluble binder resin.
  • the weight average molecular weight of the first water-soluble binder resin according to the present invention is preferably in the range of 1,000 to 200,000. Further, it is more preferably within the range of 3000 to 40000.
  • the weight average molecular weight referred to in the present invention can be measured by a known method, for example, static light scattering, gel permeation chromatography (GPC), time-of-flight mass spectrometry (TOF-MASS), etc. In the present invention, it is measured by a gel permeation chromatography method which is a generally known method.
  • GPC gel permeation chromatography
  • TOF-MASS time-of-flight mass spectrometry
  • the content of the first water-soluble binder resin in the high refractive index layer is preferably within the range of 5 to 50% by mass with respect to the solid content of 100% by mass of the high refractive index layer. It is more preferable to be within the range.
  • the first water-soluble binder resin applied to the high refractive index layer is preferably polyvinyl alcohol.
  • the water-soluble binder resin which exists in the low-refractive-index layer mentioned later is also polyvinyl alcohol. Therefore, in the following, polyvinyl alcohol contained in the high refractive index layer and the low refractive index layer will be described together.
  • the high refractive index layer and the low refractive index layer preferably contain two or more types of polyvinyl alcohol having different saponification degrees.
  • polyvinyl alcohol as a water-soluble binder resin used in the high refractive index layer is polyvinyl alcohol (A)
  • polyvinyl alcohol as a water-soluble binder resin used in the low refractive index layer is polyvinyl alcohol (B). That's it.
  • each refractive index layer contains a plurality of polyvinyl alcohols having different saponification degrees and polymerization degrees
  • the polyvinyl alcohol having the highest content in each refractive index layer is changed to polyvinyl alcohol (A ) And polyvinyl alcohol (B) in the low refractive index layer.
  • the “degree of saponification” is the ratio of hydroxy groups to the total number of acetyloxy groups (derived from the starting vinyl acetate) and hydroxy groups in polyvinyl alcohol.
  • the degree of polymerization is calculated assuming that the polyvinyl alcohol having a saponification degree difference of 3 mol% or less is the same polyvinyl alcohol. .
  • a low polymerization degree polyvinyl alcohol having a polymerization degree of 1000 or less is a different polyvinyl alcohol (even if there is a polyvinyl alcohol having a saponification degree difference of 3 mol% or less, it is not regarded as the same polyvinyl alcohol).
  • polyvinyl alcohol having a saponification degree of 90 mol%, a saponification degree of 91 mol%, and a saponification degree of 93 mol% is contained in the same layer by 10 mass%, 40 mass%, and 50 mass%, respectively.
  • These three polyvinyl alcohols are the same polyvinyl alcohol, and these three mixtures are polyvinyl alcohol (A) or (B).
  • the above-mentioned “polyvinyl alcohol having a saponification degree difference of 3 mol% or less” suffices to be within 3 mol% when attention is paid to any polyvinyl alcohol.
  • polyvinyl alcohol having a saponification degree different by 3 mol% or more is contained in the same layer, it is regarded as a mixture of different polyvinyl alcohols, and the polymerization degree and the saponification degree are calculated for each.
  • PVA203 5% by mass
  • PVA117 25% by mass
  • PVA217 10% by mass
  • PVA220 10% by mass
  • PVA224 10% by mass
  • PVA235 20% by mass
  • PVA245 20% by mass
  • most contained A large amount of PVA (polyvinyl alcohol) is a mixture of PVA 217 to 245 (the difference in the degree of saponification of PVA 217 to 245 is within 3 mol%, and thus is the same polyvinyl alcohol), and this mixture is polyvinyl alcohol (A) or ( B).
  • the difference in the absolute value of the saponification degree between the polyvinyl alcohol (A) and the polyvinyl alcohol (B) is preferably 3 mol% or more, and more preferably 5 mol% or more. If it is such a range, since the interlayer mixing state of a high refractive index layer and a low refractive index layer will become a preferable level, it is preferable. Moreover, although the difference of the saponification degree of polyvinyl alcohol (A) and polyvinyl alcohol (B) is so preferable that it is separated, it is 20 mol% or less from the viewpoint of the solubility to water of polyvinyl alcohol. It is preferable.
  • the saponification degree of polyvinyl alcohol (A) and polyvinyl alcohol (B) is preferably 75 mol% or more from the viewpoint of solubility in water. Furthermore, the intermixed state of the high refractive index layer and the low refractive index layer is that one of the polyvinyl alcohol (A) and the polyvinyl alcohol (B) has a saponification degree of 90 mol% or more and the other is 90 mol% or less. Is preferable for achieving a preferable level. It is more preferable that one of the polyvinyl alcohol (A) and the polyvinyl alcohol (B) has a saponification degree of 95 mol% or more and the other is 90 mol% or less. In addition, although the upper limit of the saponification degree of polyvinyl alcohol is not specifically limited, Usually, it is less than 100 mol% and is about 99.9 mol% or less.
  • the polymerization degree of the two types of polyvinyl alcohols having different saponification degrees is preferably 1000 or more, particularly preferably those having a polymerization degree in the range of 1500 to 5000, more preferably in the range of 2000 to 5000. Those are more preferably used. This is because when the polymerization degree of polyvinyl alcohol is 1000 or more, there is no cracking of the coating film, and when it is 5000 or less, the coating solution is stabilized. In the present specification, “the coating solution is stable” means that the coating solution is stable over time.
  • the degree of polymerization of at least one of polyvinyl alcohol (A) and polyvinyl alcohol (B) is in the range of 2000 to 5000, it is preferable because cracks in the coating film are reduced and the reflectance at a specific wavelength is improved. It is preferable that both the polyvinyl alcohol (A) and the polyvinyl alcohol (B) are 2000 to 5000, since the above effects can be exhibited more remarkably.
  • Polymerization degree P in the present specification refers to a viscosity average degree of polymerization, measured according to JIS K6726 (1994), and measured in water at 30 ° C. after completely re-saponifying and purifying PVA. From the intrinsic viscosity [ ⁇ ] (dl / g), it is obtained by the following formula (1).
  • the polyvinyl alcohol (B) contained in the low refractive index layer preferably has a saponification degree in the range of 75 to 90 mol% and a polymerization degree in the range of 2000 to 5000.
  • polyvinyl alcohol having such characteristics is contained in the low refractive index layer, it is preferable in that interfacial mixing is further suppressed. This is considered to be because there are few cracks of a coating film and set property improves.
  • the polyvinyl alcohol (A) and (B) used in the present invention may be a synthetic product or a commercially available product.
  • Examples of commercially available products used as the polyvinyl alcohol (A) and (B) include, for example, PVA-102, PVA-103, PVA-105, PVA-110, PVA-117, PVA-120, PVA-124, PVA -203, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-235 (manufactured by Kuraray Co., Ltd.), JC-25, JC-33, JF-03, JF-04 , JF-05, JP-03, JP-04JP-05, JP-45 (above, manufactured by Nihon Vinegar Pover Co., Ltd.) and the like.
  • modified polyvinyl alcohol partially modified May be included.
  • modified polyvinyl alcohol include cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, nonionic-modified polyvinyl alcohol, and vinyl alcohol polymers.
  • Examples of the cation-modified polyvinyl alcohol include primary to tertiary amino groups and quaternary ammonium groups in the main chain or side chain of the polyvinyl alcohol as described in JP-A-61-10383. It is obtained by saponifying a copolymer of an ethylenically unsaturated monomer having a cationic group and vinyl acetate.
  • Examples of the ethylenically unsaturated monomer having a cationic group include trimethyl- (2-acrylamido-2,2-dimethylethyl) ammonium chloride and trimethyl- (3-acrylamido-3,3-dimethylpropyl) ammonium chloride.
  • the ratio of the cation-modified group-containing monomer in the cation-modified polyvinyl alcohol is 0.1 to 10 mol%, preferably 0.2 to 5 mol%, relative to vinyl acetate.
  • Anion-modified polyvinyl alcohol is described in, for example, polyvinyl alcohol having an anionic group as described in JP-A-1-206088, JP-A-61-237681 and JP-A-63-307979.
  • examples thereof include a copolymer of vinyl alcohol and a vinyl compound having a water-soluble group, and a modified polyvinyl alcohol having a water-soluble group as described in JP-A-7-285265.
  • Nonionic modified polyvinyl alcohols include, for example, polyvinyl alcohol derivatives obtained by adding a polyalkylene oxide group to a part of vinyl alcohol as described in JP-A-7-9758, and JP-A-8-2595.
  • Polyvinyl alcohol etc. are mentioned.
  • vinyl alcohol polymers examples include EXEVAL (registered trademark, manufactured by Kuraray Co., Ltd.) and Nichigo G polymer (registered trademark, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).
  • Two or more kinds of modified polyvinyl alcohol can be used in combination, such as the degree of polymerization and the type of modification.
  • the content of the modified polyvinyl alcohol is not particularly limited, but is preferably in the range of 1 to 30% by mass with respect to the total mass (solid content) of each refractive index. If it is in such a range, the said effect will be exhibited more.
  • the polyvinyl alcohol (A) having a low saponification degree is used for the high refractive index layer and polyvinyl alcohol (B) having a high saponification degree is used for the low refractive index layer
  • the polyvinyl alcohol ( A) is preferably contained in the range of 40% by mass to 100% by mass with respect to the total mass of all polyvinyl alcohols in the layer, more preferably 60% by mass to 95% by mass
  • the low refractive index layer The polyvinyl alcohol (B) is preferably contained in the range of 40% by mass to 100% by mass with respect to the total mass of all the polyvinyl alcohols in the low refractive index layer, and 60% by mass to 95% by mass. Is more preferable.
  • the polyvinyl alcohol (A) having a high saponification degree is used for the high refractive index layer and polyvinyl alcohol (B) having a low saponification degree is used for the low refractive index layer
  • the polyvinyl alcohol ( A) is preferably contained in the range of 40% by mass to 100% by mass with respect to the total mass of all polyvinyl alcohols in the layer, more preferably 60% by mass to 95% by mass
  • the low refractive index layer The polyvinyl alcohol (B) is preferably contained in the range of 40% by mass to 100% by mass with respect to the total mass of all the polyvinyl alcohols in the low refractive index layer, and 60% by mass to 95% by mass. More preferred.
  • the content is 40% by mass or more, interlayer mixing is suppressed, and the effect of less disturbance of the interface appears remarkably. On the other hand, if content is 100 mass% or less, stability of a coating liquid will improve.
  • the first water-soluble binder resin other than polyvinyl alcohol is not limited as long as the high refractive index layer containing the first metal oxide particles can form a coating film. But it can be used without restriction.
  • the second water-soluble binder resin other than the polyvinyl alcohol (B) the low refractive index layer containing the second metal oxide particles is coated as described above. Any device can be used without limitation as long as it can be formed. However, in view of environmental problems and flexibility of the coating film, water-soluble polymers (particularly gelatin, thickening polysaccharides, polymers having reactive functional groups) are preferable. These water-soluble polymers may be used alone or in combination of two or more.
  • the content of other binder resin used together with polyvinyl alcohol preferably used as the water-soluble binder resin is in the range of 5 to 50% by mass with respect to 100% by mass of the solid content of the high refractive index layer. It can also be used within.
  • the binder resin is preferably composed of a water-soluble polymer. That is, in the present invention, a water-soluble polymer other than polyvinyl alcohol and modified polyvinyl alcohol may be used as the binder resin in addition to the polyvinyl alcohol and modified polyvinyl alcohol as long as the effect is not impaired.
  • the water-soluble polymer is when it is filtered through a G2 glass filter (maximum pores 40-50 ⁇ m) when dissolved in water at a concentration of 0.5% by mass at the temperature at which the water-soluble polymer is most soluble.
  • the mass of the insoluble matter separated by filtration is within 50% by mass of the added water-soluble polymer.
  • gelatin, celluloses, thickening polysaccharides, or polymers having reactive functional groups are particularly preferable. These water-soluble polymers may be used alone or in combination of two or more.
  • the first metal oxide particles applicable to the high refractive index layer are preferably metal oxide particles having a refractive index of 2.0 or more and 3.0 or less. More specifically, for example, titanium oxide, zirconium oxide, zinc oxide, synthetic amorphous silica, colloidal silica, alumina, colloidal alumina, lead titanate, red lead, yellow lead, zinc yellow, chromium oxide, second oxide Examples include iron, iron black, copper oxide, magnesium oxide, magnesium hydroxide, strontium titanate, yttrium oxide, niobium oxide, europium oxide, lanthanum oxide, zircon, and tin oxide. In addition, composite oxide particles composed of a plurality of metals, core / shell particles whose metal structure changes into a core / shell shape, and the like can also be used.
  • the high refractive index layer includes metal oxide fine particles having a high refractive index such as titanium and zirconium, that is, titanium oxide fine particles and / or zirconia oxide. It is preferable to contain fine particles.
  • titanium oxide is more preferable from the viewpoint of the stability of the coating liquid for forming the high refractive index layer.
  • the rutile type tetragonal type
  • the weather resistance of the high refractive index layer and adjacent layers is higher, and the refractive index is higher. To more preferable.
  • core / shell particles are used as the first metal oxide particles in the high refractive index layer, due to the interaction between the silicon-containing hydrated oxide of the shell layer and the first water-soluble binder resin, From the effect of suppressing interlayer mixing between the high refractive index layer and the adjacent layer, core / shell particles in which titanium oxide particles are coated with a silicon-containing hydrated oxide are more preferable.
  • the content of the first metal oxide particles according to the present invention is in the range of 15 to 80% by mass with respect to 100% by mass of the solid content of the high refractive index layer, the refractive index difference from the low refractive index layer Is preferable from the viewpoint of imparting. Further, it is more preferably in the range of 20 to 77% by mass, and further preferably in the range of 30 to 75% by mass.
  • content in case metal oxide particles other than the said core-shell particle are contained in a high refractive index layer will not be specifically limited if it is a range which can have the effect of this invention.
  • the volume average particle size of the first metal oxide particles applied to the high refractive index layer is preferably 30 nm or less, more preferably in the range of 1 to 30 nm, and more preferably in the range of 5 to 15 nm. More preferably, it is in the range.
  • a volume average particle size in the range of 1 to 30 nm is preferable from the viewpoint of low visible light transmittance and low haze.
  • the first metal oxide particles according to the present invention are preferably monodispersed.
  • the monodispersion here means that the monodispersity obtained by the following formula (2) is 40% or less. This monodispersity is more preferably 30% or less, and particularly preferably in the range of 0.1 to 20%.
  • titanium oxide particles surface-treated with a silicon-containing hydrated oxide is preferably used.
  • the titanium particles are sometimes referred to as “core / shell particles” or “Si-coated TiO 2 ”.
  • the titanium oxide particles are coated with a silicon-containing hydrated oxide, and the average particle diameter which is preferably a core portion is in the range of 1 to 30 nm, more preferably the average
  • the surface of the titanium oxide particles having a particle size in the range of 4 to 30 nm has a coating amount of silicon-containing hydrated oxide in the range of 3 to 30% by mass as SiO 2 with respect to the titanium oxide as the core. In this way, a shell made of a silicon-containing hydrated oxide is coated.
  • the interaction between the silicon-containing hydrated oxide of the shell layer and the first water-soluble binder resin causes the high refractive index layer and the low refractive index layer to The effect of suppressing the intermixing between the layers and the effect of preventing the deterioration of the binder and choking due to the photocatalytic activity of titanium oxide when titanium oxide is used as the core are exhibited.
  • the core / shell particles preferably have a silicon-containing hydrated oxide coating amount in the range of 3 to 30% by mass as SiO 2 with respect to titanium oxide as the core, more preferably 3 It is in the range of ⁇ 10% by mass, more preferably in the range of 3 to 8% by mass. If the coating amount is 30% by mass or less, a high refractive index layer can be made to have a high refractive index, and if the coating amount is 3% by mass or more, core / shell particle particles can be stably formed. can do.
  • the average particle diameter of the core / shell particles is preferably in the range of 1 to 30 nm, more preferably in the range of 5 to 20 nm, and still more preferably in the range of 5 to 15 nm.
  • optical properties such as near infrared reflectance, transparency, and haze can be further improved.
  • the average particle diameter as used in the field of this invention means a primary average particle diameter, and can be measured from the electron micrograph by a transmission electron microscope (TEM) etc. You may measure by the particle size distribution meter etc. which utilize a dynamic light scattering method, a static light scattering method, etc.
  • TEM transmission electron microscope
  • the average particle diameter of primary particles is the particle itself or the particles appearing on the cross section or surface of the refractive index layer is observed with an electron microscope, and the particle diameter of 1000 arbitrary particles is measured. It is obtained as its simple average value (number average).
  • the particle diameter of each particle is represented by a diameter assuming a circle equal to the projected area.
  • JP-A-10-158015 JP-A-2000-053421, JP-A-2000-063119.
  • the silicon-containing hydrated oxide applied to the core / shell particles may be either a hydrate of an inorganic silicon compound, a hydrolyzate or a condensate of an organosilicon compound.
  • silanol A compound having a group is preferable.
  • the core / shell particles used in the present invention may be those in which the entire surface of the titanium oxide particles that are the core is coated with a silicon-containing hydrated oxide, or part of the surface of the titanium oxide particles that are the core. It may be coated with a silicon hydrated oxide.
  • a curing agent can also be used to cure the first water-soluble binder resin applied to the high refractive index layer.
  • a curing agent can also be used to cure the first water-soluble binder resin applied to the high refractive index layer.
  • boric acid and its salt are preferable as the curing agent.
  • the curing agent include, for example, epoxy curing agents (diglycidyl ethyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-diglycidyl cyclohexane, N, N-diglycidyl- 4-glycidyloxyaniline, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, etc.), aldehyde curing agents (formaldehyde, glioxal, etc.), active halogen curing agents (2,4-dichloro-4-hydroxy-1,3,5) -S-triazine, etc.), active vinyl compounds (1,3,5-trisacryloyl-hexahydro-s-triazine, bisvinylsulfonylmethyl ether, etc.), aluminum alum and the like.
  • epoxy curing agents diglycidyl ethyl ether
  • the content of the curing agent in the high refractive index layer is preferably 1 to 10% by mass and more preferably 2 to 6% by mass with respect to 100% by mass of the solid content of the high refractive index layer.
  • the total amount of the curing agent used is preferably 1 to 600 mg per 1 g of polyvinyl alcohol, more preferably 100 to 600 mg per 1 g of polyvinyl alcohol.
  • the low refractive index layer according to the present invention includes a second water-soluble binder resin and second metal oxide particles, and further includes a curing agent, a surface coating component, a particle surface protective agent, a binder resin, a surfactant, Various additives may be included.
  • the refractive index of the low refractive index layer according to the present invention is preferably in the range of 1.10 to 1.60, more preferably 1.30 to 1.50.
  • Polyvinyl alcohol is preferably used as the second water-soluble binder resin applied to the low refractive index layer according to the present invention. Furthermore, it is more preferable that polyvinyl alcohol (B) different from the saponification degree of polyvinyl alcohol (A) present in the high refractive index layer is used in the low refractive index layer according to the present invention.
  • polyvinyl alcohol (A) and polyvinyl alcohol (B), such as a preferable weight average molecular weight of 2nd water-soluble binder resin here is demonstrated by the water-soluble binder resin of the said high refractive index layer. The description is omitted here.
  • the content of the second water-soluble binder resin in the low refractive index layer is preferably in the range of 20 to 99.9% by mass with respect to 100% by mass of the solid content of the low refractive index layer, and 25 to 80 More preferably, it is in the range of mass%.
  • the content of the other binder resin used together with polyvinyl alcohol preferably used as the second water-soluble binder resin is 0 to 10 mass with respect to 100 mass% of the solid content of the low refractive index layer. % Can also be used.
  • silica As the second metal oxide particles applied to the low refractive index layer according to the present invention, silica (silicon dioxide) is preferably used, and specific examples thereof include synthetic amorphous silica and colloidal silica. Of these, acidic colloidal silica sol is more preferably used, and colloidal silica sol dispersed in an organic solvent is more preferably used. Further, in order to further reduce the refractive index, hollow fine particles having pores inside the particles can be used as the second metal oxide particles applied to the low refractive index layer, particularly silica (silicon dioxide). The hollow fine particles are preferred.
  • the second metal oxide particles (preferably silicon dioxide) applied to the low refractive index layer preferably have an average particle size in the range of 3 to 100 nm.
  • the average particle size of primary particles of silicon dioxide dispersed in a primary particle state is more preferably in the range of 3 to 50 nm, and in the range of 3 to 40 nm. Is more preferably 3 to 20 nm, and most preferably 4 to 10 nm.
  • grains it is preferable from a viewpoint with few hazes and excellent visible light transmittance
  • the average particle size of the metal oxide particles applied to the low refractive index layer is determined by observing the particles themselves or the particles appearing on the cross section or surface of the refractive index layer with an electron microscope and measuring the particle size of 1000 arbitrary particles.
  • the simple average value (number average) is obtained.
  • the particle diameter of each particle is represented by a diameter assuming a circle equal to the projected area.
  • the colloidal silica used in the present invention is obtained by heating and aging a silica sol obtained by metathesis with an acid of sodium silicate or the like and passing through an ion exchange resin layer.
  • colloidal silica may be a synthetic product or a commercially available product.
  • the surface of the colloidal silica may be cation-modified, or may be treated with Al, Ca, Mg, Ba or the like.
  • Hollow particles can also be used as the second metal oxide particles applied to the low refractive index layer.
  • the average particle pore diameter is preferably within the range of 3 to 70 nm, more preferably within the range of 5 to 50 nm, and even more preferably within the range of 5 to 45 nm.
  • the average particle pore diameter of the hollow particles is the average value of the inner diameters of the hollow particles.
  • the refractive index of the low refractive index layer is sufficiently lowered.
  • the average particle diameter is 50 or more at random, which can be observed as an ellipse in a circular, elliptical or substantially circular shape by electron microscope observation. Is obtained.
  • the average particle hole diameter means the smallest distance among the distances between the outer edges of the hole diameter that can be observed as a circle, an ellipse, or a substantially circle or ellipse, between two parallel lines.
  • the content of the second metal oxide particles in the low refractive index layer is preferably 0.1 to 70% by mass, and preferably 30 to 70% by mass with respect to 100% by mass of the solid content of the low refractive index layer. More preferably, it is more preferably 45 to 65% by mass.
  • the low refractive index layer according to the present invention may further include a curing agent.
  • a curing agent there is no particular limitation as long as it causes a curing reaction with the second water-soluble binder resin contained in the low refractive index layer.
  • boric acid and its salt and / or borax are preferred as the curing agent when polyvinyl alcohol is used as the second water-soluble binder resin applied to the low refractive index layer.
  • boric acid and its salts known ones can be used.
  • the content of the curing agent in the low refractive index layer is preferably in the range of 1 to 10% by mass and preferably in the range of 2 to 6% by mass with respect to 100% by mass of the solid content of the low refractive index layer. It is more preferable.
  • additives for each refractive index layer In the high refractive index layer and the low refractive index layer according to the present invention, various additives can be used as necessary.
  • the content of the additive in the high refractive index layer is preferably 0 to 20% by mass with respect to 100% by mass of the solid content of the high refractive index layer.
  • additives include surfactants, amino acids, emulsion resins, lithium compounds described in paragraphs [0140] to [0154] of JP2012-139948A, and other additives described in paragraph [0155] of the same publication. Can be mentioned.
  • the method of forming the optical reflective layer group used in the present invention is preferably formed by applying a wet coating method, and further, on the support according to the present invention, the first water-soluble binder resin and the first A production method comprising a step of wet-coating a coating solution for a high refractive index layer containing metal oxide particles and a coating solution for a low refractive index layer containing a second water-soluble binder resin and a second metal oxide particle Is preferred.
  • the wet coating method is not particularly limited.
  • a sequential multilayer application method or a simultaneous multilayer application method may be used as a method of applying a plurality of layers in a multilayer manner.
  • the solvent applicable for preparing the coating solution for the high refractive index layer and the coating solution for the low refractive index layer is not particularly limited, but water, an organic solvent, or a mixed solvent thereof is preferable.
  • organic solvent examples include alcohols such as methanol, ethanol, 2-propanol and 1-butanol, esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, diethyl ether and propylene.
  • examples include ethers such as glycol monomethyl ether and ethylene glycol monoethyl ether, amides such as dimethylformamide and N-methylpyrrolidone, and ketones such as acetone, methyl ethyl ketone, acetylacetone and cyclohexanone. These organic solvents may be used alone or in combination of two or more.
  • the solvent of the coating solution is particularly preferably water or a mixed solvent of water and methanol, ethanol, or ethyl acetate.
  • the concentration of the water-soluble binder resin in the coating solution for the high refractive index layer is preferably in the range of 1 to 10% by mass.
  • concentration of the metal oxide particles in the coating solution for the high refractive index layer is preferably in the range of 1 to 50% by mass.
  • the concentration of the water-soluble binder resin in the coating solution for the low refractive index layer is preferably in the range of 1 to 10% by mass.
  • the concentration of the metal oxide particles in the coating solution for the low refractive index layer is preferably in the range of 1 to 50% by mass.
  • the method for preparing the coating solution for the high refractive index layer and the coating solution for the low refractive index layer is not particularly limited.
  • a water-soluble binder resin, metal oxide particles, and other additives added as necessary The method of adding and stirring and mixing is mentioned.
  • the order of addition of the water-soluble binder resin, the metal oxide particles, and other additives used as necessary is not particularly limited, and each component may be added and mixed sequentially while stirring. However, they may be added and mixed at once. If necessary, it is further adjusted to an appropriate viscosity using a solvent.
  • a high refractive index layer using an aqueous high refractive index coating solution prepared by adding and dispersing core / shell particles.
  • the core / shell particles are added to the coating solution for the high refractive index layer as a sol having a pH measured in the range of 5.0 to 7.5 at 25 ° C. and a negative zeta potential of the particles. It is preferable to prepare it.
  • the viscosity at 40 to 45 ° C. of the coating solution for the high refractive index layer and the coating solution for the low refractive index layer when performing simultaneous multilayer coating by the slide hopper coating method is preferably within the range of 5 to 150 mPa ⁇ s. -Within the range of s is more preferable.
  • the viscosity at 40 to 45 ° C. of the coating solution for the high refractive index layer and the coating solution for the low refractive index layer when performing simultaneous multilayer coating by the slide curtain coating method is preferably within the range of 5 to 1200 mPa ⁇ s. A range of 25 to 500 mPa ⁇ s is more preferable.
  • the viscosity at 15 ° C. of the coating solution for the high refractive index layer and the coating solution for the low refractive index layer is preferably 100 mPa ⁇ s or more, more preferably in the range of 100 to 30000 mPa ⁇ s, and in the range of 3000 to 30000 mPa ⁇ s.
  • the inside is more preferable, and the inside of the range of 10,000 to 30,000 mPa ⁇ s is particularly preferable.
  • the coating and drying method is not particularly limited, but the high refractive index layer coating solution and the low refractive index layer coating solution are heated to 30 ° C. or higher, and the high refractive index layer coating solution and the low refractive index are coated on the substrate.
  • the temperature of the formed coating film is preferably cooled (set) preferably to 1 to 15 ° C. and then dried at 10 ° C. or higher. More preferable drying conditions are a wet bulb temperature of 5 to 50 ° C. and a film surface temperature of 10 to 50 ° C.
  • the set means a step of increasing the viscosity of the coating composition and reducing the fluidity of substances in each layer and in each layer by means such as applying cold air to the coating to lower the temperature.
  • a state in which the cold air is applied to the coating film from the surface and the finger is pressed against the surface of the coating film is defined as a set completion state.
  • the time (setting time) from application of cold air to completion of setting is preferably within 5 minutes, preferably within 2 minutes. Further, the lower limit time is not particularly limited, but it is preferable to take 45 seconds or more. If the set time is too short, there are places where mixing of the components in the layer becomes insufficient. On the other hand, if the set time is too long, the interlayer diffusion of the metal oxide particles proceeds, and the difference in refractive index between the high refractive index layer and the low refractive index layer is insufficient. In addition, if the high elasticity of the heat ray blocking film unit between the high refractive index layer and the low refractive index layer occurs quickly, the setting step may not be provided.
  • the set time is adjusted by adjusting the concentration of the water-soluble binder resin and the metal oxide particles, and adding other components such as various known gelling agents such as gelatin, pectin, agar, carrageenan and gellan gum. Can be adjusted.
  • the temperature of the cold air is preferably 0 to 25 ° C, more preferably 5 to 10 ° C. Further, the time during which the coating film is exposed to the cold air is preferably 10 to 120 seconds, although it depends on the transport speed of the coating film.
  • FIG. 1 is an example in which the optical film of the present invention having an optical reflective layer is applied to an infrared reflective film, and is a schematic cross-sectional view showing a configuration provided with a reflective layer unit having a reflective layer group on one surface side of a support. It is.
  • an infrared reflective film 1 to which the optical film of the present invention is applied has a reflective layer unit U.
  • the reflective layer unit U includes, as an example, a high refractive index reflective layer containing a first water-soluble binder resin and first metal oxide particles, and a second water-soluble binder resin on the support 2.
  • a reflective layer group ML in which low-refractive index reflective layers containing second metal oxide particles are alternately stacked.
  • the reflective layer group ML is composed of n layers of reflective layers T 1 to T n , for example, T 1 , T 3 , T 5 , (omitted), T n-2 , T n with a refractive index of 1.10 to 1.
  • T n-1 are high in the refractive index range of 1.80 to 2.50.
  • An example of the configuration is a refractive index layer.
  • the refractive index as used in the field of this invention is the value measured in the environment of 25 degreeC.
  • a hard coat layer 3 for improving scratch resistance on the opposite side of the reflective layer unit and the support, and another base material (for example, the uppermost layer of the reflective layer unit of the support) It is preferable to provide an adhesive layer 4 to be bonded to the window glass.
  • the arrangement of the hard coat layer and the adhesive layer may be appropriately switched.
  • a well-known material and a formation method can be employ
  • the hard coat layer 3 preferably contains a cured product of an actinic radiation curable compound, and as the actinic radiation curable compound, a component containing a monomer having an ethylenically unsaturated double bond is preferably used.
  • the actinic radiation curable compound include an ultraviolet curable compound and an electron beam curable compound, and a compound that is cured by ultraviolet irradiation is preferable from the viewpoint of excellent mechanical film strength (abrasion resistance, pencil hardness).
  • an ultraviolet curable urethane acrylate resin for example, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, or an ultraviolet curable epoxy resin is preferable. Used. Of these, ultraviolet curable acrylate resins are preferred.
  • the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer 4 is not particularly limited, and examples thereof include acrylic pressure-sensitive adhesives, silicone pressure-sensitive adhesives, urethane pressure-sensitive adhesives, polyvinyl butyral pressure-sensitive adhesives, and ethylene-vinyl acetate pressure-sensitive adhesives. Can do.
  • the optical film of the present invention When the optical film of the present invention is attached to a window glass, water is sprayed on the window, and the method of attaching the adhesive layer of the optical film to the wet glass surface, the so-called water application method is applied again, the position is adjusted, etc. It is suitably used from the viewpoint. For this reason, an acrylic pressure-sensitive adhesive that has a weak adhesive force in the presence of water is preferably used.
  • the acrylic pressure-sensitive adhesive used may be either solvent-based or emulsion-based, but is preferably a solvent-based pressure-sensitive adhesive because it is easy to increase the adhesive strength and the like, and among them, those obtained by solution polymerization are preferable.
  • the raw material for producing such a solvent-based acrylic pressure-sensitive adhesive by solution polymerization include, for example, acrylic acid esters such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and acryl acrylate as main monomers serving as a skeleton, As a comonomer to improve cohesive strength, vinyl acetate, acrylonitrile, styrene, methyl methacrylate, etc., to further promote crosslinking, to give stable adhesive strength, and to maintain a certain level of adhesive strength even in the presence of water
  • the functional group-containing monomer include methacrylic acid, acrylic acid, itaconic acid, hydroxyethyl methacrylate, and glycid
  • a separator release sheet
  • a substrate such as polyester, polyethylene, polypropylene, paper, etc.
  • silicon polyalkylene, or fluororesin
  • a polyester film that is silicon-coated from the standpoint of properties, smoothness, and peel stability.
  • the thickness of the separator is preferably in the range of 10 to 100 ⁇ m, more preferably 20 to 60 ⁇ m. If it is 10 ⁇ m or less, it is not preferred because wrinkles are likely to occur in the film due to heat during coating and drying.
  • FIG. 2 is a schematic cross-sectional view showing another example in which the optical film of the present invention having an optical reflective layer is applied to an infrared reflective film, in which a reflective layer unit having a reflective layer group is provided on both sides of a support. is there.
  • the optical film of the present invention has a conductive layer, an antistatic layer, a gas barrier layer, an antifouling layer, a deodorizing layer, a droplet layer, a slippery layer, and abrasion resistance for the purpose of adding further functions on the support.
  • a layer, an electromagnetic shielding layer, a printing layer, a fluorescent light emitting layer, a hologram layer, a release layer, and the like may be provided.
  • an infrared reflecting film is sandwiched between two glass substrates on both sides of an infrared reflecting layer unit via an intermediate film 5 typified by polyvinyl butyral (PVB) which is a polyvinyl acetal resin film. It is preferable to manufacture it.
  • PVB polyvinyl butyral
  • the polyvinyl acetal resin film By using the polyvinyl acetal resin film, the curved surface followability of the infrared reflective film is improved.
  • FIG. 3 is a schematic view of a laminated glass provided with the infrared reflective film of the present invention.
  • the laminated glass of the present invention may be a flat laminated glass, or a laminated glass using a curved glass substrate used for a windshield of a car.
  • the laminated glass according to the present invention preferably has a visible light transmittance of 70% or more, particularly when used as a car window glass.
  • the visible light transmittance can be measured by using, for example, a spectrophotometer (U-4000 type, manufactured by Hitachi, Ltd.), JIS R3106 (1998) “Test of transmittance, reflectance, and solar heat gain of plate glass” It can be measured according to “Method”.
  • the solar heat acquisition rate of the laminated glass of the present invention is preferably 60% or less, and more preferably 55% or less. If it is this range, the heat ray from the outside can be interrupted more effectively.
  • the solar heat acquisition rate is measured using, for example, a spectrophotometer (manufactured by Hitachi, Ltd., U-4000 type) in the same manner as described above using JIS R3106 (1998) It can be determined according to “Test method for heat gain”.
  • Glass substrate A commercially available glass material can be used as the glass substrate used in the present invention.
  • the type of glass is not particularly limited, but usually soda lime silica glass is preferably used. In this case, it may be a colorless transparent glass or a colored transparent glass.
  • the outdoor glass substrate close to the incident light is preferably colorless transparent glass.
  • the glass substrate of the indoor side far from the incident light side is a green-colored colored transparent glass or dark colored transparent glass.
  • the green colored transparent glass preferably has ultraviolet absorption performance and infrared absorption performance.
  • the green colored transparent glass is not particularly limited, for example, soda lime silica glass containing iron is preferable.
  • a soda lime silica glass containing 0.3 to 1% by mass of total iron in terms of Fe 2 O 3 in a soda lime silica base glass is preferable.
  • the mass of FeO (divalent iron) is calculated as Fe 2 O 3 in total. It is preferably 20 to 40% by mass of iron.
  • soda lime silica glass having the following composition substantially. SiO 2 : 65 to 75% by mass, Al 2 O 3 : 0.1 to 5% by mass, Na 2 O + K 2 O: 10 to 18% by mass, CaO: 5 to 15% by mass, MgO: 1 to 6% by mass, terms of Fe 2 O 3 were total iron 0.3 to 1 mass%, the total cerium CeO 2 in terms and / or TiO 2: 0.5 ⁇ 2% by weight.
  • the dark transparent glass is not particularly limited, but, for example, soda lime silica glass containing iron at a high concentration is preferable.
  • both the indoor side glass base material and the outdoor side glass base material is 1.5 to 3.0 mm.
  • the indoor side glass base material and the outdoor side glass base material can have the same thickness or different thicknesses.
  • both the indoor side glass base material and the outdoor side glass base material may have a thickness of 2.0 mm or a thickness of 2.1 mm.
  • the total thickness of the laminated glass is reduced by setting the thickness of the indoor glass substrate to less than 2 mm and the thickness of the outdoor glass plate to 2 mm or more.
  • the indoor glass substrate and the outdoor glass substrate may be flat or curved. Since vehicles, particularly automobile windows, are often curved, the shape of the indoor side glass substrate and the outdoor side glass substrate is often curved. In this case, the infrared reflecting layer group is provided on the concave surface side of the outdoor glass substrate. Furthermore, if necessary, three or more glass substrates can be used.
  • the manufacturing method of the laminated glass of this invention is not restrict
  • Example 1 ⁇ Preparation of support >> ⁇ Preparation of Support 1 (PET; Comparative Example)> As a PET film, Toyobo Co., Ltd. Cosmo Shine A4300 and a film thickness of 100 ⁇ m were prepared.
  • Fine particles (Aerosil R972V manufactured by Nippon Aerosil Co., Ltd.) 11 parts by weight Ethanol 89 parts by weight
  • methylene chloride was charged into the dissolution tank, and the prepared fine particle dispersion was sufficiently stirred at the following addition amount. Slowly added. Subsequently, after being dispersed with an attritor so that the particle size of the secondary particles of the fine particles becomes a predetermined size, the fine particles are filtered through Finemet NF (manufactured by Nippon Seisen Co., Ltd.) to obtain a fine particle additive solution. .
  • Fine particle additive Methylene chloride 99 parts by mass Fine particle dispersion 5 parts by mass Among the main dope components below, methylene chloride and ethanol were charged into a pressurized dissolution tank. Next, cellulose triacetate and the prepared fine particle additive solution were added while stirring, and heated and stirred to completely dissolve. The obtained solution was used as Azumi filter paper No. manufactured by Azumi Filter Paper Co., Ltd. The main dope was prepared by filtration using 244.
  • the film was dried at a drying temperature of 160 ° C. while being stretched at a magnification.
  • the residual solvent amount at the start of drying was 20%.
  • a support 2 for comparison with a film thickness of 100 ⁇ m and a winding length of 4000 m was produced.
  • the casting conditions were adjusted so that the final film thickness was 100 ⁇ m when the draw ratio was changed.
  • PBSA was changed in the range of 10 to 70% by mass so that the total amount of cellulose triacetate and PBSA was 100 parts by mass, and the draw ratio was changed as shown in Table 1. Supports 4 to 8 were produced in the same manner except that.
  • the casting conditions were adjusted so that the final film thickness was 100 ⁇ m.
  • CAP + Polymer (B); Present Invention cellulose triacetate was converted to cellulose acetate propionate (product name CAP482-20, manufactured by Eastman Chemical Co., Ltd., acetyl group substitution degree 0.2, propionyl group substitution degree 2.56, total acyl group substitution degree 2 ., 76, Mn: 70000, Mw: 220,000), a support 10 having a thickness of 100 ⁇ m was produced.
  • the infrared reflective film shown in FIG. 1 in which the layers were alternately laminated was produced as follows.
  • the undercoat layer coating solution 1 is applied to the support 1 with an extrusion coater so as to be 15 ml / m 2, and after passing through a 50 ° C. no wind zone (1 second), it is dried at 120 ° C. for 30 seconds. A support coated with a coating layer was obtained.
  • undercoat layer coating solution 1 10g deionized gelatin 30 ml of pure water Acetic acid 20g The following crosslinking agent 0.2 mol / g gelatin The following nonionic fluorine-containing surfactant 0.2 g
  • ⁇ Preparation of deionized gelatin> Ocein from which lime was removed by performing lime treatment, water washing and neutralization treatment was extracted in hot water at 55 to 60 ° C. to obtain ossein gelatin.
  • the obtained ossein gelatin aqueous solution was subjected to both ion exchanges in a mixed bed of anion exchange resin (Diaion PA-31G) and cation exchange resin (Diaion PK-218).
  • a low-refractive index layer is formed by applying a coating layer coated on a support so that each of the high-refractive index layer and the low-refractive index layer has a dry film thickness of 130 nm and the lowermost layer is a low-refractive index layer.
  • Nine layers and eight high refractive index layers were alternately applied in total 17 layers simultaneously.
  • the obtained colloidal silica dispersion L1 was heated to 45 ° C., and 4.0% by mass of polyvinyl alcohol (B) as a polyvinyl alcohol (manufactured by Nippon Vinyl Bipo-Poval Co., Ltd., JP-45: polymerization) 4500, saponification degree 86.5 to 89.5 mol%) and 760 parts of an aqueous solution were sequentially added with stirring. Thereafter, 40 parts of a 1% by weight betaine surfactant (manufactured by Kawaken Fine Chemical Co., Ltd., Sofazoline (registered trademark) LSB-R) aqueous solution was added to prepare a coating solution L1 for a low refractive index layer.
  • B polyvinyl alcohol
  • betaine surfactant manufactured by Kawaken Fine Chemical Co., Ltd., Sofazoline (registered trademark) LSB-R
  • the raw material titanium oxide hydrate is obtained by thermal hydrolysis of an aqueous titanium sulfate solution according to a known method.
  • the base-treated titanium compound was suspended in pure water so that the concentration when converted to TiO 2 was 20 g / L. Therein, it was added with TiO 2 amount to stirring 0.4 mole% citric acid. After that, when the temperature of the mixed sol solution reaches 95 ° C., concentrated hydrochloric acid is added so that the hydrochloric acid concentration becomes 30 g / L. The mixture is stirred for 3 hours while maintaining the liquid temperature at 95 ° C. A liquid was prepared.
  • the pH and zeta potential of the obtained titanium oxide sol solution were measured, the pH was 1.4 and the zeta potential was +40 mV. Moreover, when the particle size was measured with a Zetasizer Nano manufactured by Malvern, the monodispersity was 16%.
  • titanium oxide sol solution was dried at 105 ° C. for 3 hours to obtain titanium oxide powder fine particles.
  • the powder fine particles were subjected to X-ray diffraction measurement using JDX-3530 type manufactured by JEOL Datum Co., Ltd. and confirmed to be rutile titanium oxide fine particles.
  • the volume average particle diameter of the fine particles was 10 nm.
  • a 20.0 mass% titanium oxide sol aqueous dispersion containing rutile-type titanium oxide fine particles having a volume average particle diameter of 10 nm was added to 4 kg of pure water to obtain a sol solution serving as core particles.
  • Preparation of coating liquid H1 for high refractive index layer 28.9 parts of a sol solution containing core / shell particles as the first metal oxide particles having a solid content concentration of 20.0% by mass obtained above, and 10.5 parts of a 1.92% by mass citric acid aqueous solution. And 2.0 parts of an aqueous solution of 10% by weight polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-103: polymerization degree 300, saponification degree 98.5 mol%) and 9.0 parts of a 3% by weight aqueous boric acid solution. By mixing, a core-shell particle dispersion H1 was prepared.
  • HC layer 1 ⁇ Formation of hard coat layer (HC layer 1)> Beam set 577 (Arakawa Chemical Industries, Ltd.) was used as an ultraviolet curable resin, and methyl ethyl ketone was added as a solvent. Furthermore, 0.08% by mass of a fluorosurfactant (trade name: Footage (registered trademark) 650A, manufactured by Neos Co., Ltd.) was added, and the total solid content was adjusted to 40 parts by mass. A coating layer coating solution A was prepared.
  • a fluorosurfactant trade name: Footage (registered trademark) 650A, manufactured by Neos Co., Ltd.
  • the coating liquid A for hard coat layer prepared above is coated on the surface of the support opposite to the infrared reflective layer with a gravure coater under the condition that the dry layer thickness is 5 ⁇ m, and then the drying zone temperature is 90 ° C. After drying for a minute, the hard coat layer was cured using an ultraviolet lamp, the irradiance of the irradiated part was 100 mW / cm 2 , the irradiation amount was 0.5 J / cm 2 , and the hard coat layer was formed.
  • optical films 2 to 16 were produced in the same manner as the optical film 1 using the produced supports 2 to 10 described above.
  • the optical film 6 was formed by simultaneously applying a total of 17 layers of 9 layers of low refractive index layers and 8 layers of high refractive index layers alternately on both sides of the support 5 to produce a laminate as shown in FIG. .
  • the optical film 13 was formed by simultaneously applying a total of 27 layers of 12 layers of low refractive index layers and 11 layers of high refractive index layers on one side of the support 10 alternately.
  • the supports 5, 9 and 10 were respectively washed and dried, set in a sputtering film forming apparatus, and a TiO 2 film having a thickness of 105 nm as a high refractive index layer was formed on the surface thereof.
  • Layers, SiO 2 film 9 layers of thickness 175nm as a low refractive index layer, SiO 2 film was formed infrared reflecting layer are laminated alternately such that the bottom layer.
  • an infrared reflecting film which is a laminate of 401 layers was prepared by the method described in paragraphs [0056] to [0059] of JP2012-081748A.
  • Thermal shrinkage (%) (L (23 ° C.) ⁇ L (150 ° C.)) / L (23 ° C.) ⁇ 100 L (23 ° C.): Sample length when left for 1 day in an environment of 23 ° C. and 55% RH L (150 ° C.): Environment of 23 ° C. and 55% RH after standing for 30 minutes in an environment of 150 ° C. Sample length when left for 1 day under [Light transmittance] As a spectrophotometer, U-4000 type (manufactured by Hitachi, Ltd.) was used, and the light transmittance in the region of light wavelength of 400 to 700 nm of each support was measured in the width direction of the film in an environment of 23 ° C. and 55% RH. Ten points were measured at equal intervals, the average value was obtained, and this was used as the light transmittance (%).
  • the tear strength of the support was measured according to JIS K 7128-2 (1998) by the Elmendorf tear method using a light load tear tester manufactured by Toyo Seiki Seisakusho Co., Ltd. under the following conditions.
  • a sample film was cut into a size of 63 mm ⁇ 75 mm and allowed to stand for 1 day under conditions of a temperature of 23 ° C. and 55% RH, and then measured under the same conditions.
  • measure the tear load (mN) of a total of 10 sheets in the transport direction (MD direction) and in the direction perpendicular to it (TD direction), and the average value (converted as the same tear length and thickness) was determined as the tear strength.
  • Elongation at break (%) (L ⁇ Lo) / Lo ⁇ 100
  • Lo sample length before test
  • L sample length at break [light resistance]
  • Optical films 1 to 18 are affixed to the windshield of an automobile and irradiated with a Xe lamp for 2000 hours at 23 ° C. and 55% RH. The difference in coloration is calculated from the rate of change of L * , a * , and b * below. ⁇ E (change in color) was calculated.
  • Laminated glass was produced using the optical films 1 to 18 produced above.
  • a polyvinyl butyral film having a thickness of 380 ⁇ m was applied as a polyvinyl acetal resin film to the infrared reflective layer unit to which the hard coat layer of the optical films 1 to 18 was not applied.
  • Example 1 The transmittance and light resistance of Example 1 were evaluated as laminated glass, and in addition, the following thermal wrinkles were evaluated.
  • the optical film of the present invention is clearly an optical film excellent in light transmittance, tear strength, and elongation at break relative to the comparative optical film. Moreover, when the optical film was bonded to an automobile windshield as an infrared reflective film, it was found to be excellent in light resistance and edge peeling, and even when used in laminated glass, it was found to be an infrared reflective film with good heat wrinkles. It was.
  • Example 2 ⁇ Preparation of supports 21 to 35>
  • the polymer (B) the polymer (B) in which the following molecular weight and type were changed instead of PBSA (molecular weight 230,000), and the type of cellulose ester were changed.
  • the supports 21 to 35 shown in Table 2 were prepared.
  • Example 2 Using the produced supports 21 to 35 and the optical films 21 to 35, the same evaluation as in Example 1 was performed, and the results are shown in Table 2.
  • the optical film of the present invention reproduced Example 1, and a film having good light transmittance, tear strength, elongation at break, light resistance, edge peeling, and thermal wrinkle was obtained. Moreover, the film which exists in the preferable range of the molecular weight described in the specification, the addition amount, and the cellulose ester seed
  • the optical film of the present invention is an optical film having an optical functional layer on a support, has an appropriate heat shrinkability, excellent followability when bonded to curved glass, and has transparency and tear strength. And since it is excellent in elongation at break, it is suitable for an infrared reflective film excellent in light resistance and bonding properties and a laminated glass having excellent resistance to heat wrinkles.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Laminated Bodies (AREA)
  • Optical Filters (AREA)
  • Joining Of Glass To Other Materials (AREA)

Abstract

La présente invention vise à fournir : un film optique qui comprend une couche à fonction optique sur un corps de support et qui a une transparence, une résistance à la déchirure et un allongement à la rupture excellents, tout en ayant une excellente capacité de suivi sur une surface de verre courbe au moment du collage en ayant une rétractabilité thermique adéquate ; un film réfléchissant les infrarouges qui utilise ce film optique et présente une résistance à la lumière et des propriétés de liaison excellentes ; et un verre feuilleté qui présente une excellente résistance à des déformations thermiques. À cet effet, l'invention concerne un film optique qui comprend une couche à fonction optique sur au moins une surface d'un corps de support de type film, et qui est caractérisé en ce que : le corps de support contient un dérivé de cellulose (A) ne contenant pas de noyau aromatique et un polymère (B) ayant un segment souple dans un état tel que le dérivé de cellulose (A) et le polymère (B) sont dissous l'un dans l'autre ; et le rétrécissement thermique du corps de support après avoir été laissé dans un environnement à 150°C pendant 30 minutes est dans la plage de 1,0 % à 5,0 % à la fois dans une direction dans le plan et dans une direction perpendiculaire à cette dernière.
PCT/JP2015/057712 2014-03-26 2015-03-16 Film optique, film réfléchissant les infrarouges utilisant ce dernier et verre feuilleté WO2015146676A1 (fr)

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JP2018024781A (ja) * 2016-08-10 2018-02-15 三菱ケミカル株式会社 樹脂組成物、該樹脂組成物を成形してなるフィルム、および該フィルムを成形してなる袋
WO2018186241A1 (fr) * 2017-04-03 2018-10-11 富士フイルム株式会社 Corps multicouche, article anti-réfléchissant à surface incurvée tridimensionnelle, et procédé de fabrication d'un article anti-réfléchissant
CN113165973A (zh) * 2018-12-05 2021-07-23 日本板硝子株式会社 汽车用夹层玻璃

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KR102363874B1 (ko) 2018-10-18 2022-02-15 주식회사 엘지화학 편광판, 액정 패널 및 디스플레이 장치
WO2021075429A1 (fr) * 2019-10-15 2021-04-22 Ａｇｃ株式会社 Film fonctionnel, film fonctionnel avec couche d'adhérence et verre feuilleté fonctionnel

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JP2011148976A (ja) * 2009-12-25 2011-08-04 Fujifilm Corp 成形材料、成形体、及びその製造方法、並びに電気電子機器用筐体
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JP2013254186A (ja) * 2012-05-08 2013-12-19 Fujifilm Corp 光学フィルム、偏光板、画像表示装置、及び光学フィルムの製造方法

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JP2018024781A (ja) * 2016-08-10 2018-02-15 三菱ケミカル株式会社 樹脂組成物、該樹脂組成物を成形してなるフィルム、および該フィルムを成形してなる袋
WO2018186241A1 (fr) * 2017-04-03 2018-10-11 富士フイルム株式会社 Corps multicouche, article anti-réfléchissant à surface incurvée tridimensionnelle, et procédé de fabrication d'un article anti-réfléchissant
US11567238B2 (en) 2017-04-03 2023-01-31 Fujifilm Corporation Laminate, antireflection product having three-dimensional curved surface, and method of manufacturing antireflection product
CN113165973A (zh) * 2018-12-05 2021-07-23 日本板硝子株式会社 汽车用夹层玻璃
US11964544B2 (en) 2018-12-05 2024-04-23 Nippon Sheet Glass Company, Limited Automobile laminated glass

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