Intermediate film for laminated glass, and laminated glass

Abstract

The present invention provides an interlayer film for laminated glass provided with an up-conversion function so as to be able to display high-contrast images while ensuring safety, and a laminated glass. The present invention relates to an interlayer film for laminated glass, including lanthanoid-containing inorganic fine particles having an up-conversion function and a binder resin.

Claims

1. An interlayer film for laminated glass, comprising lanthanoid-containing inorganic fine particles having an up-conversion function and a binder resin, wherein the binder resin is a polyvinyl acetal resin, wherein an amount of the lanthanoid-containing inorganic fine particles is 0.0001 to 20 parts by mass based on 100 parts mass of the binder resin, wherein the lanthanoid-containing inorganic fine particles contain Y.sub.2O.sub.3 or NaYF.sub.4, ytterbium, and at least one selected from the group consisting of erbium, holmium, and thulium as lanthanoids, wherein the lanthanoid-containing inorganic fine particles have an average particle size of 1 m or less, and wherein the interlayer film is used for producing laminated glass.

2. The interlayer film for laminated glass according to claim 1, wherein the interlayer film has a multilayer structure comprising: a first resin layer containing a thermoplastic resin, an up-conversion layer containing the lanthanoid-containing inorganic fine particles having an up-conversion function and the binder resin, and a second resin layer containing a thermoplastic resin are laminated in a stated order in the thickness direction.

3. The interlayer film for laminated glass according to claim 1, further comprising a plasticizer.

4. A laminated glass comprising a pair of glass sheets and the interlayer film for laminated glass according to claim 1 interposed between the pair of glass sheets.

5. The interlayer film for laminated glass according to claim 1, wherein the amount of the lanthanoid-containing inorganic fine particles is 0.0001 to 10 parts by mass based on 100 parts by mass of the binder resin.

Description

DESCRIPTION OF EMBODIMENTS

(1) The present invention is more specifically described in the following with reference to, but not limited to, examples.

Example 1

(1) Production of Lanthanoid-Containing Inorganic Fine Particles

(2) In an aqueous solution containing 0.1% by mass of comb-shaped polycarboxylic acid (maleic anhydride copolymer, MALIALIM AFB-1521, weight average molecular weight of 50000) were dissolved 2.98 g of yttrium nitrate, 0.83 g of ytterbium nitrate, and 0.09 g of erbium nitrate to give 150 g of a metal ion solution.

(3) Similarly, in 50 g of an aqueous solution containing 0.1% by mass of comb-shaped polycarboxylic acid was dissolved 2.81 g of potassium hydroxide to give an alkali solution. The alkali solution was gradually added to the metal ion solution with stirring so that hydroxide fine particles were precipitated (the comb-shaped polycarboxylic acid concentration after addition of the alkali solution was 0.1% by mass).

(4) Then, the precipitate was washed several times using a centrifugal device (CR21N produced by Hitachi Koki Co., Ltd.) and by ultrasonic dispersion with addition of pure water. Hydroxide fine particles were recovered from the resulting dispersion liquid using a centrifugal device, and dried at 80 C. for 24 hours. The resulting particles were fired in a firing furnace (KM-420 produced by ADVANTEC) under the conditions at 1000 C. for one hour in an air atmosphere to give lanthanoid-containing inorganic fine particles.

(2) Production of Interlayer Film for Laminated Glass

(5) A light-emitting solution was prepared by blending 8.00 g of triethylene glycol di-2-ethylhexanoate (3GO) and 0.02 g of the resulting lanthanoid-containing inorganic fine particles. A total amount of the resulting dispersion liquid and 20.00 g of polyvinyl butyral resin (acetyl group content of 13 mol %, hydroxy group content of 22 mol %, average polymerization degree of 2300) (hereafter, referred to as PVB1) were sufficiently mixed and kneaded to give a resin composition.

(6) The obtained resin composition was sandwiched between polytetrafluoroethylene (PTFE) sheets and pressurized by a hot press via a spacer having a thickness of 800 m at 150 C. and 100 kg/cm.sup.2 for 10 minutes to give an interlayer film for laminated glass having a thickness of 800 m.

(7) (3) Production of Laminated Glass

(8) The resulting interlayer film for laminated glass was cut to a size of 5 cm in height5 cm in width, and sandwiched between a pair of clear glass sheets. The resulting stack was bonded by vacuum pressing with a vacuum laminator while being held at 90 C. for 30 minutes. After the bonding, the laminated body was further bonded in an autoclave at 140 C. and 14 MPa for 20 minutes to give a laminated glass.

Example 2

(9) An interlayer film for laminated glass and a laminated glass were produced in the same manner as in Example 1, except that 0.08 g of the obtained lanthanoid-containing inorganic fine particles was added in the step of (2) Production of interlayer film for laminated glass in Example 1.

Example 3

(10) Lanthanoid-containing inorganic fine particles, an interlayer film for laminated glass, and a laminated glass were produced in the same manner as in Example 1, except that in an aqueous solution containing 0.1% by mass of comb-shaped polycarboxylic acid (MALIALIM AFB-1521, weight average molecular weight of 50000) were dissolved 2.98 g of yttrium nitrate, 0.83 g of ytterbium nitrate, and 0.09 g of holmium nitrate to give 150 g of a metal ion solution in the step of (1) Production of lanthanoid-containing inorganic fine particles in Example 1.

Example 4

(11) Lanthanoid-containing inorganic fine particles, an interlayer film for laminated glass, and a laminated glass were produced in the same manner as in Example 1, except that in an aqueous solution containing 0.1% by mass of comb-shaped polycarboxylic acid (MALIALIM, AFB-1521, weight average molecular weight of 50000) were dissolved 3.72 g of yttrium nitrate, 0.11 g of ytterbium nitrate, and 0.01 g of thulium nitrate to give 150 g of a metal ion solution in the step of (1) Production of lanthanoid-containing inorganic fine particles in Example 1.

Example 5

(12) An interlayer film for laminated glass and a laminated glass were produced in the same manner as in Example 1, except that PVB1 was changed to polyvinyl butyral resin (acetyl group content of 1 mol %, hydroxy group content of 30 mol %, average polymerization degree of 1700) (hereafter, referred to as PVB2) in the step of (2) Production of interlayer film for laminated glass in Example 1.

Example 6

(13) An interlayer film for laminated glass and a laminated glass were produced in the same manner as in Example 1, except that 0.08 g of the resulting lanthanoid-containing inorganic fine particles were added and PVB1 was changed to PVB2 in the step of (2) Production of interlayer film for laminated glass in Example 1.

Example 7

(14) Lanthanoid-containing inorganic fine particles, an interlayer film for laminated glass, and a laminated glass were produced in the same manner as in Example 1, except that in an aqueous solution containing 0.1% by mass of comb-shaped polycarboxylic acid (MALIALIM AFB-1521, weight average molecular weight of 50000) were dissolved 2.98 g of yttrium nitrate, 0.83 g of ytterbium nitrate, and 0.09 g of holmium nitrate to give 150 g of a metal ion solution in the step of (1) production of lanthanoid-containing inorganic fine particles and that PVB1 was changed to PVB2 in the step of (2) Production of interlayer film for laminated glass in Example 1.

Example 8

(15) Lanthanoid-containing inorganic fine particles, an interlayer film for laminated glass, and a laminated glass were produced in the same manner as in Example 1, except that in an aqueous solution containing 0.1% by mass of comb-shaped polycarboxylic acid (MALIALIM AFB-1521, weight average molecular weight of 50000) were dissolved 3.72 g of yttrium nitrate, 0.11 g of ytterbium nitrate, and 0.01 g of thulium nitrate to give 150 g of a metal ion solution in the step of (1) Production of lanthanoid-containing inorganic fine particles and that PVB1 was changed to PVB2 in the step of (2) Production of interlayer film for laminated glass in Example 1.

Example 9

(16) An interlayer film for laminated glass and a laminated glass were produced in the same manner as in Example 1, except that a commercially available fluoride-based lanthanoid-containing inorganic fine particles NaYF.sub.4:Yb,Er (produced by Sigma-Aldrich Co. LLC., volume average particle size of 1000 nm) having an up-conversion function were used instead of the lanthanoid-containing inorganic fine particles produced in the step of (1) Production of lanthanoid-containing inorganic fine particles and that PVB1 was changed to PVB2 in the step of (2) Production of interlayer film for laminated glass in Example 1.

Example 10

(17) An interlayer film for laminated glass and a laminated glass were produced in the same manner as in Example 1, except that commercially available fluoride-based lanthanoid-containing inorganic fine particles NaYF.sub.4:Yb,Er (produced by Sigma-Aldrich Co. LLC.) having an up-conversion function and pulverized to a volume average particle size of 230 nm with a bead mill were used instead of the lanthanoid-containing inorganic fine particles produced in the step of (1) Production of lanthanoid-containing inorganic fine particles and that PVB1 was changed to PVB2 in the step of (2) Production of interlayer film for laminated glass in Example 1.

Example 11

(18) An interlayer film for laminated glass and a laminated glass were produced in the same manner as in Example 1, except that a commercially available fluoride-based lanthanoid-containing inorganic fine particles NaYF.sub.4:Yb,Er (produced by Sigma-Aldrich Co. LLC.) having an up-conversion function and pulverized to the volume average particle size of 230 nm were used instead of the lanthanoid-containing inorganic fine particles obtained in the step of (1) Production of lanthanoid-containing inorganic fine particles, that the amount of the commercially available fluoride-based lanthanoid-containing inorganic fine particles having an up-conversion function was changed to 0.04 g, and that PVB1 was changed to PVB2 in the step of (2) Production of interlayer film for laminated glass in Example 1.

Comparative Example 1

(19) An interlayer film for laminated glass and a laminated glass were produced in the same manner as in Example 1, except that lanthanoid-containing inorganic fine particles were not added in the step of (2) Production of interlayer film for laminated glass in Example 1.

Example 12

Production of Up-Conversion Layer

(20) An amount of 8.00 g of triethylene glycol di-2-ethylhexanoate (3GO) was blended with 0.02 g of the lanthanoid-containing inorganic fine particles obtained in the step of (1) Production of lanthanoid-containing inorganic fine particles to prepare a light-emitting solution. A total amount of the obtained light-emitting solution and 20.00 g of polyvinyl butyral resin (PVB2) were sufficiently mixed and kneaded to give a resin composition. The resulting resin composition was sandwiched between polytetrafluoroethylene (PTFE) sheets, and pressurized by heat-pressing via a spacer having a thickness of 100 m at 150 C. and 100 kg/cm.sup.2 for 10 minutes to give an up-conversion layer having a thickness of 100 m.

(21) (Production of First Resin Layer and Second Resin Layer)

(22) An amount of 8.00 g of triethylene glycol di-2-ethylhexanoate (3GO) and 20.00 g of PVB2 were sufficiently mixed and kneaded to give a resin composition. The resulting resin composition was sandwiched between polytetrafluoroethylene (PTFE) sheets, and pressurized by heat-pressing via a spacer having a thickness of 400 m at 150 C. and 100 kg/cm.sup.2 for 10 minutes to give a first resin layer having a thickness of 400 m. A second resin layer was produced in the same manner.

(23) The first resin layer, the up-conversion layer, and the second resin layer were sequentially laminated in the thickness direction to give an interlayer film for laminated glass. The obtained interlayer film for laminated glass was cut to a size of 5 cm in height5 cm in width, and sandwiched between a pair of clear glass sheets. The resulting stack was bonded by vacuum pressing with a vacuum laminator while being held at 90 C. for 30 minutes. After the bonding, the laminated body was further bonded in an autoclave at 140 C. and 14 MPa for 20 minutes to give a laminated glass.

Example 13

(24) An interlayer film for laminated glass and a laminated glass were produced in the same manner as in Example 12, except that commercially available fluoride-based lanthanoid-containing inorganic fine particles NaYF.sub.4:Yb,Er (produced by Sigma-Aldrich Co. LLC.) having an up-conversion function and pulverized with a bead mill to the volume average particle size of 230 nm were used instead of the lanthanoid-containing inorganic fine particles obtained in the step of (1) Production of lanthanoid-containing inorganic fine particles in Example 1.

Example 14

(25) An interlayer film for laminated glass and a laminated glass were produced in the same manner as in Example 12, except that PVB2 resin was changed to PVB1 resin and that the amount of triethylene glycol di-2-ethylhexanoate (3GO) was changed to 12.00 g in production of an up-conversion layer.

Example 15

(26) Lanthanoid-containing inorganic fine particles were produced in the same manner as in Example 1, except that in an aqueous solution containing 0.1% by mass of comb-shaped polycarboxylic acid (MALIALIM AFB-1521, weight average molecular weight of 50000) were dissolved 2.98 g of yttrium nitrate, 0.83 g of ytterbium nitrate, and 0.09 g of holmium nitrate to give 150 g of a metal ion solution in the step of (1) Production of lanthanoid-containing inorganic fine particles in Example 1. An up-conversion layer was produced in the same manner as in Example 12, except that the resulting lanthanoid-containing inorganic fine particles were used, that the amount thereof was changed to 0.04 g, and that PVB2 was changed to polyethylene terephthalate resin. Using the up-conversion layer, an interlayer film for laminated glass and a laminated glass were produced.

Example 16

(27) An interlayer film for laminated glass and a laminated glass were produced in the same manner as in Example 12, except that commercially available fluoride-based lanthanoid-containing inorganic fine particles NaYF.sub.4:Yb,Er (produced by Sigma-Aldrich Co. LLC., volume average particle size of 1000 nm) having an up-conversion function were used instead of the lanthanoid-containing inorganic fine particles obtained in the step of (1) Production of lanthanoid-containing inorganic fine particles in Example 1, and that PVB2 was changed to polyethylene terephthalate resin in production of an up-conversion layer.

Comparative Example 2

(28) An interlayer film for laminated glass and a laminated glass were produced in the same manner as in Example 12, except that the lanthanoid-containing inorganic fine particles were not used.

(29) (Evaluation)

(30) The lanthanoid-containing inorganic fine particles, the interlayer films for laminated glass, and the laminated glasses obtained in the examples and comparative examples were evaluated by the following methods.

(31) Tables 1 and 2 show the results. In Tables 1 and 2, the amounts (parts by mass) of a thermoplastic resin, a plasticizer, and lanthanoid-containing inorganic fine particles were determined based on the amount of the thermoplastic resin set to 100 parts by mass in each resin layer.

(32) (1) Measurement of Average Particle Size

(33) The volume average particle size of the obtained lanthanoid-containing inorganic fine particles was measured with a dynamic light scattering analyzer (NICOMP-380DLS produced by PSS).

(34) (2) Composition Analysis of Lanthanoid Elements

(35) The composition ratios of elements contained in the obtained lanthanoid-containing inorganic fine particles and commercially available fluoride-based lanthanoid-containing inorganic fine particles having an up-conversion function were measured with a fluorescent X-ray analyzer (EDX-800HS produced by Shimadzu Corporation). The calculation was based on the total composition ratio of yttrium, ytterbium, erbium, holmium, and thulium taken as 100 atom %.

(36) (3) Light Emitting Properties

(37) The entire surface of the obtained laminated glass placed in a dark room was irradiated with light from an infrared ray generator (L980P300J produced by THORLABS) at a wavelength of 980 nm and an output of 30 mW and 60 mW. The laminated glass was visually observed. It is evaluated as Excellent (OO) when emission of light was clearly observed at a central portion of the laminated glass. It is evaluated as Good (O) when emission of light was not clearly but slightly observed at a central portion of the laminated glass. It is evaluated as Poor (x) when emission of light was not observed.

(38) TABLE-US-00001 TABLE 1 Inorganic fine particles Thermoplastic Volume Evaluation resin Plasticizer average Fluorescent Amount Light Amount Amount particle X-ray analysis (parts emitting (parts by (parts by size (atom %) by properties Composition mass) Composition mass) Composition (nm) Y Yb Er Ho Tm mass) 30 mW 60 mW Example 1 PVB1 100 3GO 40 Y.sub.2O.sub.3:Yb, Er 300 74.8 22.8 2.4 0.1 Example 2 PVB1 100 3GO 40 Y.sub.2O.sub.3:Yb, Er 300 74.8 22.8 2.4 0.4 Example 3 PVB1 100 3GO 40 Y.sub.2O.sub.3:Yb, Ho 320 74.6 23.1 2.3 0.1 Example 4 PVB1 100 3GO 40 Y.sub.2O.sub.3:Yb, Tm 280 97.2 2.5 0.3 0.1 Example 5 PVB2 100 3GO 40 Y.sub.2O.sub.3:Yb, Er 300 74.8 22.8 2.4 0.1 Example 6 PVB2 100 3GO 40 Y.sub.2O.sub.3:Yb, Er 300 74.8 22.8 2.4 0.4 Example 7 PVB2 100 3GO 40 Y.sub.2O.sub.3:Yb, Ho 320 74.6 23.1 2.3 0.1 Example 8 PVB2 100 3GO 40 Y.sub.2O.sub.3:Yb, Tm 280 97.2 2.5 0.3 0.1 Example 9 PVB2 100 3GO 40 NaYF.sub.4:Yb, Er 1000 78.6 19.4 2.0 0.1 Example 10 PVB2 100 3GO 40 NaYF.sub.4:Yb, Er 230 78.6 19.4 2.0 0.1 Example 11 PVB2 100 3GO 40 NaYF.sub.4:Yb, Er 230 78.6 19.4 2.0 0.2 Comparative PVB1 100 3GO 40 X X Examepl 1

(39) TABLE-US-00002 TABLE 2 Up-conversion layer First resin layer Up-conversion particles Thermoplastic Thermoplastic Volume resin Plasticizer resin Plasticizer avarage Amount Amount Amount Amount particle (parts by (parts by (parts by (parts by size Composition mass) Composition mass) Composition mass) Composition mass) Composition (nm) Example 12 PVB2 100 3GO 40 PVB2 100 3GO 40 Y.sub.2O.sub.3:Yb, Er 300 Example 13 PVB2 100 3GO 40 PVB2 100 3GO 40 NaYF.sub.4:Yb, Er 230 Example 14 PVB2 100 3GO 40 PVB1 100 3GO 60 Y.sub.2O.sub.3:Yb, Er 300 Example 15 PVB2 100 3GO 40 PET 100 Y.sub.2O.sub.3:Yb, Ho 320 Example 16 PVB2 100 3GO 40 PET 100 NaYF.sub.4:Yb, Er 1000 Comparative PVB2 100 3GO 40 PVB2 100 3GO 40 Example 2 Up-conversion layer Second resin layer Up-conversion particles Thermoplastic Evaluation Fluorescent resin Plasticizer Light X-ray analysis Amount Amount Amount emitting (atom %) (parts by (parts by (parts by properties Y Yb Er Ho Tm mass) Composition mass) Composition mass) 30 mW 60 mW Example 12 74.8 22.8 2.4 0.1 PVB2 100 3GO 40 Example 13 78.6 19.4 2.0 0.1 PVB2 100 3GO 40 Example 14 74.8 22.8 2.4 0.1 PVB2 100 3GO 40 Example 15 74.6 23.1 2.3 0.2 PVB2 100 3GO 40 Example 16 78.6 19.4 2.0 0.1 PVB2 100 3GO 40 Comparative PVB2 100 3GO 40 X X Example 2

INDUSTRIAL APPLICABILITY

(40) The present invention can provide an interlayer film for laminated glass provided with an up-conversion function so as to be able to display high-contrast images while ensuring safety, and a laminated glass. The similar effect can be achieved even in a case where NaYF.sub.4:Yb, Ho or NaYF.sub.4:Yb, Tm were used instead of NaYF.sub.4:Y, Er.