MOISTURE CURABLE POLYURETHANE COMPOSITION AND LAMINATE

Abstract

Provided is a moisture curable polyurethane composition that is a moisture curable polyurethane having an isocyanate group on one end of a molecule thereof. The moisture curable polyurethane composition contains a moisture curable polyurethane (A) and an organic solvent (B). The moisture curable polyurethane (A) is obtainable by reacting a polyisocyanate compound having at least two isocyanate groups in a molecule thereof (A1) with a low-molecular weight polyol compound having at least two hydroxyl groups in a molecule thereof and having a number average molecular weight of 50-300 (A2). Also provided is a laminate including an optical substrate and a polyurethane resin layer comprising the moisture curable polyurethane composition.

Claims

1. A moisture curable polyurethane composition comprising: a moisture curable polyurethane (A), and an organic solvent (B), the moisture curable polyurethane (A) being a moisture curable polyurethane having an isocyanate group at the end of a molecule thereof, the moisture curable polyurethane being obtained by reacting a polyisocyanate compound (A1) having two or more isocyanate groups in a molecule thereof with a low molecular weight polyol compound (A2) having two or more hydroxy groups in a molecule thereof and having a number average molecular weight of 50 to 300.

2. The moisture curable polyurethane composition according to claim 1, wherein the polyisocyanate compound (A1) having two or more isocyanate groups in a molecule thereof is an aromatic polyisocyanate compound having two or more isocyanate groups in a molecule thereof.

3. The moisture curable polyurethane composition according to claim 1, wherein the polyisocyanate compound (A1) having two or more isocyanate groups in a molecule thereof is a moisture curable polyurethane having an isocyanate group at the end of a molecule thereof, the polyisocyanate compound (A1) being obtained by reacting a polyisocyanate compound (A1-1) having two or more isocyanate groups in a molecule thereof and having a molecular weight of 400 or less with a high molecular weight polyol compound (A1-2) having two or more hydroxy groups in a molecule thereof and having a number average molecular weight of 300 to 5000.

4. The moisture curable polyurethane composition according to claim 1, wherein the organic solvent (B) is an organic solvent having a solubility parameter of 8 [(cal/cm.sup.3).sup.1/2] or more and has no active hydrogen.

5. The moisture curable polyurethane composition according to claim 1, wherein the moisture curable polyurethane (A) is a moisture curable polyurethane having an isocyanate group at the end of a molecule thereof, the moisture curable polyurethane (A) being obtained by further reacting at least one selected from a polyol compound (A3) having two or more hydroxy groups in a molecule thereof and having a number average molecular weight of 400 to 2000 and an amine compound (A4) having one or more amino groups in a molecule thereof.

6. A laminate comprising an optical base material and a polyurethane resin layer formed from the moisture curable polyurethane composition according to claim 1.

7. The laminate according to claim 6, further comprising a photochromic resin layer, wherein an order of lamination is the photochromic resin layer, the polyurethane resin layer, and the optical base material.

8. The laminate according to claim 6, further comprising a photochromic resin layer, wherein an order of lamination is the polyurethane resin layer, the photochromic resin layer, and the optical base material.

Description

EXAMPLES

[0188] The present invention is hereunder described in detail by reference to Examples and Comparative Examples, but it should be construed that the present invention is not limited to these Examples. The above-mentioned components and evaluation methods and the like are as follows.

<Moisture Curable Polyurethane Composition>

[Component A1-1]

[0189] TDI: mixture of tolylene-2,4-diisocyanate (80% by mass) and tolylene-2,6-diisocyanate (20% by mass) (molecular weight:174)

[0190] MDI: 4,4-diphenylmethanediisocyanate (molecular weight: 250)

[0191] XDI: m-xylylene diisocyanate (molecular weight: 188)

[0192] IPDI: isophorone diisocyanate (isomer mixture) (molecular weight: 222)

[Component A1-2 and Component A3]

[0193] PL1: Duranol manufactured by Asahi Kasei Corporation (polycarbonate diol including 1,5-pentanediol and hexanediol as raw materials, number average molecular weight: 500)

[0194] PL2: polypropylene glycol (number average molecular weight: 400)

[0195] PL3: Duranol manufactured by Asahi Kasei Corporation (polycarbonate diol including 1,5-pentanediol and hexanediol as raw materials, number average molecular weight: 1000)

[0196] PL4: Duranol manufactured by Asahi Kasei Corporation (polycarbonate diol including 1,5-pentanediol and hexanediol as raw materials, number average molecular weight: 2000)

[0197] PL5: polyester polyol including adipic acid and 3-methyl-1,5-pentanediol as raw materials (number average molecular weight: 500)

[0198] PL6: polyester polyol including isophthalic acid and 3-methyl-1,5-pentanediol as raw materials (number average molecular weight: 500)

[0199] PL7: Placcel manufactured by Daicel Corporation (polycaprolactonediol, number average molecular weight: 500)

[Component A2]

[0200] EG: ethylene glycol (molecular weight: 62)

[0201] PG1: 1,2-propanediol (molecular weight: 76)

[0202] PG2: 1,3- propanediol (molecular weight: 76)

[0203] BG: 1,3- butanediol (molecular weight: 90)

[0204] HG: 1,6-hexanediol (molecular weight: 118)

[0205] TMP: trimethylol propane (molecular weight: 134)

[Component A4]

[0206] IPDA: isophorone diamine (isomer mixture)

[Component B (Numbers Shown in the Brackets Represent the Solubility Parameter)]

[0207] B1: diethyl ketone (8.7)

[0208] B2: toluene (8.8)

[0209] B3: ethyl acetate (9.0)

[Other Component]

[0210] L7001: manufactured by Dow Corning Toray Co., Ltd., product name; L7001 (leveling agent)

<Photochromic Monomeric Composition>

[Component D1]

[0211] 14G: Polyethylene glycol dimethacrylate (average chain length of ethylene glycol chain: 14, average molecular weight: 736)

[0212] A-400: Polyethylene glycol diacrylate (average chain length of ethylene glycol chain: 9, average molecular weight: 508)

[Component D2]

[0213] TMPT: Trimethylolpropane Trimethacrylate

[0214] D-TMP: Ditrimethylolpropane Tetraacrylate

[0215] SI-1: γ-methacryloyloxypropyltrimethoxysilane

[0216] GMA: Glycidyl methacrylate

[0217] RX-1: Polyrotaxane having a (meth)acryloyl group

[0218] RX-1 was synthesized according to the method described in PCT International Publication No. WO2018/030275. Properties of RX-1 are as follows.

Mass average molecular weight (Mw) measured by GPC: 880000
Acryloyl group modification percentage: 85 mol %
Percentage of hydroxy groups remaining in the side chain: 15 mol %
Axis molecule; linear polyethylene glycol (PEG) having a molecular weight of 20000
Inclusion ring; α-cyclodextrin (α-CD) (introduction rate: 0.25)
End of axis molecule; sealed with adamantane
Side chain introduced into inclusion ring: (average) molecular weight of the side chain of about 600

[Photochromic Compound]

[0219] PC1: Compound represented by the following formula

##STR00006##

[Other components]

[0220] CGI: Phenyl bis (2,4,6-trimethylbenzoyl)-phosphine oxide (product name: Omnirad819 manufactured by IGM) (polymerization initiator)

[0221] HALS: Bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate (molecular weight: 508) (UV stabilizer)

[0222] HP: Ethylenebis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] (Irganox 245 manufactured by BASF) (UV stabilizer)

[0223] L7001: L7001 manufactured by Dow Corning Toray Co., Ltd. (leveling agent)

Preparation Example 1: Preparation of Moisture Curable Polyurethane Composition (PU1)

[0224] To a reaction vessel having a stirrer chip, a cooling tube, a thermometer, a nitrogen gas introduction tube, and a stirrer, TDI (90 g) as a component A1-1, PL1 (130 g) as a component A1-2, and toluene (235 g) as an organic solvent (later to be one component of the component B) were added and mixed uniformly. This mixed solution was adjusted to 90° C. under a nitrogen atmosphere and a prepolymer reaction was carried out to obtain a urethane prepolymer solution.

[0225] Furthermore, to the urethane prepolymer solution obtained by the above-mentioned method, PG1 (9.8 g) as a component A2 and ethyl acetate (125 g) as a component B were added, and the mixed solution was adjusted to 75° C. to carry out the reaction.

[0226] To the above-mentioned reaction solution, ethyl acetate (360 g) as the component B and L7001 (1.0 g) as another component were further added and stirred under the nitrogen atmosphere until the resulting mixture became uniform to obtain a moisture curable polyurethane composition (PU1). The composition and the like of the moisture curable polyurethane composition (PU1) are shown in Table 1.

(Measurement of Number Average Molecular Weight of Moisture Curable Polyurethane)

[0227] The number average molecular weight of the moisture curable polyurethane obtained in Preparation Example 1 was measured by gel permeation chromatography (GPC measurement) under the following conditions. As the apparatus, a liquid chromatograph apparatus (manufactured by Nihon Waters K.K.) was used. As the column, Shodex KD-806M column manufactured by Showa Denko K.K. (elimination limit molecule quantity: 200000000) was used. Furthermore, dimethylformamide (DMF) was used as a developing liquid, and measurement was carried out under the conditions at a flow rate of 1 mL/min and a temperature of 40° C. Then, polyethylene glycol was used as a standard sample, and the number average molecular weight was obtained by comparative conversion. Note here that a differential refractometer was used as a detector. The moisture curable polyurethane was treated with butylamine in advance to inactivate the isocyanate group and then subjected to measurement. The number average molecular weight of the moisture curable polyurethane obtained by this method was 1800.

(Measurement of Content of Isocyanate Group Included in Moisture Curable Polyurethane)

[0228] The content of an isocyanate group included in the moisture curable polyurethane was obtained by the reverse titration method of the isocyanate group. The reverse titration of the isocyanate group was carried out by the following procedure.

1) To 500 mL of dehydrated dioxane, 12.5 g of n-butylamine was added and the resulting product was stirred until the resulting mixture was uniform to prepare an n-butylamine/dioxane solution.
2) Into a 110 mL screw tube, 10 mL of the above n-butylamine/dioxane solution was collected using a whole pipette, about 20 mL of THF and 3 drops of bromocresol blue 1% solution in ethanol were added, and titrated in 0.1 mol/L sulfuric acid aqueous solution while stirring. A point at which the color changed from blue to yellowish green or yellow was defined as the end point. A 50 mL burette was used for titration. The measurement was carried out twice to obtain the average value, and the blank value was calculated from the average value (unit: mL).
3) About 1 g of the moisture curable polyurethane composition was weighed to 0.01 g units in a 110 mL screw tube, and about 20 mL of THF and 10 mL of the butylamine/dioxane solution were charged using a whole pipette and stirred until the resulting product was uniform. After the resulting product was found to be uniform, it was titrated in 0.1 mol/L sulfuric acid aqueous solution while stirring.
4) The content of an isocyanate group (amount of NCO) was calculated by the following formula.

[00001]$\mathrm{Amount}\mathrm{of}\mathrm{NCO}\left(\mathrm{wt}\%\right)=\frac{\left(42.01\times 0.1\times 2\times f\times \left(\mathrm{Blank}\mathrm{Value}-\mathrm{Titrated}\mathrm{amount}\right)\times 100\right)}{\mathrm{Amount}\mathrm{of}\mathrm{sample}\times \left(\mathrm{Solid}\mathrm{content}\mathrm{concentration}/100\right)\times 1000}$

[0229] In the formula, f is the potency of 0.1 mol/L sulfuric acid aqueous solution when used for titration, and is 1 in this titration. The solid content concentration was measured by a method described later. The content obtained by this method of the isocyanate group of the moisture curable polyurethane obtained in Preparation Example 1 was 4.7% by mass.

(Calculation of Number of Urethane Bonds Included in Moisture Curable Polyurethane)

[0230] The number of urethane bonds included in the moisture curable polyurethane was determined by calculating the number of urethane bonds included in 1 molecule from the mole ratio of each component included in 1 molecule when each component used for production was theoretically reacted, and converting the number to the number of moles included in 100 g of the moisture curable polyurethane. The number of urethane bonds determined by this method of the moisture curable polyurethane obtained in Preparation Example 1 was 0.333 mol/100 g.

(Measurement of Solid Content Concentration in Moisture Curable Polyurethane Composition)

[0231] The solid content concentration of the moisture curable polyurethane composition was measured by the following procedure. Firstly, the convection oven was set to 120° C.

1) The weight of the empty container (aluminum cup) was measured to 0.0001 g units (weight 1).
2) A container (aluminum cup) was charged with about 2 g of a moisture curable polyurethane composition and weighed (weight 2) to a unit of 0.0001 g.
3) Drying was carried out for 3 hours in a convection oven set at 120° C.
4) Each container of the moisture curable polyurethane composition after drying was weighed to a unit of 0.0001 g (weight 3), and the solid content concentration was calculated by the following formula.

[00002]$\mathrm{Solid}\mathrm{content}\mathrm{concentration}\left(\mathrm{wt}\%\right)=\frac{\left(\mathrm{Weight}3-\mathrm{Wight}1\right)}{\mathrm{Wight}2}$

[0232] The solid content concentration obtained by this method of the moisture curable polyurethane composition obtained in Preparation Example 1 was 24.2% by mass.

(Measurement of Viscosity of Moisture Curable Polyurethane Composition)

[0233] Viscosity of the moisture curable polyurethane composition was measured using a Cannon-Fenske viscometer. In other words, 10 mL of the moisture curable polyurethane composition was weighed with a whole pipette in the Cannon-Fenske viscometer, the Cannon-Fenske viscometer was set in a thermobath kept at 25° C. (25±0.1° C.), and left for 15 minutes, and the kinetic viscosity was obtained. Furthermore, the specific gravity was measured using an areometer, and then viscosity was determined from the product of the dynamic viscosity and the specific gravity. The viscosity determined by this method of the moisture curable polyurethane composition obtained in Preparation Example 1 was 5.2 mPa's.

Preparation Example 2: Preparation of Moisture Curable Polyurethane Composition (PU2)

[0234] TDI (90 g) as the component A1-1, PL2 (103 g) as the component A1-2, and toluene (193 g) as an organic solvent (later, as a component of a component B) were added to a reaction vessel having a stirrer chip, a cooling tube, a thermometer, a nitrogen gas introduction tube, and a stirrer, and the resulting product was mixed homogenously. This mixed solution was adjusted to 90° C. under a nitrogen atmosphere and subjected to a prepolymer reaction to obtain a urethane prepolymer solution.

[0235] Furthermore, PG1 (9.8 g) as a component A2 was added to the urethane prepolymer solution obtained by the above method to adjust the temperature to 75° C., and the reaction was carried out.

[0236] Ethyl acetate (396 g) as a component B, and L7001 (0.8 g) as another component were further added to the above reaction solution, and the resulting product was stirred under a nitrogen atmosphere until the resulting mixture was uniform to obtain a moisture curable polyurethane composition (PU2). The composition and the like of the moisture curable polyurethane composition (PU2) is shown in Table 1.

Preparation Example 3: Preparation of Moisture Curable Polyurethane Composition (PU3)

[0237] TDI (90 g) as the component A1-1, PL2 (103 g) as the component A1-2, and toluene (193 g) as an organic solvent (later, as a component of a component B) were added to a reaction vessel having a stirrer chip, a cooling tube, a thermometer, a nitrogen gas introduction tube, and a stirrer, and the resulting product was mixed homogenously. This mixed solution was adjusted to 90° C. and subjected to a prepolymer reaction to obtain a urethane prepolymer solution.

[0238] Furthermore, PG1 (4.9 g) as a component A2 was added to the urethane prepolymer solution obtained by the above method, and the mixed solution was adjusted to 75° C. to carry out the reaction. Furthermore, TMP (8.7 g) as a component A2 and ethyl acetate (117 g) as a component B were added, and the reaction was carried out at 75° C.

[0239] To the above reaction solution, ethyl acetate (517 g) as the component B and L7001 (1.1 g) as another component were further added, and the resulting product was stirred under a nitrogen atmosphere until the resulting mixture was uniform to obtain a moisture curable polyurethane composition (PU3). The composition and the like of the moisture curable polyurethane composition (PU3) is shown in Table 1.

TABLE-US-00001 TABLE 1 Mole Mole Moisture Composition ratio ratio curable (part by mass) when when polyurethane Component Component Component Component Other n1 = 1 n3 = 1 composition A1-1 A1-2 A2 B component n2 n5 + n6 n4 PU1 TDI PL1 PG1 B2 L7001 0.50 0.00 0.50 (90) (130) (9.8) (235) (1.0) B3 (485) PU2 TDI PL2 PG1 B2 L7001 0.50 0.00 0.50 (90) (103) (9.8) (193) (0.8) B3 (396) PU3 TDI PL2 PG1 B2 L7001 0.82 0.00 0.50 (90) (103) (4.9) (193) (1.1) TMP B3 (8.7) (634) Physical property of Physical property of moisture curable moisture curable polyurethane Moisture polyurethane composition Number Number of curable Solid content average Content urethane polyurethane concentration Viscosity molecular of NCO bonds composition (wt %) (mPa .Math. s@25° C.) weight (wt %) (mol/100 g) PU1 24.2 5.2 1800 4.7 0.333 PU2 25.6 5.5 1650 5.1 0.364 PU3 20.0 20.5 2200 1.8 0.545

Preparation Examples 4 to 24: Preparation of Moisture Curable Polyurethane Compositions (PU4 to PU24)

[0240] Moisture curable polyurethane compositions (PU4 to PU24) were prepared using components shown in Tables 2 to 4 in the same manner as in Preparation Example 1. The compositions and the like of the moisture curable polyurethane compositions (PU4 to PU24) are shown in Tables 2 to 4.

TABLE-US-00002 TABLE 2 Mole Mole Moisture Composition ratio ratio curable (part by mass) when when polyurethane Component Component Component Component Component Component Other n1 = 1 n3 = 1 composition A1-1 A1-2 A2 A3 A4 B component n2 n5 + n6 n4 PU4 TDI PL3 PG1 B2 L7001 0.50 0.00 0.50 (90) (260) (9.8) (353) (1.0) B3 (728) PU5 TDI PL4 PG1 B2 L7001 0.50 0.00 0.50 (90) (520) (9.8) (588) (1.0) B3 (1213) PU6 TDI PL5 PG1 B2 L7001 0.50 0.00 0.50 (90) (130) (9.8) (235) (1.0) B3 (485) PU7 TDI PL6 PG1 B2 L7001 0.50 0.00 0.50 (90) (130) (9.8) (235) (1.0) B3 (485) PU8 TDI PL7 PG1 B2 L7001 0.50 0.00 0.50 (90) (130) (9.8) (235) (1.0) B3 (485) PU9 TDI PL1 EG B2 L7001 0.50 0.00 0.50 (90) (130) (9.8) (235) (1.0) B3 (485) PU10 TDI PL1 PG2 B2 L7001 0.50 0.00 0.50 (90) (130) (9.8) (235) (1.0) B3 (485) Physical property of Physical property of moisture curable moisture curable polyurethane Moisture polyurethane composition Number Number of curable Solid content average Content urethane polyurethane concentration Viscosity molecular of NCO bonds composition (wt %) (mPa .Math. s@25° C.) weight (wt %) (mol/100 g) PU4 25.0 10.5 2800 3.0 0.214 PU5 25.6 23.1 5000 1.7 0.120 PU6 24.2 5.1 1800 4.7 0.333 PU7 24.2 5.0 1800 4.7 0.333 PU8 24.2 5.3 1850 4.5 0.324 PU9 24.1 5.5 1880 4.5 0.319 PU10 24.2 5.7 1880 4.5 0.319

TABLE-US-00003 TABLE 3 Mole Mole Moisture Composition ratio ratio curable (part by mass) when when polyurethane Component Component Component Component Component Component Other n1 = 1 n3 = 1 composition A1-1 A1-2 A2 A3 A4 B component n2 n5 + n6 n4 PU11 TDI PL1 BG B2 L7001 0.50 0.00 0.50 (90) (130) (9.8) (235) (1.0) B3 (485) PU12 TDI PL1 HG B2 L7001 0.50 0.00 0.50 (90) (130) (9.8) (235) (1.0) B3 (485) PU13 MDI PL1 PG1 B2 L7001 0.50 0.00 0.50 (129) (130) (9.8) (235) (1.0) B3 (485) PU14 XDI PL1 PG1 B2 L7001 0.50 0.00 0.50 (97) (130) (9.8) (235) (1.0) B3 (485) PU15 IPDI PL1 PG1 B2 L7001 0.50 0.00 0.50 (115) (130) (9.8) (235) (1.0) B3 (485) PU16 TDI PL1 PG1 IPDA B2 L7001 0.50 0.02 0.50 (90) (130) (9.8) (1.0) (235) (1.0) B1 (485) PU17 TDI PL1 PG1 B2 L7001 0.40 0.00 0.50 (90) (130) (8.0) (235) (1.0) B3 (485) Physical property of Physical property of moisture curable moisture curable polyurethane Moisture polyurethane composition Number Number of curable Solid content average Content urethane polyurethane concentration Viscosity molecular of NCO bonds composition (wt %) (mPa .Math. s@25° C.) weight (wt %) (mol/100 g) PU11 24.3 6.2 1900 4.4 0.316 PU12 24.6 7.5 1900 4.4 0.316 PU13 27.2 8.5 2200 3.8 0.273 PU14 24.7 6.5 1900 4.4 0.316 PU15 26.1 4.6 2100 4.0 0.286 PU16 24.3 9.6 2000 4.2 0.318 PU17 24.1 4.6 1500 3.2 0.311

TABLE-US-00004 TABLE 4 Mole Mole Moisture Composition ratio ratio curable (part by mass) when when polyurethane Component Component Component Component Component Component Other n1 = 1 n3 = 1 composition A1-1 A1-2 A2 A3 A4 B component n2 n5 + n6 n4 PU18 TDI PL1 PG1 B2 L7001 0.30 0.00 0.50 (90) (130) (6.0) (235) (1.0) B3 (485) PU19 TDI PL1 PG1 B2 L7001 0.20 0.00 0.50 (90) (130) (4.0) (235) (1.0) B3 (485) PU20 TDI PL1 PG1 B2 L7001 0.60 0.00 0.50 (90) (130) (11.8) (235) (1.0) B3 (485) PU21 TDI PL1 PG1 B2 L7001 0.70 0.00 0.50 (90) (130) (13.8) (235) (1.0) B3 (485) PU22 TDI PG1 B2 L7001 0.60 0.00 0.00 (90) (23.5) (50) (1.0) B3 (100) PU23 TDI PG1 PL1 B2 L7001 0.40 0.25 0.00 (90) (15.7) (65) (180) (1.0) B3 (200) PU24 TDI PL1 PG1 B2 L7001 0.08 0.00 0.60 (90) (155) (2.0) (235) (1.0) B3 (485) Physical property of Physical property of moisture curable moisture curable polyurethane Moisture polyurethane composition Number Number of curable Solid content average Content urethane polyurethane concentration Viscosity molecular of NCO bonds composition (wt %) (mPa .Math. s@25° C.) weight (wt %) (mol/100 g) PU18 23.9 4.1 1300 6.5 0.286 PU19 23.7 3.5 1100 7.6 0.273 PU20 24.4 6.5 2300 3.7 0.348 PU21 24.5 7.5 3200 2.6 0.354 PU22 43.1 5.8 570 14.7 0.526 PU23 31.0 6.5 1200 7.0 0.310 PU24 39.4 6.5 1400 6.0 0.265

Preparation Example 25: Preparation of Moisture Curable Polyurethane Composition (PU25)

[0241] A porphyrin compound (“FDB-002” manufactured by Yamada Chemical Co., Ltd., local maximum absorption wavelength: 431 nm, absorption coefficient: 380 L/molcm, half-width: 18 nm) (0.03 parts by mass), a benzotriazole-based UV absorber (“SEESORB 703” manufactured by SHIPRO KASEI KAISHA, LTD., local maximum absorption wavelength: 345 nm, absorption coefficient: 50 L/g.Math.cm, half-width: 90 nm) (7 parts by mass), and “Dial Resin BlueJ” manufactured by Mitsubishi Chemical Corporation (local maximum absorption wavelength: 590 nm, absorption coefficient: 35 L/g.Math.cm, half-width: 110 nm) (0.04 parts by mass) were added with respect to the moisture curable polyurethane composition (PU1) (300 parts by mass) and sufficiently stirred and mixed under a nitrogen atmosphere until the resulting mixture was uniform to obtain a moisture curable urethane composition (PU25) having an ultraviolet absorbing ability.

Preparation Example 26: Preparation of Photochromic Composition (1)

[0242] Polyethylene glycol dimethacrylate (14G) (average chain length of ethylene glycol chain: 14, average molecular weight: 736) (40 parts by mass), polyethylene glycol diacrylate (A-400) (average chain length of ethylene glycol chain: 9, average molecular weight: 508) (21 parts by mass), trimethylolpropane trimethacrylate (TMPT) (30 parts by mass), RX-1 (3 parts by mass), SI-1 (3 parts by mass), glycidyl methacrylate (GMA) (1 part by mass), photochromic compound PC1 (2 parts by mass), CGI (0.3 parts by mass), HALS (3 parts by mass), HP (1 part by mass), and L7001 (0.1 parts by mass) were added, and the resulting product was mixed and stirred at 70° C. for 15 minutes to obtain a photochromic composition (1) to be used in the coating method. The composition of the photochromic composition (1) is shown in Table 5.

Preparation Example 27: Preparation of Photochromic Composition (2)

[0243] A photochromic curable composition (2) was prepared in the same manner as in Preparation Example 26 except that the materials shown in Table 3 were used. The composition of the photochromic composition (1) is shown in Table 5.

TABLE-US-00005 TABLE 5 Photochromic Photochromic Other composition Component D1 Component D2 compound component No. (part by mass) (part by mass) (part by mass) (part by mass) 1 14 G (40) TMPT(30) PC1(2) CGI(0.3) A-400 (21) RX-1(3) HALS(3) SI-1(3) HP(1) GMA(1) L7001(0.1) 2 14 G (50) TMPT(30) PC1(2) CGI(0.3) D-TMP(16) HALS(3) SI-1(3) HP(1) GMA(1) L7001(0.1)

Example 1

[Formation of Photochromic Resin Layer]

[0244] Firstly, a thiourethane-based plastic lens having a center thickness of 2 mm and a refractive index of 1.60 was prepared as an optical base material. Note here that this thiourethane-based plastic lens was subjected to alkaline etching at 50° C. for 5 minutes using a 10% aqueous solution of sodium hydroxide in advance, and then sufficiently washed with distilled water.

[0245] Next, using a spin coater (1H-DX2, manufactured by Mikasa Co., Ltd.), a moisture curable primer (product name; TR-SC-P, manufactured by Tokuyama Corporation) was applied to the surface of the above plastic lens at a rotational speed of 70 rpm for 15 seconds, and then 1000 rpm for 10 seconds.

[0246] Then, the photochromic composition (1) (2 g) was applied by spin-coating onto the moisture curable primer layer of the optical base material at a rotational speed of 100 rpm for 30 seconds, and then at 800 rpm for 10 to 20 seconds so that the film thickness became 40 μm.

[0247] Thereafter, the lens having the above composition applied on the surface thereof was irradiated with light for 80 seconds using a metal halide lamp having an output of 200 mW/cm.sup.2 in a nitrogen gas atmosphere to polymerize the above composition. Thereafter, heating was further carried out at 110° C. for 1 hour to form a 40 μm-thick photochromic resin layer made of a resin obtained by polymerizing the photochromic composition (1) on the optical base material.

[Formation of Polyurethane Resin Layer]

[0248] Firstly, the optical base material having the above photochromic resin layer thereon was subjected to alkaline etching at 50° C. for 5 minutes using a 10% aqueous solution of sodium hydroxide in advance, and then sufficiently washed with distilled water.

[0249] Next, the moisture curable polyurethane composition (PU1) prepared in Preparation Example 1 was applied by spin-coating on the surface of the photochromic resin layer of the optical base material using a spin coater (1H-DX2, manufactured by Mikasa Co., Ltd.), and dried for 10 minutes at 25° C. and 50% RH. At this time, the film thickness of the polyurethane resin layer was set to 2 to 3 μm.

[Evaluation of Photochromic Optical Articles]

[0250] The photochromic optical articles obtained above were subjected to each of the following evaluations. The evaluation results are shown in Table 6.

(Photochromic Properties)

[0251] The obtained photochromic optical article was used as a sample and irradiated with light from the L-2480 (300 W) SHL-100 xenon lamp of Hamamatsu Photonics K.K. through an aeromass filter (manufactured by Corning Co., Ltd.) at 20±1° C. and a beam strength at 365 nm of 2.4 mW/cm.sup.2 and at 245 nm of 24 μW/cm.sup.2 on the surface of the photochromic optical article for 120 seconds to develop color so as to measure the photochromic properties.

[0252] Maximum absorption wavelength (Amax): The maximum absorption wavelength after color development determined by a spectrophotometer (instantaneous multi-channel photodetector MCPD1000) manufactured by Otsuka Electronics Co., Ltd. The maximum absorption wavelength is related to the color tone at the time of color development.

[0253] Color optical density {ε(120)−ε(0)}: Difference between the absorbance {ε(120)} after light irradiation for 120 seconds and the absorbance ε(0) before light irradiation at the maximum absorption wavelength. It can be said that the higher this value is, the better the photochromic property is.

[0254] Fading speed [t½ (sec.)]: Time needed after 120 seconds of light irradiation, when the light irradiation is stopped, the absorbance at the maximum absorption wavelength of the sample to be deteriorated to ½ of {ε(120)−ε(0)}. It can be said that the shorter this time is, the better the photochromic property is.

(Appearance, etc.)

[0255] Evaluation of Appearance (Cracks, Cloudiness)

[0256] The obtained photochromic optical article was observed and evaluated under an optical microscope. Evaluation criteria are shown below.

[0257] A: Uniform and no appearance defects observed.

[0258] B: Very small defect observed in appearance.

[0259] C: Partial appearance defect observed.

[0260] D: Overall appearance defect observed.

[0261] ΔYI evaluation

[0262] YI was measured using a color difference meter SM-4 manufactured by Suga Test Instruments Co., Ltd., and ΔYI was evaluated by the following formula. When the blue protective film is transferred to a photochromic optical article, ΔYI changes.

ΔYI=YI.sub.24−YI.sub.0

[0263] In the formula, YI.sub.24 is YI after the blue protective film is attached to the obtained photochromic optical article and the film is peeled off after 24 hours, and YI.sub.0 is YI before the blue protective film is attached.

[0264] Adhesion

[0265] Adhesion was evaluated by a cross-cut tape test according to JIS D-0202. In other words, using a retractable knife, the surface of the obtained photochromic optical article was cut in 1 mm interval to form a lattice pattern having 100 squares. A cellophane adhesive tape (CELLOTAPE (registered trademark) manufactured by NICHIBAN Co., Ltd.) was firmly attached, and then tensile peeling was done by pulling to 90° direction from the surface at a time, then a number of squares of the lattice pattern on which the photochromic optical article remained was evaluated.

Examples 2 and 3

[0266] A photochromic optical article was produced in the same manner as in Example 1 except that the photochromic composition and the moisture curable polyurethane composition shown in Table 6 were used. The evaluation results of the obtained photochromic optical articles are shown in Table 6.

Example 4

[0267] A photochromic optical article was produced in the same manner as in Example 1 except that the moisture curable polyurethane composition (PU1) prepared in Preparation Example 1 was applied on the surface of the photochromic resin layer of the optical base material by spin coating, followed by drying for 10 minutes under the condition of 25° C. 50% RH, and then heating at 90° C. for 3 hours. The evaluation results of the obtained photochromic optical articles are shown in Table 6.

Comparative Example 1

[0268] A photochromic optical article was produced in the same manner as in Example 1 except that a moisture curable polyurethane resin layer was not formed. The evaluation results of the obtained photochromic optical articles are shown in Table 6.

TABLE-US-00006 TABLE 6 Moisture Maximum Photochromic curable absorption Color Fading composition polyurethane wavelength optical speed No. No. composition (λmax) density (second) Appearance ΔYI Adhesion Example 1 1 PU1 585 0.88 40 A −0.5 100 Example 2 2 PU2 585 0.88 35 A −0.7 100 Example 3 1 PU3 585 0.88 40 A −0.1 100 Example 4 1 PU1 585 0.88 40 A 0 100 Comparative 1 — 585 0.88 40 C −3.9 100 Example 1

[0269] As is apparent from Table 6, the photochromic optical articles of Examples 1 to 4 in which the protective layer was formed using the moisture curable polyurethane composition are excellent in terms of not only photochromic properties but also in terms of appearance, adhesion, and weather resistance. On the other hand, the photochromic optical article of Comparative Example 1 in which the moisture curable polyurethane composition was not used had insufficient appearance and weather resistance, and was not able to have sufficient physical properties.

Example 5

[Formation of Polyurethane Resin Layer]

[0270] As the optical base material, two each of CR, TRB, MRA, MRB, TEA, TEB, and PC having a center thickness of about 2 mm described below were prepared. Note here that these optical base materials were subjected to alkaline etching at 50° C. for 5 minutes in advance using a 10% aqueous solution of sodium hydroxide, and then sufficiently washed with distilled water. Note here that the optical base materials used are as follows.

[0271] CR: Allyl-based resin plastic lens, refractive index=1.50

[0272] TRB: Urethane-based resin plastic lens, refractive index=1.53

[0273] MRA: Thiourethane-based resin plastic lens, refractive index=1.60

[0274] MRB: Thiourethane-based resin plastic lens, refractive index=1.67

[0275] TEA: Thioepoxy-based resin plastic lens, refractive index=1.71

[0276] TEB: Thioepoxy-based resin plastic lens, refractive index=1.74

[0277] PC: Polycarbonate lens with photocurable hard coat layer, refractive index 1.58

[0278] Next, using a spin coater (1H-DX2, manufactured by Mikasa Co., Ltd.), the surface of the above plastic lens was coated with the moisture curable polyurethane composition (PU1) at a rotational speed of 70 rpm for 15 seconds, and then at 900 rpm for 10 seconds to form a polyurethane resin layer having a thickness of about 7 μm. Furthermore, the coating was performed at a rotational speed of 70 rpm for 15 seconds and then at 1100 rpm for 10 seconds to form a moisture curable polyurethane resin layer having a thickness of about 5 μm. In other words, one optical base material on which a polyurethane resin layer having a thickness of about 7 μm was formed and one optical base material on which a polyurethane resin layer having a thickness of about 5 μm was formed were produced.

[Formation of Photochromic Resin Layer]

[0279] On the polyurethane resin layer of the optical base material obtained by the above method, the photochromic compositions (1) (2 g) prepared in advance were applied by spin coating at a rotational speed of 100 rpm for 30 seconds, and then at 800 rpm for 10 to 20 seconds such that the photochromic composition (1) was spread from the center of the optical base material to the outer periphery with a PET film cut out in a strip shape, and a film thickness was 40 μm.

[0280] Then, the lens having a surface coated with the above composition was irradiated with light for 80 seconds using a metal halide lamp having an output of 200 mW/cm.sup.2 in a nitrogen gas atmosphere to polymerize the composition. Then, heating was further carried out at 110° C. for 1 hour to form a 40 μm-thick photochromic resin layer made of a resin obtained by polymerizing the photochromic composition (1) on the polyurethane resin layer.

[Evaluation of Photochromic Optical Articles]

[0281] The photochromic optical article obtained above was evaluated for its photochromic property by the same method as above, and the appearance and boiling adhesion were evaluated by the following method. The evaluation results are shown in Tables 7 to 9.

(Appearance Evaluation)

[0282] The photochromic optical article was irradiated with light of a high-pressure mercury lamp, the projection surface was projected on a blank sheet of paper, and the projection surface of the entire photochromic optical article was observed and evaluated. The photochromic optical article was placed at a distance of about 70 cm from the high-pressure mercury lamp and about 20 cm from the blank paper. The evaluation criteria are shown below.

[0283] 0: No annual ring-shaped defects or less than 5 annual ring-shaped defects are observed, the annual ring-shaped defects occur when a photochromic composition spreads from the center toward the outer peripheral portion of the optical base material.

[0284] 1: Five or more and less than ten annual ring-shaped defects are observed, the annual ring-shaped defects occur when a photochromic composition spreads from the center toward the outer peripheral portion of the optical base material.

[0285] 2: Ten of more and less than 20 annual ring-shaped defects are observed on an entire surface, the annual ring-shaped defects occur when the photochromic composition spreads from the center toward the outer peripheral portion of the optical base material.

[0286] 3: Twenty or more annual ring-shaped defects are observed on an entire surface, the annual ring-shaped defects occur when the photochromic composition spreads from the center toward the outer peripheral portion of the optical base material.

(Boiling Adhesion)

[0287] The photochromic optical article was placed in boiling distilled water, and the adhesion between the photochromic resin layer and the lens was evaluated every hour by a cross-cut tape test according to JISD-0202. In other words, using a retractable knife, the surface of the photochromic resin layer was cut in 1 mm interval to form a lattice pattern having 100 squares. A cellophane adhesive tape (CELLOTAPE (registered trademark) manufactured by NICHIBAN Co., Ltd.) was firmly attached thereto, and tensile peeling was done by pulling to 90° direction from the surface at a time, then a number of squares of the lattice pattern on which the photochromic resin layer remained was measured. As the evaluation result, the test time when the remaining squares were 90 or more was described. For example, the description of 3 hours means that the number of squares remaining in the cross-cut tape test is 90 or more after 3 hours of acceleration and less than 90 after 4 hours of acceleration. Furthermore, when photochromic optical articles having 90 or more squares remains, evaluation was continuously carried out up to 5 hours of acceleration.

Examples 6 to 28

[0288] A photochromic optical article was produced in the same manner as in Example 5 except that the moisture curable urethane compositions shown in Tables 7 to 9 were used. However, in order to adjust the film thickness of the polyurethane resin layer to about 7 μm and about 5 μm, conditions such as the rotation speed of the spin coater were appropriately adjusted. The evaluation results of the obtained photochromic optical articles are shown in Tables 7 to 9.

TABLE-US-00007 TABLE 7 Moisture Maximum Photochromic curable absorption Color Fading composition polyurethane wavelength optical speed No. No. composition (λmax) density (second) Example 5 1 PU1 585 0.88 40 Example 6 1 PU2 585 0.88 40 Example 7 1 PU3 585 0.88 40 Example 8 1 PU4 585 0.88 40 Example 9 1 PU5 585 0.88 40 Example 10 1 PU6 585 0.88 40 Example 11 1 PU7 585 0.88 40 Example 12 1 PU8 585 0.88 40 Example 13 1 PU9 585 0.88 40 Example 14 1 PU10 585 0.88 40 Example 15 1 PU11 585 0.88 40 Example 16 1 PU12 585 0.88 40 Example 17 1 PU13 585 0.88 40 Example 18 1 PU14 585 0.88 40 Example 19 1 PU15 585 0.88 40 Example 20 1 PU16 585 0.88 40 Example 21 1 PU17 585 0.88 40 Example 22 1 PU18 585 0.88 40 Example 23 1 PU19 585 0.88 40 Example 24 1 PU20 585 0.88 40 Example 25 1 PU21 585 0.88 40 Example 26 1 PU22 585 0.88 40 Example 27 1 PU23 585 0.88 40 Example 28 1 PU24 585 0.88 40

TABLE-US-00008 TABLE 8 Moisture Appearance Appearance curable (Polyurethane resin layer: (Polyurethane resin layer: polyurethane about 7 μm) about 5 μm) No. composition CR TRB MRA MRB TEA TEB PC CR TRB MRA MRB TEA TEB PC Example 5 PU1 0 1 0 0 0 0 0 0 1 0 0 0 0 0 Example 6 PU2 1 2 0 0 0 0 0 1 2 0 0 0 0 0 Example 7 PU3 1 1 0 0 0 0 0 1 1 0 0 0 0 0 Example 8 PU4 1 1 0 0 0 0 0 1 1 0 0 0 0 0 Example 9 PU5 1 1 0 0 0 0 0 1 1 0 0 0 0 0 Example 10 PU6 1 1 0 0 0 0 0 1 1 0 0 0 0 0 Example 11 PU7 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Example 12 PU8 1 2 0 0 0 0 0 1 2 0 0 0 0 0 Example 13 PU9 1 2 0 0 0 0 0 1 2 0 0 0 0 0 Example 14 PU10 1 2 0 0 0 0 0 1 2 0 0 0 0 0 Example 15 PU11 1 1 0 0 0 0 0 1 1 0 0 0 0 0 Example 16 PU12 1 2 0 0 0 0 0 1 2 0 0 0 0 0 Example 17 PU13 1 2 0 0 0 0 0 1 2 0 0 0 0 0 Example 18 PU14 1 1 0 0 0 0 0 1 1 0 0 0 0 0 Example 19 PU15 1 2 0 0 0 0 0 1 2 0 0 0 0 0 Example 20 PU16 0 1 0 0 0 0 0 0 1 0 0 0 0 0 Example 21 PU17 1 1 0 0 0 0 0 1 1 0 0 0 0 0 Example 22 PU18 1 2 0 0 0 0 0 1 2 0 0 0 0 0 Example 23 PU19 2 2 0 0 0 0 0 2 2 0 0 0 0 0 Example 24 PU20 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Example 25 PU21 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Example 26 PU22 0 1 0 0 0 0 0 0 1 0 0 0 0 0 Example 27 PU23 1 1 0 0 0 0 0 1 1 0 0 0 0 0 Example 28 PU24 3 3 0 0 1 1 1 3 3 0 0 1 1 1

TABLE-US-00009 TABLE 9 Moisture Boiling adhesion Boiling adhesion curable (Polyurethane resin layer: (Polyurethane resin layer: polyurethane about 7 μm) about 5 μm) No. composition CR TRB MRA MRB TEA TEB PC CR TRB MRA MRB TEA TEB PC Example 5 PU1 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Example 6 PU2 5 5 5 4 4 3 5 5 5 5 3 3 2 5 Example 7 PU3 5 4 5 3 3 2 5 5 3 5 2 2 1 5 Example 8 PU4 5 5 5 4 4 3 5 5 5 5 3 3 2 5 Example 9 PU5 5 4 5 3 3 2 5 5 3 5 2 2 1 5 Example 10 PU6 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Example 11 PU7 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Example 12 PU8 5 5 5 4 4 3 5 5 5 5 3 3 2 5 Example 13 PU9 5 5 5 4 4 3 5 5 5 5 3 3 2 5 Example 14 PU10 5 5 5 4 4 3 5 5 5 5 3 3 2 5 Example 15 PU11 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Example 16 PU12 5 5 5 4 4 3 5 5 5 5 3 3 2 5 Example 17 PU13 5 5 5 4 4 3 5 5 5 5 3 3 2 5 Example 18 PU14 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Example 19 PU15 5 4 5 3 3 2 5 5 3 5 2 2 1 5 Example 20 PU16 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Example 21 PU17 5 5 5 5 5 5 5 5 5 5 4 4 3 5 Example 22 PU18 5 5 5 4 4 3 5 5 5 5 3 3 2 5 Example 23 PU19 5 4 5 3 3 2 5 5 3 5 2 2 1 5 Example 24 PU20 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Example 25 PU21 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Example 26 PU22 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Example 27 PU23 5 5 5 5 5 5 5 5 5 5 4 4 3 5 Example 28 PU24 5 3 4 1 1 1 4 5 2 2 0 0 0 3

[0289] As is apparent from Tables 7 to 9, the photochromic optical articles of Examples 5 to 28 in which a primer layer was formed using the moisture curable polyurethane composition (in particular, photochromic optical articles of Examples 5 to 27) not only have excellent photochromic properties, but also have excellent appearance and adhesion.

Example 29

[Formation of Polyurethane Resin Layer; Production of First Laminate]

[0290] As an optical base material, CR-39 (allyl resin plastic lens; refractive index=1.50) having a thickness of 2.0 mm was used. This optical base material was thoroughly degreased with acetone and immersed in 10% by mass aqueous solution of sodium hydroxide of 50° C. for 10 minutes, then was sufficiently washed by warm water, and dried using a drier at 70° C. for 30 minutes. The moisture curable polyurethane composition (PU25) was applied by spin coating on the optical base material (plastic lens) using a Spin Coater 1H-DX2 manufactured by Mikasa Co., Ltd., then dried for 1 hour under the conditions of 25° C. 50% RH, thereby producing the first laminate having a polyurethane layer on the plastic lens. At this time, a thickness of the polyurethane resin layer was adjusted to 5 to 7 μm.

[0291] The obtained first laminate had an appearance of A, adhesion of 100, transmittance of light having wavelength of 400 nm of light of 1%, and transmittance of light having wavelength of 420 nm of 64%. Note here that the appearance and adhesion were evaluated in the same manner as in Example 1, and ultraviolet light absorbing property and blue light absorbing property were evaluated as follows.

(Ultraviolet Absorbing Property and Blue Light Absorbing Property)

[0292] The ultraviolet absorbing property and the blue light absorbing property were evaluated by measuring UV-vis spectrum of the obtained first laminate. For the wavelength of the first laminated produced by the method mentioned above, light transmittance (T %) in the wavelength of the wavelength of 400 nm and 420 nm was measured to determine the ultraviolet absorbing property and the blue light absorbing property.

[Formation of Hard Coat Layer; Production of Second Laminate]

[0293] t-butanol (12.2 g), ethylene glycol monobutyl ether (7.0 g), acetylacetone (3.7 g), methyltriethoxysilane (0.41 g), γ-glycidoxypropyltrimethoxysilane (18.9 g), and silicone surfactant (Product name: L-7001 manufactured by Dow Corning Toray Co., Ltd.) (0.06 g) were mixed and stirred for 30 minutes at room temperature. Furthermore, 9.0 g of 0.05 N hydrochloric acid was added and stirred for 1 hour. Next, 0.1 N trimethyl ammonium chloride in methanol solution (3.2 g) was further added, and stirred for 1 hour at room temperature. Subsequently, methanol silica sol (solid content concentration: 30% by mass) (44.3 g) and aluminum acetylacetonate (0.51 g) were added and matured for whole day and night, and thereby the hard coat composition was obtained.

[0294] The first laminate was immersed in the hard coat composition described above, and pulled out in a pulling rate of 30 cm/min, thereby applying the hard coat composition on both surfaces of the first laminate. After applying, the resulting product was dried at 80° C. for 20 minutes, then maintained and cured at 120° C. for 4 hours to form the hard coat layer. The obtained hard coat layer was a colorless transparent film having a thickness of about 2 μm. The obtained second laminate had an appearance of A, adhesion of 100, transmittance of light having wavelength of 400 nm of 1%, and transmittance of light having wavelength of 420 nm of 64%.

Preparation Examples 28 to 30: Preparation of Moisture Curable Polyurethane Composition (PU26 to PU28)

[0295] Moisture curable polyurethane compositions (PU26 to PU28) were prepared using components shown in Table 10 in the same manner as in Preparation Example 1. The compositions and the like of the moisture curable polyurethane compositions (PU26 to PU28) are shown in Table 10.

TABLE-US-00010 TABLE 10 Mole Mole Moisture Composition ratio ratio curable (part by mass) when when polyurethane Component Component Component Component Other n1 = 1 n3 = 1 composition A1-1 A1-2 A2 B component n2 n5 + n6 n4 PU26 MDI PL6 PG1 B2 L7001 0.4049 0.00 0.50 (129) (130) (8.0) (282) (1.1) B3 (564) PU27 MDI PL6 PG1 B2 L7001 0.60 0.00 0.50 (129) (130) (11.8) (361) (1.4) B3 (722) PU28 MDI PL6 PG1 B1 L7001 0.60 0.00 0.50 (129) (130) (11.8) (361) (1.4) B3 (722) Physical property of Physical property of moisture curable moisture curable polyurethane Moisture polyurethane composition Number Number of curable Solid content average Content urethane polyurethane concentration Viscosity molecular of NCO bonds composition (wt %) (mPa .Math. s@25° C.) weight (wt %) (mol/100 g) PU26 24.1 6.5 1700 4.9 0.275 PU27 20.2 5.9 2700 3.1 0.296 PU28 20.1 5.5 2700 3.1 0.296

Examples 30 to 32

[0296] A photochromic optical article was produced in the same manner as in Example 5 except that the moisture curable urethane compositions shown in Tables 11 to 13 were used. However, in order to adjust the film thickness of the polyurethane resin layer to about 7 μm and about 5 μm, conditions such as the rotation speed of the spin coater were appropriately adjusted. The evaluation results of the obtained photochromic optical articles are shown in Tables 11 to 13.

TABLE-US-00011 TABLE 11 Moisture Maximum Photochromic curable absorption Color Fading composition polyurethane wavelength optical speed No. No. composition (λmax) density (second) Example 30 1 PU26 585 0.88 40 Example 31 1 PU27 585 0.88 40 Example 32 1 PU28 585 0.88 40

TABLE-US-00012 TABLE 12 Moisture Appearance Appearance curable (Polyurethane resin layer: (Polyurethane resin layer: polyurethane about 7 μm) about 5 μm) No. composition CR TRB MRA MRB TEA TEB PC CR TRB MRA MRB TEA TEB PC Example 30 PU26 0 1 0 0 0 0 0 1 1 0 0 0 0 0 Example 31 PU27 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Example 32 PU28 0 0 0 0 0 0 0 0 0 0 0 0 0 0

TABLE-US-00013 TABLE 13 Moisture Boiling adhesion Boiling adhesion curable (Polyurethane resin layer: (Polyurethane resin layer: polyurethane about 7 μm) about 5 μm) No. composition CR TRB MRA MRB TEA TEB PC CR TRB MRA MRB TEA TEB PC Example 30 PU26 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Example 31 PU27 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Example 32 PU28 5 5 5 5 5 5 5 5 5 5 5 5 5 5

[0297] As is apparent from Tables 11 to 13, the photochromic optical articles of Examples 30 to 32 in which a primer layer was formed using the moisture curable polyurethane composition not only have excellent photochromic properties, but also have excellent appearance and adhesion.

Example 33

[0298] (1) Production of Polycarbonate Sheet to which Urethane Resin Layer is Laminated

[0299] Isophorone diisocyanate, polycarbonate diol (molecular weight: 1000), and urethane resin made from isophorone diamine as a raw material were dissolved in propylene glycol monomethyl ether as an organic solvent such that a solid content concentration became 15% by mass. The resulting urethane resin solution was applied to a thickness of 10 μm onto a 300 μm-thick polycarbonate sheet, followed by drying at 110° C. for 5 minutes to produce a laminated sheet.

(2) Formation of Resin Layer Using Moisture Curable Polyurethane Composition

[0300] A moisture curable polyurethane composition (PU7) was applied to have a thickness of 7 μm onto a PET separate film, followed by drying at 100° C. for 5 minutes to form a resin layer.

(3) Production of Laminated Sheet

[0301] A urethane resin layer of the laminated sheet obtained in the above (1) was heated and pressed at 0.1 MPa at 100° C. on the resin layer formed from the moisture curable urethane composition obtained in the above (2). Next, the PET separate film was peeled off, and the urethane resin layer of the laminated sheet obtained in the above (1) was heated and pressed to the resin layer on the other side at 0.1 MPa and at 100° C. to produce a laminated sheet.

(4) Measurement of Peel Strength

[0302] The laminated sheet obtained in the above (3) was used as a test piece having an adhesive portion of 25×100 mm and mounted on a tensile tester (Autograph AGS-500NX, manufactured by Shimadzu Corporation), the tensile test was carried out at a crosshead speed of 100 mm/min, and the peel strength was measured. The measurement results are shown in Table 14.

Examples 34 to 36

[0303] The peel strength was measured in the same manner as in Example 33 except that the moisture curable polyurethane composition shown in Table 14 was used. The measurement results are shown in Table 14.

TABLE-US-00014 TABLE 14 Moisture curable Peel polyurethane strength composition (N/25 mm) Example 33 PU7 100 Example 34 PU13 70 Example 35 PU27 130 Example 36 PU24 10