Organopolysiloxane emulsion composition for release paper or release film, method for producing same, and release paper and release film

Abstract

An organopolysiloxane emulsion composition for release paper or a release film, said composition being produced by dispersing a mixture comprising components (A) to (D) as mentioned below in water: (A) an alkenyl-group-containing diorganopolysiloxane having at least two alkenyl groups per molecule and having a viscosity of 1,000 Pa.Math.s or less at 25 C., in an amount of 100 parts by mass; (B) an organohydrogenpolysiloxane having at least two SiH groups per molecule and having a viscosity of 1 Pa.Math.s or less at 25 C., in such an amount that the number of moles of an SiH group can become 0.5 to 10 times the number of moles of an alkenyl group in the component (A); (C) a curing catalyst, in an amount of 0.01 to 3 parts by mass; and (D) a polyether-modified and/or polyol-modified organosilicon compound, in an amount of 0.01 to 10 parts by mass.

Claims

1. An organopolysiloxane emulsion composition for release paper or release film that is obtained by dispersing in water a mixture comprising following components (A) to (D) and (G): (A) 100 parts by weight of an alkenyl group-containing diorganopolysiloxane having at least two alkenyl groups per molecule and having a viscosity at 25 C. of not more than 1,000 Pa.Math.s; (B) an organohydrogenpolysiloxane having at least two SiH groups per molecule and having a viscosity at 25 C. of not more than 1 Pa.Math.s, in an amount corresponding to a number of moles of SiH groups that is from 0.5 to 10 times the number of moles of alkenyl groups in component (A); (C) from 0.01 to 3 parts by weight of a curing catalyst; and (D) from 0.01 to 10 parts by weight of a polyol-modified organosilicon compound of formula (8) below ##STR00016## wherein each R.sup.1 is independently a substituted or unsubstituted monovalent hydrocarbon group of 1 to 20 carbon atoms without an aliphatic unsaturated bond; each R.sup.3 is independently a hydrogen atom, a hydroxyl group, an alkoxy group of 1 to 4 carbon atoms, or a substituted or unsubstituted alkenyl group of 2 to 20 carbon atoms; each R.sup.4 is independently a group having the following formulas:
(CH.sub.2).sub.aaO(CH.sub.2CH(OH)CH.sub.2O).sub.daR.sup.6 wherein R.sup.6 is a substituted or unsubstituted monovalent hydrocarbon group of 1 to 10 carbon atoms without an aliphatic unsaturated bond, or a hydrogen atom; aa is an integer from 1 to 10; and da is an integer from 1 to 20; q, r, and s, are integers of 0 or more; q+r+s is integers from 0 to 98; each o is independently an integer from 0 to 3; p is an integer from 0 to 3; o +each p is independently an integer from 0 to 3; when o+p is 3 for each terminal group, s is 1 or more; and (G) an emulsifying agent excluding component (D).

2. The organopolysiloxane emulsion composition for release paper or release film of claim 1, wherein the mixture further comprises (E) from 0.1 to 10 parts by weight, per 100 parts by weight of component (A), of an organopolysiloxane resin composed primarily of M units of formula (1) below and Q units of formula (2) below in a molar ratio of M units to Q units (M/Q) in the range of 1/9 to 9/1: ##STR00017## wherein each R.sup.1 is independently a substituted or unsubstituted monovalent hydrocarbon group of 1 to 20 carbon atoms without an aliphatic unsaturated bond; each R.sup.2 is independently a substituted or unsubstituted alkenyl group of 2 to 20 carbon atoms; the letter a is an integer from 0 to 3; and O.sub.1/2 indicates that another unit is bonded through O.sub.1/2.

3. The organopolysiloxane emulsion composition for release paper or release film of claim 1, wherein the mixture further comprises (F) from 0.1 to 50 parts by weight of an adhesion promoter per 100 parts by weight of component (A).

4. The organopolysiloxane emulsion composition for release paper or release film of claim 3, wherein component (F) is an organopolysiloxane resin composed primarily of (R.sup.1SiO.sub.3/2) units (T units) and (R.sup.1.sub.aR.sup.2.sub.(3-a)SiO.sub.1/2) units (M units) (wherein each R.sup.1 is independently a substituted or unsubstituted monovalent hydrocarbon group of 1 to 20 carbon atoms without an aliphatic unsaturated bond; each R.sup.2 is independently a substituted or unsubstituted alkenyl group of 2 to 20 carbon atoms; and the letter a is an integer from 0 to 3) in a molar ratio of M units to T units (M/T) in the range of 1/9 to 9/1.

5. The organopolysiloxane emulsion composition for release paper or release film of claim 1, wherein the content of the component (G) is from 0.1 to 20 parts by weight of an emulsifying agent per 100 parts by weight of component (A).

6. The organopolysiloxane emulsion composition for release paper or release film of claim 1, wherein the mixture further comprises (H) from 0.1 to 10 parts by weight of a pot-life extender per 100 parts by weight of component (A).

7. The organopolysiloxane emulsion composition for release paper or release film of claim 1, wherein component (D) is a compound of any of general formulas (9) to (10).

8. The organopolysiloxane emulsion composition for release paper or release film of claim 1, wherein component (D) is a compound having the following formulas: ##STR00018## wherein Me stands for a methyl groups.

9. The organopolysiloxane emulsion composition for release paper or release film of claim 1, wherein component (G) is selected from the group consisting of nonionic surfactants and water soluble polymers.

10. The organopolysiloxane emulsion composition for release paper or release film of claim 1, wherein component (G) is nonionic surfactants and water soluble polymers.

11. A release paper or release film obtained by applying the organopolysiloxane emulsion composition for release paper or release film of claim 1 to a paper or film substrate, and curing the applied composition.

12. A method for preparing the organopolysiloxane emulsion composition for release paper or release film of claim 1, comprising the steps of preparing: emulsion composition 1 obtained by dispersing in water a mixture comprising component (B), lacking component (C), and optionally comprising some or all of component (A) and components (D) and (G), and emulsion composition 2 obtained by dispersing in water a mixture comprising component (C), lacking component (B), and additionally comprising the remaining components, such that the sum of the silicone components in composition 2 is 3 parts by weight or less per 100 parts by weight of the sum of the silicone components in compositions 1 and 2; and mixing together compositions 1 and 2 just prior to use.

13. A method for preparing the organopolysiloxane emulsion composition for release paper or release film of claim 1, comprising the steps of preparing: emulsion composition 1 obtained by dispersing in water a mixture comprising component (B), lacking components (C) and (D), and optionally comprising some or all of component (A) and component (G), emulsion composition 2 obtained by dispersing in water a mixture comprising component (C), lacking components (B) and (D), and optionally comprising some or all of component (A) and component (G), and emulsion composition 3 obtained by dispersing in water a mixture comprising component (D), lacking component (B) and/or component (C), and additionally comprising the remaining components, such that the sum of the silicone components in composition 2 is 3 parts by weight or less per 100 parts by weight of the sum of the silicone components in compositions 1, 2 and 3; and mixing together compositions 1, 2 and 3 just prior to use.

Description

EXAMPLES

(1) The invention is concretely illustrated below by way of Examples and Comparative Examples, although the invention is not limited by these Examples. The viscosities mentioned below are all absolute viscosities measured at 25 C. with a Brookfield rotational viscometer. The vinyl group content, SiH group content and silanol group content are values determined by .sup.29Si-NMR spectroscopy. In the examples below, Me and Vi stand for, respectively, a methyl group and a vinyl group.

Examples 1 to 22, Comparative Examples 1 to 3

(2) <Starting Materials Used in the Composition>

(3) Component (A)

(4) A1: A straight-chain dimethylpolysiloxane which is capped at both ends with vinyldimethylsiloxy units (M.sup.V units) of the formula Me.sub.2(Vi)SiO.sub.1/2, has pendant dimethylsiloxane units (D units) of the formula Me.sub.2SiO.sub.2/2, has a viscosity of 500 Pa.Math.s and has a vinyl group content of 0.015 mol/100 g A2: A straight-chain dimethylpolysiloxane which is capped at both ends with M.sup.V units, has pendant D units, has a viscosity of 100 mPa.Math.s, and has a vinyl group content of 0.04 mol/100 g A3: A branched polysiloxane which is composed of 1 mol % of M.sup.V units and 0.3 mol % of methylsilsesquioxane units (T units) of the formula MeSiO.sub.3/2, with the balance being D units, has a viscosity of 300 mPa.Math.s and has vinyl group content of 0.013 mol/100 g A4: A branched polysiloxane which is composed of 1.47 mol % of M.sup.V units, 0.49 mol % of T units and 0.24 mol % of SiO.sub.4/2 units (Q units), with the balance being D units, has a viscosity of 500 mPa.Math.s and has a vinyl group content of 0.02 mol/100 g
Component (B) B1: A methylhydrogenpolysiloxane which is capped at both ends of the molecular chain with trimethylsiloxy units (M units) of the formula Me.sub.3SiO.sub.1/2, has pendant methylhydrogensiloxane units (D.sup.H units) of the formula Me(H)SiO.sub.2/2, has a viscosity of 50 mPa.Math.s and has a SiH group content of 1.1 mol/100 g B2: A methylhydrogenpolysiloxane which is capped at both ends of the molecular chain with M units, has pendant D units and D.sup.H units, has a viscosity of 30 mPa.Math.s and has a SiH group content of 1.3 mol/100 g B3: A methylhydrogenpolysiloxane which is capped at both ends of the molecular chain with dimethylhydrogensiloxane units (M.sup.H units) of the formula Me.sub.2(H)SiO.sub.1/2, has pendant D units and D.sup.H units, has a viscosity of 30 mPa.Math.s and has a SiH group content of 0.9 mol/100 g
Component (C) C1: A liquid catalyst of a platinum-vinyl siloxane complex salt dispersed in a straight-chain dimethylpolysiloxane which is capped at both ends with M.sup.V units, has pendant D units, has a viscosity of 500 mPa.Math.s and has a vinyl group content of 0.015 mol/100 g, the platinum content, in terms of the platinum metal equivalent weight, being 10 wt % (in Tables 1 to 11, the weight of the catalyst included is indicated as the platinum metal equivalent weight)
Component (D) D1: A polyether-modified silicone of the following formula

(5) ##STR00012## D2: A polyether-modified silicone of the following formula

(6) ##STR00013## D3: A polyether-modified silicone of the following formula

(7) ##STR00014## D4: A glycerol-modified silicone of the following formula

(8) ##STR00015##
Component (E) E1: A polysiloxane which is composed of M units and Q units, wherein (M units/Q units) (molar ratio)=0.8 and the content of hydroxyl groups present in the Q units is 0.05 mol/100 g, and which has a viscosity, as a 60 wt % toluene solution, of 10 mPa.Math.s E2: A polysiloxane which is composed of M units, M.sup.V units and Q units, wherein (M units+M.sup.V units)/Q units (molar ratio)=0.8, the vinyl group content is 0.07 mol/100 g and the content of hydroxyl groups present in the Q units is 0.03 mol/100 g, and which has a viscosity, as a 60 wt % toluene solution, of 10 mPa.Math.s
Component (F) F1: 3-Glycidoxypropyltrimethoxysilane F2: A polysiloxane which is composed of M units, M.sup.V units and T units (M unit+M.sup.V unit)/T unit (molar ratio)=1, wherein the vinyl group content is 0.32 mol/100 g and the content of hydroxyl groups present in the T units is 0.03 mol/100 g, and which has a viscosity of 50 mPa.Math.s
Component (G) G1: A polyoxyethylene alkyl ether surfactant (HLB, 13.6; pH, 5.4) G2: A polyvinyl alcohol which has a degree of saponification of 90 mol % and which, as a 4 wt % aqueous solution, has a viscosity at 20 C. of 20 mPa.Math.s G3: A polyoxyethylene styrenated phenyl ether surfactant (HLB, 13.0; pH, 7.0)
Component (H) H1: Ethynylcyclohexanol
<Preparation of Organopolysiloxane Emulsion Compositions>
Preparation of Emulsion Compositions for Mixing 1 to 3 in Examples and Comparative Examples:

(9) Emulsion Compositions for Mixing 1 to 3 that are shown as single columns in Tables 1 to 11 were each prepared as separate emulsion compositions according to the following recipe.

(10) The applicable components from among components (A) to (H), in the amounts (parts by weight) shown in Tables 1 to 11, were placed in a container and mixed together. The weight of component (C) included is indicated in the tables as the platinum metal equivalent weight.

(11) Water was added to the mixture, in the amounts (parts by weight) shown in Tables 1 to 11, and mixing was carried out with a homogenizing mixer, following which a homogenizer was used to render the water-containing mixture into a homogeneous emulsion composition. Each of the resulting emulsion compositions for mixture had a silicone content of 20 wt %.

(12) In the Examples and Comparative Examples, the emulsion compositions for mixing can be roughly categorized by function as follows. However, cases in which a single emulsion composition for mixing possesses a plurality of functions are also included, and so the categories are not limitative as to the actual function. Composition 1 is a base polymer emulsion composition, Composition 2 is a catalyst emulsion composition, and Composition 3 is an additive emulsion composition.

(13) Preparation of Organopolysiloxane Emulsion Compositions for Coating to be Used in Examples and Comparative Examples:

(14) The preparations obtained by mixing together emulsion compositions for mixing in the Composition 1 to 3 combinations shown in Tables 1 to 11 and diluting the mixtures two-fold with water were used as organopolysiloxane emulsion compositions for coating.

(15) <Preparation and Evaluation of Test Specimens>

(16) Appearance and Stability of Emulsion Composition:

(17) The emulsion compositions for mixing and the organopolysiloxane emulsion compositions for coating that had been prepared were each visually examined, and the appearance was rated as , (suspended matter is observable), or x (separation has occurred). The stability was evaluated by hermetically sealing each emulsion composition for mixing, and rating the appearance after 10 days of standing at 25 C. as or x (separation has occurred).

(18) Viscosity and Average Particle Size of Emulsion Composition:

(19) The viscosities of the prepared emulsion compositions for mixing and organopolysiloxane emulsion compositions for coating were each measured at 25 C. with a Brookfield rotational viscometer. The average particle sizes of the prepared emulsion compositions for mixing and organopolysiloxane emulsion compositions for coating were each measured using an N4 PLUS Submicron Particle Size Analyzer from Beckman Coulter.

(20) The organopolysiloxane emulsion compositions for coating in the Examples and Comparative Examples were evaluated by the following methods.

(21) Wettability on Substrate:

(22) A PET film having a thickness of 38 m was fixed on a flat, horizontal support, and the prepared organopolysiloxane emulsion composition for coating was applied to the surface using a wiper bar to a silicone solids weight of about 0.2 g/m.sup.2. Following application, the composition was left to stand at room temperature for 1 minute, and was then visually examined for the occurrence of bumps and crawling. The wettability was rated as x when crawling occurred over the entire surface, when crawling occurred over part of the surface, when some bumps were observed but no crawling occurred, and when no bumps or crawling were observed.

(23) Leveling Ability:

(24) A PET film having a thickness of 38 m was fixed on a flat, horizontal support, and the prepared organopolysiloxane emulsion composition for coating was applied to the surface using a wiper bar to a silicone solids weight of about 0.2 g/m.sup.2. Following application, the specimen was immediately placed in a 120 C. dryer and heat-dried for 60 seconds, after which it was left to stand for 1 minute at room temperature and the surface of the cured coat was subsequently visually examined to determine whether phenomena due to surface irregularities, such as bumps, streaks and spot anomalies had occurred.

(25) The leveling ability was rated as x when bumps, streaks and spot anomalies occurred over the entire surface, when bumps, streaks and spot anomalies occurred over part of the surface; when bumps and streaks were observable to a limited degree, but spot anomalies did not occur; and when the surface was smooth and clean.

(26) Transparency of Cured Coat:

(27) A PET film having a thickness of 38 m was fixed on a flat, horizontal support, and the prepared organopolysiloxane emulsion composition for coating was applied to the surface using a wiper bar to a silicone solids weight of about 0.2 g/m.sup.2. Following application, the specimen was immediately placed in a 120 C. dryer and heat-dried for 60 seconds, after which it was left to stand for 1 minute at room temperature and cooled to room temperature. The haze value was then measured and used to compare the transparency.

(28) The transparency was rated as x when the haze value was 10 or more, when it was at least 5 and less than 10, when it was at least 3 and less than 5; and when it was less than 3.

(29) Release Force:

(30) A PET film having a thickness of 38 m was fixed on a flat, horizontal support, and the prepared organopolysiloxane emulsion composition for coating was applied to the surface using a wiper bar to a silicone solids weight of about 0.2 g/m.sup.2. Following application, the specimen was immediately placed in a 120 C. dryer and heat-dried for 60 seconds to form a cured coat, which was used as a silicone separator. After storing this at 25 C. for 20 hours, Tesa-7475 tape was laminated thereon in accordance with the FINAT method, thereby preparing a test specimen for evaluation.

(31) Using a tensile testing machine, the Tesa-7475 tape on this test specimen was peeled off at an angle of 180 and a peel rate of 0.3 m/min, and the force required for peeling was measured as the release force (N/25 mm).

(32) Pot Life:

(33) The prepared organopolysiloxane emulsion composition for coating was left to stand for 12 hours at 25 C., following which the wettability, leveling ability and transparency were evaluated in the same way as described above.

(34) TABLE-US-00001 TABLE 1 Example 1 to 3 formulations Example 1 Example 2 Example 3 Total Total Total Ingredients Composition Composition (coating Composition Composition (coating Composition Composition (coating (pbw) 1 2 composition) 1 2 composition) 1 2 composition) A1 95 5 100 95 5 100 95 5 100 A2 A3 A4 B1 2.73 2.73 2.73 2.73 2.73 2.73 B2 B3 C1 0.01 0.01 0.01 0.01 0.01 0.01 D1 1 1 0.01 10 D2 0.01 D3 10 D4 E1 0 0 0 E2 F1 0 0 0 F2 G1 1 97 0.10 5.18 1.99 0.10 5.23 2.15 0 10 5.63 G2 2.96 0.15 2.99 0.15 3.23 0.15 G3 H1 1.04 1.04 1.03 1.03 1.13 1.13 Water 388.9 19.8 (408.7) 385.0 19.8 (404.8) 424.4 19.8 (444.2) Sx components .sup.1) 98.7 5.0 103.7 97.7 5.0 102.7 107.7 5.0 112.7 Molar ratio 1 .sup.2) 2.1 0 2.0 2.1 0 2.0 2.1 0 2.0 Molar ratio 2 .sup.3) 2.1 0 2.0 2.1 0 2.0 2.1 0 2.0 Evaluation Results Appearance Stability Viscosity 70 60 70 60 60 60 80 60 80 (mPa .Math. s) Average particle 500 700 500 800 700 800 400 700 400 size (nm) Wettability Initial Initial Initial Over time Over time Over time Leveling ability Initial Initial Initial Over time Over time Over time Transparency Initial Initial Initial Over time Over time x Over time Release force 0.25 0.30 0.23 .sup.1) Sx components refers to the silicone components among components (A) to (F). .sup.2) Ratio of number of moles of SiH groups in component (B) to number of moles of vinyl groups in component (A). .sup.3) Ratio of total number of moles of SiH groups in composition to total number of moles of vinyl groups in composition.

(35) TABLE-US-00002 TABLE 2 Comparative Example 1 to 3 formulations Comparative Example 1 Comparative Example 2 Comparative Example 3 Total Total Total Ingredients Composition Composition (coating Composition Composition (coating Composition Composition (coating (pbw) 1 2 composition) 1 2 composition) 1 2 composition) A1 95 5 100 95 5 100 90 10 100 A2 A3 A4 B1 2.73 2.73 2.73 2.73 2.73 2.73 B2 B3 C1 0.01 0.01 0.01 0.01 0.01 0.01 D1 0 15 15 0 D2 D3 D4 E1 0 0 0 E2 F1 0 0 0 F2 G1 1.95 0.10 5.13 2.25 0.10 5.88 1.85 0.20 5.13 G2 2.93 0.15 3.38 0.15 2.78 0.30 G3 H 0.51 0.51 0.61 0.61 0.49 0.49 Water 385.5 19.8 (405.3) 444.7 19.8 (464.5) 365.8 39.5 (405.3) Sx components .sup.1) 97.7 5.0 102.7 112.7 5.0 117.7 92.7 10.0 102.7 Molar ratio 1 .sup.2) 2.1 0 2.0 2.1 0 2.0 2.1 0 2.0 Molar ratio 2 .sup.3) 2.1 0 2.0 2.1 0 2.0 2.1 0 2.0 Evaluation Results Appearance Stability Viscosity 60 60 60 90 60 90 60 40 60 (mPa .Math. s) Average particle 800 700 800 400 700 400 800 1,500 800 size (nm) Wettability Initial Initial Initial Over time x Over time Over time x Leveling ability Initial Initial Initial Over time x Over time Over time x Transparency Initial Initial Initial x Over time x Over time x Over time x Release force 0.30 0.35 0.35

(36) TABLE-US-00003 TABLE 3 Example 4 and 5 formulations Example 4 Example 5 Total Total Ingredients Composition Composition Composition (coating Composition Composition Composition (coating (pbw) 1 2 3 composition) 1 2 3 composition) A1 5 100 5 100 A2 10 10 A3 85 85 A4 B1 2.74 2.74 B2 1.85 1.85 B3 0.89 0.89 C1 0.01 0.01 0.01 0.01 D1 1 1 1 1 D2 D3 D4 E1 0.1 0.1 1 1 E2 F1 0 0 F2 G1 1.74 0.10 0.24 1.74 0.10 0.26 G2 2.61 0.15 0.36 5.20 2.61 0.15 0.39 5.25 G3 H 0.92 0.12 1.04 0.92 0.13 1.05 Water 342.2 19.8 47.2 (409.2) 342.2 19.8 50.8 (412.8) Sx components .sup.1) 86.9 5.0 12.0 103.9 86.9 5.0 12.9 104.8 Molar ratio 1 .sup.2) 2.2 0 2.0 2.0 2.2 0 2.0 2.0 Molar ratio 2 .sup.3) 2.2 0 2.0 2.0 2.2 0 2.0 2.0 Evaluation Results Appearance Stability Viscosity 70 60 60 70 70 60 60 70 (mPa .Math. s) Average particle 600 700 700 600 600 700 800 600 size (nm) Wettability Initial Initial Over time Over time Leveling ability Initial Initial Over time Over time Transparency Initial Initial Overtime Over time Release force 0.25 0.20

(37) TABLE-US-00004 TABLE 4 Example 6 formulation Example 6 Total Ingredients (coating (pbw) Composition 1 Composition 2 Composition 3 composition) A1 5 100 A2 20 A3 75 A4 B1 4.98 B2 1.65 B3 3.33 C1 0.01 0.01 D1 1 1 D2 D3 D4 E1 10 E2 10 F1 0 F2 G1 1.53 0.10 0.69 5.80 G2 2.30 0.15 1.03 G3 H 0.82 0.34 1.16 Water 302.0 19.8 135.3 (457.1) Sx components.sup.1) 76.7 5.0 34.3 116.0 Molar ratio 1.sup.2) 2.1 0 7.5 2.8 Molar ratio 2.sup.3) 2.1 0 2.0 2.0 Evaluation Results Appearance Stability Viscosity (mPa .Math. s) 70 60 50 60 Average particle size (mm) 600 700 900 800 Wettability Initial Over time Leveling ability Initial Over time Transparency Initial Over time Release force 0.40

(38) TABLE-US-00005 TABLE 5 Example 7 to 9 formulations Example 7 Example 8 Example 9 Total Total Total Ingredients Composition Composition (coating Composition Composition (coating Composition Composition (coating (pbw) 1 2 composition) 1 2 composition) 1 2 composition) A1 99 1 100 98 2 100 97 3 100 A2 A3 A4 B1 2.73 2.73 2.73 2.73 2.73 2.73 B2 B3 C1 0.01 0.01 0.01 0.01 0.01 0.01 D1 1 1 1 1 1 1 D2 D3 D4 E1 0 0 0 E2 F1 0 0 0 F2 G1 2 05 0.02 5.18 2.03 0.04 5.18 2.01 0 06 5.18 G2 3.08 0.03 3.05 0.06 3.02 0.09 G3 H 1.04 1.04 1.04 1.04 1.04 1.04 Water 404.7 40 (408.7) 400.8 7.9 (408.7) 396.8 11.9 (408.7) Sx components .sup.1) 102.7 1.0 103.7 101.7 2.0 103.7 100.7 3.0 103.7 Molar ratio 1 .sup.2) 2.0 0 2.0 2.0 0 2.0 2.1 0 2.0 Molar ratio 2 .sup.3) 2.0 0 2.0 2.0 0 2.0 2.1 0. 2.0 Evaluation Results Appearance Stability Viscosity 70 50 70 70 60 70 70 60 70 (mPa .Math. s) Average particle 500 900 500 500 800 500 500 900 500 size (nm) Wettability Initial Initial Initial Over time Over time Over time Leveling ability Initial Initial Initial Over time Over time Over time Transparency Initial Initial Initial Over time Over time Over time Release force 0.22 0.22 0.25

(39) TABLE-US-00006 TABLE 6 Example 10 to 12 formulations Example 10 Example 11 Example 12 Total Total Total Ingredients Composition Composition (coating Composition Composition (coating Composition Composition (coating (pbw) 1 2 composition) 1 2 composition) 1 2 composition) A1 99 1 100 99 1 100 97 3 100 A2 A3 A4 B1 2.73 2.73 2.73 2.73 2.73 2.73 B2 B3 C1 0.01 0.01 0.01 0.01 0.01 0.01 D1 0.01 10 0.01 D2 0.01 0.01 D3 10 D4 E1 0 0 0 E2 F1 0 0 0 F2 G1 2 03 0.02 5.13 2.23 0.02 5.63 1.99 0 06 5.13 G2 3.05 0.03 3.35 0.03 2.99 0.09 G3 H1 0.51 0.51 0.56 0.56 0.51 0.51 Water 401.3 40 (405.3) 440.8 4.0 (444.8) 393.4 11.9 (405.3) Sx components .sup.1) 101.7 1.0 102.7 111.7 1.0 112.7 99.7 3.0 102.7 Molar ratio 1 .sup.2) 2.1 0 2.0 2.1 0 2.0 2.1 0 2.0 Molar ratio 2 .sup.3) 2.1 0 2.0 2.1 0 2.0 2.1 0 2.0 Evaluation Results Appearance Stability Viscosity 60 50 60 80 50 80 60 60 60 (mPa .Math. s) Average particle 800 900 800 400 900 400 800 900 800 size (nm) Wettability Initial Initial Initial Over time Over time Over time Leveling ability Initial Initial Initial Over time Over time Over time Transparency Initial Initial Initial Over time Over time Over time Release force 0.28 0.25 0.25

(40) TABLE-US-00007 TABLE 7 Example 13 formulation Example 13 Total Ingredients Composition (coating (pbw) 1 Composition 2 composition) A1 97 3 100 A2 A3 A4 B1 2.73 2.73 B2 B3 C1 0.01 0.01 D1 10 D2 D3 10 D4 E1 0 E2 F1 0 F2 G1 2.19 0.06 5.63 G2 3.29 0.09 G3 H1 0.56 0.56 Water 432.9 11.9 (444.8) Sx components.sup.1) 109.7 3.0 112.7 Molar ratio 1.sup.2) 2.1 0 2.0 Molar ratio 2.sup.3) 2.1 0 2.0 Evaluation Results Appearance Stability Viscosity (mPa .Math. s) 80 60 80 Average particle size (nm) 400 900 400 Wettability Initial Over time Leveling ability Initial Over time Transparency Initial Over time Release force 0.25

(41) TABLE-US-00008 TABLE 8 Example 14 and 15 formulations Example 14 Example 15 Total Total Composition Composition Composition (coating Composition Composition Composition (coating 1 2 3 composition) 1 2 3 composition) A1 1 100 1 100 A2 10 10 A3 89 89 A4 B1 2.73 2.73 B2 1.84 1.84 B3 0.89 0.89 C1 0.01 0.01 0.01 0.01 D1 1 1 1 1 D2 D3 D4 E1 0.1 0.1 1 1 E2 F1 0 0 F2 G1 1.82 0.02 0.24 1.82 0.02 0.26 G2 2.73 0.03 0.36 5.20 2.73 0.03 0.39 5.25 G3 H 0.46 0.06 0.52 0.48 0.06 0.54 Water 358.4 4.0 47.3 (409.7) 358.4 4.0 50.8 (413.2) Sx components .sup.1) 90.8 1.0 12.0 103.8 90.8 1.0 12.9 104.7 Molar ratio 1 .sup.2) 2.0 0 2.0 2.0 2.0 0 2.0 2.0 Molar ratio 2 .sup.3) 2.0 0 2.0 2.0 2.0 0 2.0 2.0 Evaluation Results Appearance Stability Viscosity 70 50 70 70 70 50 60 70 (mPa .Math. s) Average particle 600 900 600 500 600 900 800 600 size (nm) Wettability Initial Initial Over time Over time Leveling ability Initial Initial Over time Over time Transparency Initial Initial Over time Over time Release force 0.23 0.20

(42) TABLE-US-00009 TABLE 9 Example 16 and 17 formulations Example 16 Example 17 Total Total Composition Composition Composition (coating Composition Composition Composition (coating 1 2 3 composition) 1 2 3 composition) A1 1 100 3 100 A2 20 10 A3 79 87 A4 B1 4.97 2.74 B2 1.64 1.85 B3 3.33 0.89 C1 0.01 0.01 0.01 0.01 D1 1 1 1 1 D2 D3 D4 E1 10 0.1 0.1 E2 10 F1 0 0 F2 G1 1.61 0.02 0.69 5.80 1.78 0.06 0.24 5.20 G2 2.42 0.03 1.03 2.67 0.09 0.36 G3 H 0.43 0.17 0.60 0.46 0.06 0.52 Water 318.1 4.0 135.4 (457.5) 350.5 11.9 47.3 (409.7) Sx components .sup.1) 80.6 1.0 34.3 115.9 88.8 3.0 12.0 103.8 Molar ratio 1 .sup.2) 2.0 0 7.5 2.8 2.1 0 2.0 2.0 Molar ratio 2 .sup.3) 2.0 0 2.0 2.0 2.1 0 2.0 2.0 Evaluation Results Appearance Stability Viscosity 70 50 50 60 70 60 60 70 (mPa .Math. s) Average particle 600 900 900 800 600 900 900 600 size (nm) Wettability Initial Initial Over time Over time Leveling ability Initial Initial Over time Over time Transparency Initial Initial Over time Over time Release force 0.37 0.23

(43) TABLE-US-00010 TABLE 10 Example 18 and 19 formulations Example 18 Example 19 Total Total Composition Composition Composition (coating Composition Composition Composition (coating 1 2 3 composition) 1 2 3 composition) A1 3 100 3 100 A2 10 20 A3 87 77 A4 B1 2.74 4.97 B2 1.85 1.64 B3 0.89 3.33 C1 0.01 0.01 0.01 0.01 D1 1 1 1 1 D2 D3 D4 E1 1 1 10 E2 10 F1 0 0 F2 G1 1.78 0.06 0.26 1.57 0.06 0.69 G2 2.67 0.09 0.39 5.25 2.36 0.09 1.03 5.80 G3 H 0.47 0.06 0.53 0.42 0.17 0.59 Water 350.5 11.9 50.8 (413.2) 310.2 11.9 133.4 (457.5) Sx components .sup.1) 88.8 3.0 12.9 104.7 78.6 3.0 34.3 115.9 Molar ratio 1 .sup.2) 2.1 0 2.0 2.0 2.1 0 7.5 2.8 Molar ratio 2 .sup.3) 2.1 0 2.0 2.0 2.1 0 2.0 2.0 Evaluation Results Appearance Stability Viscosity 70 60 60 70 70 60 50 70 (mPa .Math. s) Average particle 600 900 800 600 600 900 900 600 size (nm) Wettability Initial Initial Over time Over time Leveling ability Initial Initial Over time Over time Transparency Initial Initial Over time Over time Release force 0.23 0.40

(44) TABLE-US-00011 TABLE 11 Example 20 to 22 formulations Example 20 Example 21 Example 22 Total Total Total Ingredients Composition Composition (coating Composition Composition (coating Composition Composition (coating (pbw) 1 2 composition) 1 2 composition) 1 2 composition) A1 2 100 2 100 2 100 A2 49 A3 A4 98 98 49 B1 3.87 3.87 5.75 7.25 B2 5.75 7.25 B3 C1 0.01 0.01 0.01 0.01 0.01 0.01 D1 2 2 2 D2 D3 D4 2 2 2 E1 2 2 2 2 E2 2 2 F1 2 2 10 10 F2 10 10 G1 5.50 5.98 4.01 G2 3.24 0.06 3.53 0.06 2.39 0.04 G3 2.16 0.04 2.35 0.04 1.55 0.03 H 0.55 0.55 0.60 0.60 0.61 0.61 Water 425.5 7 9 (433.4) 464.5 7.9 (472.4) 472.5 8.0 (480.5) Sx components .sup.1) 107.9 2.0 109.9 117.7 2.0 119.7 119.3 2.0 121.3 Molar ratio 1 .sup.2) 2.2 0 2.1 3.8 0 3.8 3.2 0 3.1 Molar ratio 2 .sup.3) 2.2 0 2.1 1.4 0 1.4 1.5 0 1.5 Evaluation Results Appearance Stability Viscosity 70 60 70 60 60 60 40 50 40 (mPa .Math. s) Average particle 500 800 500 800 800 800 1,700 1,300 400 size (nm) Wettability Initial Initial Initial Over time Over time Over time Leveling ability Initial Initial Initial Over time Over time Over time Transparency Initial Initial Initial Over time Over time Over time Release force 0.24 0.40 0.35