METHOD FOR PRODUCING ORGANOPOLYSILOXANE CURED PRODUCT, ORGANOPOLYSILOXANE CURED PRODUCT, LAYERED PRODUCT, AND OPTICAL PART

Abstract

Provided is a cured product using a composition that is capable of quick curing at low temperatures while having sufficient pot life at room temperature, a method of producing the same, a laminate, and an optical device. A method of producing an organopolysiloxane cured product is provided. The method includes: (i) performing, without irradiating with high-energy radiation, a hydrosilylation reaction upon a composition containing a first hydrosilylation reaction catalyst that exhibits activity in the composition and a second hydrosilylation reaction catalyst that does not exhibit activity when not irradiated with high-energy radiation, but exhibits activity in the composition when irradiated with high-energy radiation, to obtain a thickened material that is fluid at room temperature or a thermoplastic material that is non-fluid at room temperature but exhibits fluidity at 100° C.; and (ii) irradiating the thickened material or thermoplastic material obtained in step (i) with high-energy radiation to obtain a cured product.

Claims

1. A method of producing an organopolysiloxane cured product, the method including: (i) performing, without irradiating with high-energy radiation, a hydrosilylation reaction upon a composition comprising: (A) through (D): (A) an organopolysiloxane represented by the following average composition formula (1):
R.sup.1.sub.aR.sup.2.sub.bSiO.sub.(4−a−b)/2   (1); wherein R.sup.1 is an alkenyl group comprising 2-12 carbon atoms; R.sup.2 is a group selected from a monovalent hydrocarbon group comprising 1-12 carbon atoms and not comprising an aliphatic unsaturated bond, a hydroxyl group and an alkoxy group; and a and b are numbers satisfying the following conditions: 1≤a+b≤3 and 0.001≤a/(a+b)≤0.33; (B) an organopolysiloxane represented by the following average composition formula (2):
H.sub.cR.sup.3.sub.dSiO.sub.(4−c−d)/2   (2); wherein R.sup.3 is a group selected from a monovalent hydrocarbon group comprising 1-12 carbon atoms and not comprising an aliphatic unsaturated bond, a hydroxyl group, and an alkoxy group; and c and d are numbers satisfying the following conditions: 1≤c+d≤3 and 0.01≤c/(c+d)≤0.33; (C) a first hydrosilylation reaction catalyst that exhibits activity in the composition without being irradiated with high-energy radiation; and (D) a second hydrosilylation reaction catalyst that does not exhibit activity when not irradiated with high-energy radiation, but exhibits activity in the composition when irradiated with high-energy radiation; to obtain a thickened material that is fluid at room temperature, or a thermoplastic material that is non-fluid at room temperature but exhibits fluidity at 100° C.; and (ii) irradiating the thickened material or thermoplastic material obtained in step (i) with high-energy radiation.

2. The method of producing an organopolysiloxane cured product according to claim 1, wherein the high-energy radiation is selected from the group consisting of ultraviolet radiation, gamma radiation, X-ray radiation, alpha radiation, and electron beam radiation.

3. The method of producing an organopolysiloxane cured product according to claim 1, wherein component (B) is an organohydrogen polysiloxane represented by the following average unit formula (3):
(HR.sup.4.sub.2SiO.sub.1/2).sub.e(R.sup.4.sub.3SiO.sub.1/2).sub.f(HR.sup.4SiO.sub.2/2).sub.g(R.sup.4.sub.2SiO.sub.2/2).sub.h(HSiO.sub.3/2).sub.i(R.sup.4SiO.sub.3/2).sub.j(SiO.sub.4/2).sub.k(R.sup.5O.sub.1/2).sub.l   (3); wherein each R.sup.4 is, independently, a group selected from a monovalent hydrocarbon group comprising 1-12 carbon atoms and not comprising an aliphatic unsaturated bond, a hydroxyl group, and an alkoxy group; R.sup.5 is a hydrogen atom or an alkyl group comprising 1-6 carbon atoms; and e, f, g, h, i, j, k, and 1 are numbers satisfying the following conditions: e+f+g+h+i+j+k=1, 0≤1≤0.1, 0.01≤e+g+i≤0.2, 0≤e≤0.6, 0≤g≤0.6, 0≤i≤0.4, 0.01≤e+f≤0.8, 0.01≤g+h≤0.8, 0≤i+j≤0.6.

4. The method of producing an organopolysiloxane cured product according to claim 1, wherein the molar ratio ((C)/(D)) of component (C) and component (D) is 0.001-1000.

5. An organopolysiloxane cured product produced via the method according to claim 1.

6. A laminate wherein an organopolysiloxane cured product produced via the method according to claim 1 is disposed between layers.

7. The laminate according to claim 6, wherein the product is an image display device.

8. An optical device comprising an organopolysiloxane cured product produced via the method according to claim 1.

9. The method of manufacturing a laminate according to claim 15, the method including: (iii) applying the composition comprising components (A) through (D) to a substrate, and performing a hydrosilylation reaction without irradiating with high-energy radiation to form a layer of a thickened material that is fluid at room temperature, or a thermoplastic material that is non-fluid at room temperature but exhibits fluidity at 100° C.; (iv) forming an upper layer member over the layer of thickened material or thermoplastic material obtained in step (iii); and (v) irradiating the layer of thickened material or thermoplastic material with high-energy radiation from at least one of below the substrate, above the upper layer member, and the side of the layer of thickened material or thermoplastic material.

10. The method of manufacturing a laminate according to claim 15, the method including: (vi) applying the composition comprising components (A) through (D) to a substrate, and performing a hydrosilylation reaction without irradiating with high-energy radiation to form a layer of a thickened material that is fluid at room temperature, or a thermoplastic material that is non-fluid at room temperature but exhibits fluidity at 100° C.; (vii) irradiating the layer of thickened material or thermoplastic material obtained in step (vi) with high-energy radiation; (viii) forming an upper layer member over the layer of thickened material or thermoplastic material following irradiation with the high-energy radiation; and (ix) curing the layer of thickened material or thermoplastic material by heating or letting stand at room temperature.

11. The method of manufacturing a laminate according to claim 15, the method including: (x) applying the composition comprising components (A) through (D) to a substrate, and performing a hydrosilylation reaction without irradiating with high-energy radiation to form a layer of a thickened material that is fluid at room temperature, or a thermoplastic material that is non-fluid at room temperature but exhibits fluidity at 100° C.; (xi) irradiating the layer of thickened material or thermoplastic material obtained in step (x) with high-energy radiation; (xii) forming an upper layer member over the layer of thickened material or thermoplastic material following irradiation with the high-energy radiation; and (xiii) irradiating the layer of thickened material or thermoplastic material with high-energy radiation from at least one of below the substrate, above the upper layer member, and the side of the layer of thickened material or thermoplastic material.

12. A laminate obtained via the method according to claim 9.

13. A method of forming an optical device on the surface of which is formed an organopolysiloxane cured product, the method including: (xiv) applying a composition comprising (A) an organopolysiloxane represented by the following average composition formula (1):
R.sup.1.sub.aR.sup.2.sub.bSiO.sub.(4−a−b)/2   (1); wherein R.sup.1 is an alkenyl group comprising 2-12 carbon atoms; R.sup.2 is a group selected from a monovalent hydrocarbon group comprising 1-12 carbon atoms and not comprising an aliphatic unsaturated bond, a hydroxyl group and an alkoxy group; and a and b are numbers satisfying the following conditions: 1≤a+b≤3 and 0.001≤a/(a+b)≤0.33; (B) an organopolysiloxane represented by the following average composition formula (2):
H.sub.cR.sup.3.sub.dSiO.sub.(4−c−d)/2   (2); wherein R.sup.3 is a group selected from a monovalent hydrocarbon group comprising 1-12 carbon atoms and not comprising an aliphatic unsaturated bond, a hydroxyl group, and an alkoxy group; and c and d are numbers satisfying the following conditions: 1≤c+d≤3 and 0.01≤c/(c+d)≤0.33; (C) a first hydrosilylation reaction catalyst that exhibits activity in the composition without being irradiated with high-energy radiation; and (D) a second hydrosilylation reaction catalyst that does not exhibit activity when not irradiated with high-energy radiation, but exhibits activity in the composition when irradiated with high-energy radiation; to a release film, and performing a hydrosilylation reaction without irradiating with high-energy radiation to form a thermoplastic film that is non-fluid at room temperature but exhibits fluidity at 100° C.; (xv) disposing the thermoplastic film on an optical device, and heating; and (xvi) irradiating the thermoplastic film obtained in step (xv), or a melt thereof, with high-energy radiation.

14. An optical device obtained via the method according to claim 13.

15. A method of manufacturing a laminate in which an organopolysiloxane cured product is disposed between layers, the method including providing a composition comprising: (A) an organopolysiloxane represented by the following average composition formula (1):
R.sup.1.sub.aR.sup.2.sub.bSiO.sub.(4−a−b)/2   (1); wherein R.sup.1 is an alkenyl group comprising 2-12 carbon atoms; R.sup.2 is a group selected from a monovalent hydrocarbon group comprising 1-12 carbon atoms and not comprising an aliphatic unsaturated bond, a hydroxyl group and an alkoxy group; and a and b are numbers satisfying the following conditions: 1≤a+b≤3 and 0.001≤a/(a+b)≤0.33; (B) an organopolysiloxane represented by the following average composition formula (2):
H.sub.cR.sup.3.sub.dSiO.sub.(4−c−d)/2   (2); wherein R.sup.3 is a group selected from a monovalent hydrocarbon group comprising 1-12 carbon atoms and not comprising an aliphatic unsaturated bond, a hydroxyl group, and an alkoxy group; and c and d are numbers satisfying the following conditions: 1≤c+d≤3 and 0.01≤c/(c+d)≤0.33; (C) a first hydrosilylation reaction catalyst that exhibits activity in the composition without being irradiated with high-energy radiation; and (D) a second hydrosilylation reaction catalyst that does not exhibit activity when not irradiated with high-energy radiation, but exhibits activity in the composition when irradiated with high-energy radiation.

16. A laminate obtained via the method according to claim 10.

17. A laminate obtained via the method according to claim 11.

Description

EXAMPLES

[0095] Cured products were obtained from compositions containing the components described below. In the various average composition formulas, Me, Ph, and Vi respectively represent a methyl group, a phenyl group, and a vinyl group.

Example 1

[0096] A composition containing 3.5 parts by weight of a vinyl-terminated branched-chain polysiloxane (A-1) represented by the average unit formula (Me.sub.2ViSiO.sub.1/2).sub.0.044(Me.sub.3SiO.sub.1/2).sub.0.411(SiO.sub.4/2).sub.0.545, 89.7 parts by weight of a vinyl-terminated straight-chain polysiloxane (A-2) represented by the average unit formula ViMe.sub.2SiO(SiMe.sub.2O).sub.322SiMe.sub.2Vi, 6.8 parts by weight of a straight-chain polysiloxane (B-1) represented by the average unit formula HMe.sub.2SiO(SiMe.sub.2O).sub.10SiMe.sub.2H, 5 ppm platinum atoms in the form of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (C-1), and 20 ppm platinum atoms in the form of (methylcyclopentadienyl)trimethylplatinum(IV) (D-1) was prepared. The viscosity of the composition was 1,800 mPa.Math.s. Following preparation, the composition was left standing for 10 minutes, then thickened to a viscosity of 3,200 mPa.Math.s, and irradiated with a 2 W high-pressure mercury-vapor lamp equipped with an ozone-cutting filter so that the dose of 365 nm ultraviolet radiation was 5,000 mJ/cm.sup.2. Measurement immediately following irradiation showed that the composition had increased to a viscosity of 30,000 mPa.Math.s or higher while retaining fluidity; however, it was confirmed that the composition gelled and become non-fluid five minutes after UV irradiation. Measurement of the cured product with a hardness probe at 10-minute intervals showed that the cured product stabilized at a constant probe depth of 32 1 hour after UV irradiation, confirming that the curing reaction was complete.

Example 2

[0097] A composition containing 3.5 parts by weight of A-1, 6.5 parts by weight of A-2, 82.4 parts by weight of a vinyl-terminated straight-chain polysiloxane (A-3) represented by the average composition formula ViMe.sub.2SiO(SiMe.sub.2O).sub.535SiMe.sub.2Vi, 4.6 parts by weight of B-1, 10 ppm platinum atoms in the form of C-1, and 20 ppm platinum in the form of D-1 was prepared. The viscosity of the composition was 8,200 mPa.Math.s. Following preparation, the composition was left standing for 10 minutes, then thickened to a viscosity of 14,000 mPa.Math.s, and irradiated with a 2 W high-pressure mercury-vapor lamp with an ozone-cutting filter so that the dose of 365 nm ultraviolet radiation was 2,500 mJ/cm.sup.2. Measurement immediately following irradiation showed that the composition had increased to a viscosity of 50,000 mPa.Math.s or higher while retaining fluidity; however, it was confirmed that the composition gelled and become non-fluid 10 minutes after UV irradiation. Measurement of the cured product with a hardness probe at 10-minute intervals showed that the cured product stabilized at a constant probe depth of 35 1 hour after UV irradiation, confirming that the curing reaction was complete.

Example 3

[0098] A composition containing 55.7 parts by weight of a vinyl-terminated branched-chain polysiloxane (A-4) represented by the average unit formula (Me.sub.2ViSiO.sub.1/2).sub.0.1(Me.sub.3SiO.sub.1/2).sub.0.4(SiO.sub.4/2).sub.0.5, 13.3 parts by weight of a branched-chain polysiloxane (E-1) represented by the average unit formula (Me.sub.3SiO.sub.1/2).sub.0.44(SiO.sub.4/2).sub.0.56, 1.7 parts by weight of a vinyl-terminated straight-chain polysiloxane (A-3) represented by the average unit formula ViMe.sub.2SiO(SiMe.sub.2O).sub.160SiMe.sub.2Vi, 24.6 parts by weight of a straight-chain polysiloxane (B-2) represented by the average unit formula HMe.sub.2SiO(SiMe.sub.2O).sub.400SiMe.sub.2H, 4.7 parts by weight of a straight-chain polysiloxane (B-3) represented by the average unit formula Me.sub.3SiO(SiMe.sub.2O).sub.30(SiMeHO).sub.30SiMe.sub.3, 0.2 ppm platinum atoms in the form of C-1, and 5 ppm platinum atoms in the form of D-1 was prepared. The viscosity of the composition was 3,500 mPa.Math.s. The composition was heated to 90° C. for 30 minutes to obtain a thermoplastic material that was non-fluid at 25° C. but fluid at 100° C. The obtained thermoplastic material did not lose fluidity at 100° C. even after being stored at 25° C. for two months. The thermoplastic material was irradiated with a 2,500 mJ/cm.sup.2 dose of 365 nm ultraviolet radiation using a 2 W high-pressure mercury-vapor lamp equipped with an ozone-cutting filter, then heated to 120° C. for 30 minutes to obtain a cured product having a Shore D hardness of 80.

Example 4

[0099] A composition containing 32.2 parts by weight of A-4, 28.5 parts by weight of E-1, 20.7 parts by weight of A-3, 15.7 parts by weight of B-2, 2.9 parts by weight of B-3, 0.1 ppm platinum atoms in the form of C-1, and 5 ppm platinum atoms in the form of D-1 was prepared. The viscosity of the composition was 2,800 mPa.Math.s. The composition was heated to 90° C. for 30 minutes to obtain a thermoplastic material that was non-fluid at 25° C. but fluid at 100° C. The obtained thermoplastic material did not lose fluidity at 100° C. even after being stored at 25° C. for two months. The thermoplastic material was irradiated with a 2,500 mJ/cm.sup.2dose of 365 nm ultraviolet radiation using a 2 W high-pressure mercury-vapor lamp equipped with an ozone-cutting filter, then heated to 120° C. for 30 minutes to obtain a cured product having a Shore D hardness of 35.

Example 5

[0100] Using a bar coater, the composition of example 1 was applied to a thickness of 200 μm on a member formed by joining a liquid crystal panel and a polarizer plate. Following application, irradiation with a 5,000 mJ/cm.sup.2 dose of 365 nm ultraviolet radiation was performed within 5 minutes using a conveyor-type UV irradiation apparatus. A cover glass was placed thereover within 3 minutes following irradiation, and left standing at room temperature. At first, the cover glass moved when force was applied in the lateral direction; however, it began to resist movement 5 minutes after UV irradiation, and ceased to move altogether after 30 minutes.

Example 6

[0101] A composition containing 93.6 weight % of a vinyl-terminated straight-chain polysiloxane (A-5) represented by the average composition formula ViMe.sub.2SiO(SiMePhO).sub.36SiMe.sub.2Vi, 1.0 weight % of a vinyl-group-comprising polysiloxane (A-6) represented by the average composition formula (ViMe.sub.2SiO.sub.1/2)0.22(MeXSiO.sub.2/2)0.12(PhSiO.sub.3/2)0.66 (wherein X represents a glycidoxypropyl group), 3.9 weight % of a straight-chain polysiloxane (B-3) represented by the molecular formula Ph.sub.2Si(OSiMe.sub.2H).sub.2, 1.3 weight % of a branched polysiloxane (B-4) represented by the average composition formula (HMe.sub.2SiO.sub.1/2).sub.0.6(PhSiO.sub.3/2).sub.0.4, 0.2 weight % glycidoxypropyltrimethoxysilane, 5 ppm platinum atoms in the form of C-1, and 20 ppm platinum atoms in the form of D-1 was prepared. The viscosity of the composition was 6,000 mPa.Math.s. When left standing at 25° C. for 10 minutes, the composition yielded a thickened material having a viscosity of about 12,000 mPa.Math.s. The thermoplastic material was irradiated with a 2,500 mJ/cm.sup.2 dose of ultraviolet radiation using a 2 W high-pressure mercury-vapor lamp equipped with an ozone-cutting filter. Following UV irradiation, the composition had transformed into a fluid gel after 15 minutes at 25° C., and a cured product having a probe depth of 35 was obtained after 40 minutes at 25° C.

Comparative Example 1

[0102] A composition containing 3.5 parts by weight of A-1, 89.7 parts by weight of A-2, 6.8 parts by weight of B-1, and 60 ppm platinum atoms in the form of C-1 was prepared. The viscosity of the composition was 1,800 mPa.Math.s. The composition began generating heat immediately after being prepared, and gelled and became non-fluid after 1 minute. As curing had progressed too rapidly, it was impossible to prepare a sample for probe depth measurement, and the cured product exhibited reddish-brown discoloration.

Comparative Example 2

[0103] A composition containing 3.5 parts by weight of A-1, 89.7 parts by weight of A-2, 6.8 parts by weight of B-1, and 20 ppm platinum atoms in the form of D-1 was prepared. The viscosity of the composition was 1,800 mPa.Math.s. After being prepared, the composition was left standing for 10 minutes to reach a constant viscosity of 1,800 mPa.Math.s, then irradiated with a 5,000 mJ/cm.sup.2 dose of 365 nm ultraviolet radiation using a 2 W high-pressure mercury-vapor lamp equipped with an ozone-cutting filter; measurement immediately following irradiation showed that viscosity had increased to 3,200 mPa.Math.s. As the composition did not gel even after 1 hour post-irradiation, the composition was heated to 100° C., whereupon it was confirmed that the composition had finally become non-fluid after 30 minutes.

Comparative Example 3

[0104] A composition containing 55.7 parts by weight of A-4, 13.3 parts by weight of E-1, 1.7 parts by weight of A-3, 24.6 parts by weight of B-2, 4.7 parts by weight of B-, and 2 ppm platinum atoms in the form of C-1 was prepared. The viscosity of the composition was 3,500 mPa.Math.s. The composition was heated to 90° C. for 30 minutes to obtain a cured product having a Shore A hardness of 80. When the composition was heated to 50° C. for 30 minutes to obtain a softer composition, a cured product having a Shore A hardness of 40 was obtained. However, the obtained cured product did not exhibit fluidity at high temperatures, and gradually hardened over time, reaching a Shore A hardness of 75 after 2 weeks at 25° C.

Comparative Example 4

[0105] A composition containing 32.2 parts by weight of A-4, 28.5 parts by weight of E-1, 20.7 parts by weight of A-3, 15.7 parts by weight of B-2, 2.9 parts by weight of B-3, 0.1 ppm platinum atoms in the form of C-1, and 5 ppm platinum atoms in the form of D-1 was prepared. The viscosity of the composition was 2,800 mPa.Math.s. The composition was heated to 90° C. for 30 minutes, but no change whatsoever was observed in the composition.

Comparative Example 5

[0106] A composition containing 94.0 parts by weight of A-2, 4.1 parts by weight of B-2, 1.4 parts by weight of B-3, and 5 ppm platinum atoms in the form of C-1 was prepared. The viscosity of the composition was 2,100 mPa.Math.s. The composition gelled after 30 minutes at 25° C.

Comparative Example 6

[0107] Using a bar coater, the composition of comparative example 2 was applied to a thickness of 200 μm on a member formed by joining a liquid crystal panel and a polarizer plate. Following application, irradiation with a 5,000 mJ/cm.sup.2 dose of 365 nm ultraviolet radiation was performed within 5 minutes using a conveyor-type UV irradiation apparatus. A cover glass was placed thereover within 3 minutes following irradiation, and left standing at room temperature. Liquid gradually seeped from the edges of the cover glass, and the composition did not cure even after 30 minutes following UV irradiation.

Comparative Example 7

[0108] A composition containing 93.6 weight % of A-5, 1.0 weight % of A-6, 3.9 weight % of B-3, 1.3 weight % of B-4, 0.2 weight % of glycidoxypropyltrimethoxysilane, and 5 ppm platinum atoms in the form of C-1 was prepared. The viscosity of the composition was 6,000 mPa.Math.s. When left standing at 25° C. for 10 minutes, the composition yielded a thickened material having a viscosity of about 12,000 mPa.Math.s. The thermoplastic material was irradiated with a 2,500 mJ/cm.sup.2 dose of 365 nm ultraviolet radiation using a 2 W high-pressure mercury-vapor lamp equipped with an ozone-cutting filter. The composition gradually became fluid and had changed to a gel after 60 minutes at 25° C. following UV irradiation, but the probe depth continued to deepen even after 2 hours at 25° C., revealing that the curing reaction was not complete.

INDUSTRIAL APPLICABILITY

[0109] The method of producing an organopolysiloxane cured product according to the present invention yields a product that is capable of rapidly curing at low temperature while having sufficient pot life at room temperature, and thus is advantageous as a method for forming an inter-layer laminate of an image display device.