Organopolysiloxane composition, and half-cured product and cured product produced from same

Abstract

Provided is a hydrosilylation reactive composition that has a sufficient pot life at room temperature, that can be cured at low temperature by exposure to high energy radiation, and that produces a stable semi-cured product during the curing process, and to provide a semi-cured product and a cured product obtained using this hydrosilylation reactive composition. The composition comprises: (A) a compound containing at least one aliphatically unsaturated monovalent hydrocarbon group in the molecule; (B) a compound containing at least two hydrogen atoms bonded to silicon atoms in the molecule; (C) a first hydrosilylation catalyst exhibiting activity in the composition without exposure to high energy radiation; and (D) a second hydrosilylation catalyst not exhibiting activity unless exposed to high energy radiation, and exhibiting activity in the composition by exposure to high energy radiation.

Claims

1. A composition comprising: (A) a compound containing at least one aliphatically unsaturated monovalent hydrocarbon group in the molecule; (B) a compound containing at least two hydrogen atoms bonded to silicon atoms in the molecule; (C) a first hydrosilylation catalyst exhibiting activity in the composition without exposure to high energy radiation; and (D) a second hydrosilylation catalyst not exhibiting activity unless exposed to high energy radiation, and exhibiting activity in the composition by exposure to high energy radiation; wherein component (B) comprises an organohydrogenpolysiloxane represented by average composition 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); where R.sup.4 is a group selected from among an aliphatic unsaturated bond-free monovalent hydrocarbon group, a hydroxyl group and an alkoxy group having from 1 to 12 carbon atoms, R.sup.5 is a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms, and e, f, g, h, i, j, k and l are numbers that satisfy the following conditions: e+f+g+h+i+j+k=1, 0≤1≤0.1, 0.01≤e+g+i≤0.2, 0.01≤e≤0.6, 0.01≤g≤0.6, 0≤i≤0.4, 0.01≤e+f≤0.8, 0.01≤g+h≤0.8, and 0≤i+j≤0.6.

2. The composition 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 composition according to claim 1, wherein component (A) is an organopolysiloxane.

4. The composition according to claim 1, wherein component (A) is an organopolysiloxane represented by average composition formula (1):
R.sup.1.sub.aR.sup.2.sub.bSiO.sub.(4-a-b)/2  (1); where R.sup.1 is an alkenyl group having from 2 to 12 carbon atoms, R.sup.2 is a group selected from among an aliphatic unsaturated bond-free monovalent hydrocarbon group, a hydroxyl group and an alkoxy group having from 1 to 12 carbon atoms, and a and b are numbers that satisfy the following conditions: 1≤a+b≤3 and 0.001≤a/(a+b)≤0.33.

5. The composition according to claim 1, wherein the molar ratio ((C/(D)) of component (C) to component (D) is from 0.001 to 1,000.

6. The composition according to claim 1, wherein component (C) is at least one transition metal complex catalyst selected from the group consisting of platinum, palladium, rhodium, nickel, iridium, ruthenium, and iron complexes.

7. The composition according to claim 1, wherein component (D) is at least one catalyst selected from the group consisting of (substituted and unsubstituted cyclopentadienyl) trimethylplatinum (IV), β-diketonato trimethylplatinum (IV), and bis (β-diketonato) platinum (II).

8. A semi-cured product obtained by conducting a first hydrosilylation reaction on the composition according to claim 1 without exposure to high energy radiation.

9. A cured product obtained by exposing the semi-cured product according to claim 8 to high energy radiation.

10. A method for manufacturing a laminate, the method comprising: i) arranging the composition according to claim 1 on one or both surfaces of at least one of two optical members; ii) exposing the composition arranged in step i) to high energy radiation until the composition is in a non-fluid semi-cured state; iii) bonding the two optical members together via the curable silicone composition in a semi-cured state after step ii); and iv) conducting a hydrosilylation reaction on the composition in a semi-cured state in the two optical members bonded in step iii) in a temperature range from 15 to 80° C. to cure the composition.

11. The method for manufacturing a laminate according to claim 10, wherein the laminate is an optical display.

12. A method for manufacturing a laminate, the method comprising i) arranging the composition according to claim 1 on one or both surfaces of at least one of two optical members, at least one of the members being a transparent optical member; ii) conducting a hydrosilylation reaction on the composition arranged in step i) in a temperature range from 15 to 80° C. until the composition is in a non-fluid semi-cured state; iii) bonding the two optical members together via the curable silicone composition in a semi-cured state after step ii); and iv) exposing the curable silicone composition to high energy radiation in the two optical members bonded in step iii) via the transparent optical member and then conducting a hydrosilylation reaction on the composition in a semi-cured state in a temperature range from 15 to 80° C. to cure the composition.

13. The method for manufacturing a laminate according to claim 12, wherein the laminate is an optical display.

Description

EXAMPLES

(1) Cured products were obtained using compositions with the following components. In the average composition formulas, Me and Vi refer to methyl groups and vinyl groups, respectively.

Example 1

(2) A composition was prepared comprising: 3.5 parts by weight of a vinyl-capped branched polysiloxane (A-1) represented by the average composition 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-capped linear polysiloxane (A-2) represented by the average composition formula: ViMe.sub.2SiO(SiMe.sub.2O).sub.322SiMe.sub.2Vi; 6.8 parts by weight of a linear polysiloxane (B-1) represented by the average composition formula: HMe.sub.2SiO(SiMe.sub.2O).sub.10SiMe.sub.2H; 5 ppm of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (C-1) in terms of platinum atoms; and 20 ppm of (methylcyclopentadienyl) trimethylplatinum (IV) (D-1) in terms of platinum atoms. The viscosity of the composition was 1,800 mPa.Math.s. After preparing the composition and allowing it to stand for 10 minutes to reach a viscosity of 3,200 mPa.Math.s, the composition was exposed via an ozone cut filter to a 2 W high-pressure mercury lamp at a 365-nm UV exposure level of 5,000 mJ/cm.sup.2. The viscosity measured immediately thereafter was above 30,000 mPa.Math.s, but the composition remained fluid. It became a non-fluid gel after 5 more minutes of UV exposure. When the hardness of the cured product was measured by penetration every 10 minutes, the hardness stabilized at a penetration of 32 after one hour of UV exposure indicating the curing reaction was complete.

Example 2

(3) A composition was prepared comprising: 3.5 parts by weight of A-1; 6.5 parts by weight of A-2; 82.4 parts by weight of a vinyl-capped linear 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 of C-1 in terms of platinum atoms; and 20 ppm of D-1 in terms of platinum atoms. The viscosity of the composition was 8,200 mPa.Math.s. After preparing the composition and allowing it to stand for 10 minutes to reach a viscosity of 14,000 mPa.Math.s, the composition was exposed via an ozone cut filter to a 2 W high-pressure mercury lamp at a 365-nm UV exposure level of 2,500 mJ/cm.sup.2. The viscosity measured immediately thereafter was above 50,000 mPa.Math.s, but the composition remained fluid. It became a non-fluid gel after 10 more minutes of UV exposure. When the hardness of the cured product was measured by penetration every 10 minutes, the hardness stabilized at a penetration of 35 after one hour of UV exposure indicating the curing reaction was complete.

Example 3

(4) A composition was prepared comprising: 55.7 parts by weight of a vinyl-capped branched polysiloxane (A-4) represented by the average composition 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 polysiloxane (E-1) represented by the average composition 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-capped linear polysiloxane (A-3) represented by the average composition formula: ViMe.sub.2SiO(SiMe.sub.2O).sub.160SiMe.sub.2Vi; 24.6 parts by weight of a linear polysiloxane (B-2) represented by the average composition formula: HMe.sub.2SiO(SiMe.sub.2O).sub.400SiMe.sub.2H; 4.7 parts by weight of a linear polysiloxane (B-3) represented by the average composition formula: Me.sub.3SiO(SiMe.sub.2O).sub.30(SiMeHO).sub.30SiMe.sub.3; 0.2 ppm of C-1 in terms of platinum atoms; and 5 ppm of D-1 in terms of platinum atoms. The viscosity of the composition was 3,500 mPa.Math.s. The composition was heated for 30 minutes at 90° C. A thermoplastic material was obtained that was not fluid at 25° C. but was fluid at 100° C. Even after two months in storage at 25° C., the resulting thermoplastic material did not lose fluidity at 100° C. After exposure via an ozone cut filter to a 2 W high-pressure mercury lamp at a 365-nm UV exposure level of 2,500 mJ/cm.sup.2 and then heated for 30 minutes at 120° C., the thermoplastic material became a cured product with a Shore A hardness of 80.

Example 4

(5) A composition was prepared comprising: 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 of C-1 in terms of platinum atoms; and 5 ppm of D-1 in terms of platinum atoms. The viscosity of the composition was 2,800 mPa.Math.s. The composition was heated for 30 minutes at 90° C. A thermoplastic material was obtained that was not fluid at 25° C. but was fluid at 100° C. Even after two months in storage at 25° C., the resulting thermoplastic material did not lose fluidity at 100° C. After exposure via an ozone cut filter to a 2 W high-pressure mercury lamp at a 365-nm UV exposure level of 2,500 mJ/cm.sup.2 and then heated for 30 minutes at 120° C., the thermoplastic material became a cured product with a Shore A hardness of 35.

Example 5

(6) A composition was prepared comprising: 93.6 wt % vinyl-capped polysiloxane (A-5) represented by the average composition formula: ViMe.sub.2SiO(SiMePhO).sub.36SiMe.sub.2Vi; 1.0 wt % vinyl group-containing polysiloxane (A-6) represented by the average composition formula: (ViMe.sub.2SiO.sub.1/2).sub.0.22(MeXSiO.sub.2/2).sub.0.12(PhSiO.sub.3/2).sub.0.66 (where X represents a glycidoxypropyl group); 3.9 wt % linear polysiloxane (B-3) represented by the molecular formula: Ph.sub.2Si(OSiMe.sub.2H).sub.2; 1.3 wt % 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 wt % glycidoxypropyltrimethoxysilane; 5 ppm of C-1 in terms of platinum atoms; and 20 ppm of D-1 in terms of platinum atoms. The viscosity of the composition was 6,000 mPa.Math.s. When the composition was allowed to stand for 10 minutes at 25° C., a viscous material with a viscosity of about 12,000 mPa.Math.s was obtained. The viscous material was exposed via an ozone cut filter to a 2 W high-pressure mercury lamp at a 365-nm UV exposure level of 2,500 mJ/cm.sup.2. Once 15 minutes had passed at 25° C. after UV exposure, the composition had changed into a non-fluid gel. Once 40 minutes had passed at 25° C., it had become a cured product with a penetration of 35.

Comparative Example 1

(7) A composition was prepared comprising: 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 of C-1 in terms of platinum atoms. The viscosity of the composition was 1,800 mPa.Math.s. After preparation of the composition, the composition immediately gave off heat and became a non-fluid gel after one minute. Curing occurred too quickly to prepare a sample for penetration measurement, and the composition turned dark brown.

Comparative Example 2

(8) A composition was prepared comprising: 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 of D-1 in terms of platinum atoms. The viscosity of the composition was 1,800 mPa.Math.s. After preparing the composition and allowing it to stand for 10 minutes to reach a constant viscosity of 1,800 mPa.Math.s, the composition was exposed via an ozone cut filter to a 2 W high-pressure mercury lamp at a 365-nm UV exposure level of 5,000 mJ/cm.sup.2. The viscosity measured immediately thereafter had reached 3,200 mPa.Math.s. It did not gel even after 1 more hour of UV exposure. Therefore, when heated to 100° C., it gradually became non-fluid after 30 minutes.

Comparative Example 3

(9) A composition was prepared comprising: 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 of C-1 in terms of platinum atoms. The viscosity of the composition was 3,500 mPa.Math.s. The composition was heated for 30 minutes at 90° C. to obtain a cured product with a Shore A hardness of 80. When the composition was heated for 30 minutes at 50° C. to obtain a softer cured product, a cured product with a Shore A hardness of 40 was obtained. The cured product did not exhibit high-temperature fluidity and became harder over time. After two weeks at 25° C., the cured product had a Shore A hardness of 75.

Comparative Example 4

(10) A composition was prepared comprising: 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 of C-1 in terms of platinum atoms; and 5 ppm of D-1 in terms of platinum atoms. The viscosity of the composition was 2,800 mPa.Math.s. The composition was heated for 30 minutes at 90° C., but no change in the composition was observed.

Comparative Example 5

(11) A composition was prepared comprising: 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 of C1 in terms of platinum atoms. The viscosity of the composition was 2,100 mPa.Math.s. The composition gelled after 30 minutes at 25° C.

Comparative Example 6

(12) A composition was prepared comprising: 93.6 wt % of A-5; 1.0 wt % of A-6; 3.9 wt % of B-3; 1.3 wt % of B-4; 0.2 wt % of glycidoxypropyltrimethoxysilane; and 5 ppm of C-1 in terms of platinum atoms. The viscosity of the composition was 6,000 mPa.Math.s. When the composition was allowed to stand for 10 minutes at 25° C., a viscous material with a viscosity of about 12,000 mPa.Math.s was obtained. The viscous material was exposed via an ozone cut filter to a 2 W high-pressure mercury lamp at a 365-nm UV exposure level of 2,500 mJ/cm.sup.2. Once 60 minutes had passed at 25° C. after UV exposure, the composition had changed into a non-fluid gel. Once 2 hours had passed at 25° C., the penetration continued to decline and the curing reaction remained incomplete.

INDUSTRIAL APPLICABILITY

(13) Because a composition of the present invention has a sufficient pot life at room temperature and can be cured at low temperature by exposure to high energy radiation, it can be used as an adhesive or pressure-sensitive adhesive between the layers of an image display device.