UV-curable silicone composition for stereolithography, cured product thereof, and method for producing cured product
Provided is a UV-curable silicone composition containing: (A) an organopolysiloxane having, in one molecule, two groups represented by formula (1) (R 1 is a monovalent hydrocarbon group, R 2 is an oxygen atom or an alkylene group, R 3 is an acryloyloxyalkyl group, etc., p represents a number satisfying 0≤p≤10, and a represents a number satisfying 1≤a≤3); (B) an organopolysiloxane resin which comprises (a) a unit represented by formula (2) (R 1 to R 3 , a and p are the same as above), (b) a R 4 3 SiO 1/2 unit (R 4 represents a monovalent hydrocarbon group), and (c) a SiO 4/2 unit, and in which a molar ratio of the sum of the unit (a) and the unit (b) and the unit (c) is 0.6 to 1.2:1; (C) a photopolymerization initiator; and (D) an organic peroxide, wherein the UV-curable silicone composition has a viscosity applicable to a stereolithography such as a laser process, can be shaped even with a small amount of UV irradiation, and forms a cured product exhibiting excellent rubber physical properties.
1. An ultraviolet-curable silicone composition for stereolithography, comprising:
(A) 100 parts by weight of a linear diorganopolysiloxane, each end of which is capped with a group of formula (1) below per molecule
wherein each R 1 is independently a substituted or unsubstituted monovalent hydrocarbon group of 1 to 20 carbon atoms, R 2 is an oxygen atom or an alkylene group of 1 to 20 carbon atoms, each R 3 is independently an acryloyloxyalkyl group, methacryloyloxyalkyl group, acryloyloxyalkyloxy group or methacryloyloxyalkyloxy group, p is a number that satisfies 0≤p≤10, the letter ‘a’ is a number that satisfies 1≤a≤3, and the dashed line represents an available bond;
(B) from 5 to 200 parts by weight of an organopolysiloxane resin comprising (a) units of formula (2) below
wherein R 1 , R 2 , R 3 , a and p are as defined above,
(b) R 4 3 SiO 1/2 units, wherein each R 4 is independently a substituted or unsubstituted monovalent hydrocarbon group of 1 to 10 carbon atoms, and (c) SiO 4/2 units, the molar ratio of the sum of (a) units and (b) units to (c) units being from 0.6:1 to 1.2:1;
(C) from 0.01 to 20 parts by weight of a photopolymerization initiator; and
(D) from 0.1 to 20 parts by weight of an organic peroxide,
wherein R 4 of units (b) in component (B) comprises a substituted or unsubstituted alkenyl group of 2 to 6 carbon atoms and further wherein the composition has a viscosity at 23° C. of not more than 10,000 mPa·s and is suitable for use in lithography.
2. The ultraviolet-curable silicone composition for stereolithography of claim 1 which has a viscosity at 23° C. of not more than 8,000 mPa·s.
3. The ultraviolet-curable silicone composition for stereolithography of claim 1 , further comprising (E) from 0.01 to 20 parts by weight of an ultraviolet absorber which absorbs light having wavelengths between 360 and 410 nm per 100 parts by weight of component (A).
4. The ultraviolet-curable silicone composition for stereolithography of claim 1 , further comprising (F) from 0.01 to 20 parts by weight of a colorant per 100 parts by weight of component (A).
5. A cured product of the ultraviolet-curable silicone composition for stereolithography of claim 1 .
6. A method for producing the cured product of claim 5 , comprising the steps of irradiating the ultraviolet-curable silicone composition for stereolithography with from 1 to 200 mJ/cm 2 of ultraviolet light, and then curing at between 50° C. and 200° C.
7. The ultraviolet-curable silicone composition for stereolithography of claim 1 , wherein “a” in formula (1) is 2.
8. The ultraviolet-curable silicone composition for stereolithography of claim 1 , wherein component (A) has the following formula (5):
wherein R 1 is as defined above, R 5 is an alkylene group of 1 to 10 carbon atoms, Me represents a methyl group, and “b” is a number which satisfies 1≤b≤4, “n” is a number that sets the viscosity of the organopolysiloxane to 10 to 10,000 mPa·s.
9. The ultraviolet-curable silicone composition for stereolithography of claim 1 which has a viscosity at 23° C. of at least 100 mPa·s and not more than 10,000 mPa·s.
10. The ultraviolet-curable silicone composition for stereolithography of claim 1 which has a viscosity at 23° C. of at least 500 mPa·s and not more than 10,000 mPa·s.
11. The ultraviolet-curable silicone composition for stereolithography of claim 2 which consists of said components (A), (B), (C) and (D), and optionally one or more of (E) from 0.01 to 20 parts by weight of an ultraviolet absorber which absorbs light having wavelengths between 360 and 410 nm per 100 parts by weight of component (A), (F) from 0.01 to 20 parts by weight of a colorant per 100 parts by weight of component (A), silane coupling agents, tackifiers, polymerization inhibitors, antioxidants, ultraviolet absorbers that are light-resistant stabilizers, light stabilizers and another resin.