Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/16—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes

Definitions

• an organically modified silicone cured product having sufficient hardness and a glass dislocation point in a high temperature region can be obtained in a short time, so that technical or production problems of conventional materials can be solved. ..
• the ultraviolet curable silicone resin composition of the present invention is useful not only for molding materials and lens materials in the field of nanoimprint, but also as a material for optical devices or optical components, an insulating material for electronic devices or electronic components, a coating material, and the like. be.
• an asterisk (*) indicates a binding site with a silicon atom, and the configuration of each asymmetric carbon may be either cis (exo) or trans (end). good.
• n is an integer of 0 to 12, but is preferably 1 to 5. If m exceeds 12, it becomes a highly viscous liquid at room temperature, making it difficult to handle.
• the kinematic viscosity of the component (A) is not particularly limited, but is preferably 1,000 to 100,000 mm 2 / s, more preferably 5,000 to 30,000 mm 2 / s.
• the kinematic viscosity is a value at 23 ° C. measured by a Canon Fenceke type viscometer (hereinafter, the same applies).
• the component (A) can be prepared, for example, as an addition reaction product of (a): bis (dimethylsilyl) benzene and (b): vinylnorbornene according to a known method (Japanese Patent Laid-Open No. 2005-133073, etc.). can.
• the component (a) is ortho, meta, or para-substituted bis (dimethylsilyl) benzene represented by the following structural formula (8), and even if a single structure is used, two or more kinds of isomers are used. Mixtures of may be used.
• the component (b) is 5-vinylbicyclo [2.2.1] hepta-2-ene represented by the following structural formula (9), and even if a single structure is used, two or more kinds are used. A mixture of isomers may be used.
• the component (A) of the present invention has, for example, two addition-reactive carbon-carbon double bonds in one molecule for one mole of the component (a) having two SiH groups in one molecule (b). )
• the excess amount of more than 1 mol and 10 mol or less, preferably more than 1 mol and 5 mol or less of the component can be obtained by addition reaction in the presence of a hydrosilylation reaction catalyst.
• the component (A) since the component (b) having an excess molar amount with respect to the component (a) is used, the component (A) has an addition reactivity derived from the structure of the component (b). It has two carbon-carbon double bonds in one molecule.
• the above component (A) may be used alone or in combination of two or more.
• Component (B) is an organopolysiloxane represented by the following formula (10) and having an alkenyl group content of 0.2 mol / 100 g or more, and is a cured product obtained. It is a component that increases the crosslink density and enhances the hardness and glass transition point. (R 3 3 SiO 1/2 ) a (R 4 R 3 2 SiO 1/2 ) b (R 3 2 SiO) c (R 4 R 3 SiO) d (R 3 SiO 3/2 ) e (10)
• R 3 is a monovalent hydrocarbon group independently substituted or unsubstituted, and R 4 is an alkenyl group.
• the alkenyl group of R 4 is preferably an alkenyl group having 2 to 10 carbon atoms such as vinyl, allyl, and ethynyl group, more preferably an alkenyl group having 2 to 6 carbon atoms, and even more preferably a vinyl group.
• the alkenyl group bonded to the silicon atom may be present at either the end of the molecular chain or the side chain of the molecular chain in the molecule of the organopolysiloxane of the component (B), or may be present in both of them. .. In the present invention, it is particularly preferable to have an alkenyl group bonded to three or more silicon atoms in one molecule.
• the content of the alkenyl group bonded to the silicon atom in the component (B) is 0.2 mol / 100 g or more, but 0.5 mol / 100 g or more is preferable.
• the kinematic viscosity of the component (B) is preferably 100 mm 2 / s or less, more preferably 50 mm 2 / s or less at 23 ° C. Within the above range, the compatibility with the component (A) and the component (C) is enhanced, the transparency is improved, and the separation of each component can be suppressed. Further, since the entire composition has a low viscosity, the handleability is improved.
• the blending amount of the component (B) is preferably 1 to 100 parts by mass, more preferably 1 to 50 parts by mass, and more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the component (A) in the composition of the present invention. More preferred.
• the above component (B) may be used alone or in combination of two or more.
• Component (C) is a SiH group-containing addition reaction product obtained from vinylnorbornene, diallyl bisphenol A or both, and cyclic organohydrogenpolysiloxane.
• Z is the group represented by the above Y or the group represented by the following structural formula (13), and Z'is the group represented by the above Y'or the following structural formula (14).
• s is an integer of 0 to 100, preferably 1 to 10
• t is an integer of 1 to 100, preferably 1 to 20
• q and r are independently integers of 0 to 3.
• the sum of q and r at each cyclic siloxane moiety is independently 2 or 3.
• the asterisk (*) indicates the binding site with the silicon atom.
• hydrosilylation reaction catalyst can be used, and the addition reaction conditions, the use of a solvent, etc. are not particularly limited and may be carried out under known conditions.
• the amount of the component (b), diallyl bisphenol A and the cyclic siloxane represented by the above formula (15) to be used is based on the number of moles of the olefin contained in the component (b) and / or diallyl bisphenol A.
• the amount in which the molar ratio of the cyclic siloxane represented by the formula (15) is 0.9 to 1.1 times is preferable.
• R 1 is an unsubstituted or substituted monovalent hydrocarbon group other than an alkenyl group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, respectively, and f and g are 0. 7 ⁇ f ⁇ 2.1, 0.01 ⁇ g ⁇ 1, and 0.8 ⁇ f + g ⁇ 2.7.
• a substituent such as a halogen atom, cyano or an epoxy ring-containing group, for example, halogenation of chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl or the like.
• substituent such as a halogen atom, cyano or an epoxy ring-containing group, for example, halogenation of chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl or the like.
• examples thereof include an alkyl group; a 2-cyanoethyl group; a 3-glycidoxypropyl group.
• R 1 is a methyl group or a phenyl group are particularly preferable because they are industrial
• the kinematic viscosity of the component (i) is not particularly limited, but is preferably 0.1 to 100,000 mm 2 / s, more preferably 0.5 to 500 mm 2 / s.
• SiH group-containing silane compound As an example of the component (ii), a SiH group-containing silane compound represented by the following formula can be used.
• the kinematic viscosity of the component (ii) is not particularly limited, but is preferably 0.1 to 100,000 mm 2 / s, and more preferably 0.5 to 500 mm 2 / s.
• the proportion of the component (C) in the total amount of the component (C), the component (i) and the component (ii) is preferably 50% by mass or more, more preferably 80% by mass or more.
• the blending amount of the component (C), the component (i) and the component (ii) is the silicon atom for 1 mol of the addition-reactive carbon-carbon double bond of the components (A) and (B) in the composition of the present invention.
• the amount of the bonded hydrogen atom is preferably 0.5 to 2.0 mol, more preferably 0.8 to 1.5 mol.
• the platinum group metal catalyst for the hydrosilylation reaction of the component (D) and the component (D) is a platinum catalyst that is inactive under shading and is active at 25 ° C. by irradiating with light having a wavelength of 200 to 500 nm. It is a catalyst for promoting the hydrosilylation reaction between the addition-reactive carbon-carbon double bond in the component (A) or (B) and the silicon atom-bonded hydrogen atom in the component (C).
• the blending amount of the component (D) is not limited as long as it promotes the curing (hydrosilylation reaction) of the present composition, and is based on the total mass of the components (A) to (C) of the present composition.
• the amount of the platinum group metal atom in this component in the range of 0.01 to 500 ppm in mass unit is preferable, and the amount in the range of 0.05 to 100 ppm is more preferable.
• the above component (D) may be used alone or in combination of two or more.
• composition of the present invention is used as necessary in order to prevent thickening and gelation before heat curing when the composition is prepared or applied to a substrate.
• the reaction control agent of the component (E) may be added. Specific examples thereof include 3-methyl-1-butyne-3-ol, 3-methyl-1-pentyne-3-ol, 3,5-dimethyl-1-hexin-3-ol, 1-ethynylcyclohexanol, and the like.
• Ethynylmethyldecylcarbinol 3-methyl-3-trimethylsiloxy-1-butyne, 3-methyl-3-trimethylsiloxy-1-pentyne, 3,5-dimethyl-3-trimethylsiloxy-1-hexine, 1-ethynyl -1-trimethylsiloxycyclohexane, bis (2,2-dimethyl-3-butynoxy) dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,1 , 3,3-Tetramethyl-1,3-divinyldisiloxane and the like.
• 1-ethynylcyclohexanol, ethynylmethyldecylcarbinol, 3-methyl-1-butyne-3-ol, and bis (2,2-dimethyl-3-butynoxy) dimethylsilane are preferable.
• composition of the present invention impairs the object of the present invention in addition to the above-mentioned components (A) to (D) and, if necessary, the components (i), (ii), and (E). As long as it is not, it may contain other components exemplified below.
• an adhesive-imparting agent having a functional group group consisting of one or more alkenyl groups, (meth) acrylic groups, carbonyl groups, epoxy groups, alkoxysilyl groups, and amide groups in one molecule; tixotic properties such as fumed silica.
• Controlling agent Reinforcing agent such as crystalline silica; Antioxidant such as hindered phenol and hindered amine; Light stabilizer; Heat resistance improver such as metal oxide and metal hydroxide; Coloring agent such as titanium oxide; Alumina, crystal Thermal conductivity imparting filler such as reactive silica; viscosity modifier such as non-reactive silicone oil having no reactive functional group; conductivity imparting agent such as metal powder such as silver and gold; pigments and dyes for coloring And so on.
• Reinforcing agent such as crystalline silica
• Antioxidant such as hindered phenol and hindered amine
• Light stabilizer Heat resistance improver such as metal oxide and metal hydroxide
• Coloring agent such as titanium oxide; Alumina, crystal Thermal conductivity imparting filler such as reactive silica; viscosity modifier such as non-reactive silicone oil having no reactive functional group; conductivity imparting agent such as metal powder such as silver and gold; pigments and dyes for coloring And so on.
• the ultraviolet curable organically modified silicone composition of the present invention can be applied to various substrates and used as a material for optical devices or optical components, an insulating material for electronic devices or electronic components, a coating material, a molding material in nanoimprint applications, and the like. ..
• Base materials used in the fields of coating, casting, bonding and sealing of casings or members for composite materials, metal members, plastic members, ceramic members, quartz glass, electrical applications, electronic applications, optical applications, etc. Etc. can be used.
• the composition of the present invention can also be used for a substrate activated by a well-known pretreatment step such as primer treatment, plasma treatment, excimer light treatment and the like.
• a UV-LED lamp, a metal halide lamp, a mercury lamp, or the like can be used for curing the ultraviolet curable organically modified silicone composition of the present invention, and the wavelength of 200 to 500 nm, preferably 200 to 370 nm is used for photoactivation of the platinum catalyst. Light is used.
• the irradiation intensity is preferably 30 to 2,000 mW / cm 2
• the irradiation dose is preferably 3,000 to 100,000 mJ / cm 2 .
• the temperature at the time of irradiation is preferably 10 to 60 ° C, more preferably 20 to 40 ° C.
• the curing temperature and curing time are not particularly limited, but after irradiating the composition with ultraviolet rays, the temperature is 60 to 100 ° C, particularly 60 to 80 ° C. It is preferably cured for 10 to 120 minutes, especially for 30 to 60 minutes.
• Examples 1 to 4 Comparative Examples 1 to 3
• the following components (A) to (E) were mixed in the blending amounts (parts by mass) shown in Table 1 to prepare an ultraviolet curable organically modified silicone composition.
• Component Z'in the structural formula (12) is a group represented by Y', t is 1 to 11, q and r are independently integers of 0 to 2, respectively.
• Each 8 g of the obtained composition is irradiated with ultraviolet rays at room temperature (23 ° C.) so as to have an irradiation intensity of 100 mW / cm 2 and a dose of 30,000 mJ / cm 2 using a UV-LED lamp having a wavelength of 365 nm. , Was heated and cured at 60 ° C. for 1 hour. Then, the hardness of the cured product at 23 ° C. was evaluated by a JIS hardness tester durometer type. Further, the glass dislocation point of the cured product was evaluated by the TMA measuring device METTLER TOLEDO TMA / SDAT841e. The results are also shown in Table 1.
• compositions prepared in Examples 1 to 4 give a cured product having high hardness and a high glass transition point.
• the cured product from the compositions prepared in Comparative Example 1 containing no component (C) and Comparative Examples 2 and 3 not containing the component (B) has a glass dislocation point in the working environment temperature region, so that the workability is improved. It can be seen that it is inferior and there is a risk of cracking.

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• Chemical Kinetics & Catalysis (AREA)
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• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Silicon Polymers (AREA)

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• 2020
  • 2020-09-25 JP JP2020160765A patent/JP7347388B2/ja active Active
• 2021
  • 2021-07-05 KR KR1020237013646A patent/KR20230073298A/ko active Search and Examination
  • 2021-07-05 WO PCT/JP2021/025257 patent/WO2022064805A1/ja active Application Filing
  • 2021-07-05 CN CN202180065105.3A patent/CN116390989A/zh active Pending
  • 2021-07-26 TW TW110127298A patent/TW202212481A/zh unknown

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