Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/14—Polymers provided for in subclass C08G
  • C08F290/148—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/068—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/14—Polymers provided for in subclass C08G
• • 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
  • 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
  • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
  • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C09D151/085—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds on to polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
  • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
  • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C09J151/085—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds on to polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J183/00—Adhesives based on 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; Adhesives based on derivatives of such polymers
  • C09J183/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
  • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
  • H10K59/80—Constructional details
  • H10K59/87—Passivation; Containers; Encapsulations
  • H10K59/873—Encapsulations

Definitions

• the present invention relates to ultraviolet latitude-curable compositions curable by actinic rays, such as ultraviolet or electron beams, in particular ultraviolet curable compositions comprising organosilicon compounds, preferably organopolysiloxanes, and in particular obtainable therefrom.
• the present invention relates to an ultraviolet curable composition whose cured product has low viscosity and excellent coating properties.
• the curable composition of the present invention is suitable as an insulating material for electronic and electrical devices, particularly as a material for use as a coating agent or an optical adhesive. Furthermore, it has excellent coating properties and excellent wettability to substrates, and is useful as an injection molding material and an inkjet printing material.
• silicone resins Due to its high heat resistance and excellent chemical stability, silicone resins have been used as coating agents, potting agents, insulating materials, etc. for electronic and electrical devices. Among silicone resins, ultraviolet curable silicone compositions have also been reported.
• Touch panels are used in various display devices such as mobile devices, industrial equipment, and car navigation systems. In order to improve the detection sensitivity, it is necessary to suppress the electrical influence from light emitting parts such as light emitting diodes (LEDs) and organic EL devices (OLEDs), and an insulating layer is usually placed between the light emitting part and the touch screen. Placed.
• LEDs light emitting diodes
• OLEDs organic EL devices
• thin display devices such as OLEDs have a structure in which many functional thin layers are laminated.
• studies have begun to improve the overall reliability of display devices, particularly flexible display devices, by laminating a highly flexible insulating layer on a touch screen layer.
• an inkjet printing method has been adopted as a processing method for the organic layer. Therefore, for the above-mentioned insulating layer as well, there is a demand for materials that can be processed by inkjet printing.
• JP 2016-56330A discloses an ultraviolet curable organopolysiloxane composition consisting of a polysiloxane having a methacryloxy functional group, a polysiloxane having two or more acryloxy functional groups in one molecule, and a polysiloxane containing an alkenyl group at both ends.
• a silicone gel cured product obtained from the composition is disclosed. Due to its high viscosity, this composition has limitations in processing methods and cannot be applied by injection molding or inkjet methods.
• WO2018-3381 discloses an ultraviolet curable silicone composition comprising a polysiloxane having two (meth)acryloxy functional groups in one molecule and an acrylate compound that does not contain a siloxane structure.
• An inkjet ink composition is disclosed.
• the composition disclosed herein cannot be said to have a sufficiently low viscosity, and there are problems in applying it by an inkjet method.
• the content of the silicone component in the composition is high, there is a problem in adhesion to the substrate.
• UV-curable compositions containing organopolysiloxanes having acryloxy functional groups are known, but there is still a demand for UV-curable compositions that allow easy adjustment of the mechanical properties of the cured product and have excellent workability, particularly low viscosity, for application to a substrate.
• the present invention seeks to provide a silicon-atom-containing curable composition, particularly a UV-curable composition, that is solvent-free but has excellent workability when applied to a substrate, has a high ability to adjust the mechanical properties of the product obtained by curing, and also has good adhesion.
• the present invention provides, when the total mass of the composition is 100 parts by mass, (A) 1 to 99 parts by mass of a compound having one or more (meth)acryloxy groups and hydroxyl groups in one molecule and having no silicon atom; (B) 1 to 99 parts by mass of an organopolysiloxane having two or more alkenyl groups in one molecule and having no UV-curable functional group; (C) 0 to 80 parts by mass of a compound having one or more (meth)acryloxy groups and no hydroxyl group in the molecule,
• the ultraviolet curable composition obtained by using the above together has a low viscosity even without the use of an organic solvent, has excellent workability when applied to a substrate, and has an excellent cured product. It was completed after discovering that it exhibits the ability to adjust mechanical properties and good adhesion.
• the present invention relates to an ultraviolet curable composition
• an ultraviolet curable composition comprising an organosilicon compound, particularly an ultraviolet curable organopolysiloxane composition, which is cured by the formation of bonds by ultraviolet curable functional groups.
• the curing method is not limited to ultraviolet irradiation, and any method by which the ultraviolet curable functional group can undergo a curing reaction can be used, for example, by curing the composition of the invention using electron beam irradiation. It's okay.
• the ultraviolet curable composition of the present invention is a compound having (A) one or more (meth)acryloxy groups and hydroxyl groups in one molecule and no silicon atom when the total mass of the composition is 100 parts by mass. 1 to 99 parts by mass, (B) 1 to 99 parts by mass of an organopolysiloxane having two or more alkenyl groups in one molecule and having no UV-curable functional group; (C) 0 to 80 parts by mass of a compound having one or more (meth)acryloxy groups and no hydroxyl group in the molecule, and the composition is characterized in that it does not substantially contain an organic solvent. That is.
• the viscosity of a substance is a value measured using an E-type viscometer at 25°C.
• Component (A) in the curable composition is preferably a compound represented by the following formula (1A) or (1B).
• (1A) (In the formula, R 1 is a hydrogen atom or a methyl group, R 2 is a divalent linking group represented by the following formula (2A), and X is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cyclo They are an alkyl group, an arylalkyl group, an aryl group, and a (meth)acrylic group, R 3 is a hydrogen atom, a methyl group, or an ethyl group, Y is a hydroxyl group or a hydroxymethyl group, and a is an integer of 0 to 3.
• R 4 is a monovalent group represented by the following formula (2B), and R 5 and R 6 are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an arylalkyl group, It is an aryl group, e is an integer from 0 to 3, and ** is the bonding site to the carbon-carbon double bond) (2B)
• the viscosity of the entire composition measured at 25°C using an E-type viscometer is preferably 500 mPa ⁇ s or less.
• the above component (B) has an average compositional formula: R f R' g SiO (4-f-g)/2 (3) (wherein R is an alkenyl group, R' is a group selected from monovalent hydrocarbon groups excluding alkenyl groups, hydroxyl groups, and alkoxy groups, f and g are numbers that satisfy the following conditions: 1 ⁇ f+g ⁇ 3 and 0.05 ⁇ f/(f+g) ⁇ 1.0, and have at least two R in the molecule. )
• a linear, branched, or cyclic organopolysiloxane represented by the following is preferable.
• the organopolysiloxane of component (B) has the following formula (4): (4) (In the formula, among all R 1 to R 8 groups, at least two alkenyl groups exist in the molecule; the other R 1 to R 8 are each independently an unsubstituted or fluorine-substituted monovalent carbide group.
• the above component (B) may be an organopolysiloxane represented by the above formula (4) or (5).
• the above component (B) may be an organopolysiloxane having an aromatic hydrocarbon group having 6 to 20 carbon atoms.
• the above component (C) may be a compound having one (meth)acryloxy group, or a mixture of two or more compounds having one (meth)acryloxy group.
• the above component (C) is one or more compounds having one (meth)acryloxy group, one or more compounds having two or more (meth)acryloxy groups, or one or more compounds having one (meth)acryloxy group. and a mixture of one or more compounds having two or more (meth)acryloxy groups.
• Part or all of the above component (A) and component (C) may be a compound having an acryloxy group.
• the above component (A) may be a hydroxyalkyl (meth)acrylate.
• the content of aromatic hydrocarbon groups having 6 to 20 carbon atoms in component (B) is preferably 10 mol% or more of all substituents on silicon atoms.
• the viscosity of the entire composition measured at 25° C. using an E-type viscometer is preferably in the range of 5 to 60 mPa ⁇ s.
• the number of moles of hydroxyl groups per 100 g of the total composition is preferably 5 mmol or more and 150 mmol or less.
• the present invention further provides an insulating coating agent or an insulating adhesive containing the above-mentioned ultraviolet curable composition.
• the ultraviolet curable composition of the present invention is useful as an insulating coating or an insulating adhesive.
• the present invention further provides a cured product of the above ultraviolet curable composition. Furthermore, a method of using the cured product as an insulating coating layer or an insulating adhesive layer is provided.
• the present invention further provides a display device, such as a liquid crystal display, an organic EL display, and an organic EL flexible display, including a layer made of a cured product of the above-mentioned ultraviolet curable composition.
• a display device such as a liquid crystal display, an organic EL display, and an organic EL flexible display, including a layer made of a cured product of the above-mentioned ultraviolet curable composition.
• the ultraviolet curable composition of the present invention is a compound having (A) one or more (meth)acryloxy groups and hydroxyl groups in one molecule and no silicon atom when the total mass of the composition is 100 parts by mass. 1 to 99 parts by mass, (B) 1 to 99 parts by mass of an organopolysiloxane having two or more alkenyl groups in one molecule and having no UV-curable functional group; (C) 0 to 80 parts by mass of a compound having one or more (meth)acryloxy groups in the molecule and having no hydroxyl group, as an essential curable component, and, if necessary, components selected from a photoradical polymerization initiator and various additives.
• the curable composition of the present invention is characterized in that it does not substantially contain an organic solvent.
• polysiloxane refers to a polysiloxane with a degree of polymerization of siloxane units (Si-O) of 2 or more, that is, an average of 2 or more Si-O bonds per molecule. It includes siloxane oligomers such as disiloxane, trisiloxane, and tetrasiloxane, as well as siloxane polymers with a higher degree of polymerization.
• Component (A) is a compound having one or more (meth)acryloxy groups and hydroxyl groups in one molecule and no silicon atom. As long as this purpose can be achieved, there is no restriction on the molecular structure, and it can be arbitrary, such as linear, branched, cyclic, cage-like, etc.
• (meth)acryloxy group means a group selected from methacryloxy group and acryloxy group, and may include both.
• the compound having a (meth)acryloxy group includes both methacrylate compounds and acrylate compounds.
• the above component (A) is one or more compounds having a hydroxyl group in the molecule, one or more (meth)acryloxy groups, one or more compounds having two or more (meth)acryloxy groups, or one or more (meth)acryloxy groups. It may be a mixture of one or more compounds having two or more (meth)acryloxy groups and one or more compounds having two or more (meth)acryloxy groups. It is preferable to use at least one kind of compound having one (meth)acryloxy group.
• component (A) Since component (A) has a (meth)acryloxy group and a hydroxyl group in the molecule, the viscosity can be easily adjusted, and the ultraviolet curable property according to the present invention obtained using component (A) Good adhesion to substrates, in particular strong adhesive strength, can be imparted to the cured product comprising the composition.
• component (A) since component (A) has a reactive functional group, even if it is blended in a relatively large amount, it is incorporated into the curing system without any problem of bleed-out, and has the advantage of providing a cured product with high adhesive strength.
• the resulting cured product has sufficient adhesion and adhesive strength to the substrate. may not be achieved.
• component (A) preferably has one or two (meth)acryloxy groups per molecule.
• the functional group may be either (i) two acryloxy groups, (ii) two methacryloxy groups, or (iii) one acryloxy group and one methacryloxy group. It may be a combination of
• the viscosity of component (A) at 25° C. is preferably 1 to 500 mPa ⁇ s, more preferably 1 to 100 mPa ⁇ s, particularly preferably 1 to 50 mPa ⁇ s.
• component (A) is a mixture of two or more compounds, the viscosity of the mixture is preferably within the above range.
• component (A) is preferably a compound having at least one acryloxy group or a mixture containing the same. Furthermore, it may be a mixture of compounds having two or more types of acryloxy groups.
• the component (A) is preferably a compound represented by the following formula (1A) or (1B).
• (1A) (In the formula, R 1 is a hydrogen atom or a methyl group, R 2 is a divalent linking group represented by the following formula (2A), and X is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cyclo They are an alkyl group, an arylalkyl group, an aryl group, and a (meth)acrylic group, R 3 is a hydrogen atom, a methyl group, or an ethyl group, Y is a hydroxyl group or a hydroxymethyl group, and a is an integer of 0 to 3.
• R 4 is a monovalent group represented by the following formula (2B), and R 5 and R 6 are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an arylalkyl group, It is an aryl group, e is an integer from 0 to 3, and ** is the bonding site to the carbon-carbon double bond) (2B)
• R 1 is a hydrogen atom or a methyl group.
• a hydrogen atom is preferable.
• X is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an arylalkyl group, an aryl group, or a (meth)acrylic group.
• alkyl groups having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, sec-butyl group, pentyl group, hexyl group, octyl group, etc. Although examples thereof include methyl groups, methyl groups are preferred.
• Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group.
• Examples of the arylalkyl group include a benzyl group and a phenylethyl group.
• Examples of the aryl group include a phenyl group and a naphthyl group, with a phenyl group being preferred.
• R 2 is a divalent linking group represented by the above formula (2A).
• R 3 is each independently a hydrogen atom, a methyl group, or an ethyl group, and a hydrogen atom and a methyl group are preferable.
• the substituent Y on R 2 is a hydroxyl group or a hydroxymethyl group.
• a on R 2 is an integer of 0 to 3
• b is 0 or 1
• c is an integer of 0 to 3
• d is an integer of 0 to 5.
• R 4 is a monovalent group represented by the above formula (2B).
• R 5 and R 6 in the above formula (2B) are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an arylalkyl group, or an aryl group, and the groups exemplified above can be used.
• e is an integer from 0 to 3.
• Component (A) of the present invention has at least one hydroxyl group in the molecule. Therefore, when the above-mentioned X is a group other than a hydrogen atom, the above-mentioned b and d are 1 or more, and at least one of Y is a hydroxyl group.
• specific examples of compounds having one (meth)acryloxy group in the molecule include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-1-methylethyl acrylate, 2-hydroxy-1-methylethyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxy Butyl methacrylate, 4-acryloyloxyphenol, 4-methacryloyloxyphenol, 1-hydroxymethylpropyl acrylate, 1-hydroxymethylpropyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, 2-hydroxy-3- Phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, methyl-2-(2-hydroxy-1-methylethyl)acrylate, methyl-2-(2-hydroxy-1-pheny
• specific examples of compounds having two (meth)acryloxy groups in the molecule include 3-acryloyloxy-2-hydroxypropyl methacrylate, 3-methacryloyloxy-2- Hydroxypropyl methacrylate, 3-acryloyloxy-2-hydroxypropyl acrylate, glycerol diacrylate, glycerol dimethacrylate, glycerol-1,3-diglycerolate diacrylate, glycerol-1,3-diglycerolate dimethacrylate, etc. can be mentioned.
• the above component (A) can be used alone or in combination of two or more, taking into consideration the viscosity, ultraviolet curability, hardness after curing, glass transition temperature, and adhesiveness of the curable composition.
• 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, acrylic acid, 3-acryloyloxy-2-hydroxypropyl methacrylate can be preferably used; -Acryloyloxy-2-hydroxypropyl methacrylate and acrylic acid are particularly preferred compounds.
• Component (B) is an organopolysiloxane that does not have an ultraviolet curable functional group and has two or more alkenyl groups in its molecule. Such a component (B) can improve the viscosity and the mechanical strength (especially toughness and tensile elongation) of the cured product in the entire substantially solvent-free UV composition according to the invention. .
• the above component (B) has the following average composition formula: R f R' g SiO (4-f-g)/2 (3) (wherein R is an alkenyl group, R' is a group selected from monovalent hydrocarbon groups excluding alkenyl groups, hydroxyl groups, and alkoxy groups, f and g are numbers that satisfy the following conditions: 1 ⁇ f+g ⁇ 3 and 0.05 ⁇ f/(f+g) ⁇ 1.0, and have at least two R in the molecule. ) It can be a linear, branched, or cyclic organopolysiloxane represented by:
• alkenyl group represented by R in formula (3) examples include alkenyl groups having 2 to 8 carbon atoms, and specific examples include vinyl, allyl, butenyl, pentenyl, hexenyl, and octenyl groups. Vinyl group and hexenyl group can be preferably used.
• the linear, branched, or cyclic organopolysiloxane represented by the above average compositional formula has an average of at least two alkenyl groups (R) per molecule.
• the average number of alkenyl groups per molecule is preferably 2 to 10, more preferably 2 to 8.
• component (B) having alkenyl groups at both ends of the molecular chain which functions as a crosslinking agent and/or a chain extender in the crosslinked structure, and improves the rubber physical properties of the cured product, especially elongation and tensile strength. This is to contribute to improvement.
• R' is a group selected from a monovalent hydrocarbon group, a hydroxyl group, and an alkoxy group
• the monovalent hydrocarbon group includes an unsubstituted monovalent hydrocarbon group and a fluorine-substituted monovalent hydrocarbon group. included.
• the unsubstituted or fluorine-substituted monovalent hydrocarbon group is preferably a group selected from unsubstituted or fluorine-substituted alkyl, cycloalkyl, arylalkyl, and aryl groups having 1 to 20 carbon atoms. be.
• alkyl group examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, pentyl, hexyl, and octyl, with methyl and hexyl groups being particularly preferred.
• cycloalkyl group examples include cyclopentyl and cyclohexyl.
• arylalkyl group include benzyl and phenylethyl groups.
• the aryl group examples include a phenyl group and a naphthyl group.
• Examples of monovalent hydrocarbon groups substituted with fluorine include 3,3,3-trifluoropropyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl groups. .
• the fluorine-substituted monovalent hydrocarbon group is preferably 3,3,3-trifluoropropyl group.
• the organopolysiloxane represented by the above formula (3) has a viscosity at 25°C of 1 to 25,000 mPa ⁇ s, preferably 1 to 5,000 mPa ⁇ s, and most preferably 1 to 5,000 mPa ⁇ s.
• the viscosity of the organopolysiloxane can be adjusted by changing the ratio of f and g in formula (3) and the molecular weight.
• the organopolysiloxane represented by formula (3) preferably has an average of 2 to 1,000 silicon atoms, more preferably 2 to 500, particularly preferably 2 to 300 silicon atoms per molecule.
• the organopolysiloxane of component (B) is The following formula (4): (4) This is a compound represented by
• the organopolysiloxane represented by formula (4) has two or more alkenyl groups per molecule on average.
• two or more of all R 1 to R 8 groups per molecule are alkenyl groups.
• the structure of the alkenyl group is not limited to a specific chemical structure as long as it has a carbon-carbon double bond.
• the alkenyl group is particularly preferably a terminal alkenyl group, such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, and 4-vinyl group.
• Examples include, but are not limited to, alkenyl groups having 2 to 20 carbon atoms such as phenyl group.
• the alkenyl-containing group is particularly preferably a group selected from a vinyl group, an allyl group, and a hexenyl group, and particularly preferably a vinyl group and a hexenyl group.
• R 1 to R 8 other than the ultraviolet curable functional group are each independently an unsubstituted or fluorine-substituted monovalent hydrocarbon group, preferably an unsubstituted or fluorine-substituted monovalent hydrocarbon group having 1 to 20 carbon atoms.
• n in formula (4) is such that the viscosity of the organopolysiloxane represented by formula (4) at 25° C. is preferably 1 to 25,000 mPa ⁇ s, more preferably 1 to 5,000 mPa ⁇ s, particularly preferably 1 The value is ⁇ 3,000 mPa ⁇ s.
• the number of silicon atoms per molecule is from 2 to 1,000, particularly from 2 to 300, so that the compound of formula (4) has a desired viscosity.
• the organopolysiloxane of formula (4) which is the component (B), has an average number of alkenyl groups of 2 to 10, preferably 2 to 8, particularly preferably 2 per molecule.
• the organopolysiloxane of formula (4) can be used alone or as a mixture of two or more.
• the viscosity of the mixture at 25° C. is preferably within the above-mentioned viscosity range.
• each R is a group independently selected from an alkenyl group and an unsubstituted or fluorine-substituted monovalent hydrocarbon group, and at least two of all R's are alkenyl groups.
• (j+k) are positive numbers
• h is 0 or a positive number
• i is a number within the range of 0 to 100.
• the alkenyl group and monovalent hydrocarbon group are as defined above for formula (4). Further, the preferable viscosity of the organopolysiloxane represented by formula (5) is also as defined above for the organopolysiloxane represented by formula (4). Furthermore, alkoxy groups and silanol groups may remain in the molecule as long as the amount is small.
• the organopolysiloxane represented by formula (5) preferably has 4 to 30, particularly 6 to 20, silicon atoms per molecule.
• the number of alkenyl groups contained in the organopolysiloxane represented by formula (5) is, on average, 2 to 10 per molecule overall, preferably 3 to 10, more preferably 3 to 8, and particularly preferably 4 to 8.
• the compound of the above formula (3) is the following formula (6): (6) (wherein R is each independently a group selected from an alkenyl group and an unsubstituted or fluorine-substituted monovalent hydrocarbon group, x is an integer from 3 to 10, and at least 2 It may also be a cyclic organopolysiloxane represented by (having 2 alkenyl groups).
• alkenyl group and unsubstituted or fluorine-substituted monovalent hydrocarbon group that R in formula (6) can represent are as defined for formula (3) above.
• the preferred viscosity of the organopolysiloxane represented by formula (6) is as defined above for the organopolysiloxane represented by formula (3).
• the component (B) is an organopolysiloxane having an aromatic hydrocarbon group having 6 to 20 carbon atoms as a substituent as at least a portion of the monovalent hydrocarbon group.
• the aromatic hydrocarbon group having 6 to 20 carbon atoms include phenyl group, tolyl group, xylyl group, and naphthyl group, with phenyl group being preferred.
• component (B) contains an aromatic hydrocarbon group having 6 to 20 carbon atoms, in addition to improving the mechanical strength of the cured product according to the present invention, the UV curability may be further improved. .
• linear organopolysiloxane represented by the above (3), particularly formula (4) include dimethylvinylsilylpolydimethylsiloxane at both ends, dimethylvinylsilylpolydimethyl/methylphenylsiloxane copolymer at both ends, Dimethylvinylsilylpolydimethyl/diphenylsiloxane copolymer at both ends, dimethylvinylsilylpolymethylphenylsiloxane at both ends, dimethylhexenylsilylpolydimethylsiloxane at both ends, dimethylhexenylsilylpolydimethyl/methylphenylsiloxane copolymer at both ends, Dimethylhexenylsilylpolydimethyl/diphenylsiloxane copolymer, dimethylhexenylsilylpolydimethylphenylsiloxane at both ends, trimethylsilylpolydimethyl
• branched organopolysiloxane represented by the above (3), especially the formula (5) include polysiloxanes consisting of M Vi (dimethylvinylsiloxy) units and T (methylsiloxy) units, M Vi units and Q Polysiloxane consisting of (siloxy) units, polysiloxane consisting of M Vi units, M (trimethylsilyl) units and Q units, polysiloxanes consisting of M Vi units, D (dimethylsiloxy) units and T units, M Vi units and M units and T units, polysiloxanes consisting of M Vi units and T Ph (phenylsiloxy) units, polysiloxanes consisting of M Vi units, M units, and T Ph units, polysiloxanes consisting of M Vi units, D units, and T Ph units.
• Polysiloxane consisting of M Hex (dimethylhexenylsiloxy) units and T units Polysiloxane consisting of M Hex units and Q units, Polysiloxane consisting of M Hex units, M units and Q units, M Hex units and D polysiloxane consisting of M Hex units, M units and T units, polysiloxanes consisting of M Hex units and T Ph units, polysiloxanes consisting of M Hex units, M units and T Ph units, Polysiloxane consisting of M Hex units, D units and T Ph units, polysiloxanes consisting of D Hex (methylhexenylsiloxy) units and T units, polysiloxanes consisting of M units, D Vi (methylvinylsiloxy) units and T Ph units.
• Siloxane polysiloxane consisting of T Hex units, polysiloxane consisting of T Hex units and Q units, polysiloxane consisting of M units, T Hex units and Q units, polysiloxane consisting of T Hex units and T units, T Hex units and T Ph units, and polysiloxanes consisting of M units, T Hex units, and T Ph units.
• cyclic organopolysiloxane represented by formula (6) include 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5-trimethyl -1,3,5-trihexenylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, 1,3,5,7,9-pentamethyl- 1,3,5,7,9-pentavinylcyclopentasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentahexenylcyclopentasiloxane, methylvinylsiloxy group and methyl
• Examples include cyclic trisiloxane consisting of a phenylsiloxy group, and cyclic tetrasiloxane consisting of a methylvinylsiloxy group and a methylphenyl
• the organopolysiloxane represented by the above formula (3) more specifically, any one of formulas (4) to (6), can be used singly or in any combination of two or more to form the component ( It can be used as B).
• component (B) it is particularly preferable to use an organopolysiloxane represented by the above formula (4) or (5).
• Compounds recommended as component (B) are dimethylvinylsilylpolydimethyl/diphenylsiloxane copolymer at both ends, dimethylvinylsilylpolymethylphenylsiloxane at both ends, methylphenylvinylsilylpolydimethylsiloxane at both ends, 1,3-dimethyl -1,3-diphenyl-1,3-divinyldisiloxane, polysiloxane consisting of M units, D Hex units and T Ph units, polysiloxane consisting of M units, D Vi units and T Ph units, M Vi units and T It is one compound or a combination of two or more compounds selected from the group consisting of polysiloxane consisting of Ph units, polysiloxane consisting of M Vi units, D units and T Ph units.
• both-terminated dimethylvinylsilyl polydimethyl/diphenylsiloxane copolymer both-terminated dimethylvinylsilyl polymethylphenylsiloxane, and 1,3-dimethyl-1,3-diphenyl-1,3-divinyldisiloxane are particularly preferably used.
• the ultraviolet curable composition of the present invention may optionally further contain a compound (C) having one or more (meth)acryloxy groups in the molecule and having no hydroxyl group.
• a compound (C) having one or more (meth)acryloxy groups in the molecule and having no hydroxyl group there is no restriction on the molecular structure, and it can be arbitrary, such as linear, branched, cyclic, cage-like, etc.
• the above component (C) preferably has a viscosity of 1 to 500 mPa ⁇ s at 25°C, more preferably 1 to 100 mPa ⁇ s, particularly preferably 1 to 20 mPa ⁇ s, and 1 to 10 mPa ⁇ s. is most preferable.
• component (C) contains 1 to 6, preferably 1 to 4, more preferably 1 to 3 (meth)acryloxy groups per molecule.
• component (C) contains 1 to 6, preferably 1 to 4, more preferably 1 to 3 (meth)acryloxy groups per molecule.
• the above component (C) may be a single compound having one (meth)acryloxy group, or a mixture of two or more compounds having one (meth)acryloxy group.
• component (C) may be a mixture of one or more compounds having one (meth)acryloxy group and one or more compounds having two or more (meth)acryloxy groups.
• compounds having one (meth)acryloxy group include isoamyl acrylate, isoamyl methacrylate, octyl acrylate, octyl methacrylate, dodecyl acrylate, dodecyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, and stearyl methacrylate.
• acryloxypropyltristrimethylsiloxysilane methacryloxypropyltristrimethylsiloxysilane, acryloxypropyltris(trimethylsilylethyldimethylsiloxy)silane, methacryloxypropyltris(trimethylsilylethyldimethylsiloxy) ) silane, acryloxypropyltris((tristrimethylsiloxysilyl)ethyldimethylsiloxy)silane, and methacryloxypropyltris((tristrimethylsiloxysilyl)ethyldimethylsiloxy)silane, which can be used alone or in combination of two or more. be able to.
• the compound having one (meth)acryloxy group can be used alone or in combination of two or more, taking into consideration the viscosity, curability, hardness after curing, and glass transition temperature of the compound.
• 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, and (meth)acryloxypropyltristrimethylsiloxysilane are preferably used.
• 2-ethylhexyl acrylate, isobornyl acrylate, dicyclopentanyl acrylate, and (meth)acryloxypropyltristrimethylsiloxysilane are particularly preferably used.
• compounds having two or more (meth)acryloxy groups include diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, neopentyl glycol diacrylate, and neopentyl glycol dimethacrylate.
• Acrylate polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, 1,4-bis(acryloyloxy)butane, 1,4-bis(methacryloyloxy)butane, 1,6-bis(acryloyloxy)hexane, 1,6 -Bis(methacryloyloxy)hexane, 1,9-bis(acryloyloxy)nonane, 1,9-bis(methacryloyloxy)nonane, tricyclodecanedimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, tri- Methylolpropane triacrylate, trimethylolpropane trimethacrylate, tris(2-acryloyloxy)ethylisosialate, tris(2-methacryloyloxy)ethylisosialate, tris(2-acryloyloxy)ethylisosialate, tris (2-methacryloyloxy
• a combination of a compound having two or more (meth)acryloxy groups and a compound having one (meth)acryloxy group in the components (A) and (C). can be used in any ratio, but usually [total amount of compounds having two or more (meth)acryloxy groups in components (A) and (C)]/[components (A) and (C) ) is in the range of 1/99 to 75/25 (mass ratio), and may be in the range of 1/99 to 50/50, and may be in the range of 1/99 to 75/25 (mass ratio). It may be in the 30/70 range. This is because if the ratio of the compound having two or more (meth)acryloxy groups is too high, the cured product tends to have high hardness and become brittle.
• the mixing ratio of component (A) and component (B) is 1 to 99% by mass, and the ratio of component (B) to 100% by mass of the total amount of components (A) and (B).
• the content is 1 to 99% by mass.
• the preferred ratio of component (A) is 1% by mass or more and 90% by mass or less, more preferably 1% by mass or more and 70% by mass or less, and even more preferably 2% by mass of the total amount of components (A) and (B).
• the content is 50% by mass or less.
• the curable composition has an appropriate viscosity, maintains good ultraviolet curability, and is designed to have a material with good adhesive properties for the resulting cured product. can do.
• the ratio of component (A) in the total curable composition is preferably 1 to 70% by mass, more preferably 5 to 50% by mass, and 10 to 30% by mass, based on 100% by mass of the total composition. More preferably, it is expressed in mass %.
• the ratio of component (A) By increasing the ratio of component (A), the adhesiveness of the cured product can be improved.
• the ratio of component (A) is too high, the transparency of the curable composition and the resulting cured product may be impaired.
• the curable composition has an appropriate viscosity, maintains good ultraviolet curability, and the resulting cured product is designed to have good transparency and adhesive properties. be able to.
• Component (B) in the composition of the present invention may be a silicon-containing component
• component (C) may be a silicon-containing component.
• the ratio of the silicon-containing component in the total curable composition is preferably less than 50% by mass, more preferably 5 to 45% by mass, and 10 to 40% by mass, based on 100% by mass of the total composition. It is more preferable that When the ratio of the silicon-containing component is within this range, the curable composition has an appropriate viscosity, maintains good UV curability, and provides a cured product with good transparency and mechanical properties, especially tensile properties. Easy to design.
• the content of component (A), component (B), and component (C) in the ultraviolet curable composition of the present invention is 1 to 99 parts by mass, respectively, when the total mass of the composition is 100 parts by mass.
• the range is 99 to 1 part by weight, and 0 to 80 parts by weight.
• the sum of the contents of component (A), component (B), and component (C) is preferably 90 parts by mass or more, and 90 to 99.9 parts by mass. Parts by weight, particularly preferably from 90 to 99 parts by weight.
• a suitable ultraviolet curable composition is composed mostly of component (A), component (B), and optional component (C).
• the present composition may also contain other components described below.
• component (C) is an arbitrary structure in this composition, and its content may be 0 mass part.
• the concentration of hydroxyl groups in the ultraviolet curable composition of the present invention is an important guideline for designing a cured product with good adhesiveness.
• the concentration of hydroxyl groups in 100 g of the total curable composition is 5 mmol or more and 150 mmol or less, the composition maintains good ultraviolet curability and the cured product has high adhesiveness. If the concentration of hydroxyl groups is too high, the transparency of the curable composition and the resulting cured product may be impaired. More preferably, the number of moles of hydroxyl groups is in the range of 20 to 120 mmol.
• the ultraviolet curable composition of the present invention can achieve a viscosity suitable for a coating agent without substantially using an organic solvent, and can achieve a viscosity suitable for a coating agent without substantially using an organic solvent. It does not include.
• substantially free of organic solvents means that the content of organic solvents is less than 0.1% by mass of the entire composition, and is preferably analyzed using an analytical method such as gas chromatography. It means that it is below the limit.
• component (A) and component (B) by adjusting the molecular structure and molecular weight of component (A) and component (B), and by adding component (C), which is an optional component, it is possible to obtain a desired product without using an organic solvent. viscosity can be achieved.
• a photopolymerization initiator can be added to the ultraviolet curable composition of the present invention, if desired.
• a radical photopolymerization initiator can be used as the photopolymerization initiator.
• the photoradical polymerization initiator generates free radicals upon irradiation with ultraviolet rays or electron beams, which causes a radical polymerization reaction and can cure the composition of the present invention.
• a polymerization initiator is usually not necessary.
• Radical photopolymerization initiators are known to be roughly divided into photocleavable type and hydrogen abstraction type, but the photoradical polymerization initiator used in the composition of the present invention can be selected from those known in the art. It can be selected and used, and is not particularly limited to a specific one.
• photoradical polymerization initiators include acetophenone, p-anisyl, benzyl, benzoin, benzophenone, 2-benzoylbenzoic acid, 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(dimethylamino)benzophenone.
• benzoin methyl ether benzoin isopropyl ether, benzoin isobutyl ether, benzoin ethyl ether, 4-benzoylbenzoic acid, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1, 2'-biimidazole, methyl 2-benzoylbenzoate, 2-(1,3-benzodioxol-5-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-benzyl -2-(dimethylamino)-4'-morpholinobutyrophenone, ( ⁇ )-camphorquinone, 2-chlorothioxanthone, 4,4'-dichlorobenzophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2- Phenylacetophenone, 2,4-diethylthioxanthene-9-one, diphenyl(2,
• Omnirad registered trademark
• 651, 184, 1173, 2959, 127, 907, 369, 369E, and 379EG alkylphenone photopolymerization initiators, IGM Resins B.V.
• Omnirad registered trademark
• TPO H acylphosphine oxide photoinitiator
• IGM RESINS B.V. Omnirad
• MBF and 754 intramolecular hydrogen abstraction type photoinitiator
• Initiators such as Irgacure (registered trademark) OXE01 and OXE02 (oxime ester non-polymerization initiators, BASF) and the like can be mentioned.
• the amount of the photoradical polymerization initiator to be added to the composition of the present invention is not particularly limited as long as the desired photopolymerization reaction or photocuring reaction occurs, but it is generally based on the total mass of the composition of the present invention. It is used in an amount of 0.01 to 5% by weight, preferably 0.05 to 1% by weight.
• a photosensitizer can also be used in combination with the above-mentioned radical photopolymerization initiator.
• the use of a sensitizer can increase the photon efficiency of the polymerization reaction, making longer wavelength light available for the polymerization reaction compared to the use of a photoinitiator alone. It is known to be particularly effective when the coating thickness is relatively thick or when relatively long wavelength LED light sources are used.
• Examples of sensitizers include anthracene compounds, phenothiazine compounds, perylene compounds, cyanine compounds, merocyanine compounds, coumarin compounds, benzylidene ketone compounds, (thio)xanthenes or (thio)xanthone compounds, such as isopropyl.
• Thioxanthone, 2,4-diethylthioxanthone, alkyl-substituted anthracenes, squalium-based compounds, (thia)pyrylium-based compounds, porphyrin-based compounds, etc. are known, and any photosensitizer, including but not limited to these, can be used in the curing process of the present invention. It can be used in sexual compositions.
• the cured product obtained from the curable composition of the present invention is characterized by the molecular chain length and molecular structure of component (A) and component (B), the number of (meth)acryloxy groups per molecule of component (A), and the number of (meth)acryloxy groups per molecule of component (A).
• the desired cured product can be prepared.
• the physical properties and the curing speed of the curable composition can be obtained, and the viscosity of the curable composition can be designed to a desired value.
• a cured product obtained by curing the curable composition of the present invention is also included within the scope of the present invention.
• the shape of the cured product obtained from the composition of the present invention is not particularly limited, and may be a thin film-like coating layer, a molded product such as a sheet, or a specific part in an uncured state. It may be injected into a container and cured to form a filler, or it may be used as a sealing material or intermediate layer of a laminate or a display device.
• the cured product obtained from the composition of the present invention is preferably in the form of an injection-molded protective/adhesive layer and a thin coating layer, particularly preferably a thin insulating coating layer.
• the curable composition of the present invention is suitable for use as a coating agent, potting agent, or adhesive, particularly as an insulating coating agent, potting agent, or insulating adhesive for electronic and electrical devices.
• the cured product obtained by curing the curable composition of the present invention is characterized by excellent mechanical properties, particularly adhesive strength. Further, by optimizing the structure of the curable composition described above, it is also possible to design a material having good tensile elongation. For example, when evaluated using a test specimen with a thickness of 0.5 mm at 25° C. and a tensile rate of 50 mm/min, the tensile elongation is usually 20% or more. By optimizing the curable composition, it is possible to increase the tensile elongation of the cured product to 100% or more, making it useful as a layer-forming material for flexible displays.
• the cured product obtained by curing the curable composition of the present invention can be designed to have a relative permittivity of less than 3.0, and the curable composition of the present invention can be designed to have a relative dielectric constant of less than 3.0. It can also be used to form a coating layer having a dielectric constant.
• the viscosity of the entire composition must be , the value measured using an E-type viscometer is preferably 500 mPa ⁇ s or less at 25°C.
• the viscosity is preferably 300 mPa ⁇ s or less, particularly 100 mPa ⁇ s or less, although it depends on the injection gap.
• the viscosity range is preferably 5 to 60 mPa ⁇ s, more preferably 5 to 30 mPa ⁇ s, and particularly preferably 5 to 20 mPa ⁇ s, considering the application of inkjet printing methods, which are rapidly beginning to be put into practical use.
• ⁇ It is s.
• compounds having preferred viscosity can be used as each component in an optimized ratio so that the viscosity of the entire composition has the desired viscosity. .
• any of the processing methods such as injection molding, spin coating, and inkjet printing can be applied, and the curable composition of the present invention can be applied with a viscosity suitable for each of the above methods. It is preferable to have.
• additives may be added to the composition of the present invention as desired.
• Additives that can be used include leveling agents, wettability improvers, silane coupling agents, ultraviolet absorbers, antioxidants, polymerization inhibitors, fillers (reinforcing fillers, insulating fillers, thermally conductive fillers, etc.) functional fillers). If necessary, suitable additives can be added to the compositions of the invention.
• a thixotropy imparting agent may be added to the composition of the present invention as required, particularly when used as a potting agent or a sealing material.
• the ultraviolet curable organopolysiloxane composition of the present invention includes: By irradiating with high energy rays such as ultraviolet rays, a radical polymerization reaction can proceed and a cured product can be formed.
• Examples of usable high-energy rays include ultraviolet rays, gamma rays, X-rays, alpha rays, and electron beams. Particular examples include ultraviolet rays, X-rays, and electron beams irradiated from commercially available electron beam irradiation equipment. Among these, ultraviolet rays are preferable from the viewpoint of catalyst activation efficiency, and ultraviolet rays in the wavelength range of 280 to 405 nm are used for industrial purposes. preferred from the standpoint of practical use. Further, the amount of ultraviolet irradiation is preferably such that the cumulative amount of irradiation at a wavelength of 365 nm or 405 nm is within the range of 100 mJ/cm 2 to 10 J/cm 2 .
• the curable composition of the present invention has a low viscosity and is particularly useful as a material for forming an insulating layer constituting various articles, particularly electronic devices and electric devices.
• the composition of the present invention can be applied to a substrate, or sandwiched between two substrates, at least one of which is made of a material that transmits ultraviolet rays or electron beams, and the composition can be cured by irradiating the composition with ultraviolet rays or electron beams to form an insulating layer.
• a pattern can be formed when the composition of the present invention is applied to the substrate, and the composition can then be cured.
• the composition can be applied to the substrate, and when curing, the cured and uncured parts can be left by irradiating ultraviolet rays or electron beams, and the uncured parts can then be removed with a solvent to form an insulating layer of the desired pattern.
• the cured layer according to the present invention when the cured layer according to the present invention is an insulating layer, it can be designed to have a low relative dielectric constant of less than 3.0.
• the curable composition of the present invention is particularly suitable as a material for forming an insulating layer of a display device such as a touch panel or a display, since the cured product obtained from the composition has good transparency and adhesion.
• the insulating layer may be formed into any desired pattern as described above, if necessary. Therefore, a display device such as a touch panel or a display, which includes an insulating layer obtained by curing the ultraviolet-curable composition of the present invention, is also an aspect of the present invention.
• an article can be coated with the curable composition of the present invention and then cured to form an insulating coating layer (insulating film). Therefore, the composition of the present invention can be used as an insulating coating. Moreover, a cured product formed by curing the curable composition of the present invention can also be used as an insulating coating layer.
• the insulating film formed from the curable composition of the present invention can be used for various purposes. In particular, it can be used as a component of electronic devices or as a material used in the process of manufacturing electronic devices. Electronic devices include electronic equipment such as semiconductor devices and magnetic recording heads.
• the curable composition of the present invention can be used for semiconductor devices such as LSI, system LSI, DRAM, SDRAM, RDRAM, D-RDRAM, and insulating films for multi-chip module multilayer wiring boards, interlayer insulating films for semiconductors, and etching stopper films. It can be used as a surface protective film, a buffer coat film, a passivation film in LSI, a cover coat for a flexible copper clad board, a solder resist film, and a surface protective film for optical devices.
• the ultraviolet curable composition of the present invention is also suitable for use as a potting agent, particularly as an insulating potting agent for electronic devices and electrical devices.
• the ultraviolet curable composition of the present invention can be used as a material for forming a coating layer on the surface of a substrate using an inkjet printing method, in which case the composition of the present invention may contain a wettability improving agent. It is particularly preferable to contain it.
• Viscosity of curable composition and each component The viscosity (mPa ⁇ s) of the composition at 25° C. was measured using a rotational viscometer (manufactured by Tokimec Corporation, E-type viscometer VISCONIC EMD).
• hydroxyl group concentration (mmol/100 g) in 100 g of the curable composition was calculated using the mass ratio of component (A) in the composition, the mass ratio of hydroxyl groups in component (A), and the chemical formula weight of the hydroxyl groups (17.01).
• a 1 mm thick mold having a circular hole with an inner diameter of 40 mm was placed on a PET film coated with a fluoropolymer-based release agent, and about 1.3 g of a curable composition was poured into the hole.
• the composition was covered with the same PET film as above, and a 10 mm thick glass plate was placed on top of it.
• the composition was cured by irradiating the LED light with a wavelength of 405 nm with an energy amount of 2 J/ cm2 from above, to produce a disk-shaped organopolysiloxane cured product with a diameter of 40 mm and a thickness of 1 mm.
• the UV-curable compositions of the present invention have a viscosity at 25° C. that can be applied to a substrate as an injection molding material and as a coating agent, particularly by inkjet printing. It has a viscosity suitable for coating and is highly transparent. Furthermore, while the adhesiveness of the cured product obtained from the composition of the present invention is good, as shown in Table 3, the tensile elongation is high and the cured product is excellent in flexibility. Furthermore, the cured product obtained from the composition of the invention (particularly Example 5) exhibited low dielectric properties.
• the ultraviolet-curable compositions according to the comparative examples not containing component (A) showed insufficient adhesion to the substrate of the cured product obtained compared to the composition containing component (A), and were unsuitable as a material for forming an insulating layer for a display device such as a display.
• the ultraviolet curable composition of the present invention is suitable for the above-mentioned uses, particularly as a material for forming an insulating layer of display devices such as touch panels and displays, especially flexible displays.

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• 2023
  • 2023-09-19 JP JP2024548270A patent/JPWO2024063068A1/ja active Pending
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