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  • C09J7/00—Adhesives in the form of films or foils
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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
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
  • C08F299/08—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polysiloxanes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
  • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
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  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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  • 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
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  • 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
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
  • C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
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  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • 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
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  • 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
  • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
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  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
  • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
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  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
  • H10W74/47—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins
  • H10W74/476—Organic materials comprising silicon
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  • 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
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  • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
  • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
  • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
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  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
  • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
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  • C09J2483/00—Presence of polysiloxane

Definitions

• the present invention relates to a curable hot-melt silicone composition and a technology for encapsulating optical members using the composition.
• Curable silicone compositions are used in a wide range of industrial fields because they cure to form cured products with excellent heat resistance, cold resistance, electrical insulation, weather resistance, water repellency, and transparency.
• a cured product of such a curable silicone composition is more resistant to discoloration than other organic materials, and exhibits less deterioration in physical properties, making it suitable as a sealant for optical materials and semiconductor devices.
• Patent Document 1 discloses a heat-curable composition containing a hot-melt silicone having a hydrosilylation-reactive group and/or a radical-reactive group
• Patent Document 2 discloses a hydrosilylation-reactive composition.
• a reactive silicone composition is disclosed that is reactively curable, has alkenyl groups, and yields a reactive thermoplastic that fluidizes at elevated temperatures.
• these documents do not specifically disclose a hot-melt silicone composition containing a resin-linear structure-containing organopolysiloxane block copolymer having a resinous organosiloxane block having an acrylic or methacrylic group.
• the curing agent disclosed in Patent Document 1 or 2 is a hydrosilylation reaction catalyst or an organic peroxide for a heat curing reaction that requires a high temperature exceeding 150 ° C., and the curing reaction or photocuring reaction at a low temperature is nothing is stated or suggested.
• Patent Document 3 in order to meet the demand for low-temperature curing, the applicants disclosed in Patent Document 3 (unpublished at the time of filing) that an organopolysiloxane resin having a hydrosilylation-curable reactive functional group such as a vinyl group and an ultraviolet-activated A curable hot-melt silicone composition containing a hydrosilylation reaction catalyst of 100°C or less and capable of curing at a low temperature of 100°C or less is proposed.
• high-temperature curing at about 120°C may be required after activating the catalyst with high-energy beam irradiation.
• Patent Document 3 neither describes nor suggests the use of a resin-linear structure-containing organopolysiloxane block copolymer having an acryl or methacryl group and a curing agent other than a hydrosilylation reaction catalyst.
• Patent Document 4 and the like propose an active energy ray-curable hot-melt silicone composition that uses a thiol-ene reaction. These are excellent in that they can be rapidly cured even at room temperature (low temperature), but have the problem that the cured products have low yellowing resistance and are difficult to apply in applications where transparency is required.
• the object of the present invention is to enable curing in a wide range of temperatures from low to high depending on the sealing process and the heat resistance of the resin member, and in particular, to achieve good curability even at low temperatures such as room temperature.
• the present invention provides a hot-melt type silicone composition which is excellent in physical strength such as durability of the resulting cured product, transparency and resistance to yellowing, and which is excellent in handling workability such as overmolding, and its use. That is.
• the present inventors have found a resinous organosiloxane block X having an acrylic or methacrylic group, which is a silicon-bonded functional group (R A ), and a linear organosiloxane block Y consisting of diorganosiloxane units. and having at least two RA in the molecule, and (B) a curable hot melt silicone composition containing a radical polymerization initiator.
• R A silicon-bonded functional group
• B a curable hot melt silicone composition containing a radical polymerization initiator
• the present composition has excellent hot-melt properties, and depending on the selection of the radical polymerization initiator, it is possible to realize room temperature to low temperature curing properties by heat curing at high temperatures or irradiation with high energy rays, and the resulting cured product It has the advantage of being excellent in durability, transparency, and yellowing resistance to ultraviolet light, high temperature, humidity, and the like.
• the curable hot melt silicone composition of the present invention comprises (A) R A R B (3-a) SiO 1/2 (R A is a silicon atom-bonded functional group containing an acrylic or methacrylic group). is a group, R B is a monovalent organic group excluding R A , a is a number in the range of 1 to 3) and a siloxane unit ( MRA unit) represented by SiO 4/2 ( a resinous organosiloxane block X having an acrylic or methacrylic group containing Q units) and ⁇ R C 2 SiO 2/2 ⁇ ⁇ (where R C is a monovalent organic group and ⁇ is a number of 2 or more); A resin-linear structure-containing organopolysiloxane block having at least two silicon atom-bonded functional groups (R A ) in the molecule, and a linear organosiloxane block Y having the siloxane unit represented 100 parts by mass of a copolymer and (B) 0.1 to 10 parts by mass
• the component (B) may be a photoradical polymerization initiator, a thermal radical polymerization initiator, or a combination thereof, and is used in the encapsulation process using the hot-melt silicone composition according to the present invention and the heat resistance of the encapsulation target.
• the type of component (B), the curing method, and the curing temperature may be appropriately selected according to the above.
• the component (B) when at least part of the component (B) is the photoradical polymerization initiator (B1), it has photocurability by irradiation with high energy rays, so that it has good curability at room temperature, active energy ray curing.
• a hot melt silicone composition of the type can be realized.
• the above problems can be suitably solved by the above curable hot-melt silicone composition molded into a sheet or film, a peelable laminate containing the same, and a method for producing the same.
• the above problems are solved by a cured product obtained by curing the curable hot-melt silicone composition according to the present invention, a semiconductor device or optical semiconductor device having the cured product, and a method for encapsulating them. is resolved to
• the curable silicone composition of the present invention has good hot-melt properties.
• the curable silicone composition of the present invention can be cured by heating at high temperatures and/or irradiated with high-energy rays such as ultraviolet rays. It is possible to cure in a wide range of temperatures from low to high temperatures, and in particular, good curability can be achieved even at low temperatures such as room temperature, and the resulting cured product has physical strength such as durability and transparency. It has excellent yellowing resistance and excellent handling workability such as overmolding. It can be used preferably.
• such a curable hot-melt silicone composition is prepared in the form of a void-free sheet or film having a thickness of 10 to 1000 ⁇ m, or the curable silicone composition sheet or film and a release sheet or It can be provided in the form of a peelable laminate containing a film.
• the sheet or film made of the curable silicone composition of the present invention, or the peelable laminate containing the same can be cut into a desired size as required in the manufacturing process of electronic parts such as semiconductor devices. It can be applied to industrial production processes such as batch sealing and batch bonding to large-area substrates. A good encapsulation process can be realized at a low temperature of
• room temperature refers to the temperature of the environment where the person handling the curable silicone composition of the present invention is present. Room temperature generally refers to 0°C to 40°C, especially 15°C to 30°C, especially 18°C to 25°C.
• the softening point of the composition is between 50 and 200°C, and the composition has a melt viscosity at 150°C (preferably It has a melt viscosity of less than 1000 Pa ⁇ s) and has a flowable property. Therefore, in this specification, the curable silicone composition having hot-melt properties of the present invention is also simply referred to as "curable hot-melt silicone composition".
• the curable hot-melt silicone composition of the present invention has a complex viscosity of more than 10,000 Pa s before curing at 25°C, or is solid and does not have fluidity, while before curing at 80°C.
• the complex viscosity of the composition preferably has a melt viscosity of less than 10,000 Pa s, preferably the complex viscosity at 80 ° C. is in the range of 100 to 10,000 Pa s, and the composition before curing at 80 ° C. It is more preferable that the complex viscosity is in the range of 200 to 9,000 Pa ⁇ s from the viewpoint of sealing processes for semiconductors and the like using the present composition.
• the complex viscosity of the composition before curing at 80° C. is within the above range, the low-temperature fluidity is excellent, so even for a substrate with low heat resistance, the composition can be applied to the sealing site at a relatively low temperature. There is an advantage that objects can be filled or molded.
• the complex viscosity at a certain temperature refers to the complex viscosity measured at a specific temperature using a complex viscometer such as Anton Paar's MCR302 in the range of 25°C to 100°C. .
• the curable hot melt silicone composition of the present invention is (A) R A R B (3-a) SiO 1/2 (R A is a silicon atom - bonded functional group containing an acrylic or methacrylic group, R B is a monovalent organic group excluding R A , a is a number in the range of 1 to 3) resinous organosiloxane block having an acrylic group or a methacrylic group, containing a siloxane unit (M RA unit) and a siloxane unit (Q unit) represented by SiO 4/2 X and a linear organosiloxane block Y having a siloxane unit represented by ⁇ R C 2 SiO 2/2 ⁇ ⁇ (R C is a monovalent organic group and ⁇ is a number of 2 or more), 100 parts by mass of a resin-linear structure-containing organopolysiloxane block copolymer having at least two silicon-bonded functional groups (R A ) in the molecule, and
• the curable hot-melt silicone composition of the present invention may be added with other additives known in the art (for example, heat-resistant additives, etc.) as long as the intended properties of the present invention can be maintained. good.
• the present composition may and preferably also contains a photosensitizer (B').
• the composition contains the above component (A), it has curability derived from the radically polymerizable group and is a low-fluidity or non-fluidity solid at room temperature, while having hot-melt properties. However, when heated, it exhibits fluidity and is used for applications such as sealing between substrates having uneven surfaces or curved substrates, so that the gaps in the substrates etc. are filled just enough and high It is extremely useful in the encapsulation process of semiconductors and the like because it can be rapidly cured by energy ray irradiation or heating, and can be sealed with the cured product in a state of sufficiently low internal stress.
• the shape of the curable hot-melt silicone composition of the present invention is not particularly limited.
• the components and optional components contained in the composition of the present invention are described below.
• Component (A) is the main ingredient of the present composition, and is a resin-linear structure-containing organopolysiloxane having a resinous organosiloxane block X having a silicon-bonded functional group containing an acryl or methacryl group and a chain organosiloxane block Y. It is a polysiloxane block copolymer and contains at least two of said acrylic or methacrylic groups in the molecule.
• Such component (A) imparts practically sufficient hot-melt properties including good fluidity (melt viscosity) at about 80° C. to the composition as a whole, and has a specific radically polymerizable group in the molecule. Therefore, by selecting (B) a radical polymerization initiator and a curing system, it is possible to achieve good curability in a wide temperature range from low to high temperatures such as room temperature.
• component (A) is R A R B (3-a) SiO 1/2
• R A is a silicon atom - bonded functional group containing an acrylic or methacrylic group
• R B is R A is a monovalent organic group except a is a number in the range of 1 to 3) acrylic group or A chain having a resinous organosiloxane block X having a methacrylic group and a siloxane unit represented by ⁇ R C 2 SiO 2/2 ⁇ ⁇
• R C is a monovalent organic group and ⁇ is a number of 2 or more
• It is a resin-linear structure-containing organopolysiloxane block copolymer having an organosiloxane block Y and at least two silicon-bonded functional groups (R A ) in the molecule.
• the composition as a whole constitutes the component (A) in order to give a practically suitable melt viscosity (specifically, a range in which the complex viscosity of the composition before curing at 80 ° C. is less than 10,000 Pa s)
• the molar ratio (mass ratio) between the resinous organosiloxane block X and the linear organosiloxane block Y is preferably in the range of 1:99 to 80:20, more preferably in the range of 20:80 to 60:40. is more preferable.
• a block copolymer in which these organosiloxane blocks (X and Y) satisfy the above molar ratio can be obtained by carrying out a synthesis reaction by adding the raw materials described later that give the X or Y block so that the above molar ratio is obtained. be able to.
• Component (A) is a resin-linear structure-containing organopolysiloxane block copolymer having a structure in which silicon atoms constituting resinous organosiloxane block X and linear organosiloxane block Y are linked by siloxane bonds or silalkylene bonds.
• the linking group can be introduced between the blocks by condensation reaction or hydrosilylation reaction of the raw materials described later that provide the X or Y block. From the standpoint of hot-melt properties, a structure in which block X and block Y are preferably linked by a siloxane bond between silicon atoms is particularly preferred.
• Component (A) is a siloxane unit (M RA unit) having a silicon atom-bonded functional group (R A ) containing an acrylic group or a methacrylic group in the resinous organosiloxane block X and a siloxane unit represented by SiO 4/2 (Q unit), and may further have a siloxane unit (M unit) represented by R B 3 SiO 1/2 (R B is a monovalent organic group other than R A above). From the standpoint of the hot-melt properties of component (A) as a whole, the total amount of M units and MRA units per 1 mol of Q units in resinous organosiloxane block X is 0.5 to 2.0 mol.
• T units siloxane units represented by RSiO 3/2 (wherein R is a monovalent organic group which may contain RA as described above) or R 2 SiO 2/ 2 (R is the same monovalent organic group as described above), but the sum of the amounts of the T units and D units per 1 mol of Q units is preferably less than 0.1 mol.
• the ratio (molar ratio) of the amount of each siloxane unit in the resinous organosiloxane block X or the MQ-type organopolysiloxane resin that provides the block X can be easily measured by 29 Si nuclear magnetic resonance. The same applies to other components than component (A).
• Component (A) has radical polymerization reactivity derived from the siloxane units ( MRA units) in the resinous organosiloxane block X, especially high-energy ray curability at low temperatures.
• the component (A) has at least two, preferably three or more silicon-bonded functional groups (R A ) containing acrylic or methacrylic groups in the molecule.
• R A silicon-bonded functional groups
• the amount of MRA units per mole of Q units in the resinous organosiloxane block X is preferably in the range of 0.02 to 0.50 moles, more preferably in the range of 0.02 to 0.40 moles. It is more preferable to have
• the silicon atom-bonded functional group RA in component (A) is not particularly limited as long as it has an acrylic or methacrylic group in the molecule, and is directly connected to the silicon atom constituting the MRA unit or via a divalent or higher functional group. can be used. Any reaction may be used for the reaction for introducing the functional group RA having an acrylic group or a methacrylic group onto the resinous organosiloxane. good.
• R A has the general formula: is represented by In the formula, each R 1 is independently a hydrogen atom, a methyl group, or a phenyl group, and is preferably a hydrogen atom or a methyl group to form an acryl group or methacryl group moiety.
• Z is a divalent organic group that may contain a hetero atom and is bonded to the silicon atom that constitutes the main chain of the polysiloxane *, and is a divalent organic group that may contain a silicon atom, an oxygen atom, a nitrogen atom, or a sulfur atom. may be a valent organic group.
• Z is an alkylene group having 2 to 22 carbon atoms
• Z 2 is * -[(CH 2 ) 2 O] m (C n H 2n )-(m is a number ranging from 0 to 3, n is 2 a number in the range of to 10) ⁇ , and -Z 1 -R 2 2 Si-OR 2 2 Si-Z 2 - described later. Any one group selected from divalent linking groups represented by is preferable.
• the silicon-bonded functional group (R A ) has the general formula (1): is represented by In the formula, each R 1 independently represents a hydrogen atom, a methyl group or a phenyl group, preferably a hydrogen atom or a methyl group. Each R 2 independently represents an alkyl group or an aryl group, and is industrially preferably an alkyl group having 1 to 20 carbon atoms or a phenyl group, particularly preferably a methyl group.
• Z 1 represents -O(CH 2 ) m - (m is a number ranging from 0 to 3), m is preferably 1 or 2.
• Z 2 is a divalent organic group represented by —C n H 2n — (where n is a number in the range of 2 to 10) bonded to a silicon atom constituting the main chain of polysiloxane *, and n is 2 to 6 are practically preferred.
• the silicon-bonded functional group (R A ) represented by the general formula (1) includes a silicon-bonded functional group (R Alk ) containing at least one alkenyl group, and a silicon-bonded hydrogen atom and a silicon-bonded hydrogen atom in the molecule.
• Method by reacting a hydrosilane compound having an acrylic functional group (e.g., 3-(1,1,3,3-tetramethyldisiloxanyl)propyl methacrylate, etc.) in the presence of a hydrosilylation reaction catalyst It can be introduced intramolecularly.
• a hydrosilylation reaction catalyst such as dibutylhydroxytoluene (BHT).
• RB which is a monovalent organic group other than RA in component (A), is an alkyl group such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group; Aryl groups such as tolyl group, xylyl group and naphthyl group; Aralkyl groups such as benzyl group and phenethyl group; Halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group and 3,3,3-trifluoropropyl group; Alkenyl groups such as a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group may also be included.
• alkyl group such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group
• Aryl groups such as to
• R B may be an alkenyl group having 2 to 12 carbon atoms, and is preferred.
• RB(Alk) 3 SiO 1/2 (where RB(Alk) is a carbon atom It may contain a siloxane unit (M Alk unit) represented by an alkenyl group of numbers 2 to 12).
• M Alk unit is an unreacted alkenyl group when R A is introduced by a hydrosilylation reaction to a silicon atom-bonded functional group containing at least one alkenyl group in the resinous organosiloxane block X.
• the alkenyl group in the component (A) is radically polymerizable in the same manner as the functional group RA , is capable of undergoing a radical polymerization reaction in the presence of the component (B), and introduces other curing reactions. may be used to achieve a dual cure system.
• the content of the M Alk units in the resinous organosiloxane block X is preferably in the range of 0.01 to 0.25 mol, more preferably 0.05 to 0.10 mol, per 1 mol of the Q unit. A range is particularly preferred.
• the chain organosiloxane block Y in component (A) is a chain represented by ⁇ R C 2 SiO 2/2 ⁇ ⁇ composed of diorganosiloxane units represented by R C 2 SiO 2/2 It has a siloxane structure.
• R C is a monovalent organic group, and may be one or more functional groups selected from RB , which is a monovalent organic group other than the above functional groups RA and RA . , from an industrial point of view, it is particularly preferable to contain one or more of methyl group, phenyl group, vinyl group and hexenyl group.
• Such component (A) contains a siloxane unit represented by R'SiO 1/2 and a siloxane unit represented by SiO 4/2 , and may optionally contain hydroxyl groups or other siloxane units. Obtained by linking a polysiloxane resin with a chain organopolysiloxane having a chain siloxane structure represented by ⁇ R C 2 SiO 2/2 ⁇ ⁇ and having a reactive functional group at the molecular chain end.
• R' is a monovalent organic group, and a group similar to the group selected from one or more functional groups selected from the above functional groups RA and RB which is a monovalent organic group other than RA .
• the functional group RA when the functional group RA is introduced by a hydrosilylation reaction with its precursor, a hydrosilane compound having a silicon-bonded hydrogen atom and a (meth)acrylic functional group, at least part of R' is It may be and is preferably an alkenyl group having 2 to 12 carbon atoms.
• the alkenyl group represented by R' in the molecule has a (meth)acrylic functional group. It is particularly preferred to introduce the functional group RA into the molecule by reacting it with a hydrosilane compound.
• the method of connecting the organopolysiloxane resin that provides the X block and the linear organopolysiloxane that provides the Y block is a reaction that can chemically link the two blocks (hereinafter sometimes referred to as "block polymerization").
• block polymerization a reaction that can chemically link the two blocks.
• a reaction that gives a siloxane bond or a silalkylene bond is preferable, and a condensation reaction or a hydrosilylation reaction is exemplified.
• the blocks are linked by siloxane bonds
• the blocks are linked by silalkylene bonds.
• the linking reaction between blocks includes dehydration condensation reaction of silanol, decarboxylic acid condensation reaction of silanol and acetoxysilane, dehydrogenative condensation reaction of silanol and hydrogensilane, hydrolytic condensation reaction of alkoxysilane, alkenyl group and a hydrosilylation reaction between silicon-bonded hydrogen atoms.
• a condensation reaction for block polymerization it is preferable to use an acid or a base as a catalyst.
• a weak acid or weak base is preferred to maintain the structure of each siloxane block. Examples include ammonia, acetic acid, and benzoic acid.
• the catalyst is preferably a low-valent transition metal complex or a Lewis acid such as borane, more preferably a hydrosilylation reaction catalyst that is a known platinum-based metal complex.
• Component (A) the resin-linear structure-containing organopolysiloxane block copolymer, is obtained by combining an MQ-type organopolysiloxane resin that provides block X and a chain organopolysiloxane that provides block Y by the above-described block polymerization. Since the polymer itself or its precursor copolymer can be obtained, it is relatively easy to control the molecular weight by selecting raw materials. In particular, from the standpoint of hot-melt properties of the present composition, when the molecular weight of component (A) is measured by gel permeation chromatography (GPC) or the like, the molecular weight distribution curve preferably has at least one maximum.
• GPC gel permeation chromatography
• a curable hot-melt silicone composition can be designed simply by combining such component (A) with a radical polymerization initiator (B).
• Component (B) is a radical polymerization initiator, and may be (B1) a photoradical polymerization initiator, (B2) a thermal radical polymerization initiator, or a combination thereof.
• the type of component (B), the curing method, and the curing temperature may be appropriately selected according to the heat resistance of the object.
• Component (A) according to the present invention has, in addition to hot-melt properties, a silicon atom-bonded functional group containing a radically polymerizable acrylic or methacrylic group in the molecule, and optionally an alkenyl group. Good curability can be achieved by irradiation with high-energy rays and/or heating in the presence.
• Component (B) is used in an amount of 0.1 to 10 parts by mass, particularly preferably 0.2 to 5 parts by mass, per 100 parts by mass of component (A).
• the amount of component (B) used depends on the sealing process and curing time for applying the present composition, the content of silicon atom-bonded functional groups (R A ) derived from component (A), and the amount of high-energy ray irradiation. And/or it can be appropriately designed within the above range depending on the heating conditions.
• Component (B1) is a radical photopolymerization initiator, which accelerates the photocuring reaction of the acrylic group or methacrylic group of the silicon-bonded functional group (R A ) in component (A) by irradiation with high-energy rays such as ultraviolet rays. is an ingredient.
• Radical photopolymerization initiators are roughly classified into photocleavage type and hydrogen abstraction type, but the photoradical polymerization initiator used in the composition of the present invention is arbitrarily selected from those known in the art. It can be selected and used, and is not particularly limited. Some photoradical polymerization initiators can accelerate the curing reaction not only under irradiation with high-energy rays such as ultraviolet rays but also under light irradiation in the visible light range.
• radical photopolymerization initiators include 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone, ⁇ -hydroxy- ⁇ , ⁇ '-dimethylacetophenone, 2-methyl-2 ⁇ -ketol compounds such as hydroxypropiophenone and 1-hydroxycyclohexylphenyl ketone; methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1-[4 Acetophenone compounds such as -(methylthio)-phenyl]-2-morpholinopropane-1; benzoin ether compounds such as benzoin ethyl ether, benzoin isopropyl ether, and anisoin methyl ether; ketal compounds such as benzyl dimethyl ketal; aromatic sulfonyl chloride compounds such as naphthalenesulfonyl chloride; photoactive oxime compounds such as 1-phenone-1,1-
• bis-(2,6-dichlorobenzoyl)phenylphosphine oxide bis-(2,6-dichlorobenzoyl)-2,5- Dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl) )-2,4,4-trimethylpentylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine bisacylphosphine oxides such as oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide and bis-(2,4,6-trimethylbenzoyl
• acetophenone-based photopolymerization initiators suitable as the component (B1) in the present invention include Omnirad 907, 369, 369E, 379 manufactured by IGM Resins.
• Commercially available acylphosphine oxide-based photopolymerization initiators include Omnirad TPO, TPO-L, and 819 manufactured by IGM Resins.
• Commercially available oxime ester photopolymerization initiators include Irgacure OXE01 and OXE02 manufactured by BASF Japan Ltd., N-1919 manufactured by ADEKA Co., Ltd., Adeka Arcles NCI-831, NCI-831E manufactured by Changzhou Yutaka Electronic New Materials Co., Ltd. and TR-PBG-304.
• Component (B2) is a thermal radical polymerization initiator that generates radical species upon heating and accelerates the curing reaction of the acrylic or methacrylic group of the silicon-bonded functional group (R A ) in component (A).
• thermal radical polymerization initiators include azo compounds and organic peroxides.
• azo compounds 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1 '-Azobis-1-cyclohexanecarbonitrile, dimethyl-2,2'-azobisisobutyrate, dimethyl-2,2'-azobis (2-methylpropionate), dimethyl-1,1'-azobis (1 -cyclohexanecarboxylate), 4,4′-azobis(4-cyanovaleric acid), 2,2′-azobis(2-amidinopropane) dihydrochloride, 2-tert-butylazo-2-cyanopropane, 2,2 '-Azobis(2-methylpropionamide) dihydrate, 2,2'-azobis(2,4,4-trimethylpentane) and the like.
• organic peroxides include alkyl peroxides, diacyl peroxides, ester peroxides, and carbonate peroxides.
• the alkyl peroxides include dicumyl peroxide, di-tert-butyl peroxide, di-tert-butylcumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy ) hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, tert-butylcumyl, 1,3-bis(tert-butylperoxyisopropyl)benzene, 3,6,9- Triethyl-3,6,9-trimethyl-1,4,7-triperoxonane is exemplified.
• diacyl peroxides include benzoyl peroxide, lauroyl peroxide, and decanoyl peroxide.
• peroxide esters include 1,1,3,3-tetramethyl butyl peroxy neodecanoate, ⁇ -cumyl peroxy neo decanoate, tert-butyl peroxy neo decanoate, tert-butyl peroxy neoheptanoate, tert-butyl peroxypivalate, tert-hexyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, tert-amylperoxyl-2- Ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyisobutyrate, di-tert-butylperoxyhexahydroterephthalate, tert-
• Peroxycarbonates include di-3-methoxybutylperoxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, diisopropylperoxycarbonate, tert-butylperoxyisopropylcarbonate, di(4-tert-butylcyclohexyl ) peroxydicarbonate, dicetyl peroxydicarbonate, dimyristyl peroxydicarbonate.
• the present composition can also use (B') a photosensitizer in combination with (B1) a photoradical polymerization initiator.
• 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 the 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.
• Sensitizers include anthracene compounds, phenothiazine compounds, perylene compounds, cyanine compounds, merocyanine compounds, coumarin compounds, benzylidene ketone compounds, (thio)xanthene or (thio)xanthone compounds such as isopropyl Thioxanthone, 2,4-diethylthioxanthone, squalium-based compounds, (thia)pyrylium-based compounds, porphyrin-based compounds, and the like are known, and any photosensitizer may be used in the curable organopolysiloxane composition of the present invention. It can be used for products and adhesive compositions. The amount used is arbitrary, but the mass ratio of the component (B') to the component (B1) is in the range of 0 to 10, and when used, it is selected in the range of 0.01 to 5. is common.
• the present composition contains the above components (A) and (B), it forms a cured product through a radical polymerization reaction.
• the present composition when at least part of the component (B) is the radical photopolymerization initiator (B1), the present composition can be cured by irradiation with high-energy rays such as ultraviolet rays.
• the thermal radical polymerization initiator (B2) when at least part of the component (B) is the thermal radical polymerization initiator (B2), the present composition can be cured by heating.
• heating and high-energy ray irradiation can be selected or combined for curing, and can be appropriately selected according to the desired curing method and sealing process.
• the component (A) contains a hot-melt property and a (meth)acrylic group-containing group, it is melted by heating to fill the unevenness of the base material or member for sealing. and suitable for curing processes under low stress conditions.
• a photo-curing process involving irradiation with energy rays can be preferably used, in which case at least part of component (B) is (B1) a photoradical polymerization initiator, and optionally (B') a photosensitizer.
• the base material or member involved in the encapsulation process has sufficient heat resistance, or if at least part of the component (B) is the thermal radical polymerization initiator (B2), rapid curing at high temperatures is possible. It has the advantage of being
• composition according to the present invention further comprises (C) M units represented by R B 3 SiO 1/2 and R A a R B (3-a) SiO 1/2 in the molecule, and Q units, It may contain an organopolysiloxane resin containing a material amount ratio of M units to Q units in the range of 0.5 to 2.0.
• a represents an integer of 1 to 3
• R A is a silicon atom-bonded functional group containing an acrylic group or a methacrylic group
• R B is a monovalent organic group excluding R A
• At least one of the M units constituting component (C) is a triorganosiloxy unit containing a functional group R A represented by R A R B (3-a) SiO 1/2 .
• Component (C) is an MQ-type organopolysiloxane resin having an acrylic or methacrylic group in the molecule, and at least one silicon-bonded functional group containing an acrylic or methacrylic group represented by RA in the molecule. , it participates in the same curing reaction as component (A).
• Component (C) is optionally a component that adjusts the adhesion to the substrate, the crosslink density of the cured product, and the melt viscosity. And it is possible to adjust the adhesion to the substrate.
• Component (C) is a siloxane unit (T unit) represented by a small amount of RSiO 3/2 (R is the above monovalent organic group that may contain RA ) or R 2 SiO 2/2 (R is the same as above ( monovalent organic group of _ _ _ _ It is preferable to consist only of M units and Q units represented by and the sum of the amount of T units and D units per 1 mol of Q units in component (C) is preferably less than 0.1 mol.
• the ratio (molar ratio) of the amount of M units to Q units in component (C) is in the range of 0.5 to 2.0, preferably in the range of 0.5 to 1.5, and 0.5 to 2.0. It is more preferably in the range of 55 to 1.20, particularly preferably in the range of 0.60 to 1.10.
• the amount of component (C) to be used is arbitrary and not particularly limited, but it is preferably in the range of 0.1 to 50 parts by mass, preferably 0.1 to 25 parts by mass, per 100 parts by mass of component (A). is particularly preferred.
• composition of the present invention optionally contains a linear organopolysiloxane having silicon-bonded functional groups (R A ) containing acrylic or methacrylic groups that do not fall under component (A) or component (C). It's okay.
• the present composition may contain one or more chain organopolysiloxanes selected from the following components (C'1) and (C'2).
• Component (C'1) is a straight-chain organopolysiloxane having at least one functional group (R A ) in the molecule, represented by the following structural formula (C'-1).
• R 1 is independently a C1-C6 alkyl group, C2-C20 alkenyl group, C6-C12 aryl group
• R A' is independently a C1-C6 alkyl group, C2-C20 alkenyl a C6-C12 aryl group, and a silicon atom-bonded functional group (R A ) including the aforementioned acryl or methacryl groups
• n1 is a positive number
• n2 is 0 or a positive number be.
• at least one of R A' is a silicon atom-bonded functional group (R A ) containing an acryl group or a methacryl group as described above.
• n1+n2 is a positive number of 0 or more and is not limited, it is preferably in the range of 10 to 5,000, more preferably 10 to 2,000, still more preferably 10 to 1,000.
• the value of n1+n2 is such that the viscosity of component (C'1) at 25° C. is in the range of 1 to 100,000 mPa ⁇ s, more preferably 10 to 50,000 mPa ⁇ s, and still more preferably 500 to 50,000 mPa ⁇ s. Any number that satisfies the viscosity range of s may be used and is preferred.
• the component (C'2) has at least one functional group (R A ) in the molecule, represented by the following average unit formula (C'-2), and is a branched chain containing a branched siloxane unit. It is an organopolysiloxane. Unlike component (A) or component (C), component (C'2) does not contain an MQ-type organopolysiloxane resin structure, and the T unit or Q unit in its molecule is a branched chain organopolysiloxane. It is included only as a unit.
• Component (C'2) is, more specifically, a branched organopolysiloxane represented by the following siloxane unit formula.
• R A' R 1 2 SiO 1/2 a (R 1 2 SiO 2/2 ) b1 (RA ' R 1 SiO 2/2 ) b2 (R 1 SiO 3/2 ) c1 (R A' SiO 3 /2 ) c2
• R 1 and R A′ are the same groups as above
• component (C'2) may be a branched organopolysiloxane having methacryloyl group-containing organic groups only on terminal M units represented by the following siloxane unit formula.
• R A' R 1 2 SiO 1/2 a (R 1 2 SiO 2/2 ) b1 (R 1 SiO 3/2 ) c1
• R 1 and R A′ are the same groups as described above, and 0 ⁇ a ⁇ 10, 15 ⁇ b1 ⁇ 2000, 0 ⁇ c1 ⁇ 10, and at least one of R A′ is the above acrylic group. or a silicon atom-bonded functional group (R A ) containing a methacrylic group.
• the viscosity of component (C'2) at 25° C. is preferably 10 to 50,000 mPa ⁇ s, more preferably 100 to 2,000 mPa ⁇ s.
• the chain organopolysiloxane as the component (C') has at least one silicon-bonded functional group containing an acrylic or methacrylic group represented by RA in the molecule. Participates in the same curing reaction as component (A).
• Component (C′) is optionally a component that adjusts the adhesion to the substrate, the crosslink density of the cured product, and the melt viscosity. It is possible to adjust the thickness and the adhesion to the substrate, and it may be particularly useful for adjusting the crosslink density.
• the amount of linear organopolysiloxane used as component (C') is not particularly limited, but it is preferably in the range of 0.1 to 50 parts by mass, preferably 0.1 part per 100 parts by mass of component (A). A range of up to 25 parts by mass is particularly preferred.
• composition according to the present invention further contains (D) M units represented by R B 3 SiO 1/2 and Q units in the molecule, and the ratio of M units to Q units is 0.5 to 2.0. It may contain an organopolysiloxane resin containing in the range of In the formula, RB is a monovalent organic group excluding RA , and is exemplified by the same groups as above. Unlike component (C), component (D) does not contain siloxane units containing functional groups RA and RA in the molecule.
• Component (D) is an MQ-type organopolysiloxane resin that does not have acryl or methacryl groups in the molecule, does not participate in the same curing reaction as component (A), but optionally adheres to substrates. , is a component that adjusts the crosslink density and melt viscosity of the cured product. The hardness of the cured product of the present composition and the adhesion to the substrate can be adjusted according to the amount of the component used.
• Component (D) may contain a small amount of siloxane units represented by R B SiO 3/2 (T units) or R B 2 SiO 2/2 (D units), but substantially In addition, it is preferable to consist only of M units and Q units represented by R B 3 SiO 1/2 above, and the sum of the amount of T units and D units per 1 mol of Q units in component (D) is 0 It is preferably less than 0.1 mol.
• the ratio (molar ratio) of the amount of M units to Q units in component (D) is in the range of 0.5 to 2.0, preferably in the range of 0.5 to 1.5, and 0.5 to 2.0. It is more preferably in the range of 55 to 1.20, particularly preferably in the range of 0.60 to 1.10.
• the amount of component (D) used is arbitrary and not particularly limited, but is preferably in the range of 0.1 to 200 parts by mass, and in the range of 5 to 150 parts by mass, per 100 parts by mass of component (A). is more preferable, and the range of 10 to 100 parts by mass is particularly preferable.
• composition according to the invention may further comprise (E) a polydimethylsiloxane optionally bearing alkenyl groups. Since the component (E) itself has fluidity, by using it together with the component (A), etc., the melting properties of the composition, the adhesion of the cured product to the substrate, the hardness, the crosslink density, etc. may be adjusted.
• component (E) is a polydimethylsiloxane that is liquid or plastic at 25°C and optionally has at least two alkenyl groups having 2 to 20 carbon atoms in the molecule. be. From the scope of the component (E), the above component (A) is explicitly excluded, and the preferred component (E) is an alkenyl group having 2 to 20 carbon atoms in which part of the methyl groups bonded to silicon atoms is Cyclic, linear, branched, resinous and gum-like polydimethylsiloxanes optionally substituted with
• the degree of siloxane polymerization and the viscosity range of polydimethylsiloxane, which is the component (E), are not particularly limited, but the viscosity at 25 ° C. may be in the range of 1.5 to 1,000,000 mPa s.
• a cyclic polydimethylsiloxane having a degree of siloxane polymerization of 3 to 20 and optionally having an alkenyl group is included in the scope of component (E).
• the end of the molecular chain may have a structure blocked by a non-reactive trialkylsilyl group such as a trimethylsilyl group, such as a vinyldimethylsilyl group. It may have a structure blocked by a reactive functional group such as an alkenyldimethylsilyl group, an alkoxydimethylsilyl group, or a hydroxydimethylsilyl group.
• a non-reactive trialkylsilyl group such as a trimethylsilyl group, such as a vinyldimethylsilyl group.
• a reactive functional group such as an alkenyldimethylsilyl group, an alkoxydimethylsilyl group, or a hydroxydimethylsilyl group.
• the composition according to the invention may optionally contain (F) an organic solvent.
• the organic solvent may be used as a diluent for dispersing or dissolving each component in order to improve the coatability and wettability of the composition on the substrate, and is inevitably included as a solvent accompanying other raw material components. It may be a component that can be
• any organic solvent that can dissolve all or part of the constituents in the composition can be used.
• the type is not particularly limited, and those having a boiling point of 80° C. or higher and 200° C. or lower are preferably used.
• the types thereof may be non-halogen solvents or halogen solvents, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, ester solvents, alcohol solvents, ether solvents, chlorinated aliphatic hydrocarbon solvents.
• Hydrogen-based solvents, solvent volatile oils, and the like can be mentioned, and two or more of them may be combined according to coatability, wettability, and the like.
• the content of the organic solvent is small enough so that the hot-melt properties are not impaired by a large amount of the organic solvent, since the composition is a hot-melt silicone composition with low or non-fluidity at 25°C. It is necessary. As an example, it is particularly preferable that the content of component (F) is 0 to less than 5% by mass with respect to 100 parts by mass of the entire composition. In particular, when the composition is molded into a sheet or film, which will be described later, it is preferable to remove the component (F) used in the molding by heating or the like.
• the composition may further contain a known tackifier as component (G).
• Component (G) improves the adhesive strength of the cured product obtained by curing the present composition to the substrate, and can be used by selecting one or more from known adhesion imparting agents. .
• the adhesive strength may be significantly improved after a certain period of time.
• Component (G) is used in an amount of 0.01 to 5 parts by mass, particularly preferably 0.02 to 2 parts by mass, when the total composition of the present invention is 100 parts by mass. . If the amount of component (G) used is less than the lower limit, the adhesive strength to the substrate may not be sufficiently improved. may affect the appearance of the
• component (G) contains an organic compound having 2 or 3 alkoxysilyl groups at the molecular chain ends.
• the organic compound referred to here includes an organic silicon compound in addition to an alkane compound and the like.
• organic compounds having two alkoxysilyl groups at the molecular chain ends include 1,2-bis(trimethoxysilyl)ethane, 1,2-bis(triethoxysilyl)ethane, 1,2-bis (methyldimethoxysilyl)ethane, 1,2-bis(methyldiethoxysilyl)ethane, 1,3-bis(trimethoxysilyl)propane, 1,4-bis(trimethoxysilyl)butane, 1,4-bis( triethoxysilyl)butane, 1-methyldimethoxysilyl-4-trimethoxysilylbutane, 1-methyldiethoxysilyl-4-triethoxysilylbutane, 1,4-bis(methyldimethoxysilyl)butane, 1,4-bis (methyldiethoxysilyl)butane, 1,5-bis(trimethoxysilyl)pentane, 1,5-bis(triethoxysilyl)pentane, 1,4-bis((tri
• organic compounds having three alkoxysilyl groups include 1,3,5-tris ⁇ 2-(trimethoxysilyl)ethyl ⁇ -1,1,3,5,5-pentamethyltrisiloxane, 1 , 3,5-tris ⁇ 2-(methyldimethoxysilyl)ethyl ⁇ -1,1,3,5,5-tetramethyldisiloxane, 1,3,5-tris ⁇ 2-(triethoxysilyl)ethyl ⁇ -1,1,3,5,5-tetramethyldisiloxane, 1,3,5-tris ⁇ 2-(methyldiethoxysilyl)ethyl ⁇ -1,1,3,5,5-tetramethyldisiloxane, Examples include trisiloxane compounds having three alkoxysilyl groups such as 1,3,5-tris ⁇ 6-(trimethoxysilyl)hexyl ⁇ -1,1,3,5,5-tetramethyldisiloxane.
• component (G) in the present invention in addition to silane compounds such as 3-glycidoxypropyltrimethoxysilane, organosiloxane oligomers, and alkylsilicates, JP-B-52-8854 and JP-A-10-195085 Disclosed reaction mixtures of amino group-containing organoalkoxysilanes and epoxy group-containing organoalkoxysilanes, particularly carbasilatrane derivatives having silicon-bonded alkoxy groups or silicon-bonded alkenyl groups in one molecule, alkoxysilyl group-containing organic Silatrane derivatives and the like having groups can be used and are preferred. These are also disclosed in the above-mentioned Patent Documents 1 to 4, and an appropriate tackifier can be selected from these and used.
• the composition according to the present invention may further contain (H) a polyfunctional thiol compound having at least two thiol groups in the molecule. Since a polyfunctional thiol compound acts as a chain transfer agent to promote radical polymerization, a part of the component (B) according to the present invention is a radical photopolymerization initiator, and the composition is exposed to high energy such as ultraviolet rays. When curing by radiation irradiation, In addition to improving the curing speed and the deep-part curability of the cured product even when the irradiation dose of the high-energy beam is small, it also functions as a cross-linking point in the present composition.
• polyfunctional thiol compounds examples include pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(2-(3 sulfanylbutanoyloxy)ethyl)-1,3,5-triazinane-2,4,6-trione, trimethylolpropane tris(3-mercaptobutyrate), and the like.
• Component (H) may be used arbitrarily. An amount of 0 to 5 parts by weight is particularly preferred.
• the present composition may contain heat-resistant components such as iron oxide (red iron oxide), cerium oxide, cerium dimethylsilanolate, fatty acid cerium salts, cerium hydroxide, zirconium compounds, etc., as optional components as long as they do not impair the object of the present invention.
• Antioxidants such as phenol, quinone, amine, phosphorus, phosphite, sulfur, or thioether;
• Light stabilizers such as triazole or benzophenone; one or more antistatic agents such as cationic surfactants, anionic surfactants, or nonionic surfactants; and the like.
• composition according to the present invention may optionally contain pigments, dyes, inorganic fine particles (reinforcing fillers, dielectric fillers, conductive fillers, thermally conductive fillers), etc., depending on the application. It can also be blended with pigments, dyes, inorganic fine particles (reinforcing fillers, dielectric fillers, conductive fillers, thermally conductive fillers), etc., depending on the application. It can also be blended with pigments, dyes, inorganic fine particles (reinforcing fillers, dielectric fillers, conductive fillers, thermally conductive fillers), etc., depending on the application. It can also be blended with pigments, dyes, inorganic fine particles (reinforcing fillers, dielectric fillers, conductive fillers, thermally conductive fillers), etc., depending on the application. It can also be blended with pigments, dyes, inorganic fine particles (reinforcing fillers, dielectric fillers, conductive fillers, thermally conductive fillers), etc.,
• the curable hot-melt silicone composition of the present invention may be used in the form of granules, pellets, sheets or films.
• the composition may be used after being molded into a sheet or film.
• a sheet or film made of the curable silicone composition of the present invention having an average thickness of 10 to 1000 ⁇ m has hot-melt properties and can be irradiated with high-energy rays or heated depending on the type of component (B). Since it has curability due to a radical polymerization reaction that serves as a trigger, it is excellent in handling workability and melting properties, and is particularly advantageous for use in overmold molding and the like.
• the present curable hot-melt silicone composition can be used in the form of a sheet or film. It can be used as a laminate having a structure in which materials are interposed. A film-like substrate provided with this release layer (generally referred to as a release film) can be peeled off from the sheet-like material when the sheet-like material made of the curable hot-melt silicone composition is used as an adhesive or sealant. can be done.
• this laminate is also referred to as a peelable laminate.
• the sheet or film of the curable hot-melt silicone composition described above is Step (I): a step of applying the above curable hot melt silicone composition onto a substrate; Step (II): It can be obtained by a step of heating and drying the composition applied in step (I) to obtain a composition molded into a sheet or film.
• the composition itself may be melted by heating and applied to the substrate in a fluid state, or an organic solvent may be used. It may be applied onto the substrate in the form of a dispersion solution and the organic solvent removed in step (II).
• a release layer is present on the substrate, the sheet or film of the curable hot-melt silicone composition can be obtained as part of the release laminate described below.
• the method for producing the peelable laminate described above is not particularly limited, but as an example, the following step 1: a step of mixing the components of the curable hot-melt silicone composition; Step 2: a step of kneading the mixture obtained in step 1 while heating and melting; Step 3: A step of laminating the heat-melted mixture obtained in step 2 between two release films having at least one release surface so that the mixture is in contact with the release surface to form a laminate. Step 4: The laminate obtained in Step 3 is pressed between rolls, and the mixture interposed between two release films is rolled to obtain a curable hot-melt silicone composition sheet or sheet having a specific film thickness. Mention may be made of a method comprising the step of forming a film.
• step 4 rolls with cooling or temperature control capabilities may be used.
• step 4 a step of cutting the obtained laminate containing the curable hot-melt silicone composition sheet or film may be added.
• step 2 the mixture obtained in step 1 may be dispersed in an organic solvent and applied on a release film, and the organic solvent may be removed by heating or the like before step 3.
• this release film is not particularly limited, and therefore includes what is generally called a film as well as what is called a sheet. However, it is referred to herein as a release film regardless of its thickness.
• the temperature of the mixing step in step 1 is not particularly limited, but may be heated as necessary so that each component is sufficiently mixed, and the heating temperature can be, for example, 50°C or higher.
• the sheet or film of the present invention preferably has a thickness of 10 to 1000 ⁇ m, and is preferably flat. Flat means that the thickness of the resulting sheet or film is within ⁇ 100 ⁇ m or less, preferably within ⁇ 50 ⁇ m or less, more preferably within ⁇ 30 ⁇ m or less.
• the type of material for the base material of the release film that constitutes the release laminate is not particularly limited, but for example, a polyester film, polyolefin film, polycarbonate film, acrylic film, or the like can be used as appropriate.
• the sheet-like substrate is preferably non-porous.
• a release film is a film having a release layer formed by treating one or both sides of a film of such materials to impart release properties, such treatments being known in the art.
• a layer having releasability provided on the surface of the release film is called a release layer.
• the release layer enables the sheet or film made of the curable silicone composition to be easily separated from the film-like substrate. It is also called a release liner, separator, release layer or release coating layer.
• the release layer can be formed as a release layer having a release coating capability such as a silicone-based release agent, a fluorine-based release agent, an alkyd-based release agent, or a fluorosilicone-based release agent.
• fine physical irregularities may be formed on the surface of the film-like substrate to reduce adhesion to the curable silicone composition, or the film-like substrate may be made of the curable hot-melt silicone composition of the present invention or a cured product thereof.
• the substrate may be made of a material that is difficult to adhere to the layer.
• the above-described laminate is formed by peeling off one of the two release films that constitute the laminate, and then attaching an uncured sheet or film-like member made of a curable silicone composition that is not in contact with the release film to the adherend.
• the uncured sheet or film-like member can be peeled off from another film-like substrate, that is, a release film.
• the curable silicone composition can be handled in the form of granules, pellets, or sheets at room temperature, and is a low-flowing or non-flowing solid at 25°C.
• non-flowing means that it does not deform and/or flow in the absence of external force. It does not deform and/or flow in the absence of Such non-fluidity means that, for example, the composition is substantially deformed even when the molded composition is placed on a hot plate at 25° C. and no external force is applied to the composition or a certain load is applied to the composition. and/or non-flowing. If the composition is non-flowing at 25° C., the shape retention of the composition at that temperature is good and the surface tackiness is low, so that the composition can be easily handled even in an uncured state.
• the softening point of the present composition is preferably 100°C or less.
• Such a softening point is high when the composition with a height of 22 mm is pressed on a hot plate with a load of 100 g weight for 10 seconds from above, and the amount of deformation of the composition is measured after the load is removed. It means the temperature at which the amount of deformation in the longitudinal direction becomes 1 mm or more.
• the curable hot-melt silicone composition sheet obtained by the production method of the present invention is a curable silicone composition containing the components described above and has hot-melt properties.
• the curable hot-melt silicone composition sheet of the present invention can be used as a heat-meltable pressure-sensitive adhesive, sealant, and/or adhesive.
• the curable hot-melt silicone composition sheet has excellent moldability, gap-filling properties, and adhesive strength, and can be used as a die attach film or film adhesive. It can also be suitably used as a curable hot-melt silicone composition sheet for overmolding, compression molding or press molding.
• the release film After peeling off the curable hot-melt silicone composition sheet obtained by the manufacturing method of the present invention from the release film, it is placed on a desired portion of a semiconductor or the like, melted by heating, and the base material.
• a film adhesive layer is formed on and between the adherends, making use of the gap-filling properties for the unevenness and gaps on the adherends, and the adherends are temporarily fixed, arranged, and laminated, and further, the The curable hot-melt silicone composition layer is cured by irradiation with high-energy rays or by heating to form a cured product of the curable silicone sheet between the adherends, thereby adhering the adherends.
• the release film may be peeled off after heating the curable hot-melt silicone composition sheet to form a cured product. The timing of release from the curable silicone composition or cured product obtained therefrom may be selected.
• the curable silicone composition sheet Since the curable silicone composition sheet has hot-melt properties, it can be softened or fluidized by heating the sheet before the final curing. , the unevenness and gaps can be filled without gaps to form an adhesive surface with the adherend.
• various constant temperature baths, hot plates, electromagnetic heating devices, heating rolls and the like can be used as means for heating the curable hot-melt silicone composition sheet.
• an electric heat press, a diaphragm type laminator, a roll laminator, etc. are preferably used. .
• the curable hot-melt silicone composition according to the present invention can be designed as a photocurable composition by irradiation with high-energy rays, or as a thermosetting composition by heating, depending on the selection of component (B). can also be designed.
• component (B) is (B1) a photoradical polymerization initiator
• the curable silicone composition of the present invention can be applied to the composition of the present invention (or its semi-cured product) by high-energy rays such as ultraviolet rays.
• high-energy rays such as ultraviolet rays.
• a radical polymerization reaction proceeds to form a cured product.
• Usable high-energy rays include ultraviolet rays, gamma rays, X-rays, ⁇ -rays, electron beams, and the like.
• ultraviolet rays, X-rays, and electron beams emitted from a commercially available electron beam irradiation device can be mentioned. It is preferable from the viewpoint of industrial use.
• the irradiation dose varies depending on the type of the high-energy beam active catalyst, in the case of ultraviolet rays, the cumulative irradiation dose at a wavelength of 365 nm is preferably within the range of 100 mJ/cm 2 to 100 J/cm 2 .
• low temperature means, for example, 100° C. or lower, specifically a temperature range of 15° C. to 100° C., and a temperature of 80° C. or lower can be selected.
• reaction of the composition of the present invention proceeds in a temperature range of 15 to 100 ° C., it is preferably around room temperature (a temperature range that can be reached without heating or cooling, and 20 to In particular, the temperature range of 25° C. is included), the composition may be left standing, may be cooled to room temperature or lower and 15° C.
• heating above 100° C. may be temporarily performed, or heat and pressure bonding may be performed at the same time to allow the curing reaction to proceed at the same time as the pressure bonding.
• the curable silicone composition of the present invention is heated to 100° C. or higher to allow the radical polymerization reaction to proceed and cure to occur. can form objects.
• the heating temperature can be appropriately selected according to the heat resistance of the base material, the sealing process, and the like. If the base material has high heat resistance, it can be heated at a high temperature of 150° C. or higher.
• the cured product of the curable hot-melt silicone composition of the present invention is characterized by excellent resistance to yellowing under conditions of high temperature, high humidity, or exposure to ultraviolet light. That is, by using the present composition, in a high temperature exposure test at 150 ° C. or an accelerated weathering test (hereinafter referred to as a QUV test) in accordance with ASTM G 154 Cycle 4, the thickness of the cured product is 200 um After 500 hours A cured product with a b * value of 2.0 or less, preferably 1.0 or less, can be obtained.
• conventional active energy ray-curable hot-melt silicone compositions that can be cured at low temperatures have low resistance to yellowing of the cured product and are not suitable for applications requiring transparency.
• the cured product according to the present invention can be rapidly cured at low temperatures if necessary, has excellent yellowing resistance, and has high transparency even when used under severe conditions. can be maintained, there is an advantage that it can be suitably applied to optical material applications including sealants for optical semiconductors.
• the composition according to the present invention can be suitably used for sealing a substrate having poor heat resistance with a transparent cured product.
• the curable hot-melt silicone composition of the present invention has hot-melt properties, excellent handling and curability when melted (hot-melt), and a cured product obtained by curing the composition at high temperatures. Since it is excellent in color resistance under the environment, it is useful for semiconductor members such as encapsulants for light-emitting/optical devices and light-reflecting materials, and optical semiconductors having the cured product. Furthermore, since the cured product has excellent mechanical properties, it can be used as a sealing agent for semiconductors; a sealing agent for power semiconductors such as SiC and GaN; suitable as an agent.
• the sheet-shaped curable hot-melt silicone composition of the present invention is also suitable as a material for sealing and bonding large-area substrates using press molding, compression molding, or a vacuum laminator.
• it is suitable for use as a sealing agent for semiconductors that use an overmolding method at the time of molding.
• the sheet of the present composition can be used as a curable film adhesive or as a stress buffer layer between two substrates having different coefficients of linear expansion.
• the curable hot-melt silicone composition of the present invention can be used for large-area sealing of semiconductor substrates (including wafers).
• sheets obtained by molding the curable hot-melt silicone composition of the present invention into sheets can be used as die attach films, sealing of flexible devices, stress relaxation layers for bonding two different substrates, and the like. can. That is, the curable silicone composition of the present invention may be a sealant intended for single-sided encapsulation, or a sealant intended for double-sided encapsulation accompanied by adhesion between two substrates. and have favorable properties suitable for these applications.
• the use of the cured product obtained by curing the curable silicone composition of the present invention is not particularly limited.
• the composition of the present invention has hot-melt properties, excellent curability, excellent moldability and mechanical properties, and its cured product has excellent yellowing resistance and can maintain high transparency. is.
• the cured product obtained by curing the present composition can be suitably used as a member for semiconductor devices, and is suitable as a sealing material for semiconductor elements, IC chips, etc., and as an adhesive/bonding member for conductor devices. can be used.
• the composition of the present invention in particular is an optically transparent cured product. It can be suitably used in applications where it is necessary to transmit light in order to form
• it is preferably a light-emitting semiconductor device which is a light-emitting/optical device, an optical member for a display, a member for a solar panel, particularly a sealing material or an adhesive member used in these devices.
• the cured product of the present invention has excellent yellowing resistance (coloring resistance) when exposed to high temperatures and ultraviolet rays, so it is used as a sealant or adhesive for electronic materials where transparency, light resistance, and heat resistance are important. It can be used more preferably as a member.
• the curable hot-melt silicone composition according to the present invention is Step (E-1): A step of bringing the curable hot-melt silicone composition according to the present invention into close contact with a part or all of a substrate, which is a semiconductor device, an optical semiconductor device, or a precursor thereof; Step (E-2): Encapsulation of a semiconductor device or an optical semiconductor device, including a step of curing an uncured curable hot-melt silicone composition at room temperature or by heating after optionally irradiating with high-energy rays. It can be suitably used for the stopping method.
• the curable hot-melt silicone composition of the present invention is caused to flow by heating to fill irregularities and voids in the substrate, which is a semiconductor device, an optical semiconductor device, or a precursor thereof. By doing so, it is possible to seal a semiconductor device or an optical semiconductor device with a cured product having excellent gap-filling properties between base materials.
• a toluene solution of a platinum/1,3-divinyltetramethyldisiloxane complex was added to the mixture in an amount of 2 ppm in terms of mass of platinum, and the mixture was stirred for 4 hours while adjusting the temperature so that the temperature of the mixture was 40°C to 50°C.
• A1 Organopolysiloxane A2 shown in Synthesis Example (1): Organopolysiloxane A3 shown in Synthesis Example (2) Organopolysiloxane B1 shown in Synthesis Example (3); 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Product name: Omnirad TPO, manufactured by IGM Resins) B2: 2-hydroxy-2-methylpropiophenone (manufactured by Tokyo Kasei Kogyo)
• C1 A siloxane unit represented by (CH 3 ) 3 SiO 1/2 (M unit), a siloxane unit represented by RA (CH 3 ) 2 SiO 1/2 (M RA unit: RA is Synthesis Example 1 ) and a siloxane unit (Q unit) represented by SiO 4/2 , and the weight average molecular weight (Mw) measured by GPC using toluene as a solvent is 19,000 g.
• M unit siloxane unit represented by (CH 3 ) 3 SiO 1/2 and SiO 4/2
• Mw weight average molecular weight measured by GPC using toluene as a solvent
• E1 Polydimethylsiloxane raw rubber with both molecular chain ends/side chain vinyl functional and a plasticity of 120 (vinyl content: 0.84% by mass)
• E2 Both-ends trimethylsiloxy group-blocked polydimethylsiloxane crude rubber with a plasticity of 170
• E3 Both-ends dimethylvinylsiloxy-functional polydimethylsiloxane with a viscosity of 39,000 mPa s (vinyl content: 0.09% by mass)
• F1 Toluene
• Comparative Example 2 D1 component 42 parts by mass, D2 component 23 parts by mass, E3 component 30 parts by mass, average structural formula: (Me2HSiO1 / 2 ) 0.3 (PhSiO3 /2 ) 0.7
• a toluene solution containing 3 parts by mass of the organohydrogenpolysiloxane represented by and 0.0020 parts by mass of a (methylcyclopentadienyl)trimethylplatinum complex was prepared to have a solid content concentration of 70%.
• Comparative Example 3 0.1 parts by mass of B1 component, 38.9 parts by mass of D1 component, 20.9 parts by mass of D2 component, 27.6 parts by mass of E3 component, formula: Me3SiO ( Me2SiO ) 29 [Me ( HSC3H6 )SiO ] 3SiMe3
• Me3SiO ( Me2SiO ) 29 [Me ( HSC3H6 )SiO ] 3SiMe3 A toluene solution containing 12.5 parts by mass of an organopolysiloxane containing 3-mercaptopropyl groups represented by the following was prepared so that the solid content concentration of the composition was 70%.
• the PET film was peeled off from the hot-melt film laminate, and the laminate was sandwiched between two sheets of non-alkaline glass (75 mm long x 50 mm wide x 1.1 mm thick, manufactured by Corning: Eagle XG) to prevent air bubbles from entering. made.
• non-alkaline glass 75 mm long x 50 mm wide x 1.1 mm thick, manufactured by Corning: Eagle XG
• a UV-LED ultraviolet irradiation device manufactured by JATEC
• the same laminate was irradiated with ultraviolet rays with a wavelength of 405 nm so that the ultraviolet irradiation amount (illuminance) was 4,000 mJ/cm 2 as an integrated light amount.
• a specimen was obtained by curing the melt layer.
• CM-5 manufactured by Konica Minolta
• Table 1 Compositions, hot melt properties, UV curability, etc. of Examples 1 to 7 and Comparative Example 1 Table 2 UV curability of Comparative Examples 1 to 3 and presence or absence of white turbidity after irradiation Table 3 b * values (yellowing) of cured test pieces according to Examples and Comparative Examples
• Comparative Example 2 when used in the manufacturing process of display devices or electronic devices containing substrates with low stability at high temperatures. and can be cured at room temperature by irradiation with high-energy rays, and is expected to provide a cured product with excellent appearance stability and transparency.
• Table 2 when a siloxane having no resin-linear structure was used as in Comparative Example 1, the curability was insufficient and it was not suitable for sealing.
• Tables 2 and 3 the composition of Comparative Example 2 has high yellowing resistance, but cannot be rapidly cured at room temperature, which may limit the applications in which it can be used.

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