Classifications

• • 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
  • C08G77/38—Polysiloxanes modified by chemical after-treatment
• • 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
  • C08G77/06—Preparatory processes
  • C08G77/08—Preparatory processes characterised by the catalysts used
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • 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
  • C08G77/48—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
  • C08G77/50—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
• • 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
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/12—Chemical modification
  • C08J7/123—Treatment by wave energy or particle radiation
• • 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
• • 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
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
• • 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
  • 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
• • 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
  • 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
  • C09J7/38—Pressure-sensitive adhesives [PSA]
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2383/00—Characterised by the use 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; Derivatives of such polymers
  • C08J2383/04—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
  • 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
• • 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
  • 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
  • C09J2301/302—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 pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
• • 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
  • 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
  • C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
• • 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
  • 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
• • 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
  • C09J2483/00—Presence of polysiloxane

Definitions

• the present invention is characterized by having both (meth)acrylic functional groups and other aliphatic unsaturated carbon-carbon bond-containing groups (alkenyl groups, etc.) in the molecule, and having both heat-curing and photo-curing properties.
• the present invention relates to a method of using an organopolysiloxane adhesive composition characterized by reducing the adhesion of the agent to substrates.
• Organopolysiloxane pressure-sensitive adhesive compositions are superior in electrical insulation, heat resistance, cold resistance, adhesion to various adherends, and, if necessary, transparency, compared to acrylic or rubber-based pressure-sensitive adhesive compositions. It is widely used in the manufacture of semiconductor wafers, electronic and electrical devices such as smartphones and tablet PCs, and display devices such as displays. In particular, in recent years, in the processing of semiconductor wafers and the assembly process of electronic/electrical devices and displays, members and protective films are temporarily fixed with relatively weak adhesive strength, and members temporarily fixed with adhesives are used as the process progresses. In order to proceed with the process by peeling, there is a demand for a composition that forms a slightly adhesive adhesive compared to conventional organopolysiloxane adhesive compositions.
• an adhesive sheet has been used in which an adhesive is applied to a base material made of a film in the dicing/pickup/mounting steps after the step of grinding the back surface.
• adhesive strength is required and situations where easy peelability is required. That is, among these steps, in the step of grinding the back surface of the semiconductor wafer, the adhesive sheet is required to be sufficiently adhered to the semiconductor wafer without being peeled off in order to protect the patterned surface of the semiconductor wafer.
• after grinding it is required to be able to be easily peeled off from the semiconductor wafer.
• the adhesive sheet is required to have low adhesiveness.
• a chain (straight) polymer having a (meth)acrylic functional group and other aliphatic unsaturated carbon-carbon bond-containing groups in a certain ratio and providing a coating viscosity as a raw material of an adhesive is disclosed.
• organopolysiloxane compounds having a linear and branched molecular structure, and co-modified organopolysiloxane compounds with such multiple curing reactive functional groups, in curing reaction mechanisms involving hydrosilylation reactions there is no description or suggestion of the pressure-sensitive adhesive composition containing these and the characteristics of its curing (in particular, two-stage curability and change in adhesive strength).
• Patent Document 4 contains an organopolysiloxane compound containing a (meth)acrylic functional group-containing group, contains a platinum-based catalyst and a photoinitiator, is capable of curing reaction by photopolymerization reaction and addition reaction, and has heat resistance.
• sealants comprising an organopolysiloxane composition having excellent properties, discoloration resistance and low tackiness, and a cured product thereof.
• the document does not specifically disclose a co-modified organopolysiloxane containing a (meth)acrylic functional group-containing group and an alkenyl group.
• a pressure-sensitive adhesive composition containing and its curing characteristics (particularly two-stage curability and change in adhesive strength).
• JP 2012-012545 A Japanese Patent Application Laid-Open No. 2012-136678 JP 2013-166877 A Japanese Patent Application Laid-Open No. 2013-203794
• the present invention has been made to solve the above problems, and an organopolysiloxane pressure-sensitive adhesive that has necessary and sufficient adhesive strength in a process such as temporary fixing, and can be very easily peeled off from a substrate in a subsequent process.
• An object of the present invention is to provide an organopolysiloxane compound that serves as a raw material for.
• a further object of the present invention is to provide a curable organopolysiloxane composition containing the organopolysiloxane compound, an organopolysiloxane pressure-sensitive adhesive composition containing the same, and a method of using the organopolysiloxane pressure-sensitive adhesive composition.
• the object of the present invention is to provide a silicon atom-bonded functional group containing a specific acrylic group or methacrylic group, and a silicon atom containing at least one aliphatic unsaturated carbon-carbon bond such as an alkenyl group in the molecule. This can be achieved with linear co-modified organopolysiloxanes containing linking functional groups.
• the object of the present invention can be achieved by a curable organopolysiloxane composition and an organopolysiloxane adhesive composition containing the co-modified organopolysiloxane.
• the pressure-sensitive adhesive layer which is a semi-cured product containing the co-modified organopolysiloxane, is formed by a heat-curing reaction, and then light-cured.
• the adhesive strength of the pressure-sensitive adhesive layer to the base material is significantly reduced before and after the photocuring reaction.
• the pressure-sensitive adhesive layer according to the present invention has a necessary and sufficient adhesive strength after heat curing, and is then photocured by irradiating with high energy rays to reduce the adhesive strength and make it easy to peel. is feasible.
• a chain-shaped co-modified organopolysiloxane having both heat-curing and photo-curing properties wherein the semi-cured product after heat-curing has necessary and sufficient adhesive strength, and after the photo-curing reaction can provide an organopolysiloxane compound that can be used as a raw material for an organopolysiloxane pressure-sensitive adhesive that can be very easily peeled off from a substrate.
• the present invention can provide a curable organopolysiloxane composition containing the organopolysiloxane compound, in particular, the adhesive strength of the adhesive layer to the substrate is significantly reduced before and after the photocuring reaction, It is possible to provide an organopolysiloxane pressure-sensitive adhesive composition capable of realizing easy peeling and a method for using the same.
• the curable organopolysiloxane composition containing the co-modified organopolysiloxane according to the present invention has a viscosity that allows coating, is excellent in curability, and exhibits good adhesion to substrates due to the curing reaction. , a cured product (particularly a cured product film) having excellent transparency can be obtained. Furthermore, according to the present invention, it is possible to realize a silicone-based pressure-sensitive adhesive layer/adhesion layer whose adhesive strength changes before and after the photocuring reaction, and can be used as a protective member in a wide range of applications and devices or devices equipped with them. It is possible to provide a method of manufacture and a method of protection comprising:
• the co-modified organopolysiloxane according to the present invention is a chain polysiloxane molecule, and may be linear or may have a branched structure having a branch in part.
• Such a co-modified organopolysiloxane has siloxane units (M units) represented by R 3 SiO 1/2 at the molecular chain ends, and its main chain is essentially represented by R 2 SiO 2/2 .
• each of the above Rs is independently a monovalent organic group, at least one of all Rs is a silicon atom-bonded functional group (R A ) containing an acrylic group or a methacrylic group, and at least One is a silicon-bonded functional group (R Vi ) containing at least one aliphatically unsaturated carbon-carbon bond (excluding the functional group R A above). From the viewpoint of cross-linking reactivity, it is preferable that at least two out of all the siloxane units constituting the co-modified organopolysiloxane are silicon-bonded functional groups (R OH ).
• the co-modified organopolysiloxane according to the present invention has a linear or It has a branched polysiloxane structure, and is particularly preferably a linear co-modified organopolysiloxane.
• the linear polysiloxane structure is composed only of M units at both ends and D units constituting the main chain.
• the degree of siloxane polymerization of the co-modified organopolysiloxane according to the present invention is not particularly limited. It is preferably in the range of ⁇ 10,000, more preferably in the range of 25-2,000. When a resinous organopolysiloxane containing a large amount of T units and Q units and a highly polymerized organopolysiloxane are used, it may be difficult to apply the curable composition.
• Such co-modified organopolysiloxanes are characterized by the siloxane units described above.
• Formula: M (2+m+2p) D n T m Q p is represented by
• n is a positive number
• n and m are 0 or positive numbers
• the total number of siloxane units (that is, the degree of siloxane polymerization) "2 + m + 2 p + n + m + p" is a number in the range of 10 to 10,000.
• at least 90 mole percent of all siloxane units, excluding terminal M units, are D units.
• the co-modified organopolysiloxane of the present invention is represented by MD n M, where n+2 is a number within the range of 10-10,000.
• the co-modified organopolysiloxane according to the present invention contains, in its molecule, a silicon atom-bonded functional group (R A ) containing an acrylic or methacrylic group, and at least one aliphatic unsaturated carbon-carbon bond. It is characterized by containing a silicon-bonded functional group (R Vi ) (excluding the functional group R A described above).
• R A silicon atom-bonded functional group
• R Vi silicon-bonded functional group
• the silicon atom-bonded functional group (R A ) is a functional group that exhibits photocurability by irradiation with high energy rays in the presence of a photoradical polymerization initiator
• the silicon atom-bonded functional group (R Vi ) is It is a functional group that exhibits thermosetting properties in the presence of a hydrosilylation reaction catalyst.
• the adhesive layer made of the semi-cured material after the heat-curing reaction has high initial adhesive strength. and by irradiating the semi-cured product with high-energy rays, the adhesive force is greatly reduced, and easy peelability can be realized.
• the co-modified organopolysiloxane according to the present invention contains all functional groups bonded to the silicon atoms constituting the polysiloxane.
• R A silicon atom-bonded functional group
• the content is preferably in the range of 0.20 to 5.0 mol%, more preferably in the range of 0.30 to 5.0 mol%.
• a silicon atom-bonded functional group (R Vi ) containing at least one aliphatic unsaturated carbon-carbon bond in the molecule (with the proviso that ,
• the average amount of the silicon-bonded functional group (R A ) containing an acrylic group or a methacrylic group is 2.0 to 50.0 mol per 1 mol (excluding the functional group that is the above R A ). It is included in the range, preferably 2.0 to 10.0 mol. If the content of the photocurable silicon atom-bonded functional group (R A ) is less than the above lower limit, the photocuring reaction may not proceed sufficiently, and the adhesive properties may not change to an easily peelable cured product.
• the content of the heat-curable (hydrosilylation-reactive) silicon-bonded functional group (R Vi ) is less than the above lower limit, sufficient initial adhesive properties may not be achieved. If it exceeds, the carbon-carbon double bond site such as the vinyl group portion becomes excessive, and the adhesive property does not change to an easily peelable cured product, or the adhesive property is hardened too strongly and adhesiveness cannot be obtained. Sometimes. From the viewpoint of cross-linking reactivity, at least two of all functional groups bonded to silicon atoms constituting polysiloxane (all R in each siloxane unit) are silicon atom-bonded functional groups (R Vi ). is preferably
• 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 heteroatom and is bonded to the silicon atom that constitutes the main chain of the polysiloxane *, and may contain an oxygen atom, a nitrogen atom, or a sulfur atom. can be a base.
• Z is an alkylene group having 2 to 22 carbon atoms
• Z 2 is * -[(CH 2 ) 2 O] m (CH 2 ) n - (m is a number ranging from 0 to 3, n is 3 to number in the range of 10) is a divalent organic group ⁇ It is preferably a group selected from
• the silicon-bonded functional group (R A ) has the general formula (1-1): 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 —(CH 2 ) n — (where n is a number in the range of 3 to 10) bonded to a silicon atom constituting the main chain of polysiloxane *, and n is 2 to 6 is practically preferred.
• the silicon-bonded functional group (R A ) represented by general formula (1-1) includes a silicon-bonded functional group (R Vi ) containing at least one alkenyl group and a silicon-bonded hydrogen in the molecule.
• Reaction with a hydrosilane compound having an atom and a (meth)acrylic functional group e.g., 3-(1,1,3,3-tetramethyldisiloxanyl)propyl methacrylate, etc.
• a hydrosilylation reaction catalyst can be introduced into the molecule by The same reaction may and preferably be carried out in the presence of a polymerization inhibitor such as dibutylhydroxytoluene (BHT).
• BHT dibutylhydroxytoluene
• a silicon atom-bonded functional group (R Vi ) containing at least one aliphatically unsaturated carbon-carbon bond is an aliphatic carbon-carbon double bond (C ⁇ C) capable of addition reaction. It is an organic group containing one or more saturated carbon-carbon bonds, and is a component that imparts hydrosilylation reactivity and heat curability to the co-modified organopolysiloxane of the present invention.
• the silicon-bonded functional group (R Vi ) does not include the above-mentioned silicon-bonded functional group (R A ) containing an acrylic group or a methacrylic group, and R Vi and RA are different functional groups. be.
• the co-modified organopolysiloxane of the present invention preferably contains at least two silicon-bonded functional groups (R Vi ) in the molecule.
• the silicon-bonded functional group (R Vi ) is preferably an alkenyl group having 2 to 20 carbon atoms, examples of which include vinyl, allyl, butyl and hexenyl.
• Group (C6) is particularly preferred.
• the silicon atom-bonded functional group (R A ) and the silicon atom-bonded functional group (R Vi ) may be bonded to the silicon atoms at the molecular chain ends of the linear siloxane. , may be side chain modifying groups bonded to silicon atoms on the polysiloxane main chain.
• the co-modified organopolysiloxane according to the present invention may be a single co-modified organopolysiloxane, or two or more co-modified organopolysiloxanes having different degrees of siloxane polymerization, modification rates by the above R A and R Vi , and different main chain structures or terminal structures. It may also be a mixture of polysiloxanes.
• organic groups other than the silicon-bonded functional groups (R A ) and silicon-bonded functional groups (R Vi ) are methyl Alkyl groups such as groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, and heptyl groups; Aryl groups such as phenyl groups, tolyl groups, xylyl groups, and naphthyl groups; Aralkyl groups such as benzyl groups and phenethyl groups; Halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group and 3,3,3-trifluoropropyl group may also be included. From an industrial point of view, it is particularly preferred to contain a methyl group.
• the co-modified organopolysiloxane according to the present invention has both heat curability by hydrosilylation reaction and photocurability by irradiation with high energy rays, it cures through a plurality of curing mechanisms or two or more curing steps. is suitable as a raw material for curable organopolysiloxane compositions.
• the co-modified organopolysiloxane according to the present invention has a viscosity that can be applied, and the semi-cured product obtained by the heat curing reaction has excellent initial adhesive strength to the substrate, and the adhesive strength to the substrate.
• organopolysiloxane pressure-sensitive adhesive composition characterized by the change in pressure-sensitive adhesive strength triggered by the irradiation of is particularly useful as a raw material for the pressure-sensitive adhesive layer.
• the curable organopolysiloxane composition according to the present invention contains (A) the co-modified organopolysiloxane described above, and has both heat curability due to a hydrosilylation reaction and photocurability due to irradiation with high-energy rays.
• the curable organopolysiloxane composition according to the present invention is (A) a co-modified organopolysiloxane according to the present invention; (B) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in the molecule; (C) a hydrosilylation reaction catalyst, and (D) a photoradical polymerization initiator, optionally further comprising (E) (E) a siloxane unit (M unit) represented by R 3 SiO 1/2 (wherein R independently represents a monovalent organic group) in the molecule, and SiO 4/2 an organopolysiloxane resin containing the represented siloxane units (Q units) in a ratio of M units to Q units in the range of 0.5 to 2.0; (F) polydimethylsiloxane optionally having an alkenyl group, and (G) an organic solvent.
• Components (B) to (G) are described below.
• Component (B) is an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule, and functions as a cross-linking agent for the curable organopolysiloxane composition. Specifically, the silicon atom-bonded functional group (R Vi ) containing at least one aliphatic unsaturated carbon-carbon bond in component (A) is reacted with (C) in the presence of a hydrosilylation reaction catalyst, A pressure-sensitive adhesive layer that is a cured product can be formed.
• the adhesive layer has excellent initial adhesive strength to the substrate, it contains an unreacted photocurable silicon atom-bonded functional group (R A ), so it adheres by two-stage curing triggered by high-energy ray irradiation. The force is greatly reduced, exhibiting easy peelability.
• R A photocurable silicon atom-bonded functional group
• Such component (B) includes cyclic organohydrogenpolysiloxanes having at least three silicon-bonded hydrogen atoms in the molecule, and linear or branched organohydrogenpolysiloxanes having at least two silicon-bonded hydrogen atoms in the molecule. It may be at least one selected from chain organohydrogenpolysiloxanes. The component (B) may also be a mixture of two or more of the above organohydrogenpolysiloxanes.
• cyclic organohydrogenpolysiloxane for example, the following formula: [(R 3 HSiO) m3 (R 3 2 SiO) m4 ] is represented by Here, m3+m4 is a number in the range of 3 to 20, m3 is a number of 3 or more, and m4 is a number of 0 or more.
• R 3 is a monovalent hydrocarbon group having 1 to 10 carbon atoms excluding an alkenyl group, examples of which are the same as those for R 2 , preferably a methyl group or a phenyl group.
• the straight-chain or branched-chain organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in the molecule has at least two silicon-bonded hydrogen atoms in the side chain portion and the molecular chain end is an organohydrogenpolysiloxane such as a polyorganohydrogensiloxane or an organohydrogensiloxane-diorganosiloxane copolymer blocked with a trialkylsiloxy group, an aryldialkylsiloxy group, or the like.
• the degree of siloxane polymerization is in the range of 5-500, preferably in the range of 5-200.
• 1,3,5,7-tetramethylcyclotetrasiloxane tris(dimethylhydrogensiloxy)methylsilane, tris(dimethylhydrogensiloxy)phenylsilane, 1-(3-glycan sidoxypropyl)-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-di(3-glycidoxypropyl)-1,3,5,7-tetramethylcyclotetrasiloxane, 1-( 3-glycidoxypropyl)-5-trimethoxysilylethyl-1,3,5,7-tetramethylcyclotetrasiloxane, trimethylsiloxy group-blocked methylhydrogenpolysiloxane at both molecular chain ends, trimethylsiloxy group at both molecular chain ends blocked dimethylsiloxane/methylhydrogensiloxane copolymer, dimethylpolysiloxane blocked at both molecular chain ends
• the amount of component (B) used can be appropriately selected according to the desired adhesive strength and curing characteristics. From the standpoint of compatibility, it is preferably in the range of 0.1 to 5 parts by mass, more preferably 0.5 to 4.5 parts by mass, per 100 parts by mass of the co-modified organopolysiloxane, component (A). A range of 0.0 to 3.5 parts by weight is particularly preferred. If the amount of component (B) used is less than the lower limit, the cross-linking agent may be insufficient, and the composition may have insufficient heat-curing properties. The change in adhesive strength becomes small, and the object of the present invention may not be achieved.
• the amount of component (B) to be used is the number of moles of silicon-bonded hydrogen atoms in component (B) relative to the number of moles of aliphatic unsaturated carbon-carbon bonds such as alkenyl groups in the composition.
• number (hereinafter referred to as "SiH/Vi ratio”) is preferably in the range of 0.1 to 40, more preferably in the range of 0.5 to 30, still more preferably in the range of 1.0 to 30 is particularly preferred. Within this range, the overall crosslink density can be appropriately adjusted, and the desired properties of storage elastic modulus and adhesion of the cured product can be exhibited.
• the SiH/Vi ratio is less than the lower limit, adhesive residue may occur when the cured product is brought into close contact with the substrate. The adhesion properties of the cured product may become unstable.
• Component (C) is a hydrosilylation reaction catalyst, and by heating or the like promotes the hydrosilylation reaction of component (B) with aliphatic unsaturated carbon-carbon bonds such as alkenyl groups in component (A) and other optional components. It is a component that
• hydrosilylation reaction catalysts examples include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. Platinum-based catalysts are preferred because they can significantly accelerate the curing of the present composition. Examples of the platinum-based catalyst include platinum fine powder, chloroplatinic acid, an alcohol solution of chloroplatinic acid, platinum-alkenylsiloxane complexes, platinum-olefin complexes, and platinum-carbonyl complexes, and platinum-alkenylsiloxane complexes are particularly preferred. .
• alkenylsiloxane examples include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, alkenylsiloxanes in which some of the methyl groups of these alkenylsiloxanes are substituted with groups selected from the group consisting of nitriles, amides, dioxolanes, and sulfolanes, ethyl groups, phenyl groups, etc.; vinyls of these alkenylsiloxanes; Alkenylsiloxanes substituted with allyl groups, hexenyl groups and the like are exemplified.
• these hydrosilylation reaction catalysts are catalysts dispersed or encapsulated in thermoplastic resins such as silicone resins, polycarbonate resins and acrylic resins.
• thermoplastic resins such as silicone resins, polycarbonate resins and acrylic resins.
• Thermoplastic resin fine particles containing a hydrosilylation reaction catalyst particularly thermoplastic resin fine particles containing a platinum-containing hydrosilylation reaction catalyst may be used.
• non-platinum metal catalysts such as iron, ruthenium, and iron/cobalt may be used.
• thermoplastic resin fine particles containing a platinum-containing hydrosilylation reaction catalyst that can be used in the present invention are fine particles in which a hydrosilylation reaction catalyst such as a platinum-based catalyst is dissolved or dispersed in a thermoplastic resin.
• Any microcapsule fine particles having a structure in which a hydrosilylation reaction catalyst such as a platinum-based catalyst is contained as a nucleus in a shell of a plastic resin may be used.
• ) is preferably 75°C or higher, more preferably 80°C or higher, and particularly preferably in the range of 80 to less than 250°C.
• Such thermoplastic resins may be used singly or plurally.
• the average particle size of the hydrosilylation reaction catalyst-containing thermoplastic resin fine particles is not limited, but is preferably in the range of 0.1 to 500 ⁇ m, more preferably in the range of 0.3 to 100 ⁇ m.
• the content of the hydrosilylation reaction catalyst is not particularly limited, but it is within the range where the amount of platinum-based metal is in the range of 0.1 to 200 pm with respect to the total amount of solids in the composition. , 0.1 to 150 ppm, 0.1 to 100 ppm, and may range from 0.1 to 50 ppm.
• the platinum-based metal is a Group VIII metal element consisting of platinum, rhodium, palladium, ruthenium, and iridium.
• the solid content refers to the components that form the cured layer when the curable organopolysiloxane composition according to the present invention undergoes a curing reaction (mainly the main agent, adhesion-imparting component, cross-linking agent, catalyst and other non-volatile components ) and does not contain volatile components such as solvents that volatilize during heat curing.
• the content of the platinum-based metal in the curable organopolysiloxane composition according to the present invention is 50 ppm or less (45 ppm or less, 35 ppm or less, 30 ppm or less, 25 ppm or less, or 20 ppm or less), after curing, heating, ultraviolet rays, etc. In the case of exposure to high-energy rays of , discoloration and coloring of the transparent adhesive layer can be suppressed in some cases.
• the content of the platinum-based metal is 0.1 ppm or more, and if it is less than the lower limit, it may cause poor curing.
• the curable organopolysiloxane compositions of the present invention may optionally contain a cure retardant.
• the curing retarder suppresses the cross-linking reaction between the aliphatic unsaturated carbon-carbon bond-containing groups and the silicon-bonded hydrogen atoms in the composition, extends the pot life at room temperature, and improves the storage stability. It is blended in. Therefore, it is practically an essential component for the curable organopolysiloxane composition of the present invention.
• curing retarders are exemplified by acetylene compounds, enyne compounds, organic nitrogen compounds, organic phosphorus compounds, oxime compounds and phosphorus compounds.
• the phosphorus-containing hydrosilylation reaction retarder is at least one selected from the group consisting of phosphine-based compounds, phosphoric acid-based compounds, phosphonic acid-based compounds, phosphine oxide-based compounds, phosphorous acid-based compounds, and phosphonous acid-based compounds.
• Examples include components described in JP-A-2007-308542 such as 1,3-bis(diphenylphosphino)propane.
• the curable organopolysiloxane composition of the present invention exhibits a viscosity increase of 1.5 times or less after 8 hours at room temperature after preparation of the composition, and can be cured at 80 to 200°C. is preferably Suppression of thickening is important from the standpoint of handling workability, pot life, and properties after curing. Because we can. Incidentally, such a composition can be realized by selecting a suitable combination and blending amount of each of the above components, a hydrosilylation catalyst, and a curing retarder.
• Component (D) is a radical photopolymerization initiator, and is a component that 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. .
• a pressure-sensitive adhesive layer made of a semi-cured product containing unreacted functional groups (R A ) derived from the component (D) and the component (A) with a high-energy ray, the base material of the pressure-sensitive adhesive layer The adhesive strength against is greatly reduced, and an easily peelable cured product is formed.
• 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.
• photoradical polymerization initiators include 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone, ⁇ -hydroxy- ⁇ , ⁇ '-dimethylacetophenone, 2-methyl-2-hydroxypropyl ⁇ -Ketol compounds such as piophenone and 1-hydroxycyclohexylphenyl ketone; )-phenyl]-2-morpholinopropane-1 and other acetophenone compounds; benzoin ether compounds such as benzoin ethyl ether, benzoin isopropyl ether and anisoin methyl ether; ketal compounds such as benzyl dimethyl ketal; 2-naphthalenesulfonyl chloride Aromatic sulfonyl chloride compounds such as; 1-phenone-1,1-propanedione-2-(o-ethoxycarbonyl) photoactive oxime compounds such as oxime; benzophenone, benzoylbenzoic acid, 3,3'-di
• the amount of component (D) used depends on the content of the silicon atom-bonded functional group (R A ) derived from component (A), the desired change in adhesive strength of the cured product triggered by irradiation with high-energy rays, and the ease of peeling. Although it can be appropriately designed according to the requirements, the amount of 0.1 to 20 parts by weight is preferable, and the amount of 0.5 to 15 parts by weight is particularly preferable, per 100 parts by weight of component (A).
• (D') photosensitizer can also be used in combination with (D) a 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 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 (D') to the component (D) 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 composition according to the present invention may contain (E) an organopolysiloxane resin in addition to the components (A) to (D).
• the component (E) is a component that optionally adjusts the adhesion to the substrate, and the hardness of the semi-cured product after the hydrosilylation reaction and the adhesion to the substrate can be adjusted depending on the amount of the component used. is possible.
• Siloxane units (M units) represented in the molecule by (a) R 3 SiO 1/2 (wherein R independently represents a monovalent organic group), and (b) SiO 4/2 is an organopolysiloxane resin containing a siloxane unit (Q unit) represented by
• the molar ratio of M units to Q units is preferably between 0.5 and 2.0. If this molar ratio is less than 0.5, the adhesion of the cured product to the substrate may be reduced, and if it is greater than 2.0, the cohesive force of the substances constituting the adhesion layer will be reduced. is.
• the above molar ratio can be easily measured by 29 Si nuclear magnetic resonance.
• Component (E) may consist only of (a) M units and (b) Q units, but may be R 2 SiO 2/2 units (D units) and/or RSiO 3/2 units (T units). may include In the formula, each R independently represents a monovalent organic group.
• the total content of (a) M units and (b) Q units in component (E) is preferably 50% by weight or more, more preferably 80% by weight or more, and particularly preferably 100% by weight.
• the monovalent organic group is not particularly limited, but the silicon atom-bonded functional group (R A ) containing an acrylic group or a methacrylic group represented by the general formula (1) in the component (A) , a silicon-bonded functional group (R Vi ) containing at least one aliphatically unsaturated carbon-carbon bond (excluding the functional group R A above), and other organic groups such as a methyl group. may be one or more organic groups.
• component (E) may contain hydrolyzable groups such as hydroxyl groups or alkoxy groups, and these hydrolyzable groups can be hydrolyzed with a silylating agent such as trimethylsilane to form hydroxyl groups. Alternatively, it may be an organopolysiloxane resin with a reduced content of hydrolyzable groups.
• component (E) is an optional component, it can be blended in an amount of 0.0 to 150 parts by mass with respect to 100 parts by mass of component (A), and the amount of 0.5 to 50 parts by mass is A range of 1.0 to 20 parts by mass is particularly preferred.
• composition according to the invention may furthermore contain polydimethylsiloxanes, which may optionally contain alkenyl groups.
• component (F) does not participate in the cross-linking reaction by components (A) to (D) and optional component (E), but by using this component, it is necessary to coat the curable organopolysiloxane composition.
• it may also be possible to improve the peeling properties of the cured product.
• component (F) is a Cyclic, linear, branched, resinous and gum-like polydimethylsiloxanes which may be substituted with alkenyl groups.
• the siloxane polymerization degree and viscosity range are not particularly limited, but the viscosity at 25 ° C. may be in the range of 1.5 to 1,000,000 mPa s, and the liquid state having a viscosity of 100,000 mPa s or more at 25 ° C.
• Polydimethylsiloxane or plasticity measured according to the method specified in JIS K6249 25 ° C, 4.2 g spherical sample, 1 kgf load is applied for 3 minutes, the thickness is read to 1/100 mm , multiplied by 100
• 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 (F).
• the composition according to the present invention may further contain (G) a polyfunctional thiol compound having at least two thiol groups in the molecule.
• the polyfunctional thiol compound promotes the radical polymerization reaction, so even when the amount of UV irradiation is small, it can improve the curing speed and the deep curability of the cured product, and also functions as a cross-linking point in the 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 (G) is optional, but the amount used is 0 to 20 parts by mass per 100 parts by mass of component (A), and the amount of 0 to 10 parts by mass is An amount of 0 to 5 parts by weight is particularly preferred.
• the composition according to the present invention has a relatively low viscosity of its constituent components, it can be designed as a low-solvent type or solvent-free composition, but may optionally contain (H) 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 preferably from 0 to less than 60% by mass, less than 50% by mass, and substantially within the range of from 0 to 30% by mass with respect to 100 parts by mass of the entire composition. .
• the solid content concentration forming solid content by the curing reaction is 30 to 100% by mass of the entire composition. can be easily designed within the range of
• the curable organopolysiloxane composition according to the present invention can optionally contain components other than the above components within a range that does not impair the technical effects of the present invention.
• adhesion promoter such as polydimethyldiphenylsiloxane other than component (F); phenol, quinone, amine, phosphorus, phosphite, sulfur, or thioether Antioxidants; light stabilizers such as triazoles or benzophenones; flame retardants such as phosphates, halogens, phosphorus, or antimony; cationic surfactants, anionic surfactants, or nonionic
• pigments, dyes, inorganic fine particles may optionally be blended.
• the method for preparing the curable organopolysiloxane composition of the present invention is not particularly limited, and is carried out by homogeneously mixing each component.
• An organic solvent may be added as necessary, and a known stirrer or kneader may be used to mix and prepare.
• the present composition exhibits hydrosilylation reactivity when heated, it is preferable to mix under temperature conditions of less than 100°C, preferably less than 50°C.
• the curable organopolysiloxane composition according to the present invention contains the component (A), it has both heat curing properties and photo-curing properties when irradiated with high-energy rays.
• the semi-cured product functions as an adhesive layer with excellent initial adhesive strength, and by irradiating it with high-energy rays, the adhesive strength of the adhesive layer to the substrate is greatly reduced, and the cured product is easy to peel. can be easily removed from the substrate. How to use it will be explained below.
• the curable organopolysiloxane composition according to the present invention forms a coating film by coating it on a substrate, and is applied under temperature conditions of 80 to 200°C, preferably 90 to 150°C.
• a hydrosilylation reaction gives a semi-cured product that functions as an adhesive layer with excellent initial adhesive strength.
• the heating time required for curing can be appropriately selected according to the thickness of the pressure-sensitive adhesive layer and the amount of catalyst used, but is generally in the range of 0.5 to 90 minutes. Since the adhesive layer obtained by heat curing using the composition according to the present invention contains unreacted silicon atom-bonded functional groups (R A ), further photocuring reaction is triggered by high-energy beam irradiation. maintain sexuality.
• Coating methods include gravure coating, offset coating, offset gravure, roll coating, reverse roll coating, air knife coating, curtain coating, and comma coating.
• the amount of coating can be designed to have a desired thickness according to the application such as a display device. Well, it may be from 10 to 800 ⁇ m, but it is not limited to these.
• the semi-cured product before the photocuring reaction has sufficient initial adhesive strength.
• Adhesive strength measured at a tensile speed of 300 mm/min is 2.5 gf/inch or more, preferably 3.0 gf/inch or more, particularly 3.0 to 50.0 gf/inch.
• Layers can be designed.
• the above thickness (75 ⁇ m) is the thickness of the cured layer itself, which serves as a reference for objectively defining the adhesive strength of the cured layer according to the present invention. Needless to say, the thickness is not limited to 75 ⁇ m, and any thickness can be used as a cured layer or pressure-sensitive adhesive layer.
• the adhesive layer which is a semi-cured product obtained by heat curing, undergoes a further photocuring reaction triggered by the irradiation of high-energy rays, and its adhesive strength is greatly reduced, and it is easy to peel, and it is easy to peel off from the base material.
• a hard cured product that leaves no adhesive residue is formed and can be easily peeled off from the substrate.
• the adhesive strength to the base material is reduced by photocuring due to irradiation of high energy rays. It is reduced by 10% or more before and after the reaction, preferably by 30% or more, and particularly preferably by 50% or more.
• Such changes in adhesive force can be quantitatively measured by the above-described adhesive force measurement test using a SUS plate or the like.
• High-energy rays used for the photocuring reaction include ultraviolet rays, electron beams, radiation, and the like, and ultraviolet rays are preferred from the standpoint of practicality.
• High-pressure mercury lamps, medium-pressure mercury lamps, Xe—Hg lamps, deep UV lamps, and the like are suitable as the ultraviolet light source, and ultraviolet irradiation with a wavelength of 280 to 400 nm, preferably 300 to 400 nm, is preferred.
• Light sources with emission bands may also be used.
• the irradiation dose of high - energy rays can be appropriately designed. At 000 mJ/cm 2 , a favorable change in the adhesive strength of the adhesive layer according to the present invention is realized with the irradiation of high-energy rays as a trigger. Irradiation with high-energy rays may be performed with a substrate interposed therebetween as long as the substrate carrying the pressure-sensitive adhesive layer according to the present invention does not absorb electromagnetic waves in the above wavelength range. That is, if a certain amount of irradiation can be realized, high-energy rays may be irradiated through a base material or a cover material such as a protective film.
• the curable organopolysiloxane composition according to the present invention and the pressure-sensitive adhesive layer (including semi-cured products and cured products) obtained by curing the organopolysiloxane pressure-sensitive adhesive composition are substantially transparent, translucent or opaque. and the transparency can be designed according to the application of the pressure-sensitive adhesive layer.
• the transmittance of light at a wavelength of 450 nm of the adhesive layer composed of a cured layer with a thickness of 100 ⁇ m is 80% or more when the value of air is 100%, and is preferably is 90% or more, and may be designed to be 95% or more.
• the adhesive layer may be translucent to opaque. Filler components or additives that impair the
• the pressure-sensitive adhesive layer according to the present invention is subjected to surface treatment such as primer treatment, corona treatment, etching treatment, plasma treatment, etc. on the surface of the pressure-sensitive adhesive layer or base material in order to improve the adhesion to the adherend.
• surface treatment such as primer treatment, corona treatment, etching treatment, plasma treatment, etc.
• the adhesion layer of the present invention is excellent in adhesion to substrates such as display devices. Also, by omitting these steps, higher production efficiency may be achieved.
• the curable organopolysiloxane composition according to the present invention is coated on a release liner and then heated under the temperature conditions described above to semi-harden due to a condensation reaction. or sheet-like substrate (hereinafter referred to as "film-like substrate"), or after coating on the film-like substrate, curing by heating under the above temperature conditions, and An adhesive layer can be formed on the surface of the material.
• this pressure-sensitive adhesive layer has excellent initial adhesiveness and contains a photocurable functional group derived from the component (A). Adhesive properties change to releasability.
• a cured layer obtained by curing the organopolysiloxane composition of the present invention on these film-like substrates, particularly laminates provided with a film-like cured layer, can be used as adhesive tapes, protective films intended for attachment and detachment, and bandages. , cold supports, transfer films, labels, emblems and decorative or instructional markings.
• the cured layer formed by curing the organopolysiloxane composition of the present invention may be used in the construction of automobile parts, toys, electronic circuits, or keyboards.
• cured layers, particularly film-like cling layers, formed by curing the organopolysiloxane compositions of the present invention may be used to protect, construct and utilize laminated touch screens or flat panel displays.
• substrate types include paperboard, cardboard, clay-coated paper, polyolefin-laminated paper, especially polyethylene-laminated paper, synthetic resin film/sheet, natural fiber cloth, synthetic fiber cloth, artificial leather cloth, and metal foil.
• synthetic resin films and sheets are preferred, and examples of synthetic resins include polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyethylene terephthalate, cyclopolyolefin, and nylon.
• heat-resistant synthetic resin films such as polyimide, polyetheretherketone, polyethylenenaphthalate (PEN), liquid crystal polyarylate, polyamideimide, and polyethersulfone are suitable.
• transparent substrates specifically transparent materials such as polypropylene, polystyrene, polyvinylidene chloride, polycarbonate, polyethylene terephthalate, and PEN, are suitable.
• the base material is preferably film-like or sheet-like.
• the thickness is not particularly limited, and can be designed to have a desired thickness depending on the application.
• a support film that has been subjected to primer treatment, corona treatment, etching treatment, or plasma treatment may be used.
• the surface opposite to the cured layer/cured adhesion layer of the film-like substrate is surface-treated such as anti-scratch, anti-fouling, anti-fingerprint, anti-glare, anti-reflection, and anti-static treatment. good too.
• the pressure-sensitive adhesive layer according to the present invention may be a single layer or a multiple layer formed by laminating two or more pressure-sensitive adhesive layers depending on the required properties.
• the multi-layered adhesive layer may be formed by laminating films prepared one by one, or the step of applying and curing the curable silicone composition on a film base material having a release layer may be performed multiple times. good.
• the pressure-sensitive adhesive layer according to the present invention may be given a role as a functional layer selected from a dielectric layer, a conductive layer, a heat dissipation layer, an insulating layer, a reinforcing layer, etc., in addition to bonding or adhesion between members.
• the pressure-sensitive adhesive layer which is a semi-cured material obtained by heating and curing the curable organopolysiloxane according to the present invention, has excellent initial adhesiveness and contains a photocurable functional group derived from the component (A). Therefore, with high-energy beam irradiation as a trigger, the adhesive force decreases and the adhesive characteristics change to make it easy to peel off. Since a cured adhesion layer that can be removed very easily is formed, it is extremely useful for temporary fixing of a functional layer or a functional layer that is supposed to be attached and detached.
• the pressure-sensitive adhesive layer has release coating ability. It is preferably treated as a laminate film adhered in a releasable state on a film substrate having a release layer.
• the release layer is sometimes called a release liner, separator, release layer, or release coating layer, and is preferably a release coating such as a silicone-based release agent, a fluorine-based release agent, an alkyd-based release agent, or a fluorosilicone-based release agent.
• It may be a release layer having an ability, a base material having fine physical irregularities formed on the surface of the base material, or a base material itself that is difficult to adhere to the adhesion layer of the present invention.
• a release layer obtained by curing a fluorosilicone release agent as the release layer.
• the pressure-sensitive adhesive layer according to the present invention has the above-described characteristic pressure-sensitive adhesive properties and can realize transparency and low haze, it can be used as an elastic adhesion layer or a temporary fixing layer in various electronic devices or It is useful as a protective film during the processing of electrical device members and semiconductor wafers. Similarly, it is also useful as an electronic material, display device member or transducer member (including for sensors, speakers, actuators, and generators), and the preferred use of the cured product is an electronic component or display device member is.
• the cured product according to the present invention may be transparent or opaque. It is particularly useful for a so-called touch panel application that can operate a device, especially an electronic device, by touching it with a device such as a touch panel.
• the cured product layer of the present invention is not required to be transparent, and is applicable to film-like or sheet-like members used in sensors, speakers, actuators, etc., where the adhesion layer itself is required to have a certain degree of stretchability or flexibility. may
• Articles containing a cured layer obtained by curing the curable silicone composition of the present invention may be adhesive tapes, particularly protective tapes intended for attachment and detachment. , a sheet-like member made of a fiber product such as non-woven fabric or paper, and the adhesion layer.
• the types of such adhesive tapes are not particularly limited, and include insulating tapes, heat-resistant tapes, solder masking tapes, mica tape binders, temporary fixing tapes (particularly including temporary fixing tapes for silicone rubber parts, etc.), and splicing tapes. (particularly including splicing tapes for silicone release papers).
• the cured product obtained by curing the curable silicone composition of the present invention has excellent initial adhesiveness and contains photocurable functional groups derived from component (A).
• the adhesive strength decreases and the adhesive characteristics change to easily peelable, so the adhesion characteristics and appearance of the adhesive layer are stable. Since it can be removed from the material surface, it can be particularly suitably used as a functional film that is temporarily used on the assumption that it can be attached and detached for display devices, semiconductors, and the like.
• display devices such as CRT displays, liquid crystal displays, plasma displays, organic EL displays, inorganic EL displays, LED displays, surface electrolytic displays (SED), and field emission displays (FED), and touch panels using these, which will be described later. It is extremely useful as a temporary fixing adhesive used in the production of.
• a laminate having a cured adhesion layer formed by curing the curable silicone composition may be formed on the above-mentioned film-like substrate.
• a release layer may be provided.
• the sheet-like substrate has at least one release layer, and the release layer is in contact with the cured adhesion layer. Thereby, the cured adhesion layer can be easily peeled off from the sheet-like substrate.
• the release agent contained in the release layer is not particularly limited, and includes the same release agents as described above.
• the above-mentioned laminate may be able to handle the adhesive layer separated from the film-like substrate alone, or may have two film-like substrates.
• film substrate a first release layer formed on the film-like substrate; It may comprise a pressure-sensitive adhesive layer layer formed by applying the curable organopolysiloxane composition on the release layer and heat-curing it, and a second release layer laminated on the adhesion layer. .
• the laminate of the above form forms an adhesion layer by, for example, applying the above curable organopolysiloxane composition onto one release layer formed on a film-like substrate and curing the composition. Then, another release layer may be laminated on the adhesion layer.
• the laminate having the above configuration can be obtained, for example, by sandwiching the above curable silicone composition between the first film-like substrate and the second film-like substrate, heating the composition, and pressing or rolling it to a certain thickness. It may be produced by curing the composition after molding.
• the first sheet base material may have a first release layer, or the first sheet base material itself may have releasability.
• the second sheet substrate may have a second release layer, or the second sheet substrate itself may have peelability.
• the cured adhesion layer is the first release layer and/or the second release layer. It is preferred to contact the layer.
• the sheet substrate having releasability examples include a sheet substrate made of a material having releasability such as a fluororesin film, or a material having no or low releasability such as a polyolefin film and a material such as silicone or fluororesin.
• a sheet substrate made of one to which a release agent is added may be mentioned.
• examples of sheet substrates having a release layer include polyolefin films coated with a release agent such as silicone and fluororesin.
• the laminate can be used, for example, by peeling off the adhesive layer from the film-like substrate after applying the cured adhesive layer to the adherend.
• the thickness of the adhesion layer (adhesive layer) obtained by heating and curing the curable organopolysiloxane composition according to the present invention is preferably 5 to 10000 ⁇ m, especially 10 ⁇ m or more or 8000 ⁇ m or less, especially 20 ⁇ m or more or 5000 ⁇ m is particularly preferred.
• the adhesive layer (adhesive layer) obtained by heat-curing the curable organopolysiloxane composition of the present invention can be used for protection, construction and utilization of laminated touch screens or flat panel displays.
• adhesion layers eg, silicone PSA, silicone adhesive, and silicone sealant
• a film comprising a cured product obtained by curing the composition can be used for various display devices for displaying characters, symbols, and images.
• the surface shape of such a display device may be a curved or curved shape instead of a flat surface, and in addition to various flat panel displays (FPD), curved displays used in automobiles (including electric vehicles) and aircraft.
• FPD flat panel displays
• curved displays used in automobiles (including electric vehicles) and aircraft.
• a curved transmissive screen is exemplified.
• these display devices may be provided with a touch panel function that enables input operations by touching an icon, notification display, or operation button for executing a function or program on the screen or display.
• Devices include display devices such as CRT displays, liquid crystal displays, plasma displays, organic EL displays, inorganic EL displays, LED displays, surface electrolytic displays (SED), field emission displays (FED), and touch panels using these. Application is possible.
• the cured product obtained by curing the composition has excellent adhesion to the substrate and viscoelastic properties, so it can be used as a member for transducers such as membranes for speakers (sensors, speakers, actuators, and generators. ), and furthermore, it can be used as a sealing layer or adhesion layer for use in secondary batteries, fuel cells, or solar cell modules.
• the ratio of the number of SiH groups to hexenyl groups is 0.88.
• IR spectrometry confirms the disappearance of the SiH groups, and the molar ratio of methacrylate groups to hexenyl groups is 4.7, the formula: 145.6 g of a toluene solution of linear organopolysiloxane (A-1) represented by the following was obtained.
• the molar ratio of methacrylate groups to hexenyl groups was determined by 13C NMR.
• the ratio of the number of SiH groups to vinyl groups bonded to silicon atoms is 0.80.
• the disappearance of the SiH groups was confirmed by IR spectroscopy, and the molar ratio of methacrylate groups to vinyl groups is 3.5, the formula: 142.1 g of a toluene solution of linear organopolysiloxane (A-3) represented by the following was obtained.
• the molar ratio of methacrylate groups to vinyl groups was determined by 13C NMR.
• 0.0240 g of a toluene solution of a platinum/1,3-divinyltetramethyldisiloxane complex (containing 4.8 ⁇ 10 ⁇ 5 g of Pt alone) was added thereto, and the temperature of the mixture was adjusted to 40° C. to 50° C. The mixture was stirred for 4 hours while adjusting the temperature to .
• the ratio of the number of methacrylate groups to vinyl groups contained in the organopolysiloxane resin is 0.1.
• siloxane unit M 25.5 g of a xylene solution of an organopolysiloxane resin (E-3) containing a siloxane unit (Q unit) represented by SiO 4/2 was obtained.
• Table 1 shows the adhesive strength of the SUS plate measured at a tensile speed of 300 mm/min using the 180° peeling test method according to JIS Z 0237 as "initial adhesive strength".
• a UV-LED ultraviolet irradiation device manufactured by JATEC
• ultraviolet rays with a wavelength of 365 nm were applied from the PET surface side so that the ultraviolet irradiation amount (illuminance) was 2,000 mJ / cm as an integrated light amount. was irradiated, and the adhesive strength of the test piece after ultraviolet irradiation was measured in the same manner as described above. When the adhesive layer became cloudy and visibility was lost due to irradiation with ultraviolet light, it was evaluated as x.
• the heat-cured products of the compositions containing the co-modified organopolysiloxane of the present invention according to Examples 1 to 12 had an initial adhesive strength in a practically sufficient range, and a certain range depending on the composition design. It is possible to realize even the adhesive strength that has been given. Furthermore, the adhesive layer significantly decreased its adhesive strength by irradiation with ultraviolet rays, changed its adhesive properties to easily peelable, and maintained its transparency. Therefore, when used in the manufacturing process of semiconductor wafers, display devices, electronic devices, etc., it is expected to be highly useful as a protective film, a temporary fixing film, and the like.

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• 2022
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