WO2020090797A1 - 硬化反応性シリコーン組成物及びその硬化物並びにそれらの用途 - Google Patents
硬化反応性シリコーン組成物及びその硬化物並びにそれらの用途 Download PDFInfo
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- WO2020090797A1 WO2020090797A1 PCT/JP2019/042320 JP2019042320W WO2020090797A1 WO 2020090797 A1 WO2020090797 A1 WO 2020090797A1 JP 2019042320 W JP2019042320 W JP 2019042320W WO 2020090797 A1 WO2020090797 A1 WO 2020090797A1
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- reactive silicone
- silicone composition
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- sheet
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Definitions
- the present invention relates to a curable reactive silicone composition, a cured product thereof, and a heat-meltable adhesive material made of the composition, and uses such as a laminate made of the composition or the cured product.
- the present invention also relates to a method for producing the laminate.
- the present invention also relates to a method of making a sheet of a curable reactive silicone composition.
- Silicone materials are used for various purposes because they have excellent properties such as heat resistance, chemical resistance, and electrical insulation. Silicone materials can be formed on various substrates such as plastic, metal, glass, ceramics, paper, and wood, and have various applications such as daily necessities, medical supplies, and electronic products.
- a silicone material formed on a substrate is used as an adhesive material. Specifically, it is used as an adhesive for various functional tapes for medical use, such as industrial protective tapes and masking tapes, as well as optical members for displays (display devices, functional films, lenses, etc. Later, it is used as it is by being incorporated into the device.
- Silicone materials are usually obtained by crosslinking organopolysiloxanes by a hydrosilylation reaction.
- a transition metal complex catalyst that is activated by heat is usually used from the viewpoint of workability and the like.
- a catalyst activated by irradiation with high energy rays such as ultraviolet rays. Is used.
- Patent Document 1 describes a high solid content silicone-based pressure-sensitive adhesive composition containing such a high energy ray activating catalyst. The composition is adhered in an uncured state. There was a problem of low adhesion to.
- Patent Document 2 describes a composition containing a linear organopolysiloxane curable by a photoactive catalyst and a branched organopolysiloxane. The composition is in a cured state. However, there is a problem that the adhesion to the adherend is low.
- the present invention has sufficient toughness and sufficient adhesiveness to temporarily fix various base materials even in an uncured state, and has heat melting property, and is excellent in moldability of a sheet, and the like. It is an object of the present invention to provide a curable reactive silicone composition that can be rapidly cured by irradiation with high energy to obtain high adhesive strength, and a cured product thereof that can obtain high adhesive force by pressure bonding. A further object of the present invention is to provide a pressure-sensitive adhesive that is used for the above-mentioned curing reactive silicone composition and its cured product. Similarly, it is an object of the present invention to provide a laminate including a layer formed of the curable reactive silicone composition or a cured product thereof, and a method for producing the laminate. Moreover, this invention aims at providing the manufacturing method of the sheet
- the purpose of the present invention is to (A) 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 a siloxane unit (Q unit), (B) a linear or branched organopolysiloxane having at least two aliphatic unsaturated carbon-carbon bond-containing groups in one molecule and having a siloxane polymerization degree in the range of 80 to 3000, (C) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule, and (D) A catalyst for hydrosilylation reaction, which does not exhibit activity without irradiation with high energy rays, but exhibits activity in the composition upon irradiation with high energy rays,
- the content of the component (A) is more than 55 mass% and less than 90 mass% of the total mass of the components (A) to (
- At least a part of the component (A) is (Alk) R ′ 2 SiO 1/2 (wherein Alk each independently represents an aliphatic unsaturated carbon-carbon bond-containing group, and R ′ are mutually independent).
- the aliphatic unsaturated carbon-carbon bond-containing group is preferably an alkenyl group, an alkenyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group.
- the siloxane polymerization degree of the component (B) is 100 to 2000.
- At least a part of the component (C) is (c1) an organohydrogenpolysiloxane having at least 3 silicon-bonded hydrogen atoms in the molecule, and (c2) One or more kinds selected from linear organohydrogenpolysiloxanes having a silicon-bonded hydrogen atom at the molecular chain terminal are preferable.
- the curing-reactive silicone composition of the present invention (hereinafter sometimes simply referred to as “the composition of the present invention”) is heat-meltable, and particularly, has a melt viscosity at 100 ° C. of 100,000 Pa ⁇ s or less. Preferably.
- the composition of the present invention preferably has a property as an adhesive, and specifically, in a state before the curing reaction, a curability of a 200 ⁇ m thick curable reactive silicone composition between two glass plates. It is preferable that the curable layer has a shear adhesive strength of 0.1 MPa or more, which is measured by a method defined in JIS K 6850 using a layered test body.
- the present invention also relates to a member, component or sheet made of at least the above-mentioned curing reactive silicone composition.
- the present invention also relates to a heat-meltable adhesive material comprising the above-mentioned curable silicone composition. That is, the curable silicone composition described above can be used as a heat-meltable adhesive material.
- the present invention also relates to a cured product of the above curable silicone composition.
- the above-mentioned cured product is preferably cured by irradiation with high energy rays.
- the cured product of the present invention also preferably has a property as an adhesive, and specifically, a cured product layer having a thickness of 200 ⁇ m and composed of a cured product of the above curing reactive silicone composition, between two glass plates. It is preferable that the cured product layer has a shear adhesive strength of 0.4 MPa or more, which is measured by a method defined by JIS K 6850.
- the present invention also relates to an adhesive material comprising a cured product of the above-mentioned curing reactive silicone composition. That is, the cured product of the above curable silicone composition can be used as an adhesive material.
- the present invention also relates to a member, a part or a sheet comprising at least the above-mentioned adhesive.
- the present invention also relates to a laminate comprising a layer or member made of the above-mentioned curing reactive silicone composition.
- the present invention also relates to a laminate including a layer or a member made of a cured product of the above-mentioned curing reactive silicone.
- These laminates may include at least a part of a sheet-like member having a release layer, for example, a member, a part or a sheet comprising at least the above composition or a cured product thereof has a release layer. It may be a releasable laminate which is placed so as to face the sheet-shaped member and is peeled off from the release layer at the time of use to use the above composition or a cured product thereof as an adhesive.
- the laminated body may be at least one selected from a display device, an electronic component, and a solar cell module, and may be, for example, a display device which is a liquid crystal display or an organic EL display. Further, the above-mentioned curing reactive silicone composition or its cured product may be used as a sealing material for electronic parts such as LEDs and micro LEDs.
- the laminate of the present invention can be used in various articles together with at least one substrate.
- the substrate may be an image display panel, a touch panel, an optical film, or a front surface or back surface protection sheet.
- the article is preferably a display device (display).
- the display device is a liquid crystal display or an organic EL display.
- the substrate may be a solar cell, a sealing material layer, or a front surface or back surface protection sheet.
- the article is preferably a solar cell module.
- the invention also relates to the process for producing these laminates.
- the laminate obtained by these manufacturing methods may be an intermediate material such as a peelable pressure-sensitive adhesive sheet, or a final product such as a display device having a pressure-sensitive adhesive layer or a precursor thereof.
- the method for producing a laminate of the present invention may be characterized by including a step of heating the above-mentioned curable reactive silicone composition to 80 ° C. or higher to melt it, and molding or filling the melt.
- the curing reactive silicone composition is irradiated with high energy rays after or simultaneously with disposing the curing reactive silicone composition on or between at least one member. It may include a step. It is preferable that the irradiation with the high energy rays is performed through a transparent portion such as a transparent portion or a gap that can transmit the high energy rays.
- the method for producing a laminate of the present invention comprises a step of laminating the above-mentioned curable reactive silicone composition or a cured product thereof between members, and pressing the member with the cured reactive silicone composition or a cured product thereof. It may have a step of
- a sheet comprising at least the above-mentioned curing reactive silicone composition may be obtained by a method for producing a sheet including the following steps.
- Step 1 From a solution prepared by dissolving the organopolysiloxane resin as the component (A) and the linear or branched diorganopolysiloxane as the component (B) in a part or all of the organic solvent at 150 ° C.
- Step 2 After adding the organohydrogenpolysiloxane of the component (C) and the hydrosilylation reaction catalyst of the component (D) to the hot-melt solid content obtained in the step 1, the mixture is heated at a temperature of 120 ° C. or lower. Kneading while melting, Step 3: Laminating the mixture after heating and melting obtained in Step 2 between sheet base materials having at least one release surface Step 4: Stretching the laminate obtained in Step 3 between rolls, A step of molding a sheet made of a curable reactive silicone composition having a film thickness.
- the curing-reactive silicone composition of the present invention has sufficient toughness and sufficient adhesive strength for temporarily fixing various base materials, has heat melting property, and has excellent moldability such as a sheet. It is possible to rapidly cure by irradiation with high energy rays and obtain high adhesive strength. Further, the curable reactive silicone composition of the present invention can be easily molded into a form such as a sheet. In addition, since the surface of the curable reactive silicone composition of the present invention or the cured product thereof has pressure-sensitive adhesiveness, it is possible to obtain high adhesiveness by pressing the cured product onto various base materials. Further, when the cured product is in the form of a layer, when the cured product layer is peeled off, the cured product layer undergoes interfacial peeling and cohesive failure of the cured product layer is less likely to occur.
- the curable reactive silicone composition of the present invention has heat-melting property, it can be softened or flowed by heating, and it can follow unevenness on a member well in a molten state to fill a step, and a gap fill. It has excellent properties. Further, the curing-reactive silicone composition of the present invention is cooled to form a solid layer of the non-fluidizing curing-reactive silicone composition at a low temperature (less than 80 ° C.), or the melt is exposed to high energy rays such as ultraviolet rays.
- the curable reactive silicone composition of the present invention has heat-melting property, the melted fluid can be molded into a desired shape such as a sheet.
- a molded article such as a sheet made of a curing-reactive silicone composition before the curing reaction has a heat-melting property, an adhesive property, and a curing-reactive property by itself. By heating and melting by heating, the fluid may be caused to flow into the irregularities of the base material.
- the curing-reactive silicone composition of the present invention if necessary, is irradiated with high energy rays such as ultraviolet rays to proceed with the curing reaction to form a cured product layer, which is fixed between members. Since it forms a cured product layer having sufficient adhesive force and having no heat-melting property after the curing reaction, it can be used as an adhesive layer between members.
- high energy rays such as ultraviolet rays
- the curing-reactive silicone composition of the present invention uses a catalyst for hydrosilylation reaction which is active in the composition upon irradiation with high energy rays such as ultraviolet rays, it is cured by irradiation with high energy rays once. If the irradiation of high energy rays is stopped due to the necessity of the process such as sealing of the member, the curing reaction will proceed with time at low temperature (less than 80 ° C, especially including 23 to 25 ° C). Thus, there is an advantage that a cured product that is an adhesive material is formed.
- the curing-reactive silicone composition of the present invention and its cured product have the advantages described above, and thus can be used as an adhesive. Further, it is possible to provide a laminate including the curable reactive silicone composition of the present invention and a layer formed of the cured product, and a method for producing the laminate.
- the sheet of the present invention can provide a sheet comprising at least the curable reactive silicone composition of the present invention.
- FIG. 10 is a diagram illustrating an overall configuration of a sheet manufacturing apparatus according to a tenth example.
- the present inventors have combined each component of a so-called MQ resin, a predetermined linear or branched organopolysiloxane, a predetermined organohydrogenpolysiloxane, and a high energy ray activating catalyst in a predetermined mode.
- the curing-reactive composition is non-fluid at 25 ° C. and has heat-melting property in an uncured state, so that it has excellent gap fill property and moldability, and has sufficient adhesive force for temporary fixing between members.
- the present invention has been completed by finding that it is possible to form a cured product having excellent adhesiveness to an adherend by advancing a curing reaction by irradiation with high energy rays such as ultraviolet rays.
- the above-mentioned linear or branched organopolysiloxane has at least two aliphatic unsaturated carbon-carbon bond-containing groups in one molecule, and the siloxane polymerization degree is in the range of 80 to 3000.
- mass% is synonymous with “weight%”
- the standard is the total mass (total weight) of the composition or the like of the present invention, unless otherwise specified.
- the curing reactive silicone composition of the present invention is (A) 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 a siloxane unit (Q unit), (B) a linear or branched organopolysiloxane having at least two aliphatic unsaturated carbon-carbon bond-containing groups in one molecule and having a siloxane polymerization degree in the range of 80 to 3000, (C) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule, and (D) A catalyst for hydrosilylation reaction, which does not exhibit activity without irradiation with high energy rays, but exhibits activity in the composition upon irradiation with high energy rays,
- the content of the component (A) is more than 55 mass% and less than 90 mass% of the total mass of
- the cure-reactive silicone composition of the present invention is non-flowable at 25 ° C.
- non-fluidity means that it does not flow in an unloaded state, and for example, the ring-and-ball method for hot melt adhesives defined in JIS K 6863-1994 "Test method for softening point of hot melt adhesives". Shows the state below the softening point measured by the softening point test method. That is, in order to be non-fluid at 25 ° C, the softening point needs to be higher than 25 ° C. This is because when the resin is non-fluid at 25 ° C, the shape retention at that temperature is good.
- the composition of the present invention needs to have sufficient toughness. If this is insufficient, the uncured product tends to be brittle and shape retention tends to be difficult, and the effects expected as an adhesive such as temporary fixing ability may not be obtained.
- the cured composition of the present invention is required to have heat melting property. As a result, processing into various shapes is facilitated, and the unevenness on the member can be satisfactorily followed in the molten state to fill the step, and the gap fillability is excellent. On the other hand, if the melt viscosity is too high, the formability into a sheet or the like and the processability into various shapes may deteriorate, and the gap fill property may also become insufficient. From the viewpoint of workability at the time of processing and molding, the melt viscosity is preferably 100,000 Pa ⁇ s or less at 100 ° C., more preferably 10 to 100,000 Pa ⁇ s, and more preferably 10 to 50.
- a composition having a relatively low melt viscosity at 100 ° C. can be designed by using the component (B) described later, and for example, the melt viscosity at 100 ° C. is 10 to 10,000 Pa ⁇ s. , 100 to 5,000 Pa ⁇ s, 100 to 3,000 Pa ⁇ s, 100 to 1,000 Pa ⁇ s, or 1,000 Pa ⁇ s or less. It is possible to design In addition, it goes without saying that these curing-reactive silicone compositions exhibit a lower melt viscosity at a temperature higher than 100 ° C. and exhibit a sufficiently low softening point equal to or lower than these melt viscosities.
- the curable reactive silicone composition of the present invention having the above-mentioned properties has heat melting property (so-called hot melt property) and can be softened or flowed by heating.
- the softening or fluidizing temperature is preferably from 60 to 120 ° C, more preferably from 65 ° C to 110 ° C, even more preferably from 80 ° C to 105 ° C.
- the curing-reactive silicone composition of the present invention preferably has a property of remarkably softening or fluidizing particularly when heated to 80 ° C. or higher.
- the component (A) is one of the main components of the cure-reactive silicone composition of the present invention.
- the component (A) may be a single organopolysiloxane resin or a mixture of two or more organopolysiloxane resins.
- the component (A) is a component that imparts heat-melting property (hot melt property) or pressure-sensitive adhesive property to the curable reactive silicone composition of the present invention, or imparts pressure-sensitive adhesive property to the cured product thereof, High adhesion to various bases or substrates can be imparted.
- the component (A) is a siloxane unit (M unit) represented by (a) R 3 SiO 1/2 (wherein R is independently a monovalent organic group) in the molecule, and ( b) An organopolysiloxane resin containing a siloxane unit (Q unit) represented by SiO 4/2 .
- the organopolysiloxane resin as the component (A) is well mixed and compatible with the organopolysiloxane as the component (B).
- the softening point of the mixture is raised to a temperature sufficient to show the heat melting property (hot melt property) at 25 ° C. (room temperature) or higher, for example, 50 ° C. or higher. Therefore, it is preferable in the industrial production process to use a softening point higher than the temperature of the component (A).
- the range of 00 to 1.20: 1.00 is more preferable, and the range of 0.60: 1.00 to 1.10: 1.00 is even more preferable.
- the above molar ratio can be easily measured by 29 Si nuclear magnetic resonance.
- the component (A) may be composed of only (a) M units and (b) Q units, but R 2 SiO 2/2 units (D units) and / or RSiO 3/2 units (T units). May be included.
- R's each independently represent a monovalent organic group.
- the total content of (a) M units and (b) Q units in the component (A) 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 can be divided into, for example, an aliphatic unsaturated carbon-carbon bond-containing group and an aliphatic unsaturated carbon-carbon bond-free group.
- the aliphatic unsaturated carbon-carbon bond-containing group and the aliphatic unsaturated carbon-carbon bond-free group respectively include a monovalent unsaturated hydrocarbon group and an oxygen atom-containing monovalent unsaturated hydrocarbon group, and A monovalent saturated hydrocarbon group and an oxygen atom-containing monovalent saturated hydrocarbon group are included.
- the monounsaturated or saturated hydrocarbon group is, for example, a substituted or unsubstituted one having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms.
- Examples thereof include a valent unsaturated hydrocarbon group and a substituted or unsubstituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms.
- Examples of the unsubstituted monovalent unsaturated hydrocarbon group having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms include vinyl group, allyl group and propenyl group. Examples thereof include alkenyl groups such as groups, butenyl groups, pentenyl groups and hexenyl groups. Examples of the substituted monounsaturated hydrocarbon group having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms include, for example, these monovalent unsaturated hydrocarbon groups.
- a group in which a part of the hydrogen atoms of the group is replaced by a halogen atom (fluorine, chlorine, bromine or iodine) and the like can be mentioned.
- Examples of the unsubstituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, pentyl group, hexyl group and octyl group; cyclohexyl group, cycloheptyl group and the like. Examples thereof include a cycloalkyl group; aryl groups such as phenyl group, tolyl group and xylyl group; aralkyl groups such as benzyl group, ⁇ -methylstyryl group and 2-phenylethyl group.
- substituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms for example, a part of hydrogen atoms of these monovalent unsaturated hydrocarbon groups is substituted with a halogen atom (fluorine, chlorine, bromine or iodine) or the like. There are some. Specifically, fluorinated monovalent saturated hydrocarbon groups such as 3,3,3-trifluoropropyl group, 4,4,5,5,5-pentafluorolbutyl group, 3,3,4,4,4.
- Perfluoroalkyl group such as 5,5,6,6,6-nonafluorohexyl group; chlorinated monovalent saturated hydrocarbon group, for example, chloroalkyl group such as 3-chloropropyl group, chlorophenyl group such as dichlorophenyl group Is mentioned.
- a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms is preferable.
- a methyl group is preferable as the substituted or unsubstituted alkyl group having 1 to 12 carbon atoms.
- a substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms is preferable.
- the substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms is preferably vinyl group.
- oxygen atom-containing monovalent unsaturated or saturated hydrocarbon group examples include, for example, substituted or unsubstituted oxygen atom-containing monovalent unsaturated hydrocarbon groups having 2 to 12 carbon atoms, and 1 to 12 carbon atoms. And a substituted or unsubstituted monovalent saturated hydrocarbon group containing an oxygen atom.
- Examples of the substituted or unsubstituted monovalent unsaturated hydrocarbon group having 2 to 12 carbon atoms include an alkenyloxyalkyl group, an acryloxyalkyl group and a methacryloxyalkyl group.
- Examples of the alkenyloxyalkyl group include allyloxymethyl group, 3-allyloxypropyl group and the like.
- Examples of the acryloxyalkyl group include an acryloxymethyl group and a 3-acryloxypropyl group.
- Examples of the methacryloxyalkyl group include a methacryloxymethyl group and a 3-methacryloxypropyl group.
- Examples of the substituted or unsubstituted, oxygen atom-containing monovalent saturated hydrocarbon group having 1 to 12 carbon atoms include alkoxy groups having 1 to 12 carbon atoms.
- alkoxy group having 1 to 12 carbon atoms examples include methoxy group, ethoxy group, propoxy group, butoxy group, isopropoxy group and the like.
- halogen atom fluorine, chlorine, bromine or iodine
- the organopolysiloxane resin as the component (A) may contain a small amount of hydroxyl groups bonded to silicon atoms.
- the content of the hydroxyl group is preferably 0.2 mol or less, more preferably 0.1 mol or less, based on 1 mol of all silicon atoms.
- the organopolysiloxane resin as the component (A) contains an alkoxy group bonded to a silicon atom such as a methoxy group and an ethoxy group, the content thereof is 0.2 mol or less with respect to 1 mol of all silicon atoms. Is preferable, and 0.1 mol or less is more preferable.
- At least a part of the component (A) is (A1) in the molecule of (Alk) R ′ 2 SiO 1/2 (In the formula, Alk independently of each other is an aliphatic unsaturated carbon-carbon.
- a siloxane unit (M unit) represented by a bond-containing group, R'independently of each other represents an aliphatic unsaturated carbon-carbon bond-free group, and a siloxane unit represented by SiO 4/2 It is preferably a curing-reactive organopolysiloxane resin containing at least (Q units).
- the aliphatic unsaturated carbon-carbon bond-containing group which is Alk is preferably the alkenyl group, alkenyloxyalkyl group, acryloxyalkyl group or methacryloxyalkyl group described above.
- the aliphatic unsaturated carbon-carbon bond-free group which is R' is preferably the alkyl group, aryl group or aralkyl group described above. Further, some of these groups may be substituted with a halogen atom or the like.
- the aliphatic unsaturated carbon-carbon bond-containing group which is Alk may be a vinyl group, an allyl group or a hexenyl group, and the aliphatic unsaturated carbon-carbon bond-free group which is R'is It is preferably a methyl group or a phenyl group.
- the component (A) when the component (A) other than the (A1) curing-reactive organopolysiloxane resin is present, the component (A) is preferably non-curing reactive.
- R of the non-curing reactive component (A) is preferably the aliphatic unsaturated carbon-carbon bond-free group described above, and more preferably an alkyl group, an aryl group or an aralkyl group. Further, some of these groups may be substituted with a halogen atom or the like.
- the aliphatic unsaturated carbon-carbon bond-free group represented by R is preferably a methyl group, a phenyl group or the like.
- the proportion of the (A1) curing-reactive organopolysiloxane resin in the component (A) is not particularly limited, but in order to achieve an appropriate hardness for the composition of the present invention or the cured product thereof as an adhesive material. Is preferably 50% by weight or less, more preferably 30% by weight or less, still more preferably 20% by weight or less based on 100% by weight of the entire component (A).
- the content of the component (A1) in the component (A) is preferably in the range of 0 to 20% by mass, particularly preferably in the range of 0 to 15% by mass, and the composition of the present invention or a cured product thereof.
- the adhesive material made of can have appropriate hardness and flexibility as an adhesive layer for a display device, a solar cell module, or the like.
- a component (A) for example, (Me 3 SiO 1/2 ) 0.45 (SiO 4/2 ) 0.55 (HO 1/2 ) 0.05 (Me 3 SiO 1/2 ) 0.40 (SiO 4/2 ) 0.60 (HO 1/2 ) 0.10 (Me 3 SiO 1/2 ) 0.52 (SiO 4/2 ) 0.48 (HO 1/2 ) 0.01 (Me 3 SiO 1/2 ) 0.40 (Me 2 ViSiO 1/2 ) 0.05 (SiO 4/2 ) 0.55 (HO 1/2 ) 0.05 (Me 3 SiO 1/2 ) 0.45 (SiO 4/2 ) 0.55 (MeO 1/2 ) 0.10 (Me 3 SiO 1/2 ) 0.25 (Me 2 PhSiO 1/2 ) 0.20 (SiO 4/2 ) 0.55 (HO 1/2 ) 0.05 (Me 3 SiO 1/2 ) 0.40 (Me 2 SiO 2/2 ) 0.05 (SiO 4/2 ) 0.55 (HO 1/2 ) 0.05 (Me 3 SiO 1/2 )
- the blending amount of the component (A) is the same as that of the components (A) to (C) of the composition. It is in the range of more than 55 mass% to less than 90 mass% with respect to the total mass, and the range of 60 to 85 mass% is preferable. If the amount of the component (A) is less than the lower limit, it may not be possible to impart sufficient tackiness, non-fluidity at 25 ° C. and heat-meltability to the curable reactive silicone composition of the present invention. On the other hand, when the amount of the component (A) blended exceeds the upper limit, the curable reactive silicone composition of the present invention becomes too hard and brittle, and therefore may not be suitable for use as an adhesive material for temporary fixing. ..
- the component (B) is one of the main components of the cure-reactive silicone composition of the present invention.
- the component (B) may be a single organopolysiloxane or a mixture of two or more kinds of organopolysiloxane.
- the curable reactive silicone composition of the present invention or a cured product thereof has sufficient adhesive force, and in its adhesive mode, cohesive failure occurs when peeled from an adherend. It is also possible to form a difficult adhesive layer. If permanent adhesion to an adherend is required, a composition having a high adhesive force that causes cohesive failure of the pressure-sensitive adhesive layer at the time of peeling can be designed.
- the component (B) is a linear or branched organopolysiloxane having at least two aliphatic unsaturated carbon-carbon bond-containing groups in one molecule, and has a siloxane polymerization degree in the range of 80 to 3000. ..
- the degree of siloxane polymerization of the component (B), organopolysiloxane is preferably 100 to 2000, more preferably 120 to 1500, and particularly preferably 150 to 1500.
- the adhesive force of the pressure-sensitive adhesive layer made of the composition or the cured product and the adhesion mode to the adherend are desired while maintaining the heat-meltability of the curing-reactive silicone composition of the present invention. It is also easy to design the pressure-sensitive adhesive layer that is unlikely to cause cohesive failure when peeled from the adherend.
- the aliphatic unsaturated carbon-carbon bond-containing group is preferably the above-mentioned alkenyl group, alkenyloxyalkyl group, acryloxyalkyl group or methacryloxyalkyl group.
- alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group and a hexenyl group. Vinyl groups are particularly preferred. Further, some of these groups may be substituted with a halogen atom or the like.
- the aliphatic unsaturated carbon-carbon bond-containing group may be present at either the terminal of the molecular chain or the side chain of the molecular chain, or may be present at both of them. Good.
- the aliphatic unsaturated carbon-carbon bond-containing group is preferably bonded to a silicon atom.
- the content of the aliphatic unsaturated carbon-carbon bond-containing group is preferably 0.001 to 10% by weight, preferably 0.005 to 5% by weight, and 0.01 to 1% by weight based on the weight of the component (B). % Is more preferable.
- the component (B) may have an aliphatic unsaturated carbon-carbon bond-free group in addition to the aliphatic unsaturated carbon-carbon bond-containing group.
- the aliphatic unsaturated carbon-carbon bond-free group is preferably the above-mentioned alkyl group, aryl group or aralkyl group.
- the alkyl group include a cycloalkyl group such as a cyclohexyl group and a cycloheptyl group in addition to a methyl group, an ethyl group, a propyl group, a pentyl group, a hexyl group, an octyl group and the like.
- Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group and the like.
- Examples of the aralkyl group include a benzyl group, an ⁇ -methylstyryl group and a 2-phenylethyl group.
- the aliphatic unsaturated carbon-carbon bond-free group is more preferably an alkyl group, and particularly preferably a methyl group. Further, some of these groups may be substituted with a halogen atom or the like.
- component (B) those having the following average composition formula (1) are preferable.
- R 1 is an alkenyl group having 2 to 12 carbon atoms. Specific examples thereof include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, and a dodecenyl group, and among these, a vinyl group and an allyl group. Alternatively, a hexenyl group is preferable.
- R 2 is a group selected from a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms which does not have an aliphatic unsaturated bond, a hydroxyl group and an alkoxy group.
- a part of the hydrogen atoms may be replaced with a halogen atom or a hydroxyl group.
- Examples of the monovalent saturated hydrocarbon group having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, An alkyl group such as dodecyl group, phenyl group, tolyl group, xylyl group, naphthyl group, anthracenyl group, phenanthryl group, aryl group such as pyrenyl group, benzyl group, phenethyl group, naphthylethyl group, naphthylpropyl group, anthracenylethyl group Groups, aralkyl groups such as phenanthrylethyl group and pyrenylethyl group, and hydrogen atoms of these aryl groups or aralkyl groups, alkyl groups such as methyl
- a and b are numbers satisfying the following conditions: 1 ⁇ a + b ⁇ 3 and 0.0003 ⁇ a / (a + b) ⁇ 0.33, preferably the following conditions: 1.5 ⁇ a + b ⁇ 2.5 and It is a number that satisfies 0.0006 ⁇ a / (a + b) ⁇ 0.2. This is because when a + b is 1 or more, the flexibility of the cured product increases, while when a + b is 3 or less, the mechanical strength of the cured product increases. Also, if a / (a + b) is 0.001 or more, the mechanical strength of the cured product will be high, while if it is 0.33 or less, the flexibility of the cured product will be high.
- Such a component (B) has a general formula: R 6 3 SiO (R 6 2 SiO) m1 SiR 6 3
- each R 6 is independently a substituted or unsubstituted monovalent hydrocarbon group, and examples thereof include the monovalent unsaturated hydrocarbon group and the monovalent saturated hydrocarbon group described above. However, at least two R 6 s in one molecule are monovalent unsaturated hydrocarbon groups, preferably alkenyl groups, and more preferably vinyl groups.
- the siloxane polymerization degree of “m1 + 2” is a number in the range of 80 to 3,000, more preferably a number in the range of 100 to 2000, and a number in the range of 120 to 1500. Is even more preferable, and a number in the range of 150 to 1500 is particularly preferable. “+2” is the sum of the siloxane units at both ends.
- the composition at 25 ° C. may be in a liquid state, and the composition may not be able to achieve the hot melt property (hot melt property).
- hot melt property hot melt property
- the adhesiveness to the adherend is low, and practically sufficient adhesive force may not be realized.
- m1 + 2 exceeds the upper limit, the adhesive strength after curing may be insufficient.
- the component (C) is one of the main components of the curable reactive silicone composition of the present invention and functions as a crosslinking agent.
- the component (C) may be a single organohydrogenpolysiloxane or a mixture of two or more organohydrogenpolysiloxanes.
- the component (C) is an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule.
- the component (C) is the component (B) or the component (A) when the component (A) has an aliphatic unsaturated carbon-carbon bond-containing group (that is, when the component (A1) is included).
- the component (B) contains a hydrosilyl group (—SiH) that is added to the aliphatic unsaturated carbon-carbon bond.
- the component (C) is an organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule.
- the group bonded to a silicon atom other than the silicon-bonded hydrogen atom in the component (C) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.
- Alkyl groups having 1 to 12 carbon atoms such as undecyl group and dodecyl group; aryl groups having 6 to 20 carbon atoms such as phenyl group, tolyl group and xylyl group; number of carbon atoms such as benzyl group and phenethyl group 7-20 aralkyl groups; halogen-substituted alkyl groups having 1-12 carbon atoms such as 3-chloropropyl group and 3,3,3-trifluoropropyl group are exemplified, and from the viewpoint of economical efficiency and heat resistance, A methyl group and a phenyl group are preferred.
- a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a sec-butoxy group and a tert group are contained within a range not impairing the object of the present invention.
- -A small amount of an alkoxy group such as butoxy group or a hydroxyl group may be bonded.
- the molecular structure of the component (C) is not limited, and examples thereof include linear, partially branched linear, branched, cyclic, or three-dimensional network structures.
- the component (C) may be a single organopolysiloxane having these molecular structures, or a mixture of two or more kinds of organopolysiloxanes having these molecular structures.
- the viscosity of the component (C) at 25 ° C. is not limited, but is preferably 10,000 mPa ⁇ s or less, in the range of 1 to 1,000 mPa ⁇ s, or in the range of 5 to 500 mPa ⁇ s. This is because when the viscosity of the component (C) is at least the lower limit of the above range, the influence on the melt viscosity and adhesive strength of the curable silicone composition (uncured product) is suppressed, while on the other hand, within the above range. This is because when it is at most the upper limit, the transparency and handling workability of the obtained composition will be improved.
- the component (C) is preferably the following component (c1) and component (c2): (C1) Organohydrogenpolysiloxane having at least three silicon-bonded hydrogen atoms in the molecule (c2) Includes a straight-chain organohydrogenpolysiloxane having a silicon-bonded hydrogen atom at the molecular chain end.
- the component (c1) is an organohydrogenpolysiloxane having 3 or more silicon-bonded hydrogen atoms in one molecule, and functions as a cross-linking agent in the hydrosilylation reaction with the (B) component / (A1) component, It is a component that adjusts the hardness of the cured product according to the amount added.
- Examples of the component (c1) include 1,3,5,7-tetramethylcyclotetrasiloxane, tris (dimethylhydrogensiloxy) methylsilane, tris (dimethylhydrogensiloxy) phenylsilane, and 1- (3- Glycidoxypropyl) -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, both ends of the molecular chain trimethylsiloxy group-blocked methylhydrogenpolysiloxane, both ends of the molecular chain trimethylsiloxy Group-blocked dimethyl siloxane / methyl hydrogen siloxane copolymer, dimethyl hydrogen at both molecular chain ends Sil
- organopolysiloxane as the component (c1) examples include the following organopolysiloxanes.
- Me and Ph represent a methyl group and a phenyl group, respectively, and b2, c2, d2, and e2 are positive numbers, respectively, provided that the sum of b2, c2, d2, and e2 in one molecule. Is 1.
- the component (c1) may be an organohydrogenpolysiloxane represented by the following average composition formula.
- R 4 is a group selected from a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, which does not have an aliphatic unsaturated bond, a hydroxyl group and an alkoxy group.
- the monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, the hydroxyl group and the alkoxy group are the same as described above.
- R 5 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group and a hexyl group.
- R 4 SiO 1/2 The above “HR 4 2 SiO 1/2 ", “R 4 3 SiO 1/2”, “HR 4 SiO 2/2 “, “R 4 2 SiO 2/2 “, “HSiO 3/2 “, The constituent units of “R 4 SiO 3/2 ” and “SiO 4/2 ” are organohydrogenpolysiloxanes called MH units, M units, DH units, D units, TH units, T units, and Q units, respectively.
- R 5 O 1/2 which is a unit of a partial structure, is a group bonded to an oxygen atom in a D unit, a DH unit, a T unit, a TH unit, or a Q unit, and is a silicon atom in an organopolysiloxane.
- a bonded hydroxyl group (Si—OH) or a silicon atom-bonded alkoxy group that remains unreacted during the production of an organopolysiloxane is mainly present at the molecular chain terminal of the organohydrogenpolysiloxane, and the DH unit is present in the molecular chain of the organohydrogenpolysiloxane.
- the component (c2) is a linear organohydrogenpolysiloxane having a silicon-bonded hydrogen atom at the terminal of the molecular chain, and functions as a chain length extender in the hydrosilylation reaction with the (B) component / (A1) component, It is a component that improves the flexibility of the cured reaction product.
- Examples of the component (c2) include 1,1,3,3-tetramethyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, and dimethylhydrogensiloxy at both molecular chain ends.
- HMe 2 SiO Ph 2 SiO
- m2 is an integer of 1 to 100
- n2 is an integer of 1 to 50.
- HMe 2 SiO Ph 2 SiO
- m2 SiMe 2 H
- HMePhSiO Ph 2 SiO
- m2 SiMePhH
- HMePhSiO Ph 2 SiO
- n2 SiMePhH
- the content of the component (C) is such that the amount of silicon-bonded hydrogen atoms in the component (C) is 0.5 mol or more per 1 mol of the total aliphatic unsaturated carbon-carbon bond in the composition,
- the amount of silicon-bonded hydrogen atoms in the component (C) is preferably 0.5 to 50 mol, and more preferably 0.5 to 10 mol, based on 1 mol of the total aliphatic unsaturated carbon-carbon bond in the composition.
- the amount is more preferable, and the amount of 0.5 to 2 mol is even more preferable.
- the component (D) is a catalyst for hydrosilylation reaction, which does not show activity without irradiation of high energy rays, but shows activity in the composition by irradiation of high energy rays.
- the component (D) is a so-called high energy ray activating catalyst or a photoactivating catalyst and is known in the art.
- high energy rays examples include ultraviolet rays, gamma rays, X rays, ⁇ rays, and electron rays.
- ultraviolet rays, X-rays, and electron beams emitted from commercially available electron beam irradiation devices are mentioned.
- ultraviolet rays are preferable from the viewpoint of efficiency of catalyst activation, and ultraviolet rays in the wavelength range of 280 to 380 nm are preferable. It is preferable from the viewpoint of industrial use.
- the irradiation dose varies depending on the type of high energy ray activated catalyst, but in the case of ultraviolet rays, the integrated irradiation dose at a wavelength of 365 nm is preferably within the range of 100 mJ / cm 2 to 10 J / cm 2 .
- component (D) include (methylcyclopentadienyl) trimethylplatinum (IV), (cyclopentadienyl) trimethylplatinum (IV), (1,2,3,4,5-pentamethylcyclopenta).
- Dienyl trimethylplatinum (IV), (cyclopentadienyl) dimethylethylplatinum (IV), (cyclopentadienyl) dimethylacetylplatinum (IV), (trimethylsilylcyclopentadienyl) trimethylplatinum (IV), (methoxy Carbonylcyclopentadienyl) trimethylplatinum (IV), (dimethylphenylsilylcyclopentadienyl) trimethylcyclopentadienylplatinum (IV), trimethyl (acetylacetonato) platinum (IV), trimethyl (3,5-heptanedio) Nate) platinum (IV), trimethyl (methyl acetoacetate) G)) platinum (IV),
- the content of the component (D) is an amount necessary for curing the composition, and preferably the amount in which the metal atom in the catalyst is in the range of 1 to 500 ppm by mass unit with respect to the composition. And preferably in the range of 5 to 200 ppm.
- the composition of the present invention may further comprise a set retarder.
- the curing retarder can suppress the hydrosilylation reaction and delay the curing reaction.
- the set retarder may be a single set retarder or a mixture of two or more set retarders.
- an alkyne alcohol such as 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 2-phenyl-3-butyn-2-ol; 3- Enyne compounds such as methyl-3-penten-1-yne, 3,5-dimethyl-3-hexene-1-yne; 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclo Examples include tetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, benzotriazole, triphenylphosphine, and 1,2-bis (diphenylphosphino) ethane. It
- the composition of the present invention may contain a catalyst for hydrosilylation reaction which is active in the composition without irradiation with high energy rays.
- Examples of the hydrosilylation reaction catalyst include platinum catalysts, rhodium catalysts, palladium catalysts, nickel catalysts, iridium catalysts, ruthenium catalysts and iron catalysts, and platinum catalysts are preferable.
- platinum-based catalyst platinum-based compounds such as platinum fine powder, platinum black, platinum-supported silica fine powder, platinum-supported activated carbon, chloroplatinic acid, alcohol solution of chloroplatinic acid, olefin complex of platinum, alkenylsiloxane complex of platinum, etc. Are exemplified, and an alkenylsiloxane complex of platinum is particularly preferable.
- the alkenyl siloxane includes 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, Examples thereof include alkenylsiloxanes in which a part of methyl groups of these alkenylsiloxanes are substituted with ethyl groups, phenyl groups and the like, and alkenylsiloxanes in which vinyl groups of these alkenylsiloxanes are substituted with allyl groups, hexenyl groups and the like.
- 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferable because the stability of the platinum-alkenylsiloxane complex is good. Further, since the stability of the platinum-alkenylsiloxane complex can be improved, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 1,3-diallyl-1,1 are added to the complex.
- the catalyst for hydrosilylation reaction here is a catalyst that exhibits activity without irradiation with high energy rays, but among them, those that exhibit activity even at relatively low temperatures are preferable. Specifically, those which are active in the composition in the temperature range of 0 to 200 ° C. and accelerate the hydrosilylation reaction are preferable.
- the content of the catalyst for hydrosilylation reaction varies depending on the type of the catalyst and the type of the composition, but it is usually preferable that the metal atom in the catalyst is in the range of 0.01 to 100 ppm in mass unit relative to the composition. , 0.1 to 50 ppm is more preferable.
- the composition of the present invention contains, if necessary, other organopolysiloxanes, adhesion promoters, silica, glass, alumina, inorganic fillers such as zinc oxide; organic resin fine powders such as polymethacrylate resin; phosphors, It may contain heat-resistant agents, dyes, pigments, flame retardants, solvents and the like.
- inorganic fillers such as zinc oxide
- organic resin fine powders such as polymethacrylate resin
- phosphors phosphors
- It may contain heat-resistant agents, dyes, pigments, flame retardants, solvents and the like.
- the amount of addition of these optional components and the method thereof are known to those skilled in the art.
- the composition of the present invention is preferably a solventless type, for example, in order to form a thin film of the composition of the present invention, or to apply a desired pattern by printing, a solvent to the composition of the present invention May be added.
- the solvent that can be used is not limited as long as it dissolves the composition of the present invention and gives a uniform solution.
- normal hexane normal pentane, normal octane, isooctane, decalin, and other aliphatic hydrocarbons
- toluene xylene, mesitylene, and other aromatic hydrocarbons
- diisopropyl ether dibutyl ether, tetrahydrofuran, and other ethers
- ethyl acetate butyl acetate and the like
- glycol esters such as propylene glycol monomethyl ether acetate and dipropylene glycol monomethyl ether acetate.
- the composition of the present invention can be produced by mixing the components (A) to (D) and, if necessary, other optional components.
- the composition of the present invention may be prepared by mixing it at the time of use, but it is preferable to prepare it by mixing it before use.
- composition of the present invention is preferably a one-component type in which the components (A) to (D) coexist.
- the composition of the present invention can be prepared, for example, by adding and mixing the component (D) while heating and kneading the components (A) to (C) in the temperature range of 80 to 120 ° C.
- the composition as a whole is softened and the component (D) can be uniformly dispersed throughout the composition. Therefore, in particular, it is possible to avoid curing failure during molding of a sheet or the like and partial cohesive failure during adhesion. is there.
- the temperature is lower than the lower limit, the softening may be insufficient, and it may be difficult to uniformly disperse the component (D) even if mechanical force is used.
- the composition of the present invention has a low melt viscosity at 100 ° C., and is therefore excellent in uniform mixing.
- the powder mixer used in this production method is not limited, and batch (batch) such as a kneader, a Banbury mixer, a Henschel mixer, a planetary mixer, a two-roll mill, a three-roll mill, a Ross mixer, a Laboplast mill, which has a heating / cooling function, is used.
- a single-screw extruder having a heating / cooling function a continuous-screw extruder such as a twin-screw extruder, which is not particularly limited, but it depends on the efficiency of processing time and the controllability of shear heat generation. To be selected. In terms of processing time, a continuous type such as a single screw extruder or a twin screw extruder may be used, or a batch type mixer such as Labo Plastomill may be used.
- the curing-reactive silicone composition of the present invention which is non-fluid at 25 ° C. and has heat-melting property, is more preferably prepared by a production method comprising the following two steps.
- Step 1 From a solution prepared by dissolving the organopolysiloxane resin as the component (A) and the linear or branched diorganopolysiloxane as the component (B) in a part or all of the organic solvent at 150 ° C.
- Step 2 After adding the organohydrogenpolysiloxane of the component (C) and the hydrosilylation reaction catalyst of the component (D) to the hot-melt solid content obtained in the step 1, the mixture is heated at a temperature of 120 ° C. or lower. The process of kneading while melting.
- Step 1 is a step of mixing the hot-melt silicone component, that is, the organopolysiloxane resin as the component (A) and a part or all of the linear or branched organopolysiloxane (B).
- the hot-melt silicone component that is, the organopolysiloxane resin as the component (A) and a part or all of the linear or branched organopolysiloxane (B).
- a part or all of the organohydrogenpolysiloxane of the component (C) to be mixed in the step 2 may be combined and mixed in this step.
- the step of dispersing or dissolving) in an organic solvent is typically a step of using a mixing or stirring device using mechanical force.
- the organopolysiloxane resin as the component (A) and the linear or branched diorganopolysiloxane as the component (B) used in the present invention are soluble in an organic solvent. Further, the above-mentioned organopolysiloxane resin is generally industrially synthesized in a state of being dissolved in an organic solvent.
- the mixing or stirring device using mechanical force is not particularly limited, but a kneader having a heating / cooling function, a Banbury mixer, a Ross mixer, a Hobart mixer, a dental mixer, a planetary mixer, a kneader mixer, a homomixer, a paddle.
- Batch-type devices such as a mixer, a line mixer, a homodisper, a propeller stirrer, a vacuum kneader, a high-speed disperser, a Labo Plastomill and a Henschel mixer can be mentioned.
- a hot-melt solid content By removing the organic solvent while heating the mixture containing the organic solvent at a temperature of 150 ° C. or higher, preferably 200 ° C. or higher, a hot-melt solid content can be obtained.
- the removal of the organic solvent is preferably carried out while performing uniform mixing, and it can be carried out in the above-mentioned mixing or stirring apparatus using a mechanical force, which is provided with a heat treatment means. It is particularly preferable to use a continuous heating and kneading device such as a single-screw extruder having a heating function, a twin-screw extruder, or a continuous kneader.
- the above mixture containing an organic solvent is treated with a continuous heating and kneading device such as an extruder heated to 200 ° C. or higher to remove the organic solvent and continuously collect it as a hot-melt solid. It is possible to
- step 2 a mixture of the organopolysiloxane resin of the component (A) obtained in the step 1 and the linear or branched organopolysiloxane of the component (B) is added to the organohydrogenpolysiloxane of the component (C). And a hydrosilylation reaction catalyst of the component (D) are mixed, and each raw material is kneaded in the presence of the catalyst without proceeding the curing reaction, and finally a curable silicone composition having a hot melt property.
- temperature control in the process is an important factor.
- the organopolysiloxane resin of the component (A), the linear or branched organopolysiloxane of the component (B), the organohydrogenpolysiloxane of the component (C), and (D) is blended, and it is preferable that the heating and kneading temperature after blending the component (D) is maintained at 120 ° C. or lower.
- the temperature before blending the component (D) may be higher than 120 ° C.
- a part of the component (B) can be blended alone or in advance by mixing with the component (C) or the component (D).
- the step 2 is preferably performed under a deaeration condition by a deaeration mechanism such as a vacuum pump in order to remove bubbles described below from the composition.
- Step 2 can be carried out by the batch (batch) type apparatus described in Step 1 and a mixing or stirring apparatus equipped with a temperature control mechanism, preferably a degassing mechanism, but it is possible to continuously add several points of additives.
- a continuous heating and kneading device such as a single-screw extruder, a twin-screw extruder, and a continuous kneader from the viewpoint that they can be charged separately.
- a twin-screw extruder equipped with a temperature control mechanism and a degassing mechanism.
- step 1 which is the previous step of step 2
- a hot-melt mixture (compound) heated to 150 ° C. or higher is obtained.
- the mixture is a hot-melt solid content, has no fluidity at room temperature, and does not contain an organic solvent and other volatile components. Further, since the mixture has fluidity at a temperature of 150 ° C. or higher, unless a special cooling operation or the like is performed after the step 1, the kneading apparatus in the step 2, preferably a twin-screw extruder or the like is used. It is possible to feed to a continuous heating and kneading device.
- the resulting hot-melt mixture (compound) is reheated and melted and supplied to the kneader used in the step 2, which will be described later.
- the use of bulk melters can be mentioned.
- step 2 When step 2 is carried out by a twin-screw extruder, the feeding position and feeding order of each component to the twin-screw extruder are not particularly limited, and it is also possible to feed a plurality of components at the same position.
- the hot-melt solid content obtained in step 1 is continuously supplied in the state of being heated and melted (feed), and the downstream portion (supply position 2) of the component (C). Is continuously supplied (feed), and further, the component (D) is continuously supplied (feed) at the downstream portion (supply position 3).
- the temperature of the barrel constituting the twin-screw extruder can be finely controlled. It is possible to achieve both high mixing efficiency and suppression of heat history during the process, and control.
- the temperature from the supply position 1 to the supply position 2, the supply position 2 to the supply position 3, and the temperature after the supply position 3 can be independently controlled, and finer control can be performed as necessary. For example, if it is possible to knead at a temperature of 120 ° C.
- the temperature control upstream from that can be performed at a temperature exceeding 120 ° C. (for example, It can be carried out at 150 ° C. and is preferable from the viewpoint of mixing efficiency.
- step 2 in order to remove bubbles from the composition, it is preferable to perform the degassing condition by a degassing mechanism such as a vacuum pump.
- a degassing mechanism such as a vacuum pump.
- the means for supplying (feeding) the hot-melt solid content to the heating and kneading device is not particularly limited, but the temperature adjusting means (specifically, for the purpose of maintaining the tank having a heating / cooling mechanism and the temperature).
- a commercially available system can be used, and examples thereof include a bulk melt system manufactured by GRACO and a bulk melter manufactured by Nordson.
- the means for supplying (feeding) the component (C) to the heating and kneading device is not particularly limited, but it is selected from pumps having a constant supply capability according to the viscosity at 25 ° C and the supply amount. Examples include gear pumps, plunger pumps, press pumps, and the like.
- the hydrosilylation reaction catalyst of the component (D) is a solid at 25 ° C.
- it is preferably supplied as a liquid masterbatch premixed with the component (B).
- the supply device is selected from pumps having a constant supply property, and examples thereof include a gear pump, a plunger pump, and a press pump.
- the curing retarder When the curing retarder is supplied in step 2, it may be supplied together with the organohydrogenpolysiloxane as the component (C) or may be supplied together with the hydrosilylation reaction catalyst as the component (B). In (A) and (B), the components may be mixed together.
- a pressure-sensitive adhesive sheet can be manufactured by continuously performing the step (step 4) of molding a curable silicone sheet having a specific film thickness.
- the composition of the present invention is non-fluid at 25 ° C., has sufficient toughness, has the above-mentioned heat melting property, and has sufficient tackiness in an unreacted state. Therefore, it can be molded into a desired shape for use, and can be used as a heat-meltable adhesive by arranging it on a specific adherend.
- the heat melting property of the composition of the present invention is as described above.
- the composition of the present invention can be processed into objects having various shapes, preferably by heating and melting at 80 ° C. or higher, and then cooling, and for example, a sheet or powder having a thickness of 5 ⁇ m to 5 mm can be used. Alternatively, it can be tablet-shaped.
- the composition of the present invention can be heated and melted by using an apparatus having a heating / extruding function and processed into an object having a desired shape.
- the object maintains the curing reactivity and the heat melting property, and therefore, as the heat melting adhesive material, a member, a part, a sheet, or the like. It is particularly preferable to use it in the form of
- the composition of the present invention is itself an adhesive material, but by subjecting it to a curing reaction by irradiation with high energy rays such as ultraviolet rays, an adhesive cured product (including a semi-cured product) is obtained.
- the composition of the present invention is useful as various potting agents, sealants, adhesives / adhesives, preferably optical adhesives / adhesives, and particularly optical adhesives for displays. It is useful as an adhesive.
- the composition of the present invention has sufficient adhesive force for temporary fixing in the state before the curing reaction and is heat-meltable, so that it easily follows irregularities and gaps of an adherend. It is possible to form an adhesive layer having excellent properties.
- the cured product is less colored at high temperature or under high temperature and high humidity, and is less likely to cause turbidity. Therefore, it is used as a fixing layer or an adhesive layer between members constituting a laminated body such as a display device (solar cell module). Extremely useful.
- the adhesive strength of the composition of the present invention is not particularly limited, but a test in which a curable layer having a thickness of 200 ⁇ m made of the curable reactive silicone composition is formed between two glass plates before the curing reaction. It is preferable that the curable layer has a shear adhesive strength of 0.1 MPa or more, which is measured using a body by a method defined in JIS K 6850.
- the composition of the present invention has a property of initiating a curing reaction by irradiation with a high energy ray described later to form a cured product having tackiness, but if necessary, only a partial curing reaction is performed. It may be carried out to form a semi-cured product.
- the “semi-cured state” means that the composition has no viscosity in the low temperature region (15 to 80 ° C.) including room temperature (25 ° C.), that is, non-fluidity, as a result of the progress of the curing reaction.
- thermoplastic that exhibits fluidity at 100 ° C, and still maintain the curing reactivity, and set the curing conditions such as further irradiation of high energy rays or leaving and heating. By doing so, the curing reaction proceeds further, and the curing reaction product in the semi-cured state is referred to as “semi-cured product”.
- the state where the curing reaction of the composition is stopped and the curing reactivity is lost as a result of the progress of the curing reaction, and the state where the curing reaction does not proceed further is referred to as “main curing state”.
- the term "thickened substance” means that the viscosity at 25 ° C is between 1.5 times and 100 times the initial viscosity of the composition.
- thermoplastic material means that the viscosity at 100 ° C. is 1,000,000 mPa ⁇ s or less.
- the semi-cure reaction can be carried out by any method that limits cure before the composition of the present invention is completely or finally cured.
- semi-curing can be performed by limiting the high energy dose to limit the activation of the catalyst.
- semi-curing is also carried out by incorporating a hydrosilylation reaction catalyst other than the component (D) into the composition of the present invention in addition to the component (D), and carrying out the hydrosilylation reaction without irradiation with high energy rays.
- the composition can be semi-cured by heating the composition at a temperature of less than 150 ° C., preferably less than 125 ° C., more preferably less than 100 ° C., and performing a hydrosilylation reaction.
- the heating time is usually 0.2 to 4 hours, preferably 0.5 to 2 hours, though it depends on the kind and blending amount of each component in the composition.
- the curing-reactive silicone composition of the present invention activates the hydrosilylation catalyst, which is the component (D), by irradiating the composition of the present invention (or a semi-cured product thereof) with high energy rays such as ultraviolet rays, A cured product can be formed by the progress of the hydrosilylation reaction in the composition.
- high energy rays are as described above.
- the irradiation dose varies depending on the type of high energy ray activated catalyst, but in the case of ultraviolet rays, the integrated irradiation dose at 365 nm is preferably within the range of 100 mJ / cm 2 to 100 J / cm 2 , and 500 mJ / cm 2 It may be in the range of ⁇ 50 J / cm 2, or in the range of 500 mJ / cm 2 ⁇ 20 J / cm 2 . That is, the curing reactive silicone composition of the present invention can start the curing reaction triggered by irradiation with high energy rays such as ultraviolet rays. If the hydrosilylation catalyst as the component (D) is activated once, the curing reaction will proceed with time at room temperature and the like to form a cured product even if irradiation with high energy rays is stopped.
- the cured product of the present invention can be used as various materials.
- the hardness of the cured product obtained by curing the curing-reactive silicone composition of the present invention is not particularly limited, and at 25 ° C., the degree of penetration defined by JIS K 2220 (hereinafter simply referred to as “needle penetration”). Degree)) from a gel-like cured product having a hardness of 70 or less to a relatively hard resin-like cured product having a Shore D hardness of 80.
- the cured product of the present invention is light transmissive, and more preferably transparent.
- a light-transmissive, especially transparent cured product can be suitably used for optical applications.
- the cured product of the present invention has an optical path length of 6 mm measured according to JIS K7105, a parallel light transmittance of 90% or more at 25 ° C., and a parallel light transmittance of 200 ° C. It is preferable that the transmittance is 99% or more.
- the cured product of the present invention can have tackiness (pressure-sensitive adhesiveness).
- the adhesive strength or adhesive strength of the cured product is not particularly limited, but a cured product layer of 200 ⁇ m thick formed of the cured product of the curable reactive silicone composition of the present invention is formed between two glass plates, and JIS K 6850 is used. It is preferable that the shear adhesive strength of the cured product layer is 0.4 MPa or more, which is measured by the method defined in 1.
- the peeling mode of the cured product of the present invention from the adherend may be interfacial peeling or cohesive failure (permanent adhesion) of the pressure-sensitive adhesive layer.
- the adhesive force of the adhesive material layer composed of the cured product and the adhesion mode to the adherend can be designed as desired. It is also easy to design an adhesive layer that is less likely to cause cohesive failure during peeling.
- the cured product of the present invention can have a certain stretchability or flexibility. Therefore, you may use the hardened
- the curable reactive silicone composition of the present invention and its cured product can be used as an adhesive.
- the pressure-sensitive adhesive of the present invention can have a high adhesive force and can be satisfactorily adhered or adhered to various adherends. Further, the pressure-sensitive adhesive material of the present invention can form a pressure-sensitive adhesive layer in which cohesive failure is less likely to occur at the time of peeling from an adherend, but the present invention is not limited to this and may be accompanied by cohesive failure.
- the behavior at the time of peeling the cured reactive silicone composition of the present invention and the cured product pressure-sensitive adhesive layer from the adherend can be preferably controlled according to the application.
- the application For example, in applications where an action as a (pressure-sensitive) pressure-sensitive adhesive is expected, there is no residue on the adherend surface, or even a small amount of residue is possible.
- it does not pose a problem to exhibit high adhesiveness that causes cohesive failure.
- the curing-reactive silicone composition of the present invention can be used as a heat-melting pressure-sensitive adhesive material as a heat-melting pressure-sensitive adhesive material having excellent moldability, gap fill property and pressure-sensitive adhesive strength before the curing reaction. Further, the cured product of the curing-reactive silicone composition of the present invention can be used as an adhesive material having excellent adhesive strength, although the heat-melting property and the curing reactivity are substantially lost.
- the pressure-sensitive adhesive material composed of the curing-reactive silicone composition is used to temporarily fix the member or to form a pressure-sensitive adhesive material layer on the adherend that makes the best use of the gap fill property for unevenness and gaps, and After fixing, disposing, and pasting, the adhesive material made of the curing reactive silicone composition is irradiated with high energy rays such as ultraviolet rays to form an adhesive material made of a cured material between adherends. You may let me. Further, since the pressure-sensitive adhesive made of the cured product of the curing-reactive silicone composition of the present invention can be used as a pressure-sensitive adhesive by itself, the heat-meltability of the curing-reactive silicone composition of the present invention is utilized. Then, it may be molded into a sheet or the like and then cured to be handled alone as an adhesive member having a desired shape.
- Laminate It is possible to provide a laminate comprising a layer made of the curable reactive silicone composition of the present invention or a layer or member made of a cured product of the composition.
- the laminate is not particularly limited, but a pressure-sensitive adhesive sheet (including an adhesive sheet and a pressure-sensitive adhesive (PSA) sheet), a releasable sheet laminated with a release layer
- PSA pressure-sensitive adhesive
- It may be a laminate, and at least one kind selected from a display device, an electronic component or a solar cell module, which comprises a layer made of the above-mentioned curing reactive silicone composition or a layer made of a cured product obtained by curing reaction of the composition. It may be an article.
- the pressure-sensitive adhesive sheet of the present invention includes at least one pressure-sensitive adhesive layer made of the curable reactive silicone composition of the present invention or a cured product (including a semi-cured product) of the present invention on at least one sheet substrate.
- the pressure-sensitive adhesive sheet includes an adhesive sheet or a pressure-sensitive adhesive sheet for the purpose of pressure bonding, and the adhesive state thereof may be such that it undergoes interfacial peeling when peeled from the adherend. It may be in a permanently bonded state with cohesive failure of the layers.
- the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present invention is the curable reactive silicone composition (uncured product) of the present invention, the above semi-cured product, or main cured product, which is uncured according to its use and purpose of use, It is provided as a semi-cured or full-cured state.
- the pressure-sensitive adhesive of the present invention does not have fluidity at 25 ° C., is in an uncured state, has sufficient pressure-sensitive adhesive force for temporary fixing, and constitutes a pressure-sensitive adhesive layer that can be freely molded by heating and melting.
- the following uses are also possible. Needless to say, the following use is essentially impossible with an adhesive layer made of a usual cured product.
- the adhesive sheet of the present invention can be used, for example, as follows. That is, an adhesive sheet comprising an uncured composition of the present invention or a semi-cured composition of the present invention and having a heat-meltable adhesive material layer is formed on a sheet (release film) having a release layer. Form. Next, the pressure-sensitive adhesive sheet is peeled off from the release film, the exposed pressure-sensitive adhesive layer is adhered onto a target base material (adherend), and then heated to a temperature above the melting temperature of the pressure-sensitive adhesive layer. By this operation, the adhesive layer adheres well to the surface of the base material, and when there is a step or the like on the surface, it is possible to follow this.
- the second base material is placed on the pressure-sensitive adhesive layer formed through the curing operation and the peeling operation to adhere the both.
- the base material is a base material that is transparent or has a transparent portion for high energy rays such as ultraviolet rays, it is uncured and adhered at a constant temperature, and then high energy such as ultraviolet rays is applied. It is also possible to irradiate the pressure-sensitive adhesive layer with a wire to form a laminate.
- the type of the above sheet-shaped substrate is not particularly limited, and includes paperboard, cardboard paper, clay-coated paper, polyolefin laminated paper, especially polyethylene laminated paper, synthetic resin film sheet, natural fiber cloth, synthetic fiber cloth, Examples are artificial leather cloth and metal foil.
- synthetic resin films and sheets are preferable, and examples of synthetic resins include polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyethylene terephthalate, cyclopolyolefin, and nylon.
- a film of heat resistant synthetic resin such as polyimide, polyether ether ketone, polyethylene naphthalate (PEN), liquid crystal polyarylate, polyamide imide, and polyether sulfone is suitable.
- transparent materials such as polypropylene, polystyrene, polyvinylidene chloride, polycarbonate, polyethylene terephthalate, and PEN are suitable.
- the thickness of the sheet-shaped substrate is not particularly limited, and can be designed to have a desired thickness depending on the application.
- a step of stretching the melt as it is with a roll or the like as described later, or a rolling step with a hot press or the like is required, and the sheet base material is also used. Since it may be deformed by being exposed to heat or pressure, it is preferable to use a sheet base material having a necessary thickness.
- the thickness is preferably 50 ⁇ m or more, more preferably 75 ⁇ m or more, and a thick base material of up to about 300 ⁇ m can be used depending on the conditions and intended use.
- a support film that has been subjected to primer treatment, corona treatment, etching treatment, and plasma treatment may be used.
- the surface of the film-shaped substrate opposite to the pressure-sensitive adhesive layer surface may be surface-treated, for example, to prevent scratches, stains, fingerprints, antiglare, antireflection and antistatic. ..
- the sheet-shaped substrate has at least one release layer, and the release layer is in contact with the pressure-sensitive adhesive layer.
- the release layer is sometimes called a release liner, a separator, a release layer or a release coating layer, and is preferably a release agent such as a silicone release agent, a fluorine release agent, an alkyd release agent, or a fluorosilicone release agent.
- a release layer obtained by curing a fluorosilicone release agent is preferable to use as the release layer.
- the fluorosilicone-based release agent is a curable organopolysiloxane composition containing one or more kinds of organopolysiloxane having a fluorine-containing substituent bonded to a silicon atom in one molecule, and particularly, intramolecular It is preferable to use a curable organopolysiloxane composition containing an organopolysiloxane containing at least one fluorine-containing substituent selected from a fluoroalkyl group such as a perfluorobutylethyl group and a perfluoropolyether group.
- a fluoroalkyl group such as a perfluorobutylethyl group and a perfluoropolyether group.
- the organopolysiloxane containing a fluorine-containing substituent may further have a curing reactive group such as an alkenyl group in the same molecule, and is a combination of two or more different organopolysiloxanes containing a fluorine-containing substituent. And may be used in a specific mixing ratio.
- the pressure-sensitive adhesive sheet of the present invention has a structure in which the curable reactive silicone composition of the present invention or a cured product thereof (including a semi-cured product) is laminated between two sheet base materials, each sheet base material and adhesive It is preferable to design so as to have a constant peel force difference between the peel forces of the volatile silicone composition.
- the peeling force can be controlled by selecting the above-mentioned fluorosilicone-based release agent, selecting the crosslinked structure / crosslinking density, and the thickness of the release layer.
- a release coating film having an appropriate release force may be selected from commercially available products, and a film that gives desired release characteristics may be appropriately designed and used.
- the pressure-sensitive adhesive sheet of the present invention is obtained by, for example, heating and melting the curing-reactive silicone composition (uncured material) of the present invention on a sheet-shaped substrate, applying the composition, and applying an adhesive having a predetermined thickness. It can be produced by forming a functional layer and then, as it is, or by semi-curing or main curing the adhesive layer, if necessary.
- the advantages of the uncured, semi-cured, and fully cured states and the advantages of each state are as described above, and they can be used properly according to need.
- the pressure-sensitive adhesive sheet may be referred to as a "sheet made of a curable reactive silicone composition".
- the curable reactive silicone composition (uncured product) of the present invention it is particularly preferable to apply the melted composition by heating at 80 ° C. or higher, which has the above-mentioned heating and extrusion functions. You may heat-melt using a device and apply.
- the sheet-shaped composition of the present invention is controlled to a specific thickness by a batch-type cooling press, a rotating roll or the like.
- the pressure-sensitive adhesive sheet of the present invention is more preferably prepared by a production method comprising the following two steps in addition to the suitable Step 1 and Step 2 in the production of the above-mentioned curable reactive silicone composition.
- Step 3 Laminating the mixture after heating and melting obtained in Step 2 between sheet base materials having at least one release surface
- Step 4 Stretching the laminate obtained in Step 3 between rolls, A step of molding a sheet made of a curable reactive silicone composition having a film thickness
- steps 3 and 4 can be manufactured by an apparatus designed to enable continuous operation subsequent to the step 2 described above. Particularly, it is preferable in order to suppress the time of exposure to high temperature to a short time.
- the curing-reactive silicone composition one having a melt viscosity at 100 ° C. of 100,000 Pa ⁇ s or less is preferably used, and the melt carried out in step 3 and step 4 is stretched as it is by a roll or the like. It is possible to carry out the process or the rolling process by hot pressing at a lower temperature and a lower pressure.
- Step 3 is a step of laminating the mixture after heating and melting obtained in step 2 between the sheet base materials having at least one release surface, and is a preliminary step for pressure molding in step 4.
- pressure molding by roll stretching can be performed on the peelable sheet to obtain a sheet-shaped molded article, and After molding, only the peelable sheet can be removed from the sheet-shaped molded article by utilizing the peeling surface.
- the mixture after heating and melting obtained in the process 2 preceding this is laminated between two sheet base materials. It is preferable that both of the two sheet base materials have a release surface, depending on the usage form of the sheet made of the resulting curable reactive silicone composition, and in step 3, the mixture obtained in step 2 is used for each sheet base material. It is particularly preferable to be laminated between the release surfaces.
- the sheet made of the thin layer-shaped curable reactive silicone composition is sandwiched between the releasable sheets and peeled from both sides through the pressure molding in the step 4 and the subsequent arbitrary cutting.
- step 3 the mixture obtained in step 2 is optionally preformed and then laminated on two sheet base materials.
- the step is not particularly limited, but the mixture obtained in step 2 is supplied by being discharged or applied onto the release layer of one of the sheet base materials, and the mixture is supplied from above the other sheet base material. A laminated body is formed by laminating the peeling layers.
- each sheet base material is conveyed to a position where the mixture of step 2 is supplied through a rotary roll, and a lamination operation between the films is performed. Done.
- the diameter and width of the rotary roll are not particularly limited, but a structure capable of uniformly pressing in the width direction is desirable.
- the pressurizing method is not particularly limited, but an air cylinder or hydraulic type is preferable.
- the supply amount of the mixture obtained in step 2 in step 3 between the sheet base materials can be designed according to the production rate and scale.
- the mixture obtained in Step 2 can be supplied between the sheet base materials at a supply rate of 1 to 10 kg / hour, but needless to say, the present invention is not limited to this.
- the amount of the mixture obtained in Step 2 to be laminated between the sheet base materials needs to be determined according to the average thickness of the sheet made of the curable reactive silicone composition designed in Step 4. In addition, it is necessary that the thickness is such that rolling can be performed in step 4.
- step 3 the mixture after heat-melting obtained in step 2 is formed into a sheet or a string (having a small diameter by a die and a nozzle). It is preferable that the particles are discharged while being molded into a rod-shaped molded product discharged from the hole portion and laminated between the sheet base materials.
- the entire laminate obtained in step 3 is cooled or temperature adjusted after the above-mentioned temporary molding as a step before step 4 or in step 4. It is preferable to include a step. This is because the heat-melted material is cooled to be in a solid state so that the pressure molding in the step 4 is effectively performed.
- the cooling step is not particularly limited, but the mixture supplied or laminated on the sheet base material by a cooling roll, cold air or the like is cooled in the range of ⁇ 50 ° C. to room temperature by using a cooling means such as air cooling or a cooling solvent. It can be performed by cooling with.
- step before step 4 or the step 4 includes a step of adjusting the temperature of the entire laminated body at a temperature of 80 to 120 ° C. The details of the temperature adjustment will be described in step 4.
- Step 4 is a step of stretching the laminate obtained in Step 3 above between rolls and molding a sheet made of a curable reactive silicone composition having a specific film thickness. In this step, the resulting mixture is stretched under pressure to form a uniform sheet.
- the number of sets of rolling rolls may be single or plural.
- the rolling process in step 4 can be performed on the laminated body obtained in step 3 by using a known rolling method such as roll rolling.
- a sheet made of the curable reactive silicone composition having a desired thickness can be designed by adjusting a gap between the rolls.
- the average thickness is 10 to 2000 ⁇ m.
- the gap between the rolls is adjusted within a range of 1.5 to 4.0 times the average thickness of the sheet made of the target curing reactive silicone composition. Particularly preferred.
- a substantially flat sheet of the curable reactive silicone composition having a thickness of 10 to 2000 ⁇ m can be obtained.
- peelability including a pressure-sensitive adhesive sheet having low defects and excellent handling workability due to peeling A laminated body can be obtained.
- attaching a film thickness meter it becomes possible to measure the film thickness of the laminate obtained in step 3, the film thickness can be easily adjusted, and the film thickness can be controlled.
- Step 4 when the laminate obtained in Step 3 is stretched between rolls, the roll further has a temperature adjusting function, and the temperature of the entire laminate is adjusted during roll rolling, and heating or cooling is performed as necessary. Is preferred. By adjusting the temperature, the gap between the rolls can be kept stable, and the flatness and uniformity (uniformity of film thickness) of the obtained hot-melt adhesive sheet can be improved.
- the specific temperature control range can be appropriately designed according to the heat resistance of the sheet base material, the thickness of the adhesive sheet (designed thickness), its reactivity, etc., but is generally within the range of 5 to 120 ° C. is there.
- the melt viscosity of the mixture after heating and melting obtained in step 2 is high, if the temperature of the mixture is remarkably lowered at the time of laminating with a roll, the viscosity of the mixture becomes too high, which makes it difficult to control the film thickness. Sometimes.
- the mixture can be supplied to the rotary roll at a temperature substantially the same as the outlet temperature of the heating and kneading device, and it is possible to prevent the viscosity from increasing.
- step 2 From the viewpoint of industrial mass production from step 2 to step 4, it is preferable to be a continuous step, but when handling a thermosetting composition as a hot melt composition, some points of step 2 ( When the composition is exposed to a high temperature for a long time from the supply point 2), the curing reaction of the composition is allowed to proceed, which adversely affects the curability of the finally obtained sheet composed of the hot-melt curing reactive silicone composition. There are cases. In order to prevent this, it is important to control the temperature during kneading, but the time from the end of steps 2 to 4 to the start of cooling of the obtained sheet is short, specifically, 30 It is preferably within minutes, preferably within 15 minutes, and more preferably within 5 minutes. In the manufacturing process, when the time of exposure to high temperature is within the above range, even if a sheet made of a thermosetting curable reactive silicone composition is produced, the reaction does not proceed and a sheet excellent in hot melt property is obtained. It is possible to manufacture.
- a peelable laminate in which a sheet made of a hot-melt curable reactive silicone composition is interposed between the peelable sheets can be obtained, but a laminate containing the sheet is optionally cut. You may have a process. This makes it possible to obtain a peelable laminate including a hot-melt sheet having a desired size.
- the device for cutting is not limited, but a device capable of continuously cutting in the width direction and the length direction is preferable, and it is desirable that the line speed can be adjusted.
- a sheet cutter manufactured by Soltec Industry Co., Ltd. can be used for continuous cutting. If the device for cutting has a foreign substance inspection machine, foreign substances can be detected, marked, and removed before cutting.
- a release laminate having a sheet made of a hot-melt curable reactive silicone composition interposed between the release sheets is formed into a state of a release laminate, and thereafter, a step for practical purpose of quality control (for example, a step of measuring characteristic values and managing the presence / absence of foreign matter may be included and preferable. It is preferable that the step is performed by a foreign matter detection device equipped with an optical measuring means such as a camera or a video.
- the pressure-sensitive adhesive sheet of the present invention includes a pressure-sensitive adhesive layer made of a curing-reactive silicone composition in an uncured state, for example, by applying a high-energy ray to the adherend after applying the pressure-sensitive adhesive layer to an adherend.
- the curing-reactive silicone composition may be cured, and the adhesive layer after curing may be peeled from the sheet-shaped substrate for use.
- the pressure-sensitive adhesive layer made of the uncured or semi-cured cured reactive silicone composition may be peeled off from the sheet-shaped substrate and used.
- the pressure-sensitive adhesive layer may be in an uncured state, a semi-cured state, or a main cured state as long as it is a pressure-sensitive adhesive layer derived from the above-mentioned curing-reactive silicone composition.
- the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present invention is composed of an uncured or semi-cured cured reactive silicone composition
- the pressure-sensitive adhesive layer has heat-meltability, and thus after being applied to the pressure-sensitive adhesive layer adherend.
- the adhesive layer is softened or fluidized, and for example, even if the adherend surface of the adherend has irregularities, the adhesive layer is filled with no gaps. can do.
- the heating means for the adhesive sheet for example, various constant temperature baths, hot plates, electromagnetic heating devices, heating rolls and the like can be used. In order to perform the bonding and the heating more efficiently, for example, an electric heat press, a diaphragm type laminator, a roll laminator, or the like is preferably used.
- the softening temperature of the pressure-sensitive adhesive layer is 50 ° C. or higher, the processing characteristics and the storage characteristics at room temperature can be made sufficient.
- the softening temperature of the adhesive layer is 100 ° C. or lower, not only heat damage to the image display panel and the like can be suppressed, but also the adhesive layer can be prevented from flowing out and protruding. Therefore, the softening temperature of the adhesive layer is preferably 50 to 100 ° C, more preferably 55 ° C or higher or 95 ° C or lower, and further preferably 60 ° C or higher or 90 ° C or lower.
- the thickness of the adhesive layer is preferably 20 to 500 ⁇ m, more preferably 25 ⁇ m or more or 350 ⁇ m or less, and particularly preferably 50 ⁇ m or more or 250 ⁇ m or less.
- the adhesive sheet of the present invention in one aspect thereof, At least one sheet-like substrate, It comprises at least one adhesive layer formed on the sheet-shaped substrate,
- the pressure-sensitive adhesive layer contains the above-mentioned curing reactive silicone composition or a cured product (including a semi-cured product) thereof.
- the number of sheet-shaped substrates may be two.
- the adhesive sheet of the present invention A first sheet-shaped substrate, A second sheet-shaped substrate, At least one pressure-sensitive adhesive layer formed between the first sheet-shaped base material and the second sheet-shaped base material, The adhesive layer may be in contact with the first sheet base material and the second sheet base material.
- the pressure-sensitive adhesive sheet in the above-described form has, for example, the curable reactive silicone composition of the present invention sandwiched between a first sheet-shaped base material and a second sheet-shaped base material, and a constant thickness with a press or roll while heating. It can be obtained by molding.
- the pressure-sensitive adhesive layer is a heat-meltable pressure-sensitive adhesive layer made of an uncured curing-reactive silicone composition.
- the composition is exposed to ultraviolet rays or the like. You may manufacture by irradiating with a high energy ray.
- the pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer made of a cured product of the curing-reactive silicone composition.
- the first sheet-shaped base material may be provided with a first release layer, or the first sheet-shaped base material itself may be provided with releasability.
- the second sheet-shaped substrate may have a second release layer, or the second sheet-shaped substrate itself may have a releasability.
- the curable reactive silicone composition of the present invention or its cured product comes into contact with the first release layer and / or the second release layer, and if the pressure-sensitive adhesive layer is formed into a sheet, the pressure-sensitive adhesive layer It is particularly preferable that they are bonded so that the peeling surfaces face each other and form a peelable laminate.
- the pressure-sensitive adhesive layer can be used as a pressure-sensitive adhesive sheet, for example, by applying the pressure-sensitive adhesive layer to an adherend and then peeling the pressure-sensitive adhesive layer from the sheet-shaped substrate.
- the first or second sheet-shaped substrate that may have a release layer is the same as the already-illustrated sheet-shaped substrate (such as a synthetic resin film), and the release layer is also the same as the already-illustrated release layer. It is the same. Further, the first sheet base material and / or the second sheet base material may be light transmissive, and more preferably transparent.
- any one of the sheet-shaped base materials is transparent
- irradiation with high energy rays is applied to the first sheet-shaped base material or It can be carried out through the second sheet-shaped substrate, and the pressure-sensitive adhesive layer made of the curable reactive silicone composition of the present invention can be changed to a pressure-sensitive adhesive layer made of a cured product of the composition.
- the thickness of the pressure-sensitive adhesive layer is preferably 20 to 500 ⁇ m, more preferably 25 ⁇ m or more or 350 ⁇ m or less, and particularly preferably 50 ⁇ m or more or 250 ⁇ m or less. However, it is not limited to these thicknesses.
- the curable reactive silicone composition of the present invention or an adhesive material comprising the cured product thereof can be used for adhering various objects.
- a laminated body can be manufactured as an article of the present invention using the adhesive material of the present invention.
- the present invention is At least one substrate, An article comprising at least one adhesive component, comprising:
- the present invention also relates to a laminate, which is an article, in which the pressure-sensitive adhesive material part includes the curing-reactive silicone composition of the present invention or a pressure-sensitive adhesive material made of a cured product thereof.
- the shapes of the base body and the adhesive component are arbitrary, and can be various three-dimensional shapes.
- the adhesive component can be on or in the substrate. Preferably, at least a part of the base adheres to the adhesive component.
- the pressure-sensitive adhesive material component has a pressure-sensitive adhesive force and can adhere well to various substrates. Further, the base may be permanently adhered by the pressure-sensitive adhesive component, and it is possible to design the adhesion mode in which cohesive failure does not occur when the pressure-sensitive adhesive component is peeled from the base, and the interface peels.
- the present invention At least one substrate,
- the present invention also relates to an article, wherein the pressure-sensitive adhesive layer contains the curable reactive silicone composition of the present invention or a pressure-sensitive adhesive made of a cured product thereof.
- the shape of the substrate is a sheet or a film
- the shape of the adhesive layer is a layer.
- at least a part of the surface of the substrate adheres to the adhesive layer.
- the properties of the adhesive layer are as described above.
- the adhesive layer can be present between a plurality of bases or substrates, and preferably a plurality of bases or substrates are joined together.
- the substrate or the substrate may be porous or non-porous.
- porous substrate or the porous substrate examples include woven fabrics, nonwoven fabrics, fiber products such as paper, synthetic resin films and sheets made porous by stretching, and combinations thereof.
- the fibers may be natural fibers, synthetic fibers or a mixture thereof.
- the pressure-sensitive adhesive of the present invention can be present in at least a part of the holes of the base or the substrate.
- a porous substrate or substrate such as cloth or paper is impregnated with the composition of the present invention (including impregnation and cooling in a heating and melting state), and if necessary, high energy rays such as ultraviolet rays are further irradiated. Irradiation and curing can produce such articles.
- non-porous substrate or non-porous substrate examples include synthetic resin film / sheet, metal foil, and combinations thereof.
- synthetic resin films and sheets are preferable, and examples of synthetic resins include polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol (PVA), polycarbonate, polyethylene terephthalate, cyclopolyolefin, and nylon.
- a film of heat resistant synthetic resin such as polyimide, polyether ether ketone, polyethylene naphthalate (PEN), liquid crystal polyarylate, polyamide imide, and polyether sulfone is suitable.
- transparent materials such as polypropylene, polystyrene, polyvinylidene chloride, PVA, polycarbonate, polyethylene terephthalate, PEN or a mixture thereof are suitable for applications such as display devices where visibility is required.
- the thickness of the substrate is not particularly limited and can be designed to have a desired thickness according to the application.
- a substrate that has been subjected to primer treatment, corona treatment, etching treatment, or plasma treatment may be used.
- the surface of the substrate opposite to the pressure-sensitive adhesive layer contact surface may be subjected to surface treatment such as scratch prevention, stain prevention, fingerprint adhesion prevention, antiglare, antireflection and antistatic.
- the pressure-sensitive adhesive component or the pressure-sensitive adhesive layer is useful as a member of various electronic devices or electric devices.
- the shear storage modulus G ′ of the pressure-sensitive adhesive component or the pressure-sensitive adhesive layer at 25 ° C. (room temperature) is in the range of 0.01 to 15 MPa (more preferably 0.1 to 10 MPa, more preferably 0.2 to 10 MPa). 5 MPa is even more preferable.)
- the pressure-sensitive adhesive component or the pressure-sensitive adhesive layer is an elastic adhesive component or an elastic adhesive layer
- the electronic component or a member for a transducer sensor, speaker, actuator and generator. It is useful as a.
- the adhesive may be opaque or transparent.
- An opaque or low-light-transmissive adhesive material is not required to be transparent, and is a film-like or sheet-like member used for sensors, speakers, actuators, etc. in which the parts or layers themselves are required to have a certain elasticity or flexibility. Useful for purposes. It is also useful as a sealing material or an adhesive material used in a secondary battery such as a lithium-ion battery or a fuel cell.
- the base or the substrate is preferably a member for an optical device.
- the substrate may be an image display panel, a touch panel, a polarizing film, a retardation film, a color filter, a viewing angle widening film, a brightness enhancement film, an optical film such as a reflection sheet, or a front surface or back surface protection sheet.
- the pressure-sensitive adhesive layer is, for example, a surface protection sheet and an optical film, an optical film and a touch panel, a surface protection sheet and an image display panel, a back protection sheet and an image display panel, a surface protection sheet and a touch panel, a touch panel and an image display panel. Can be joined.
- the optical device can be configured by bonding two members selected from an image display panel, a touch panel, an optical film, and a front surface or back surface protection sheet via at least one adhesive material. .. It should be noted that they may be attached one by one or two at the same time, and the attaching method and order are not limited at all.
- high energy rays such as ultraviolet rays are further applied from the optical device constituting member side. Irradiation can also be used to cure such compositions or semi-cured products thereof.
- the composition of the present invention is slightly irradiated with a high energy ray to be semi-cured, and then light-shielded so that the component (D) is not further activated, and the member is bonded.
- the component (D) may be further activated and then completely or finally cured by irradiation with a high energy ray again.
- the material of the front surface or the back surface protective sheet is not particularly limited, for example, glass, or (meth) acrylic resin such as polymethyl methacrylate, polycarbonate resin, cycloolefin polymer, acetyl cellulose resin such as triacetyl cellulose, Examples thereof include polyester resins such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate, plastics such as acyclic olefin resins such as polypropylene and polyethylene, and mixtures of these plastics.
- acrylic resin such as polymethyl methacrylate, polycarbonate resin, cycloolefin polymer, acetyl cellulose resin such as triacetyl cellulose
- polyester resins such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate
- plastics such as acyclic olefin resins such as polypropylene and polyethylene, and mixtures of these plastics.
- the surface protection sheet may be an integrated touch panel, for example, a touch-on lens (TOL) type or a one glass solution (OGS) type. Further, the surface protection sheet may have a print step portion printed in a frame shape on the peripheral portion thereof.
- TOL touch-on lens
- OGS one glass solution
- a structure in which a surface protective sheet is laminated on a functional film such as a touch panel via an adhesive sheet is adopted. If the concealment printing part (thickness: about 5 to 80 ⁇ m) is attached and the adhesive does not sufficiently enter into the inside corner of the step formed on the edge of the concealing printing part, bubbles will remain and the screen The visibility will be reduced. Further, there is a possibility that the film member may be bent in the vicinity of the step and the appearance may be poor, or that residual strain due to the bending of the film may be a starting point to cause foaming or peeling between the laminated members.
- the composition of the present invention can be applied without causing such bubbles in the range of 5 ⁇ m to 20 ⁇ m and even in the presence of the steps in the range of 50 ⁇ m to 80 ⁇ m without leaving air bubbles. .. Moreover, even if one of the adherends is a flexible film member, the surface of the film member can be smoothed without distortion by hot-melting the composition of the present invention. It is possible to bond and integrate members without causing distortion or deformation in
- the touch panel is not particularly limited, and may be a resistive film type, a capacitance type, an electromagnetic induction type, or a combination thereof.
- the touch panel preferably includes at least one cover film, a transparent electrode layer such as an ITO or ATO film, or a glass substrate.
- the touch panel may further include a decorative film or the like.
- the image display panel is not particularly limited as long as it displays image information, and for example, in the case of a liquid crystal display, a polarizing film, a retardation film, a color filter, a viewing angle widening film, a brightness enhancement film, a reflection film. It is composed of an optical film such as a sheet, a liquid crystal material, a transparent substrate, and a backlight system (usually, the surface to which the adhesive material is adhered to the image display panel is the optical film). , VA system, IPS system, etc., but any system may be used.
- the image display panel may be an in-cell type in which a touch panel function is built in the TFT-LCD, or an on-cell type in which a touch panel function is built in between a glass substrate provided with a polarizing plate and a color filter.
- the image display panel is composed of an organic EL element substrate or a laminate of the organic EL element substrate and other optical films.
- the article of the present invention is preferably a display, and is a CRT display, a liquid crystal display, a plasma display, an organic EL display, an inorganic EL display, an LED display, a surface conduction electron-emitting device display (SED), a field emission type.
- a display (FED) is more preferable, and a liquid crystal display or an organic EL display is even more preferable.
- the image display surface of the display may be flat (planar), curved or curved.
- the optical display of the present invention includes, for example, communication devices such as mobile phones and fixed phones; computer devices such as tablet terminals, desktop terminals, and notebook terminals; TVs; printers; ATMs (automated teller machines); in-vehicle monitors or Navigation system; Digital camera; Video camera; Medical device; PDA (mobile terminal); Watch; Electronic paper; CD, DVD or Blue-ray disc player; Solid electronic recording medium player such as SSM or HD; E-book device; Mobile device It is applied to amusement equipment such as game equipment and fixed game equipment; POS system; fish finder; automatic ticket vending machine; instrument panel.
- communication devices such as mobile phones and fixed phones
- computer devices such as tablet terminals, desktop terminals, and notebook terminals
- TVs printers
- ATMs automated teller machines
- Digital camera Video camera
- Medical device PDA (mobile terminal); Watch; Electronic paper; CD, DVD or Blue-ray disc player
- Solid electronic recording medium player such as SSM or HD
- E-book device
- the base or the substrate may be a solar cell, a sealing material layer, a front surface or back surface protection sheet. Therefore, the pressure-sensitive adhesive layer is, for example, a surface protection sheet and a solar cell, a back surface protection sheet and a solar cell, a surface protection sheet and a sealing material layer, a back surface protection sheet and a sealing material layer, a sealing material layer. Solar cells can be joined.
- the curable reactive silicone composition of the present invention or the pressure-sensitive adhesive comprising the cured product thereof has pressure-sensitive adhesiveness, and thus can be used for construction and use of a laminated touch screen or a flat panel display.
- a known method of using the pressure-sensitive adhesive layer can be used without particular limitation.
- the curable reactive silicone composition of the present invention or an adhesive made of a cured product thereof is an optically transparent silicone pressure-sensitive adhesive disclosed in the above-mentioned JP-A-2014-522436 or JP-A-2013-512326.
- the adhesive film or the adhesive layer can be used for manufacturing a display device such as a touch panel.
- the cured product obtained by curing the organopolysiloxane composition of the present invention can be used as the adhesive layer or the adhesive film described in JP-A-2013-512326 without any particular limitation.
- the touch panel of the present invention is a substrate such as a conductive plastic film having a conductive layer formed on one surface thereof, and the present invention attached to the surface on which the conductive layer is formed or the opposite surface thereof. It may be a touch panel including the curing-reactive silicone composition or the pressure-sensitive adhesive made of the cured product thereof.
- the substrate is preferably a sheet-shaped or film-shaped substrate, and a resin film or a glass plate is exemplified.
- the conductive plastic film may be a resin film or a glass plate having an ITO layer formed on one surface thereof, particularly a polyethylene terephthalate film.
- the curable reactive silicone composition of the present invention or the pressure-sensitive adhesive comprising the cured product thereof may be used as an adhesive film for a polarizing plate used for manufacturing a display device such as a touch panel, and is described in JP2013-065009A. It may be used as a pressure-sensitive adhesive layer used for bonding between the touch panel and the display module.
- FIG. 1 is a cross-sectional view showing a laminated body of one embodiment of the present invention.
- the laminate 1 of one embodiment of the present invention comprises a first member 20, a second member 21, and a curing-reactive silicone composition of the present invention arranged between two members 20, 21 or curing thereof. And an adhesive material 15 made of a material.
- the two members 20 and 21 are adhered by the adhesive material 15.
- These optical members may be transparent or opaque, one or both of them may be a single base material, and may be an independent laminated body such as a backlight unit. It may be an optical member.
- the member constituting the laminate of the present invention is generally provided with a plate-shaped portion having a planar spread, the plate-shaped portion or the member itself may be curved, It may have three-dimensional unevenness derived from the application.
- the two optical members 20 and 21 can be arbitrarily combined.
- the two optical members 20 and 21 may be the same as or different from each other.
- the members 20 and 21 are generally used as a constituent member of an optical display. More specifically, the members 20 and 21 are optical members, for example, lenses (which may be made of resin or glass), optical sheet-like members (color filters, polarizing plates, retardation plates, viewing angle widening films). , A brightness enhancement film, a reflection sheet, a transparent conductive film), an optical protective material which may be transparent (a transparent protective material (transparent protective film), etc., made of glass, resin or resin coating layer), front surface It may be a display panel, a touch panel (made of glass or resin), a transparent electrode layer such as an ITO or ATO film. Needless to say, an optical protective material may be further provided on the surface of the display panel or the touch panel.
- lenses which may be made of resin or glass
- optical sheet-like members color filters, polarizing plates, retardation plates, viewing angle widening films.
- an optical protective material which may be transparent (a transparent protective material (transparent protective
- the optical member may be a backlight unit itself including a light emitting layer and a display surface (display panel) described later, or a component in a display device such as a component or a touch panel, in which the entire optical member is an independent laminated member.
- the optical member may further include an adhesive layer 15 made of the main cured product. That is, the concept of the optical member includes an image display panel, an optical panel, a front panel, a backlight unit, a touch panel unit, etc., which will be described later.
- the material of the members 20 and 21 is not particularly limited as long as it is generally used for the above-mentioned applications, but glass, an inorganic optical material such as indium tin oxide (ITO), or a polycarbonate resin, Acrylic resin, epoxy resin, polystyrene resin, polyamide resin, polyimide resin, polyethylene resin, polypropylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol (PVA) resin, polyethylene terephthalate (PET) resin, cyclopolyolefin resin, poly Examples of the organic optical materials include ether ether ketone resins, polyethylene naphthalate (PEN) resins, liquid crystal polyarylate resins, polyamide imide resins, polyether sulfone resins, and mixtures thereof.
- ITO indium tin oxide
- a polycarbonate resin Acrylic resin, epoxy resin, polystyrene resin, polyamide resin, polyimide resin, polyethylene resin, polypropylene
- polyimide resin polyether ether ketone resin, polyethylene naphthalate (PEN) resin, liquid crystal polyarylate resin, polyamide imide resin, polyether sulfone resin or a mixture thereof may be used.
- PEN polyethylene naphthalate
- polypropylene resin polystyrene resin, polyvinylidene chloride resin, PVA resin, polycarbonate resin, PET resin, PEN resin, or a mixture thereof may be used.
- the members 20 and 21 may be subjected to a surface treatment generally performed as a constituent member of an optical display.
- the surface treatment may be, for example, a primer treatment or a corona treatment.
- the two optical members may peel off at the adhesive interface due to the difference in coefficient of thermal expansion between the two members.
- the curable reactive silicone composition of the present invention can be cured by heating and melting between members so as to follow gaps and irregularities on the members, and the cured product has flexibility, so The influence of the difference in expansion coefficient can be reduced, and the two members 20 and 21 different from each other can be bonded well. Therefore, the pressure-sensitive adhesive comprising the present invention or a cured product thereof can be suitably used for bonding different members, particularly for bonding an organic material and an inorganic material having a large thermal expansion coefficient difference.
- the laminated body 1 shown in FIG. 1 includes two members, but the number of members is not particularly limited as long as it includes a plurality of members, particularly an optical member.
- the adhesive material 15 shown in FIG. 1 is formed between the two members 20 and 21 as a whole, but is formed in a part between the two members 20 and 21, for example, in the form of one or more dots. It may have been done.
- the adhesive material 15 shown in FIG. 1 is formed between the two members 20 and 21, it may also be formed on the surface 20b opposite to the adhesive surface 20a of the member 20. It may be formed on the surface 21a opposite to the adhesive surface 21b, or may be formed on both surfaces 20b and 21a.
- FIG. 2 is a flowchart showing a method for manufacturing a laminated body according to an embodiment of the present invention.
- a method for producing a laminate according to an embodiment of the present invention is directed to disposing the curable reactive silicone composition of the present invention on one surface or both surfaces of at least one of the two members, and applying the two members to the curable silicone.
- An arrangement and a bonding step S1 for bonding via the composition, and a curing step S2 for curing the composition by initiating a hydrosilylation reaction by irradiation with high energy rays such as ultraviolet rays are included.
- the composition of the present invention is arranged on the member using, for example, the above-mentioned coating method.
- the composition of the present invention may be arranged on one surface of one member.
- the curable reactive silicone composition of the present invention arranged on both sides of a member or an adhesive material which is a cured product thereof and which is not used for bonding with other optical members is used as an adhesive surface on a release layer or another member. It may be used for joining.
- composition of the present invention may be arranged on one surface of each of the two members in the arrangement step S1.
- the “one surface” is the surface facing the other optical member.
- the composition of the present invention may be arranged on the other surface located on the opposite side to the one surface.
- FIG. 3 is a conceptual diagram of a method for manufacturing a laminated body including a heating and melting step.
- the adhesive material 15A made of the curable reactive silicone composition of the present invention is heated to 80 ° C. or higher to be melted, and the melt is specified to correspond to the concave portion of the member 21.
- the pressure-sensitive adhesive material of the present invention is heat-meltable, it can be easily molded into a desired shape such as a sheet shape, and by having such a step, if necessary, it is possible to fill irregularities or gaps on the member and follow it. It has excellent properties and has an advantage that a flat adhesive surface can be formed if necessary. In particular, even if the material of the member, which is difficult to adhere due to the unevenness or the gap, has the adhesiveness, the curable reactive silicone composition of the present invention can be easily adhered by heating and melting it. In addition, there is a case where a stronger adhesive layer can be formed by the curing step described later.
- the composition of the present invention is cured in a low temperature region (15 to 80 ° C.) including room temperature (25 ° C.).
- “low temperature” refers to a temperature range of 15 ° C. to 80 ° C., for example.
- the reaction of the composition of the present invention (including a semi-cured product) is allowed to proceed in the temperature range of 15 to 80 ° C., it is preferably around room temperature (a temperature range that can be reached without heating or cooling, 20 to
- the composition may be allowed to stand in a temperature range of 25 ° C., may be cooled to room temperature or lower and 15 ° C. or higher, and may be heated to room temperature or higher and 80 ° C. or lower.
- a method for producing a laminate according to a further embodiment of the present invention is the method of arranging the curing-reactive silicone composition of the present invention on one surface or both surfaces of at least one member of two optical members, and curing the two optical members.
- high energy rays are irradiated. Thereby, a cured product obtained by curing the composition of the present invention is obtained.
- the high energy rays are those mentioned above and are preferably ultraviolet rays.
- FIG. 4 is a sectional view showing an optical display according to an embodiment of the present invention.
- An optical display 200 according to an embodiment of the present invention includes the above laminated body 1 and an image display panel 201.
- the laminate 1 and the image display panel 201 are adhered to each other via an adhesive layer (not shown).
- This adhesive layer may be composed of the curable reactive silicone composition of the present invention or a cured product thereof.
- the second optical member 21 of the laminated body 1 is in contact with the adhesive layer.
- the first optical member 20 of the laminate 1 may be a polarizing film and the second optical member 21 may be a retardation film.
- the 1st optical member 20 of the laminated body 1 can be a polarizing film
- the 2nd optical member 21 can be a surface protection film, for example.
- the image display panel 201 is not particularly limited as long as it displays image information.
- a liquid crystal display LCD
- a polarizing film a retardation film
- a color filter a viewing angle widening film
- a brightness a brightness.
- An improvement film an optical film such as a reflection sheet, a liquid crystal material, a transparent substrate, and a backlight system (usually, the pressure-sensitive adhesive component or the pressure-sensitive adhesive layer adheres to the image display panel is an optical film)
- the STN method, the VA method, the IPS method, and the like are used depending on the control method of the liquid crystal material, but any method may be used.
- the image display panel 201 may be an in-cell type in which a touch panel function is built in a TFT-LCD, or an on-cell type in which a touch panel function is built in between a glass substrate provided with a polarizing plate and a color filter. ..
- the image display panel 201 is composed of an organic EL element substrate or a laminated body of an organic EL element substrate and other optical films.
- the optical display 200 may be a cathode ray tube (CRT) display or a flat panel display (FPD).
- FPD for example, a light receiving display device such as an LCD or an electrochromic display (ECD), or an electroluminescent display (ELD) such as an organic EL display or an inorganic EL display, a plasma display (PDP), a surface conduction electron-emitting device.
- a field emission display (FED) such as a display (SED) and a light emitting display device such as an LED display can be mentioned.
- FIG. 5 is a sectional view showing an optical display according to another embodiment of the present invention.
- An optical display 300A according to another embodiment of the present invention includes an image display panel 301, an optical member 20, and a curable reactive silicone composition of the present invention disposed between the image display panel 301 and the optical member 20, or a composition thereof. And an adhesive layer 15 made of a cured product.
- the image display panel 301 can be an example of the image display panel 201 of FIG.
- the optical display 300A is obtained by, for example, disposing the optical member 20 on one surface 301a of the image display panel 301 via a curable layer made of the curable reactive silicone composition of the present invention, which is heated and melted as necessary. It can be obtained by irradiating the curable layer with a high energy ray to cure it.
- a curable layer made of the curable reactive silicone composition of the present invention which is heated and melted as necessary, is formed on one surface 20 a of the optical member 20.
- the optical member 20 can be obtained by arranging the optical member 20 on one surface 301a of the image display panel 301 via the curable layer, and further irradiating the curable layer with a high energy ray to cure it.
- FIG. 6 is a sectional view showing an optical display according to another embodiment of the present invention.
- An optical display 300B according to another embodiment of the present invention is an image display panel 301, a touch panel 302, and the curable reactive silicone composition of the present invention or a cured product thereof arranged between the image display panel 301 and the touch panel 302. And an adhesive layer 15 made of.
- the touch panel 302 is not particularly limited, and may be a resistive film type, an electrostatic capacitance type, an electromagnetic induction type, or a combination thereof.
- the touch panel 302 preferably includes at least one cover film, a transparent electrode layer such as an ITO or ATO film, or a glass substrate.
- the touch panel may further include a decorative film or the like.
- the curing reactivity of the present invention is provided between a display unit such as a liquid crystal / organic EL and a display forming member such as a touch panel or a cover lens, or between display forming members.
- a display unit such as a liquid crystal / organic EL
- a display forming member such as a touch panel or a cover lens
- the visibility of the optical display can be improved by adhering or sticking with the silicone composition or the cured product thereof.
- the curing-reactive silicone composition of the present invention has sufficient tackiness, can realize high conformability to unevenness of a member by heating and melting, and has a relatively low temperature after irradiation with high energy rays such as ultraviolet rays, Specifically, it has a property of being rapidly cured at a temperature of 40 ° C. or lower. Therefore, in the optical display of the present invention, deformation and deterioration of a heat-unstable material are suppressed, and further, under high temperature and high humidity. Since the cured product is less likely to be turbid or colored even when exposed to, it is possible to improve the reliability as an optical display.
- the optical display of the embodiment of the present invention further comprises Further comprising a shield substrate provided on the surface facing the display surface of the front panel and having a surface on which the transparent conductive film is formed,
- the display device may have a structure in which the transparent conductive film and the bezel are electrically connected via a conductive material.
- a shield substrate such as an Electro-Magnetic Interference (EMI) substrate having a conductive layer on one side can be further inserted between the display module and the front panel. Since such a shield substrate has an electromagnetic wave shielding function, it prevents the front panel from malfunctioning due to electromagnetic waves emitted from the display module.
- a conductive layer made of a transparent conductive film such as ITO is formed on one surface of the shield substrate uniformly or in a mesh shape. Then, in order to set the potential of the conductive layer to the GND of the display module, the adhesive member or the like arranged on the outer periphery of the bezel may be formed of a conductive adhesive member such as Ag paste.
- the bezel of the display module is made of metal and is GND-connected inside the display module.
- the metal bezel and the conductive layer of the shield substrate can be surely GND-connected by using a conductive material as the adhesive member, it is possible to provide a display device having a strong electromagnetic wave resistance.
- FIG. 7 is an exploded perspective view showing an optical display according to another embodiment of the present invention.
- FIG. 8 is a partial sectional view showing an optical display according to another embodiment of the present invention.
- a display device 400 (optical display) according to the present invention includes a display panel 110 having a display surface 111, a frame portion 121, and an opening end 122 inside the frame portion 121.
- the bezel 120 that covers the peripheral edge of the display panel 110 on the display surface 111 side with the frame 121, the front panel 130 that is provided on the display surface 111 side of the display panel 110 with the bezel 120 interposed therebetween, and the open end of the bezel 120.
- a resin member 140 that fills a gap 172 formed in the overlapping portion of the bezel 120 and the display surface 111 without a gap in the direction perpendicular to the display surface 111, and the display surface 111 and the front surface.
- an OCR 150 filled between the panel 130 and the panel 130.
- the display surface 111 refers to the entire surface of the display panel 110 on the front panel 130 side.
- FIG. 8 shows a so-called two-stage dam structure, in which a dam (resin member) 140 is further provided on the bezel 120 and a space 173 with the front panel 130 is filled with an OCR 150 made of a hardened product.
- the resin member 140 under the bezel may be only the upper stage or the lower stage unlike the drawing.
- the display panel 110 is mounted on the backlight unit 171, and the bezel 120 and the backlight unit 171 are fixed by a fitting structure (not shown), whereby the display module 170 is configured.
- the entire surface of the display module 170 and the front panel 130 such as a touch panel are attached via the OCR 150.
- the curing-reactive silicone composition of the present invention is used for the inner layer of the front panel 130, the OCR 150, the resin member 140 under the bezel (which may be the upper stage or the lower stage), and the like.
- cured material can be applied.
- the use is not limited to these applications, and the curable reactive silicone composition of the present invention or an adhesive material made of the cured product thereof is used for joining and filling in each member or between each member shown in FIGS. 7 and 8. be able to.
- the use of the curing-reactive silicone (organopolysiloxane) composition of the present invention and the cured product obtained by curing the same is not limited to the above-mentioned ones, and the curing-reactive silicone composition of the present invention or Adhesive sheets equipped with an adhesive material made of the cured product are instruments for TV receivers, computer monitors, personal digital assistant monitors, surveillance monitors, video cameras, digital cameras, mobile phones, personal digital assistants, automobiles, etc. Panel displays, instrument panel displays for various equipment, devices and equipment, automatic ticket vending machines, automated teller machines, in-vehicle display devices, in-vehicle transparent screens, etc. for displaying characters, symbols and images Can be used for the display device.
- the surface shape of such a display device may be a curved surface shape or a curved shape instead of a flat surface, and in addition to various flat panel displays (FPD), a curved surface display used for automobiles (including electric vehicles) and aircrafts.
- FPD flat panel displays
- a curved surface display used for automobiles (including electric vehicles) and aircrafts Alternatively, a curved transmission screen is exemplified.
- these display devices include various icons such as icons for executing functions or programs on a screen or a display, notification display of e-mail programs, car navigation devices, membranes for speakers, audio devices, air conditioners, etc.
- the operation buttons of the device may be displayed, and a touch panel function may be added which enables input operation by touching these icons, notification display, and operation buttons with a finger.
- the device is a display device such as a CRT display, a liquid crystal display, a plasma display, an organic EL display, an inorganic EL display, an LED display, a surface electrolytic display (SED), a field emission display (FED), or a touch panel using these. It can be applied.
- the curing reactive silicone composition of the present invention or the pressure-sensitive adhesive comprising the cured product thereof has excellent adhesiveness and viscoelasticity, and thus is a member for a transducer such as a membrane for a speaker (sensor, speaker, actuator, and, It can be used as a film or sheet-shaped member (including for generators), and can also be used as a sealing layer or an adhesive layer used in a secondary battery, a fuel cell or a solar cell module.
- the curing-reactive silicone composition of the present invention or the pressure-sensitive adhesive comprising the cured product thereof may be substantially transparent, does not cause problems such as poor curing and deterioration of curability, and is a base for various display devices and the like.
- a display device for a vehicle which has excellent visibility and operability of display contents over a long period of time because of its excellent adhesion to a material, particularly a display device for a vehicle which includes a curved screen or a curved display and optionally has a touch panel function. It can be used suitably.
- the pressure-sensitive adhesive layer of the present invention can be suitably applied or replaced as a part or all of the adhesive layer or the pressure-sensitive adhesive layer required to have transparency in these documents.
- the curable reactive silicone composition of the present invention or the pressure-sensitive adhesive made of the cured product replaces the currently used adhesive layer or pressure-sensitive adhesive layer which is required to have transparency in other known curved display devices. Needless to say, it is preferable to adjust the design of the display device and the thickness of the member by a known method in order to further utilize the advantages of the curable reactive silicone composition of the present invention or the adhesive material made of the cured product. ..
- a transparent film-like substrate provided with a curing reactive silicone composition of the present invention or an adhesive material made of a cured product thereof is used to prevent scratches, stains, fingerprints, antistatics, and reflection on the display surface. It may be used for the purpose of prevention and peep prevention.
- a spacer having a thickness of 200 ⁇ m and a predetermined amount of the curing reactive silicone composition are placed between two glass plates (length 75 mm ⁇ width 25 mm ⁇ thickness 2 mm) and heated to a temperature higher than the softening point of the composition by hot pressing, After pressurizing, the mixture was cooled to 25 ° C., and a curable reactive silicone composition (uncured product) having a cylindrical shape with a diameter of 20 mm and a thickness of 200 ⁇ m was sandwiched between two glass plates to prepare a test body.
- This test body was irradiated with ultraviolet rays having a wavelength of 365 nm through a glass plate so that the irradiation amount was 10 J / cm 2, and then aged at room temperature for 6 hours, and the two glass plates had a diameter of 20 mm and a thickness of 200 ⁇ m.
- a test body in which the cylindrical silicone cured product was sandwiched was prepared.
- Examples 1 to 9 and Comparative Examples 1 to 8 Curing reactive silicone compositions of Examples and Comparative Examples were prepared by uniformly heating and mixing each component with the composition (parts by mass) shown in Table 1 using the following components.
- Me is a methyl group and Vi is a vinyl group.
- a1-1 (Me 3 SiO 1/2 ) 0.46 (SiO 4/2 ) 0.54 (HO 1/2 ) 0.05 a1-2: (Me 3 SiO 1/2 ) 0.48 (SiO 4/2 ) 0.52 (HO 1/2 ) 0.04 a2-1: (ViMe 2 SiO 1/2 ) 0.046 (Me 3 SiO 1/2 ) 0.394 (SiO 4/2 ) 0.56 (HO 1/2 ) 0.05
- B-1 ViMe 2 SiO (Me 2 SiO) 151 SiMe 2 Vi
- B-2 ViMe 2 SiO (Me 2 SiO) 830 SiMe 2 Vi
- B′-1 ViMe 2 SiO (Me 2 SiO) 45 SiMe 2 Vi
- B′-2 ViMe 2 SiO (Me 2 SiO) 4770 SiMe 2 Vi
- c1 Me 3 SiO (Me 2 SiO) 30 (MeHSiO) 30 SiMe 3 c2: HMe 2 SiO (Me 2 SiO) 24 SiMe 2 H
- D-1 methylcyclopentadienyl trimethylplatinum (IV) was used.
- compositions of Comparative Examples 7 and 8 were very brittle at 25 ° C. (insufficient toughness) and could not be subjected to a shear adhesion test.
- Each of the curing-reactive silicone compositions of Examples 1 to 9 has heat-melting property and sufficient toughness, and itself (unreacted) functions as an adhesive material and is rapidly irradiated with ultraviolet rays.
- a cured product was formed on, and the cured product also had sufficient tackiness.
- both the curing-reactive silicone composition and the cured product thereof had appropriate viscoelasticity, and had practically sufficient properties as an adhesive material.
- adhesive strength and elongation are greatly improved after curing, it is useful as a material for temporarily fixing members before curing and irradiating high energy rays such as ultraviolet rays to form an elastic adhesive material that firmly bonds the members. is there.
- these curing-reactive silicone compositions and cured products thereof were transparent and had properties as an optically transparent adhesive (OCA) or an optically transparent resin (OCR).
- the curing reactive silicone compositions of Comparative Examples 1 to 8 do not satisfy the requirements of the composition of the present invention, they do not have sufficient adhesive strength before the curing reaction, and thus they are used as hot melt adhesives. It cannot be used (Comparative Examples 1 to 4 and 6), cannot achieve a practical adhesive force even after the curing reaction (Comparative Examples 3, 5 and 6), or is very brittle before the curing reaction and is temporarily bonded. However, it could not be used as an adhesive (Comparative Examples 7 and 8).
- a curing reactive silicone composition was prepared according to the following steps 1 to 4 and was formed into a sheet.
- the configuration of the twin-screw extruder used for sheeting and the overall configuration of sheeting are shown in FIGS. 9 and 10.
- Step 1 Mixing components (A) and (B) to obtain a hot-melt solid content] 2.50 kg of xylene, 6.45 kg of component (a1-1) (white solid at 25 ° C.), 0.42 kg of component (a2-1) (white solid at 25 ° C.), and component (B-2) 3. 13 kg of a cylindrical metal can (pail can) was charged, and the mixture was dissolved and mixed at room temperature using a motor-type stirring device.
- the obtained solution was continuously fed at 10 kg / hr from the charging section provided at the uppermost stream of the twin-screw extruder in which the screw was continuously rotated.
- the set temperature of the charging part was 150 ° C.
- suction is performed from a vent provided in the middle of the twin-screw extruder at a vacuum degree of ⁇ 0.08 MPa using a vacuum pump to obtain xylene, the component (a1-1) and the component (a2-1), or The low molecular weight organopolysiloxane component contained in the component (B-2) was removed.
- a molten transparent fluid was continuously obtained from the most downstream outlet of the twin-screw extruder. This was received in a pail and cooled and solidified.
- Step 2 A step of adding components (C) and (D) to the hot-melt solid content obtained in step 1, and then kneading while heating and melting at a temperature of 120 ° C. or less]
- a heating and kneading operation was performed by the following method.
- a hot melter (VersaPail melter manufactured by Nordson Co., Ltd.) was attached to a pail can filled with the hot-melt solid obtained in the above step 1, and a twin screw extruder in which a screw was continuously rotated was used as a line shown in FIG.
- Feed was continuously made from 9A at 9.66 kg / hr.
- the set temperature of the hot melter was 170 ° C.
- a mixture of the components (c1) and (c2) (weight ratio 0.21: 0.79) was continuously fed at 0.14 kg / hr from a line 9B shown in FIG.
- the set temperature of the charging part was 150 ° C.
- 0.20 kg / of a masterbatch (containing 0.1% by weight of the component (D)) consisting of (methylcyclopentadienyl) trimethyl platinum (IV) as the component (D) and the component (B-2) It was continuously fed from the line 9C in FIG.
- the set temperature of the charging part was 80 ° C.
- the vent provided at the most downstream portion of the twin-screw extruder was used to degas using a vacuum pump.
- a colorless and transparent melt was obtained from the most downstream outlet of the twin-screw extruder.
- the obtained composition was non-fluid at 25 ° C. and had a heat-melting property (hot melt property).
- Step 3 A step of laminating the mixture after heating and melting obtained in step 2 between films having at least one release surface
- the most downstream discharge port of the twin-screw extruder was a T-die, and a device having a function of stretching and laminating films and a function of sheet cutting was installed downstream thereof as shown in FIG. The melt discharged from the T-die set at 90 ° C.
- Step 4 A step of stretching the laminate obtained in Step 3 between rolls to form a sheet having a specific film thickness
- a sheet made of a hot-melt curable reactive silicone composition having a thickness of 1 mm is formed between two peelable films.
- the whole was cooled by air cooling.
- Examples 11 to 19 The kneaded melt obtained in Examples 1 to 9 above is laminated between two peelable films. Subsequently, the laminate is stretched between rolls whose temperature is controlled at 80 ° C., so that a sheet made of a hot-melt curable reactive silicone composition having a thickness of 1 mm is laminated between two peelable films. The laminated body thus formed is formed, and the whole is cooled by air cooling. When the peelable film was separated from the obtained laminate, a flat and homogeneous transparent hot-melt curable reactive silicone composition sheet without bubbles could be obtained.
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Abstract
Description
(A)分子内にR3SiO1/2(式中、Rは互いに独立して一価有機基を表す)で表されるシロキサン単位(M単位)、及び、SiO4/2で表されるシロキサン単位(Q単位)を含むオルガノポリシロキサン樹脂、
(B)一分子中に少なくとも2個の脂肪族不飽和炭素-炭素結合含有基を有し、シロキサン重合度が80~3000の範囲である直鎖状又は分岐鎖状オルガノポリシロキサン、
(C)一分子中に少なくとも2個のケイ素結合水素原子を有するオルガノハイドロジェンポリシロキサン、並びに、
(D)高エネルギー線の照射がないと活性を示さないが、高エネルギー線の照射により組成物中で活性を示すヒドロシリル化反応用触媒
を含み、
(A)成分の含有量が(A)成分~(C)成分の質量の総和の55質量%超~90質量%未満であり、
(C)成分の含有量が、組成物中の全脂肪族不飽和炭素-炭素結合1モルに対して、(C)成分中のケイ素結合水素原子が0.5モル以上となる量であり、
25℃において非流動性であり、さらに、加熱溶融性を有する、硬化反応性シリコーン組成物によって達成される。
(c1)分子内に少なくとも3個のケイ素結合水素原子を有するオルガノハイドロジェンポリシロキサン、及び、
(c2)分子鎖末端にケイ素結合水素原子を有する直鎖状オルガノハイドロジェンポリシロキサン
から選ばれる1種類以上であることが好ましい。
工程1:有機溶剤中に、(A)成分のオルガノポリシロキサン樹脂、および、一部または全部の(B)成分の直鎖状又は分岐鎖状ジオルガノポリシロキサンを溶解させた溶液から、150℃以上の温度で有機溶剤の除去を行い、ホットメルト性の固形分を得る工程、
工程2:工程1で得たホットメルト性の固形分に、(C)成分のオルガノハイドロジェンポリシロキサン、及び(D)成分のヒドロシリル化反応用触媒を加えた後、120℃以下の温度で加熱溶融しながら混練する工程、
工程3:工程2で得た加熱溶融後の混合物を、少なくとも1の剥離面を備えたシート基材間に積層する工程
工程4:工程3で得た積層体をロール間で延伸し、特定の膜厚を有する硬化反応性シリコーン組成物からなるシートを成型する工程。
本発明の硬化反応性シリコーン組成物は、
(A)分子内にR3SiO1/2(式中、Rは互いに独立して一価有機基を表す)で表されるシロキサン単位(M単位)、及び、SiO4/2で表されるシロキサン単位(Q単位)を含むオルガノポリシロキサン樹脂、
(B)一分子中に少なくとも2個の脂肪族不飽和炭素-炭素結合含有基を有し、シロキサン重合度が80~3000の範囲である直鎖状又は分岐鎖状オルガノポリシロキサン、
(C)一分子中に少なくとも2個のケイ素結合水素原子を有するオルガノハイドロジェンポリシロキサン、並びに、
(D)高エネルギー線の照射がないと活性を示さないが、高エネルギー線の照射により組成物中で活性を示すヒドロシリル化反応用触媒
を含み、
(A)成分の含有量が(A)成分~(C)成分の質量の総和の55質量%超~90質量%未満であり、
(C)成分の含有量が、組成物中の全脂肪族不飽和炭素-炭素結合1モルに対して、(C)成分中のケイ素結合水素原子が0.5モル以上となる量であり、
25℃において非流動性であり、さらに、加熱溶融性を有するという性質を備える。
本発明の硬化反応性シリコーン組成物は、25℃において非流動性である。ここで、非流動性とは、無負荷の状態で流動しないことを意味し、例えば、JIS K 6863-1994「ホットメルト接着剤の軟化点試験方法」で規定されるホットメルト接着剤の環球法による軟化点試験方法で測定される軟化点未満での状態を示す。つまり、25℃において非流動性であるためには、軟化点が25℃よりも高い必要がある。25℃において非流動性であると、該温度での形状保持性が良好であるからである。ここで、形状保持に加えて、本発明の組成物は十分な靭性を有することが必要である。これが不十分な場合、未硬化物が脆く、形状保持が難しくなる傾向があり仮固定能などの粘着剤として期待される効果が得られない場合がある。
(A)成分は本発明の硬化反応性シリコーン組成物の主要な成分の1つである。(A)成分は単一のオルガノポリシロキサン樹脂であってもよく、2種以上のオルガノポリシロキサン樹脂の混合物でもよい。
本発明の一態様では、(A)成分の少なくとも一部が、(A1)分子内に(Alk)R’2SiO1/2(式中、Alkは互いに独立して脂肪族不飽和炭素-炭素結合含有基を表し、R’は互いに独立して脂肪族不飽和炭素-炭素結合不含基を表す)で表されるシロキサン単位(M単位)、及び、SiO4/2で表されるシロキサン単位(Q単位)を少なくとも含む硬化反応性オルガノポリシロキサン樹脂であることが好ましい。
(Me3SiO1/2)0.45(SiO4/2)0.55(HO1/2)0.05
(Me3SiO1/2)0.40(SiO4/2)0.60(HO1/2)0.10
(Me3SiO1/2)0.52(SiO4/2)0.48(HO1/2)0.01
(Me3SiO1/2)0.40(Me2ViSiO1/2)0.05 (SiO4/2)0.55(HO1/2)0.05
(Me3SiO1/2)0.45(SiO4/2)0.55(MeO1/2)0.10
(Me3SiO1/2)0.25(Me2PhSiO1/2)0.20(SiO4/2)0.55(HO1/2)0.05
(Me3SiO1/2)0.40(Me2SiO2/2)0.05(SiO4/2)0.55(HO1/2)0.05
(Me3SiO1/2)0.40(MeSiO3/2)0.05(SiO4/2)0.55(HO1/2)0.05
(Me3SiO1/2)0.40(Me2SiO2/2)0.05(MeSiO3/2)0.05(SiO4/2)0.50(HO1/2)0.05
(Me:メチル基、Ph:フェニル基、Vi:ビニル基、MeO:メトキシ基、HO:ケイ素原子結合水酸基。なお、ケイ素原子に対する水酸基の相対量を表すために、ケイ素原子含有単位の添字の合計量を1としており、(HO)1/2単位の添字が当該相対量を示す)
を挙げることができる。
(B)成分は本発明の硬化反応性シリコーン組成物の主要な成分の1つである。(B)成分は単一のオルガノポリシロキサンであってもよく、2種以上のオルガノポリシロキサンの混合物でもよい。
R6 3SiO(R6 2SiO)m1SiR6 3
で表される直鎖状のオルガノポリシロキサンであることが好ましい。ただし、(B)成分は、その一部に、R6SiO3/2又はSiO4/2で表される分岐シロキサン単位を含んでよく、分岐鎖状のオルガノポリシロキサンであってもよい。
(C)成分は本発明の硬化反応性シリコーン組成物の主要な成分の1つであり、架橋剤として機能する。(C)成分は単一のオルガノハイドロジェンポリシロキサンであってもよく、2種以上のオルガノハイドロジェンポリシロキサンの混合物でもよい。
(c1)分子内に少なくとも3個のケイ素結合水素原子を有するオルガノハイドロジェンポリシロキサン
(c2)分子鎖末端にケイ素結合水素原子を有する直鎖状オルガノハイドロジェンポリシロキサン
を含む。
(HMe2SiO1/2)b2(PhSiO3/2)c2
(HMePhSiO1/2)b2(PhSiO3/2)c2
(HMePhSiO1/2)b2(HMe2SiO1/2)c2(PhSiO3/2)d2
(HMe2SiO1/2)b2(Ph2SiO2/2)c2(PhSiO3/2)d2
(HMePhSiO1/2)b2(Ph2SiO2/2)c2(PhSiO3/2)d2
(HMePhSiO1/2)b2(HMe2SiO1/2)c2(Ph2SiO2/2)d2(PhSiO3/2)e2
HMe2SiO(Ph2SiO)m2SiMe2H
HMePhSiO(Ph2SiO)m2SiMePhH
HMePhSiO(Ph2SiO)m2(MePhSiO)n2SiMePhH
HMePhSiO(Ph2SiO)m2(Me2SiO)n2SiMePhH
(D)成分は、高エネルギー線の照射がないと活性を示さないが、高エネルギー線の照射により組成物中で活性を示すヒドロシリル化反応用触媒である。(D)成分は、いわゆる高エネルギー線活性化触媒又は光活性化触媒と呼ばれるものであり、本技術分野では公知である。
本発明の組成物は硬化遅延剤を更に含むことができる。硬化遅延剤は、ヒドロシリル化反応を抑制し、硬化反応を遅らせることができる。硬化遅延剤は、単一の硬化遅延剤であってもよく、2種以上の硬化遅延剤の混合物でもよい。
本発明の組成物は、高エネルギー線の照射なしで、組成物中で活性を示すヒドロシリル化反応用触媒を含むことができる。
本発明の組成物は、必要に応じて、他のオルガノポリシロキサン、接着性付与剤、シリカ、ガラス、アルミナ、酸化亜鉛等の無機質充填剤;ポリメタクリレート樹脂等の有機樹脂微粉末;蛍光体、耐熱剤、染料、顔料、難燃性付与剤、溶剤等を含むことができる。これらの任意成分の添加量及びその方法は、当業者に公知である。
本発明の組成物は、(A)~(D)成分、並びに、必要に応じて他の任意成分を混合することによって製造することができる。本発明の組成物は使用時に混合して調製してもよいが、使用前に、予め混合して調製しておくことが好ましい。
工程1:有機溶剤中に、(A)成分のオルガノポリシロキサン樹脂、および、一部または全部の(B)成分の直鎖状又は分岐鎖状ジオルガノポリシロキサンを溶解させた溶液から、150℃以上の温度で有機溶剤の除去を行い、ホットメルト性の固形分を得る工程、
工程2:工程1で得たホットメルト性の固形分に、(C)成分のオルガノハイドロジェンポリシロキサン、及び(D)成分のヒドロシリル化反応用触媒を加えた後、120℃以下の温度で加熱溶融しながら混練する工程。
(A)成分のオルガノポリシロキサン樹脂、(B)成分の直鎖状は又は分岐鎖状オルガノポリシロキサンと、(C)成分のオルガノハイドロジェンポリシロキサン、ならびに任意の成分を配合した後、(D)成分のヒドロシリル化反応用触媒を配合することが好ましく、かかる(D)成分を配合した後の加熱混錬温度を120℃以下に保つことが好ましい。(D)成分を配合する以前の温度は120℃を超える温度(例えば150℃)で行ってもよく、温度制御が可能であれば、混合効率を改善するために好ましい場合がある。
また、一部の(B)成分を単独で、または(C)成分、もしくは(D)成分と事前に混合して配合することもできる。なお、工程2は、後述する気泡を組成物中から除去するため、真空ポンプ等の脱気機構により、脱気条件下で行うことが好ましい。
工程2において、硬化遅延剤を供給する場合は、(C)成分のオルガノハイドロジェンポリシロキサンと共に供給してもよく、(B)成分のヒドロシリル化反応触媒と共に供給してもよく、さらには工程1において(A)成分と(B)成分を混合する際に合わせて混合してもよい。
本発明の組成物は、25℃で非流動性であり、かつ、十分な靭性を有しており、さらに、上記の加熱溶融性を備え、かつ、未反応の状態で十分な粘着性を有するため、所望の形状に成型して使用することができ、且つ、特定の被着体上に配置することで、加熱溶融性粘着材として使用することができる。
本発明の組成物は後述する高エネルギー線の照射により硬化反応を開始させ、粘着性を備えた硬化物を形成する性質を有するものであるが、必要に応じて、部分的な硬化反応のみを行って半硬化物を形成させてもよい。ここで、「半硬化状態」とは、硬化反応が進行した結果、組成物が、室温(25℃)を含む低温領域(15~80℃)において、流動性を有しない増粘体すなわち非流動性である、100℃では流動性を示す熱可塑体を形成可能であり、また、硬化反応性を依然として維持しており、高エネルギー線の更なる照射の継続又は放置・加熱等の硬化条件を設定することにより更に硬化反応が進行する状態をいい、当該半硬化状態の硬化反応物を「半硬化物」という。なお、硬化反応が進行した結果、組成物の硬化反応が停止して硬化反応性を失い、それ以上硬化反応が進行しない状態に達したものを「本硬化状態」という。また、増粘体とは、25℃での粘度が組成物の初期粘度の1.5倍から100倍の間であることを意味する。また、熱可塑体とは、100℃での粘度が1,000,000mPa・s以下であることを意味する。
本発明の硬化反応性シリコーン組成物は、本発明の組成物(又はその半硬化物)に紫外線等の高エネルギー線を照射することで、(D)成分であるヒドロシリル化触媒を活性化せしめ、組成物におけるヒドロシリル化反応が進行することで、硬化物を形成することができる。高エネルギー線の種類は前記の通りである。照射量は、高エネルギー線活性型触媒の種類により異なるが、紫外線の場合は、365nmでの積算照射量が100mJ/cm2~100J/cm2の範囲内であることが好ましく、500mJ/cm2~50J/cm2の範囲内であってもよく、500mJ/cm2~20J/cm2の範囲内であってもよい。すなわち、本発明の硬化反応性シリコーン組成物は、紫外線等の高エネルギー線の照射をトリガーとして硬化反応を開始することができる。なお、(D)成分であるヒドロシリル化触媒は一度活性化すれば、高エネルギー線の照射を停止しても、室温等で硬化反応が経時的に進行し、硬化物を形成する。
本発明の硬化反応性シリコーン組成物及びその硬化物は粘着材として利用することができる。
本発明の硬化反応性シリコーン組成物からなる層又は当該組成物の硬化物からなる層又は部材を備える積層体を提供することができる。前記積層体は、特に制限されるものではないが、粘着性シート(接着性シート感圧接着(PSA)性シートを含む)、それらが剥離層を備えたシート状部材に積層された剥離性の積層体であってよく、前記硬化反応性シリコーン組成物からなる層又は当該組成物を硬化反応させて得た硬化物からなる層を備える表示装置、電子部品又は太陽電池モジュールから選ばれる少なくとも1種類の物品であってもよい。
本発明の粘着シートは、少なくとも1つのシート基材上に本発明の硬化反応性シリコーン組成物又はその硬化物(半硬化物を含む)からなる、少なくとも1つの粘着材層を備える。なお、粘着シートには、接着シート又は圧着を目的とする感圧接着シートが含まれ、その接着状態は、被着体からの剥離時に界面剥離となるものであってもよく、剥離時に粘着材層の凝集破壊を伴う永久接着状態であってもよい。
本発明の粘着性シートは、例えば、以下のようにして使用することができる。すなわち、未硬化の本発明の組成物乃至半硬化状態の本発明の組成物からなり、加熱溶融性の粘着材層を備えた粘着性シートを、剥離層を備えたシート(剥離フィルム)上に形成する。次に、前記粘着シートを剥離フィルムから剥離させ、露出した粘着材層を目的とする基材(被着体)上に粘着した後、該粘着層の溶融温度以上に加熱する。本操作により、粘着層は基材表面によく密着し、また、表面に段差等がある場合、これに追従することが可能である。硬化操作、剥離操作を経て形成された粘着剤層の上に、第2の基材を乗せ、両者を粘着することもできる。前記基材が紫外線等の高エネルギー線に対して透明又は透過部を有する基材であれば、未硬化の状態で、該基材を一定の温度下で粘着させた後、紫外線等の高エネルギー線を粘着材層に照射して、積層体を構成することも可能である。
上記シート状基材の種類は特には限定されるものではなく、板紙,ダンボール紙,クレーコート紙,ポリオレフィンラミネート紙,特にはポリエチレンラミネート紙,合成樹脂フィルム・シート,天然繊維布,合成繊維布,人工皮革布,金属箔が例示される。特に、合成樹脂フィルム・シートが好ましく、合成樹脂として、ポリイミド、ポリエチレン、ポリプロピレン、ポリスチレン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリカーボネート、ポリエチレンテレフタレート、シクロポリオレフィン、ナイロンが例示される。特に耐熱性が要求される場合には、ポリイミド、ポリエーテルエーテルケトン、ポリエチレンナフタレート(PEN)、液晶ポリアリレート、ポリアミドイミド、ポリエーテルスルフォン等の耐熱性合成樹脂のフィルムが好適である。一方、表示デバイス等視認性が求められる用途においては、透明基材、具体的にはポリプロピレン、ポリスチレン、ポリ塩化ビニリデン、ポリカーボネート、ポリエチレンテレフタレート、PEN等の透明材料が好適である。
一方、本発明の粘着性シートの厚さを薄く設計する場合、後述するように溶融物をそのままロール等により延伸する工程、あるいは、熱プレスなどによる圧延工程などが必要になり、シート基材も熱や圧力に曝され、変形を生じる場合があるため、必要な厚さのシート基材を用いることが好ましい。例えば、ポリエチレンテレフタレートの場合、好ましくは50μm以上、さらに好ましくは75μm以上であり、条件や使用用途によっては、300μm程度までの厚い基材を用いることができる。
本発明の粘着性シートは、例えば、シート状基材上に、本発明の硬化反応性シリコーン組成物(未硬化物)を、必要に応じて加熱溶融して、塗布し、所定の厚みの粘着性層を形成し、そのまま、若しくは、必要に応じて、当該粘着性層を半硬化、又は、本硬化させることによって製造することができる。なお、未硬化、半硬化、本硬化状態の形成及び各状態の利点は前記のとおりであり、必要に応じて使い分けが可能である。以下、当該粘着シートは、「硬化反応性シリコーン組成物からなるシート」と呼ぶことがある。
工程3:工程2で得た加熱溶融後の混合物を、少なくとも1の剥離面を備えたシート基材間に積層する工程
工程4:工程3で得た積層体をロール間で延伸し、特定の膜厚を有する硬化反応性シリコーン組成物からなるシートを成型する工程
工程4は、上記の工程3で得た積層体をロール間で延伸し、特定の膜厚を有する硬化反応性シリコーン組成物からなるシートを成型する工程であり、シート基材上から工程2で得た混合物を加圧延伸し、均一なシートの形態に成型する工程である。圧延ロールの組数は単一であっても複数であっても良い。
工程4において、工程3で得た積層体をロール間で延伸する場合、当該ロールがさらに、温度調節機能を備え、ロール圧延時に積層体全体の温度調節、必要に応じて加熱または冷却を行うことが好ましい。当該温度調節により、ロール間の間隙を安定して保ち、得られるホットメルト性を有する粘着シートの平坦性および均一性(膜厚の均一性)を改善できる実益がある。具体的な温度調節の範囲は、シート基材の耐熱性や粘着シートの厚さ(設計厚み)、その反応性等に応じて適宜設計可能であるが、概ね、5~120℃の範囲内である。
前記工程2から工程4まで工業的に量産するという観点から連続工程であることが好ましいが、ホットメルト性の組成物として熱硬化性のものを取り扱う場合、前記の通り、工程2のあるポイント(供給ポイント2)から高温に長時間晒されると、組成物の硬化反応が進行しうる状態となり、最終的に得られるホットメルト性の硬化反応性シリコーン組成物からなるシートの硬化性に悪影響が及ぶ場合がある。これを防ぐために前述の混錬中の温度管理が重要となるが、さらに、工程2から工程4が終了し、得られたシートの冷却が始まるまでの時間は短時間、具体的には、30分以内であることが好ましく、好ましくは15分以内、さらに好ましくは5分以内である。製造工程において、高温にさらされる時間が前記範囲内であると、熱硬化性の硬化反応性シリコーン組成物からなるシートを生産しても、反応が進むことなく、ホットメルト性に優れたシートを製造することが可能である。
工程4により、剥離性シート間にホットメルト性の硬化反応性シリコーン組成物からなるシートが介装された剥離性積層体を得ることができるが、任意により、当該シートを含む積層体を裁断する工程を有してよい。これにより、所望のサイズのホットメルト性のシートを含む剥離性積層体を得ることができる。裁断する装置は限定されないが、幅方向、および長さ方向を連続的に裁断できる装置が好ましく、ラインスピードが調整できる事が望ましい。ソルテック工業株式会社製のシートカッターを用いると連続で裁断できる。裁断する装置には、異物検査機を有すると裁断する前に異物を検知しマーキングし除去できる。
また、工程4により、剥離性シート間にホットメルト性の硬化反応性シリコーン組成物からなるシートが介装された剥離性積層体の状態となるが、極端なU字のパスラインが存在するとそこでフィルムがシリコーンシートから剥がれやすいので、パスラインとしては延伸する回転式のロール以降は直線的であることが好ましい。この理由から裁断工程の前に巻き取り装置などで巻き取るのは避けた方が良く、連続的に裁断工程にて所望のサイズにカットしていくことが好ましい。
工程4により、剥離性シート間にホットメルト性の硬化反応性シリコーン組成物からなるシートが介装された剥離性積層体の状態となるが、その後、実用上、品質管理を目的とする工程(例えば、特性値の計測や異物の有無を管理する工程)を含んでもよく、かつ、好ましい。当該工程は、カメラやビデオ等の光学的測定手段を備えた異物検知装置によって行われることが好ましい。
少なくとも1つのシート状基材、
前記シート状基材上に形成された少なくとも1つの粘着材層
を備えており、
前記粘着材層が上記の硬化反応性シリコーン組成物又はその硬化物(半硬化物含む)を含む。
第1のシート状基材、
第2のシート状基材、
第1のシート状基材及び第2のシート状基材の間に形成された少なくとも1つの粘着材層
を備え、
前記粘着材層が前記第1のシート基材及び前記第2のシート基材に接触する形態であってもよい。
本発明の硬化反応性シリコーン組成物又はその硬化物からなる粘着材は様々な物体の接着に使用することができる。また、本発明の粘着材を使用して本発明の物品として積層体を製造することができる。
少なくとも1つの基体、
少なくとも1つの粘着材部品
を備える物品であって、
前記粘着材部品が本発明の硬化反応性シリコーン組成物又はその硬化物からなる粘着材を含む、物品である積層体にも関する。
少なくとも1つの基板、
少なくとも1つの粘着材層
を備える積層体を含む物品であって、
前記粘着材層が本発明の硬化反応性シリコーン組成物又はその硬化物からなる粘着材を含む、物品にも関する。
本発明の硬化反応性シリコーン組成物又はその硬化物からなる粘着材は、感圧接着性を備えることから、積層タッチスクリーン又はフラットパネルディスプレイの構築及び利用に使用することができ、その具体的な使用方法は、感圧接着剤層(特に、シリコーンPSA)の公知の使用方法を特に制限なく用いることができる。
図1は、本発明の一実施形態の積層体を示す断面図である。本発明の一実施形態の積層体1は、第1の部材20と、第2の部材21と、2つの部材20、21の間に配置された本発明の硬化反応性シリコーン組成物又はその硬化物からなる粘着材15と、を備えている。積層体1では、2つの部材20、21が粘着材15により接着されている。これらの光学部材は透明であっても、不透明であってもよく、一方又は両方の部材が、単独の基材であってもよく、バックライトユニットのようにそれ自体が独立した積層体である光学部材であってもよい。なお、本発明の積層体を構成する部材は、平面状の広がりを有する板状部分を備えていることが一般的であり、当該板状部分又は部材自身が湾曲していてもよく、部材の用途に由来する三次元的な凹凸を備えていてもよい。
図4は、本発明の一実施形態の光学ディスプレイを示す断面図である。本発明の一実施形態の光学ディスプレイ200は、上記の積層体1と、画像表示パネル201と、を備えている。
前面パネルの表示面に対向する面に設けられ、透明導電膜が形成された面を有するシールド基板を更に備え、
前記透明導電膜とベゼルとが導電性材料を介して電気的に接続された構造を備えた表示装置であってよい。
レオメーター(Anton Paar製のPhysica MCR301)を使用して、周波数1Hzにて、100℃における複素粘度(Pa・s)を測定し、「硬化反応性シリコーン組成物の溶融粘度」とした。
2枚のガラス板(縦75mm×横25mm×厚さ2mm)の間に、厚み200μmのスペーサー、および所定量の硬化反応性シリコーン組成物を置き、熱プレスで組成物の軟化点以上に加熱、加圧した後、25℃に冷却し、2枚のガラス板の間に直径20mm×厚さ200μmの円柱状の硬化反応性シリコーン組成物(未硬化物)を挟んだ試験体を作製した。
上記と同様の方法で、2枚のガラス板(縦75mm×横25mm×厚さ2mm)の間に、直径20mm×厚さ200μmの円柱状の硬化反応性シリコーン組成物(未硬化物)を挟んだ試験体を作成した。
下記の成分を用いて、表1に示す組成(質量部)で各成分を均一に加熱混合することにより、実施例及び比較例の硬化反応性シリコーン組成物を調製した。各構造式において、Meはメチル基であり、Viはビニル基である。
a1-1:(Me3SiO1/2)0.46(SiO4/2)0.54(HO1/2)0.05
a1-2:(Me3SiO1/2)0.48(SiO4/2)0.52(HO1/2)0.04
a2-1:(ViMe2SiO1/2)0.046(Me3SiO1/2)0.394(SiO4/2)0.56(HO1/2)0.05
B-1:ViMe2SiO(Me2SiO)151SiMe2Vi
B-2:ViMe2SiO(Me2SiO)830SiMe2Vi
B’-1:ViMe2SiO(Me2SiO)45SiMe2Vi
B’-2:ViMe2SiO(Me2SiO)4770SiMe2Vi
c1:Me3SiO(Me2SiO)30(MeHSiO)30SiMe3
c2:HMe2SiO(Me2SiO)24SiMe2H
実施例1~9の硬化反応性シリコーン組成物は、いずれも、加熱溶融性を備え、十分な靱性を有し、それ自体(未反応)が粘着材として機能すると共に、紫外線の照射によって、速やかに硬化物を形成し、当該硬化物も十分な粘着性を備えるものであった。更に、硬化反応性シリコーン組成物及びその硬化物は、いずれも適度な粘弾性を備えており、粘着材として実用上十分な性質を有していた。また、硬化後に接着強度と伸びが大きく向上するため、硬化前に部材間を仮固定し、紫外線等の高エネルギー線照射により、部材間を強固に接着する弾性粘着材を形成する材料として有用である。また、これらの硬化反応性シリコーン組成物及びその硬化物は透明であり、光学透明接着材(OCA)又は光学透明樹脂(OCR)としての性質を備えていた。
以下の工程1~4に従って硬化反応性シリコーン組成物を調製し、シート化まで行った。
シート化に用いる二軸押出機の構成およびシート化の全体の構成を図9および図10に示した。
[工程1:(A)成分及び(B)成分を混合し、ホットメルト性の固形分を得る工程]
キシレン 2.50kg、(a1-1)成分(25℃において白色固体状) 6.45kg、(a2-1)成分(25℃において白色固体状) 0.42kg、及び(B-2)成分 3.13kgを円筒状の金属缶(ペール缶)の投入し、モーター式攪拌装置を用いて、室温で溶解、混合した。
得られた溶液を、スクリューを連続回転させた二軸押出機の最上流に設けた投入部より、10kg/hrで連続的にフィードした。ここで、投入部の設定温度は150℃とした。同時に、二軸押出機の中途に設けたベントから、真空ポンプを用いて真空度-0.08MPaの条件で吸引し、キシレン、及び前記(a1-1)成分、(a2-1)成分、乃至(B-2)成分中に含まれる低分子量のオルガノポリシロキサン成分を除去した。二軸押出機の最下流の排出口から、溶融した透明流動物を連続的に得た。これをペール缶に受け、冷却固化した。得られた固形物の加熱残量(200℃、1時間)は99.5重量%であった。
[工程2:工程1で得たホットメルト性の固形分に、(C)成分、及び(D)成分を加えた後、120℃以下の温度で加熱溶融しながら混練する工程]
スクリューを連続回転させた二軸押し出し機を用い、以下の方法で加熱混錬操作を行った。
上記工程1で得られたホットメルト性の固形物を充填したペール缶に、ホットメルター(ノードソン社製のVersaPailメルター)を装着し、スクリューを連続回転させた二軸押し出し機に図9に示すライン9Aからから9.66kg/hrで連続的にフィードした。ホットメルターの設定温度は170℃とした。
次に、(c1)成分と(c2)成分の混合物(重量比 0.21:0.79)を0.14kg/hrで図9に示すライン9Bから連続的にフィードした。ここで、投入部の設定温度は150℃とした。
続いて、(D)成分としての(メチルシクロペンタジエニル)トリメチル白金(IV)と(B-2)成分からなるマスターバッチ((D)成分 0.1重量%を含む) を0.20kg/hrで図9のライン9Cから連続的にフィードした。ここで、投入部の設定温度は80℃とした。さらに、二軸押出機の最下流部に設けたベントから、真空ポンプを用いて脱気した。二軸押出機の最下流の排出口から、無色透明な溶融物を得た。得られた組成物は、25℃で非流動であり加熱溶融性(ホットメルト性)を有していた。
[工程3:工程2で得た加熱溶融後の混合物を、少なくとも1の剥離面を備えたフィルム間に積層する工程]
次に二軸押出機の最下流の排出口をTダイとし、その下流に図10に示すようにフィルムを延伸、及び積層する機能、及びシートカットを行う機能を備えた装置を設置した。90℃に設定されたTダイより吐出した溶融物を、2枚の剥離性フィルム(50ミクロンのポリエチレンテレフタレート上にフロロシリコーン剥離剤をコーティングしたもの)の間に連続的に供給し、積層した。
[工程4:工程3で得た積層体をロール間で延伸し、特定の膜厚を有するシートを成型する工程]
工程3で得られた積層体を、90℃に温度制御されたロール間で延伸することで、厚さ1mmのホットメルト性の硬化反応性シリコーン組成物からなるシートが2枚の剥離性フィルム間に積層された積層体を形成させ、空冷により全体を冷却した。
得られた積層体から剥離性フィルムを分離したところ、泡がなく平坦で均質なタックフリーの透明なホットメルト性の硬化反応性シリコーン組成物からなるシートを得ることができた。
前記の実施例1~9で得られた混錬後の溶融物を2枚の剥離性フィルム間に積層する。続いて、当該積層体を、80℃に温度制御されたロール間で延伸することで、厚さ1mmのホットメルト性の硬化反応性シリコーン組成物からなるシートが2枚の剥離性フィルム間に積層された積層体を形成させ、空冷により全体を冷却する。
得られた積層体から剥離性フィルムを分離したところ、泡がなく平坦で均質透明なホットメルト性の硬化反応性シリコーン組成物からなるシートを得ることができる。
15 粘着材
15A 加熱溶融前の粘着材
15B 加熱溶融後の粘着材(ギャップフィル)
20 第1の光学部材
20a 接着面
20b 面
21 第2の光学部材
21a 面
21b 面
120 ベゼル
121 枠部
122 開口端
130 前面パネル
140 樹脂部材(ダム)上下段
150 OCR
170 表示モジュール
171 バックライトユニット
172 間隙
200 光学ディスプレイ
201 画像表示パネル
300A 光学ディスプレイ
300B 光学ディスプレイ
301 画像表示パネル
301a 面
302 タッチパネル
400 表示装置(光学ディスプレイ)
5 T型ダイ
6 バルクメルター
7 T型ダイを備える二軸押出機
8A ポンプ
8B ポンプ
8C 真空ポンプ
9A ライン1
9B ライン2
9C ライン3
10A 剥離シート
10B 剥離シート
11A 延伸ロール(任意で温度調節機能をさらに備えてもよい)
11B 延伸ロール(任意で温度調節機能をさらに備えてもよい)
12 膜厚計
13A 引張ロール
13B 引張ロール
14 異物検査機
15 シートカッター
Claims (22)
- (A)分子内にR3SiO1/2(式中、Rは互いに独立して一価有機基を表す)で表されるシロキサン単位(M単位)、及び、SiO4/2で表されるシロキサン単位(Q単位)を含むオルガノポリシロキサン樹脂、
(B)一分子中に少なくとも2個の脂肪族不飽和炭素-炭素結合含有基を有し、シロキサン重合度が80~3000の範囲である直鎖状又は分岐鎖状オルガノポリシロキサン、
(C)一分子中に少なくとも2個のケイ素結合水素原子を有するオルガノハイドロジェンポリシロキサン、並びに、
(D)高エネルギー線の照射がないと活性を示さないが、高エネルギー線の照射により組成物中で活性を示すヒドロシリル化反応用触媒
を含み、
(A)成分の含有量が(A)成分~(C)成分の質量の総和の55質量%超~90質量%未満であり、
(C)成分の含有量が、組成物中の全脂肪族不飽和炭素-炭素結合1モルに対して、(C)成分中のケイ素結合水素原子が0.5モル以上となる量であり、
25℃において非流動性であり、
さらに、加熱溶融性を有する、硬化反応性シリコーン組成物。 - (A)成分の少なくとも一部が、分子内に(Alk)R’2SiO1/2(式中、Alkは互いに独立して脂肪族不飽和炭素-炭素結合含有基を表し、R’は互いに独立して脂肪族不飽和炭素-炭素結合不含基を表す)で表されるシロキサン単位(M単位)、及び、SiO4/2で表されるシロキサン単位(Q単位)を少なくとも含む硬化反応性オルガノポリシロキサン樹脂である、請求項1記載の硬化反応性シリコーン組成物。
- (A)成分が一般単位式:(R3SiO1/2)a(SiO4/2)b(式中、Rは互いに独立して一価有機基であり、a及びbはそれぞれ正数であり、a+b=1、a/b=0.5~1.5である)で表されるオルガノポリシロキサン樹脂である、請求項1又は2に記載の硬化反応性シリコーン組成物。
- (B)成分のシロキサン重合度が100~2000である、請求項1乃至3のいずれか1項に記載の硬化反応性シリコーン組成物。
- (C)成分の少なくとも一部が、
(c1)分子内に少なくとも3個のケイ素結合水素原子を有するオルガノハイドロジェンポリシロキサン、及び、
(c2)分子鎖末端にケイ素結合水素原子を有する直鎖状オルガノハイドロジェンポリシロキサン
から選ばれる1種類以上である、請求項1乃至4のいずれか1項に記載の硬化反応性シリコーン組成物。 - 100℃における溶融粘度が100,000Pa・s以下である、請求項1乃至5のいずれか1項に記載の硬化反応性シリコーン組成物。
- 硬化反応前の状態において、2枚のガラス板間に硬化反応性シリコーン組成物からなる200μm厚の硬化性層を形成した試験体を用いて、JIS K 6850で定められた方法で測定した、該硬化性層のせん断接着強度が0.1MPa以上である、請求項1乃至6のいずれか1項に記載の硬化反応性シリコーン組成物。
- 請求項1乃至7のいずれか1項に記載の硬化反応性シリコーン組成物から少なくともなる部材、部品又はシート。
- 請求項1乃至7のいずれか1項に記載の硬化性シリコーン組成物からなる加熱溶融性粘着材。
- 請求項1乃至7のいずれか1項に記載の硬化反応性シリコーン組成物の硬化物。
- 高エネルギー線の照射によって硬化された、請求項10記載の硬化物。
- 2枚のガラス板間に、請求項1乃至7のいずれか1項に記載の硬化反応性シリコーン組成物の硬化物からなる200μm厚の硬化物層を形成し、JIS K 6850で定められた方法で測定した、該硬化物層のせん断接着強度が0.4MPa以上である、請求項10又は11に記載の硬化物。
- 請求項1乃至7のいずれか1項に記載の硬化反応性シリコーン組成物の硬化物からなる粘着材。
- 請求項10乃至12のいずれか1項に記載の硬化物から少なくともなる部材、部品又はシート。
- 請求項1乃至7のいずれか1項に記載の硬化反応性シリコーン組成物からなる層又は部材を備える、積層体。
- 請求項1乃至7のいずれか1項に記載の硬化反応性シリコーン組成物の硬化物からなる層又は部材を備える、積層体。
- 剥離層を備えたシート状部材を少なくとも一部に含む、請求項15又は16に記載の積層体。
- 表示装置、電子部品又は太陽電池モジュールから選ばれる少なくとも1種である、請求項15又は16に記載の積層体。
- 請求項1乃至7のいずれか1項に記載の硬化反応性シリコーン組成物を80℃以上に加熱して溶融させ、溶融物を成型乃至充填する工程を含むことを特徴とする、請求項15乃至18のいずれか1項に記載の積層体の製造方法。
- 請求項1乃至7のいずれか1項に記載の硬化反応性シリコーン組成物を少なくとも1つの部材上又は部材間に配置した後又は配置と同時に、該硬化反応性シリコーン組成物に高エネルギー線を照射する工程を備える、請求項15乃至18のいずれか1項に記載の積層体の製造方法。
- 請求項1乃至7のいずれか1項に記載の硬化反応性シリコーン組成物又はその硬化物を部材間に挟んで積層する工程、及び、
前記硬化反応性シリコーン組成物又はその硬化物により前記部材を圧着する工程
を備える、請求項15乃至18のいずれか1項に記載の積層体の製造方法。 - 以下の工程を備えることを特徴とする、請求項1乃至7のいずれか1項に記載の硬化反応性シリコーン組成物からなるシートの製造方法。
工程1:有機溶剤中に、(A)成分のオルガノポリシロキサン樹脂、および、一部または全部の(B)成分の直鎖状又は分岐鎖状ジオルガノポリシロキサンを溶解させた溶液から、150℃以上の温度で有機溶剤の除去を行い、ホットメルト性の固形分を得る工程、
工程2:工程1で得たホットメルト性の固形分に、(C)成分のオルガノハイドロジェンポリシロキサン、及び(D)成分のヒドロシリル化反応用触媒を加えた後、120℃以下の温度で加熱溶融しながら混練する工程、
工程3:工程2で得た加熱溶融後の混合物を、少なくとも1の剥離面を備えたシート基材間に積層する工程
工程4:工程3で得た積層体をロール間で延伸し、特定の膜厚を有する硬化反応性シリコーン組成物からなるシートを成型する工程。
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Also Published As
Publication number | Publication date |
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EP3875543A4 (en) | 2022-08-10 |
CN113166546B (zh) | 2023-02-21 |
JPWO2020090797A1 (ja) | 2021-09-30 |
JP7419251B2 (ja) | 2024-01-22 |
KR20210084572A (ko) | 2021-07-07 |
CN113166546A (zh) | 2021-07-23 |
US20220340756A1 (en) | 2022-10-27 |
EP3875543A1 (en) | 2021-09-08 |
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