WO2024106077A1 - 接合部材の解体方法及び易解体性の液状シリコーン系接着剤 - Google Patents
接合部材の解体方法及び易解体性の液状シリコーン系接着剤 Download PDFInfo
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- WO2024106077A1 WO2024106077A1 PCT/JP2023/036985 JP2023036985W WO2024106077A1 WO 2024106077 A1 WO2024106077 A1 WO 2024106077A1 JP 2023036985 W JP2023036985 W JP 2023036985W WO 2024106077 A1 WO2024106077 A1 WO 2024106077A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
Definitions
- the present invention relates to a method for dismantling joined components using a curable liquid silicone adhesive, which allows for easy and rapid collection, repair and recycling of automobile parts, such as automobile electrical components, and electrical and electronic products, and to an easily dismantled liquid silicone adhesive used in said method.
- JP 2003-026784 A proposes that bonding members made of a polyol-based curable composition are softened or liquefied by heating them to 150 to 200°C, and then the members bonded with the cured product are dismantled.
- JP 2002-327163 A proposes that the adhesive strength of the bonded portion of a bonded structure made with a moisture-curing adhesive mainly composed of a urethane prepolymer is reduced by contacting the bonded portion with a halogen-based organic solvent, and then the constituent members of the bonded structure are peeled off and dismantled from the bonded portion.
- JP 2008-120903 A proposes a removable adhesive tape that uses an adhesive composed of a vinyl monomer mixture mainly composed of alkyl (meth)acrylate, which maintains a high normal adhesive strength when bonded, but when separating and dismantling the bonded portion, the adhesive strength is reduced by heating, allowing easy separation and dismantling.
- Japanese Patent No. 6221630 proposes that by incorporating a tackifying resin into the oxyalkylene polymer, it becomes possible to rework it, and that it can be rebonded even after reworking, thereby maintaining its sealing performance.
- silicone-based adhesives and sealants have superior properties such as heat resistance and weather resistance compared to the organic adhesives mentioned above, and are therefore widely used in the automotive, electrical and electronics, and construction fields.
- silicone-based adhesives and sealants are difficult to decompose even when heated, which makes them difficult to repair or recycle.
- Masking silicone adhesives have been proposed as silicone adhesives that can easily dismantle components and exhibit sealing properties.
- Masking silicone adhesives that do not contain adhesion promoters include silicone adhesives that have a release agent added to them to give them releasability to glass and metal.
- the release agent itself decomposes thermally and loses its effectiveness, and the silicone adhesive bonds to the components due to heat, making dismantling difficult and making it difficult to recover and repair.
- the present invention has been made in consideration of the above circumstances, and aims to provide a method for dismantling joined members in which the joined adhesive members are silicone-based adhesives and which can be easily recycled in a short time with little energy consumption while still maintaining sealing performance at room temperature (23°C ⁇ 15°C, the same applies below) and even after being exposed to high temperatures of about 150°C, and an easily dismantled liquid silicone-based adhesive for use in the method for dismantling said joined members.
- Patent Document 5 JP 2022-183437 A (JP Patent Application No. 2021-090750) (Patent Document 5), in which a specific ratio of aluminum hydroxide, which decomposes at around 160°C, is mixed into a curable liquid silicone adhesive, allowing the joined adhesive members to maintain their sealing properties even after being exposed to room temperature and even high temperatures of around 150°C, while exposing them to high temperatures of 160°C or higher to reduce their sealing properties, making it easier to separate the members from each other.
- this method requires long heating times of several hours using a heating furnace, and therefore consumes a lot of energy.
- Patent Document 6 a method was proposed for easily dismantling multiple components by irradiating microwaves to a joint member in which multiple components are joined together using a curable liquid silicone adhesive containing particles that generate heat when exposed to microwaves and a hydroxide compound whose decomposition temperature is 180 to 600°C.
- this method still requires several minutes, and a faster dismantling process is desired.
- a curable liquid silicone adhesive containing 25 to 80 mass % of a hydroxide compound (particularly a metal hydroxide or a metal oxide hydroxide) with a decomposition temperature of 180 to 600°C and containing 3 mass % or less of a material that generates heat by electromagnetic induction is cured, and that a joint member formed by joining multiple members, including members at least a part of whose joining interface is metal, maintains its sealing properties even after being exposed to room temperature and even to a high temperature of about 150°C, and that by heating the metal part of the joining interface of the joint member by electromagnetic induction, the joint member can be easily dismantled in a short time with little energy consumption, and the dismantled members can be recycled, thus
- the present invention provides the following method for dismantling joined members and an easily dismantlable liquid silicone adhesive.
- a method for dismantling a joined member in which a plurality of members including members at least a portion of whose joining interface is made of metal are joined together using a cured product obtained by curing a curable liquid silicone-based adhesive containing 25 to 80 mass % of a hydroxide compound having a decomposition temperature of 180 to 600°C and containing 3 mass % or less of a material that generates heat by electromagnetic induction, comprising the steps of: heating the metal portion of the joining interface by electromagnetic induction to separate the members containing the metal from among the members, thereby dismantling the joined member.
- [2] The method for dismantling joined members according to [1], wherein the curable liquid silicone adhesive is a condensation curing liquid silicone adhesive, an addition reaction curing liquid silicone adhesive, or an ultraviolet curing liquid silicone adhesive.
- the hydroxide compound having a decomposition temperature of 180 to 600° C. is at least one selected from aluminum hydroxide, magnesium hydroxide, and aluminum oxide hydroxide (boehmite).
- the frequency of the electromagnetic induction heating is 100 kHz or more and 500 kHz or less.
- the metal parts of the joint interface are heated by electromagnetic induction heating, which indirectly heats the cured product of the adhesive member, the curable liquid silicone adhesive, and reduces its adhesive and/or sealing properties, allowing the metal-containing members at the joint interface to be peeled off in a short time with little energy, so that the joined members can be easily dismantled and recycled.
- the curable liquid silicone adhesive used in this dismantling method is useful as an adhesive or sealing material for joints that require heat resistance and recycling.
- the "heat resistance temperature" of the parts to be dismantled means the upper limit of the temperature at which the parts do not undergo thermal decomposition or softening when left to stand at a specific temperature for one minute.
- Example 1 is an image of a surface state of an ADC12 substrate before electromagnetic induction heating in Example 1 of the present invention, observed with a digital microscope.
- 1 is an image of a surface state of an ADC12 substrate after electromagnetic induction heating in Example 1 of the present invention, observed with a digital microscope.
- the method for dismantling a joined member of the present invention includes a step of dismantling a joined member in which a plurality of members, including a member at least a part of which at the joining interface is made of a cured product obtained by curing a curable liquid silicone adhesive containing 25 to 80 mass% of a hydroxide compound (particularly a metal hydroxide or a metal oxide hydroxide) with a decomposition temperature of 180 to 600°C and containing 3 mass% or less of a material that generates heat by electromagnetic induction, by heating the metal part of the joining interface by electromagnetic induction to separate the members containing the metal from among the members.
- a curable liquid silicone adhesive containing 25 to 80 mass% of a hydroxide compound (particularly a metal hydroxide or a metal oxide hydroxide) with a decomposition temperature of 180 to 600°C and containing 3 mass% or less of a material that generates heat by electromagnetic induction, by heating the metal part of the joining interface by electromagnetic induction to separate the members
- the curable liquid silicone adhesive used in the present invention is an adhesive that cures to become an adhesive member that bonds a plurality of components including components in which at least a portion of the bonding interface is made of metal, contains a hydroxide compound (A) having a decomposition temperature of 180 to 600°C, has a content of a material that generates heat by electromagnetic induction of 3 mass% or less, and uses a polymer whose main chain consists of siloxane bonds as a base polymer, and is preferably of a condensation curing type, an addition reaction curing type, or an ultraviolet curing type.
- A hydroxide compound having a decomposition temperature of 180 to 600°C
- the hydroxide compound having a decomposition temperature of 180 to 600° C. is usually preferably a metal hydroxide or a metal oxide hydroxide, and examples of such hydroxide compounds include aluminum hydroxide having a decomposition temperature of about 180° C., magnesium hydroxide having a decomposition temperature of about 300° C., and aluminum oxide hydroxide (boehmite) having a decomposition temperature of about 500° C.
- the "decomposition temperature” is the temperature at which the hydroxide compound begins to decompose and generate water.
- the water generated by this decomposition is used to generate air bubbles in the cured product of the curable liquid silicone adhesive, which reduces the adhesive strength, making it easier to dismantle the joining components in a short time.
- particulate compounds with an average particle size of 50 ⁇ m or less, preferably 0.5 to 20 ⁇ m, are used. If the average particle size is greater than 50 ⁇ m, the decomposition properties will decrease.
- the average particle size can be determined as the cumulative weight average value D50 (or median size) using a particle size distribution measuring device using the laser light diffraction method or the like.
- the surface of the hydroxide compound may be untreated or may have been surface-treated (hydrophobized).
- a treatment agent is one that is commonly used, such as a silane coupling agent or a fatty acid.
- Surface treatment can be carried out by a known method. There is no particular limit to the amount of treatment, but it is preferably 3% by mass or less (usually 0.1 to 3% by mass), and particularly preferably 0.2 to 2% by mass.
- hydroxide compound may be used alone, two or more types with different average particle sizes or surface treatment methods may also be used in combination.
- the content of the hydroxide compound is 25-80% by mass of the entire curable liquid silicone adhesive, preferably 30-70% by mass, and more preferably 35-65% by mass. If it is less than 25% by mass, the decomposition (foaming) of the hydroxide compound is insufficient and dismantling properties are reduced, and if it is more than 80% by mass, the viscosity of the composition increases, and mixing and dispensing properties during application are reduced.
- Examples of materials that generate heat by electromagnetic induction include metal materials and carbon materials such as carbon fiber and carbon black.
- Examples of metal materials used in the curable liquid silicone adhesive include aluminum powder, iron powder, copper powder, and alloy powders thereof.
- the curable liquid silicone adhesive used in the present invention contains as little material that generates heat by electromagnetic induction as possible, but even if it contains a material that generates heat by electromagnetic induction as a component contained in an optional additive such as a colorant, the amount of this material in the curable liquid silicone adhesive should be 3% by mass or less (0-3% by mass), and in particular 1% by mass or less (0-1% by mass). If it exceeds 3% by mass, dismantling properties will decrease.
- the electromagnetic induction heating used for heating in the present invention can heat conductive metal materials and carbon materials (e.g., carbon fiber, graphite, carbon black, etc.).
- the joining interface of the metals used in the joining members can be heated by electromagnetic induction, which can efficiently cause separation in a short time.
- the energy of electromagnetic induction is also used to heat the adhesive members (cured adhesive), which reduces dismantling properties.
- the organic resin in contact with the adhesive members is heated to a level exceeding its heat resistance when the adhesive members are heated, causing the organic resin to melt or decompose, making the members unsuitable for recycling.
- the condensation-curing liquid silicone adhesive is a liquid silicone adhesive that contains, in addition to the above-mentioned (A) hydroxide compound having a decomposition temperature of 180 to 600°C, (B) a linear diorganopolysiloxane (base polymer) having both molecular chain terminals blocked with hydroxyl groups and/or hydrolyzable silyl groups bonded to silicon atoms, (C) a hydrolyzable organosilane compound and/or a partial hydrolysis condensate thereof (crosslinking agent) having three or more hydrolyzable groups bonded to silicon atoms in the molecule, (D) a curing catalyst, and (E) a silane coupling agent (adhesion imparting agent), and obtains a cured product by utilizing a hydrolysis and condensation reaction caused by moisture (humidity) in the air at room temperature.
- A hydroxide compound having a decomposition temperature of 180 to 600°C
- B a linear diorganopolysilox
- Condensation curing liquid silicone adhesives include: (A) a hydroxide compound having a decomposition temperature of 180 to 600° C.: an amount of 25 to 80% by mass of the total adhesive; (B) a linear diorganopolysiloxane having both molecular chain terminals blocked with silicon-bonded hydroxyl groups and/or hydrolyzable silyl groups: 100 parts by mass, (C) a hydrolyzable organosilane compound having three or more hydrolyzable groups bonded to silicon atoms in the molecule and/or a partial hydrolysis condensate thereof: 0.1 to 40 parts by mass, An easily dismantlable condensation-curing liquid silicone-based adhesive containing (D) 0.001 to 20 parts by mass of a curing catalyst and (E) 0.05 to 20 parts by mass of a silane coupling agent, and containing 3% by mass or less of the material that generates heat by electromagnetic induction, is preferred.
- the organopolysiloxane used as the base polymer (main component) is a linear diorganopolysiloxane in which both ends of the molecular chain are blocked with hydroxyl groups (silanol groups) bonded to silicon atoms and/or hydrolyzable silyl groups.
- the hydrolyzable silyl groups are preferably alkoxysilyl groups or alkoxy-substituted alkoxysilyl groups.
- each end of the molecular chain has one hydroxyl group (i.e., a hydroxysilyl group or a silanol group) bonded to a silicon atom.
- both ends of the molecular chain have two or three alkoxy groups (i.e., alkoxysilyl groups) or alkoxy-substituted alkoxy groups (i.e., alkoxyalkoxysilyl groups) bonded to silicon atoms (i.e., present as dialkoxyorganosilyl groups or bis(alkoxyalkoxy)organosilyl groups, or trialkoxysilyl groups or tris(alkoxyalkoxy)silyl groups).
- the alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, particularly 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a tert-butoxy group, a hexyloxy group, an octyloxy group, etc.
- the alkoxy-substituted alkoxy group is preferably an alkoxy-substituted alkoxy group having 2 to 10 carbon atoms, particularly 2 to 4 carbon atoms, such as a methoxyethoxy group, an ethoxyethoxy group, or a methoxypropoxy group.
- the diorganopolysiloxane in which both molecular chain terminals are blocked with hydroxyl groups and/or hydrolyzable silyl groups bonded to silicon atoms, it is particularly preferred that the diorganopolysiloxane has hydroxyl groups (silanol groups), methoxy groups, or ethoxy groups at both terminals, preferably only at both terminals.
- organic groups bonded to silicon atoms include unsubstituted or substituted monovalent hydrocarbon groups having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms.
- monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, heptyl, octyl, and 2-ethylhexyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl and allyl; aryl groups such as phenyl, tolyl, and naphthyl; aralkyl groups such as benzyl, phenylethyl, and phenylpropyl; groups in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups have been replaced with
- the viscosity of the organopolysiloxane as the base polymer (main agent) at 23°C is preferably 50 to 1,000,000 mPa ⁇ s, and more preferably 100 to 300,000 mPa ⁇ s. If the viscosity is below the lower limit, the resulting cured product may not have sufficient mechanical properties, and if it exceeds the upper limit, workability may decrease. In the present invention, the viscosity is the value at 23°C measured using a rotational viscometer (e.g., BL type, BH type, BS type, cone-plate type, rheometer, etc.) (the same applies below).
- a rotational viscometer e.g., BL type, BH type, BS type, cone-plate type, rheometer, etc.
- the organopolysiloxane used as the base polymer (main agent) may be used alone or in combination of two or more types.
- the hydrolyzable organosilane compound and/or its partial hydrolysis condensate as the (C) crosslinking agent (curing agent) is a hydrolyzable organosilane compound and/or its partial hydrolysis condensate having three or more hydrolyzable groups bonded to silicon atoms in the molecule (i.e., a siloxane compound such as a siloxane oligomer having three or more residual hydrolyzable groups in the molecule).
- the (C) component acts as a crosslinking agent (curing agent) in which three or more hydrolyzable groups present in the molecule undergo a hydrolysis/condensation reaction with the linear diorganopolysiloxane having both molecular chain ends blocked with hydroxyl groups and/or hydrolyzable silyl groups bonded to silicon atoms as the base polymer to form a crosslinked structure.
- curing agent crosslinking agent
- the hydrolyzable groups possessed by the hydrolyzable organosilane compound include alkoxy groups, alkoxy-substituted alkoxy groups, acyloxy groups, alkenoxy groups, ketoxime groups, aminoxy groups, and amide groups each having 1 to 10 carbon atoms.
- Examples include alkoxy groups such as methoxy groups, ethoxy groups, and propoxy groups; alkoxy-substituted alkoxy groups such as methoxyethoxy groups, ethoxyethoxy groups, and methoxypropoxy groups; acyloxy groups such as acetoxy groups and octanoyloxy groups; alkenoxy groups such as vinyloxy groups, isopropenoxy groups, and 1-ethyl-2-methylvinyloxy groups; ketoxime groups such as dimethylketoxime groups, methylethylketoxime groups, and methylisobutylketoxime groups; aminoxy groups such as dimethylaminooxy groups and diethylaminooxy groups; and amide groups such as N-methylacetamide groups and N-ethylacetamide groups.
- the hydrolyzable organosilane compound may have an organic group bonded to the silicon atom other than the hydrolyzable group.
- organic groups bonded to the silicon atom other than the hydrolyzable group include unsubstituted or substituted monovalent hydrocarbon groups having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms.
- alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, and octadecyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl and allyl; aryl groups such as phenyl, tolyl, xylyl, and naphthyl; aralkyl groups such as benzyl, phenethyl, and phenylpropyl; and groups in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups have been substituted with halogen atoms such as fluorine, bromine, and chlorine, or with cyano groups, for example, halogenated alkyl groups such as
- hydrolyzable organosilane compounds and their partial hydrolysis condensates include alkoxysilanes such as methyltrimethoxysilane, ethyltrimethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltris(1-cyclopenten-1-yloxy)silane, tetramethoxysilane, and tetraethoxysilane; ketoxime silanes such as methyltris(dimethylketoxime)silane, methyltris(methylethylketoxime)silane, ethyltris(methylethylketoxime)silane, methyltris(methylisobutylketoxime)silane,
- alkoxy-substituted alkoxysilanes such as phenyltri(methoxymethoxy)silane, methyltri(ethoxymethoxy)silane, ethyltri(ethoxymethoxy)silane, vinyltri(ethoxymethoxy)silane, phenyltri(ethoxymethoxy)silane, tetra(methoxymethoxy)silane, and tetra(ethoxymethoxy)silane; aminoxysilanes such as methyltris(N,N-diethylaminooxy)silane; amidosilanes such as methyltris(N-methylacetamido)silane, methyltris(N-butylacetamido)silane, and methyltris(N-cyclohexylacetamido)silane; alkenoxysilanes such as methyltriisopropenoxysilane, vinyltriiso
- the hydrolyzable organosilane compound used as a crosslinking agent is clearly distinguished from the silane coupling agent (E) used as an adhesion promoter, which will be described later, in that it does not have in its molecule a monovalent hydrocarbon group substituted with a functional group having a heteroatom such as a nitrogen atom, oxygen atom, or sulfur atom.
- hydrolyzable organosilane compounds and/or their partial hydrolysis condensates may be used alone or in combination of two or more.
- the amount of hydrolyzable organosilane compound and/or its partial hydrolysis condensate as a crosslinking agent is 0.1 to 40 parts by mass, preferably 1 to 20 parts by mass, per 100 parts by mass of linear diorganopolysiloxane in which both molecular chain terminals are blocked with hydroxyl groups and/or hydrolyzable silyl groups bonded to silicon atoms. If the amount of hydrolyzable organosilane compound and/or its partial hydrolysis condensate is less than the lower limit (0.1 part by mass), there is a risk of reduced curability and storage stability. If the amount exceeds the upper limit (40 parts by mass), not only is it uneconomical, but the elongation of the obtained cured product may decrease and its durability may decrease.
- the curing catalyst may be a condensation catalyst that has been generally used as a curing accelerator for condensation-curing liquid silicone adhesives (room-temperature curing organopolysiloxane compositions), and examples of such catalysts include organotin compounds such as dibutyltin methoxide, dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin dineodecanoate, dimethyltin dimethoxide, and dimethyltin diacetate; organotitanium compounds such as tetrapropyl titanate, tetrabutyl titanate, tetra-2-ethylhexyl titanate, diisopropoxytitanium bis(ethylacetoacetate), and dimethoxytitanium diacetylacetonate;
- the amount of the curing catalyst is 0.001 to 20 parts by mass, preferably 0.005 to 5 parts by mass, and more preferably 0.01 to 2 parts by mass, per 100 parts by mass of the linear diorganopolysiloxane whose molecular chain is terminated at both ends with hydroxyl groups and/or hydrolyzable silyl groups bonded to silicon atoms. If the amount of the curing catalyst is less than the lower limit (0.001 parts by mass), the catalytic effect may not be obtained, and if the amount of the curing catalyst is more than the upper limit (20 parts by mass), not only is it uneconomical, but the durability of the composition may decrease or the adhesiveness may decrease.
- Condensation-curing liquid silicone adhesives further contain, as component (E), a silane coupling agent (a hydrolyzable silane compound having in its molecule a monovalent hydrocarbon group substituted with a functional group (excluding guanidyl groups) having a heteroatom such as a nitrogen atom, oxygen atom, or sulfur atom, known as a carbon functional silane compound) that improves adhesive strength and acts as an adhesive property imparting component.
- a silane coupling agent a hydrolyzable silane compound having in its molecule a monovalent hydrocarbon group substituted with a functional group (excluding guanidyl groups) having a heteroatom such as a nitrogen atom, oxygen atom, or sulfur atom, known as a carbon functional silane compound
- the silane coupling agent used as the adhesiveness-imparting component is preferably a silane coupling agent known in the art.
- those having an alkoxy group or an alkenoxy group as the hydrolyzable group are preferred, and specific examples include alkoxy groups such as methoxy groups, ethoxy groups, and propoxy groups, and alkenoxy groups such as vinyloxy groups, isopropenoxy groups, and 1-ethyl-2-methylvinyloxy groups.
- the monovalent hydrocarbon group substituted with a functional group having a heteroatom such as a nitrogen atom, an oxygen atom, or a sulfur atom is preferably a monovalent hydrocarbon group having 1 to 20 carbon atoms and at least one unsubstituted or substituted amino group, unsubstituted or substituted imino group, mercapto group, epoxy group, (meth)acryloxy group, or the like.
- ⁇ -acryloxypropyl group examples include a ⁇ -acryloxypropyl group, a ⁇ -methacryloxypropyl group, a ⁇ -(3,4-epoxycyclohexyl)ethyl group, a ⁇ -glycidoxypropyl group, an N- ⁇ (aminoethyl) ⁇ -aminopropyl group, a ⁇ -aminopropyl group, and a group represented by the following formula: and a ⁇ -mercaptopropyl group.
- the silane coupling agent may have an organic group bonded to the silicon atom other than the monovalent hydrocarbon group substituted with the hydrolyzable group and functional group.
- a monovalent hydrocarbon group having 1 to 10 carbon atoms is preferable, and examples thereof include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, heptyl, and octyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl and allyl; aryl groups such as phenyl, tolyl, and xylyl; and aralkyl groups such as benzyl and phenethyl. Of these, methyl and ethyl groups are preferable.
- silane coupling agent examples include ⁇ -acryloxypropyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, and compounds represented by the following formula:
- the silane compounds include silane compounds represented by the formula (I), ⁇ -mercaptopropyltrimethoxysilane, ⁇ -glycidoxypropyltriisopropenoxysilane, ⁇ -glycidoxypropylmethyldiisopropenoxysilane, etc. In particular, it is preferable to use an amino group-containing silane,
- Silane coupling agents may be used alone or in combination of two or more.
- the amount of the silane coupling agent (E) to be blended is 0.05 to 20 parts by mass, preferably 0.1 to 15 parts by mass, and particularly preferably 0.5 to 10 parts by mass, per 100 parts by mass of linear diorganopolysiloxane in which both molecular chain terminals are blocked with hydroxyl groups and/or hydrolyzable silyl groups bonded to silicon atoms. If the amount is less than 0.05 parts by mass, sufficient adhesion cannot be obtained, and if the amount exceeds 20 parts by mass, the resulting cured product will have poor weather resistance and mechanical properties.
- optional components can be added to the condensation-curing liquid silicone adhesive as long as they do not impair the objectives of the present invention.
- These optional components include inorganic fillers other than component (A), colorants such as pigments, dyes, and fluorescent brighteners; antibacterial agents; antifungal agents; plasticizers such as silicone oil (nonfunctional organopolysiloxane); etc.
- the inorganic filler other than the optional component (A) include carbon such as acetylene black, dry process silica (fumed silica, etc.), wet process silica (precipitated silica, etc.), fine quartz powder, diatomaceous earth powder, fine particulate alumina, magnesia powder, calcium carbonate such as colloidal calcium carbonate and heavy calcium carbonate, and fine powder inorganic fillers obtained by surface-treating these with silanes, silazanes, low-polymerization polysiloxanes, etc. (excluding component (A)).
- carbon such as acetylene black, dry process silica (fumed silica, etc.), wet process silica (precipitated silica, etc.), fine quartz powder, diatomaceous earth powder, fine particulate alumina, magnesia powder, calcium carbonate such as colloidal calcium carbonate and heavy calcium carbonate, and fine powder inorganic fillers obtained by surface-treating these with silanes,
- the blending amount is preferably 0.1 to 800 parts by mass, and more preferably 0.5 to 600 parts by mass, per 100 parts by mass of the linear diorganopolysiloxane having both molecular chain terminals capped with silicon-bonded hydroxyl groups and/or hydrolyzable silyl groups.
- the condensation-curing liquid silicone adhesive can be prepared by uniformly mixing the above-mentioned components in a known mixer in a moisture-free state (in a dry atmosphere or under reduced pressure) in accordance with conventional methods.
- the resulting condensation-curing liquid silicone adhesive will cure, for example, by leaving it at room temperature (23°C ⁇ 15°C).
- the molding method and curing conditions can be any known method and condition that suits the type of condensation-curing liquid silicone adhesive.
- the adhesive can be cured by leaving it in the air under conditions of 23°C/50% RH for a few hours to a few days (for example, 6 hours to 7 days).
- the addition reaction curing liquid silicone adhesive is a liquid silicone adhesive that contains, in addition to the above-mentioned (A) hydroxide compound having a decomposition temperature of 180 to 600°C, (F) an alkenyl group-containing organopolysiloxane (base polymer) having an alkenyl group such as a vinyl group bonded to a silicon atom at the molecular chain end, (G) an organohydrogenpolysiloxane (crosslinking agent) having at least two hydrogen atoms bonded to silicon atoms (SiH groups) in the molecule, (H) a platinum group metal catalyst (hydrosilylation addition reaction catalyst), and (I) an adhesion imparting agent, and which obtains a cured product by crosslinking via an addition reaction (hydrosilylation reaction) of SiH groups to vinyl groups.
- A hydroxide compound having a decomposition temperature of 180 to 600°C
- F an alkenyl group-containing organopolysiloxane (
- Addition reaction curing liquid silicone adhesives include: (A) a hydroxide compound having a decomposition temperature of 180 to 600° C.: an amount of 25 to 80% by mass of the total adhesive; (F) alkenyl group-containing organopolysiloxane having an alkenyl group bonded to a silicon atom at a molecular chain terminal: 100 parts by mass, (G) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in the molecule: an amount such that the number of silicon-bonded hydrogen atoms is 0.01 to 3 moles per mole of silicon-bonded alkenyl groups in component (F); An easily dismantlable addition reaction curing liquid silicone adhesive is preferred which contains: (H) a platinum group metal catalyst: 0.01 to 1,000 ppm, calculated as the mass of platinum group metal atoms based on the total amount of components (F) and (G); and (I) an adhesion imparting agent: 0.05 to 20 parts by mass, and in which the content
- the alkenyl-containing organopolysiloxane used as the base polymer (main component) is a linear diorganopolysiloxane whose molecular chain ends (one or both ends) are blocked with silyl groups having alkenyl groups such as vinyl groups bonded to silicon atoms, and is an organopolysiloxane having an average of at least one, preferably two or more (usually 2 to 20, particularly 2 to 10, and even more preferably about 2 to 5) alkenyl groups bonded to silicon atoms in the molecule.
- alkenyl group examples include lower alkenyl groups such as vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, and cyclohexenyl groups, which usually have 2 to 6 carbon atoms, preferably about 2 to 4 carbon atoms.
- the alkenyl-containing organopolysiloxane used as the base polymer (main component) may have an alkenyl group on a side chain of the molecular chain, so long as it has an alkenyl group bonded to a silicon atom at one or both ends of the molecular chain.
- the organic group bonded to the silicon atom other than the silicon-bonded alkenyl group is not particularly limited as long as it does not have an aliphatic unsaturated bond, and examples thereof include unsubstituted or substituted monovalent hydrocarbon groups, excluding aliphatic unsaturated bonds, having usually 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms.
- Examples of the unsubstituted or substituted monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl, tolyl, xylyl, and naphthyl; aralkyl groups such as benzyl and phenethyl; and halogenated alkyl groups such as chloromethyl, 3-chloropropyl, and 3,3,3-trifluoropropyl, in which some or all of the hydrogen atoms of these groups are replaced with halogen atoms such as chlorine, fluorine, and bromine.
- alkyl groups and aryl groups and more preferably methyl and phenyl groups.
- alkenyl-containing organopolysiloxanes include dimethylpolysiloxanes blocked at both ends with dimethylvinylsiloxy groups, dimethylsiloxane-methylvinylsiloxane copolymers blocked at both ends with dimethylvinylsiloxy groups, dimethylsiloxane-diphenylsiloxane copolymers blocked at both ends with dimethylvinylsiloxy groups, dimethylsiloxane-methylvinylsiloxane-diphenylsiloxane copolymers blocked at both ends with dimethylvinylsiloxy groups, methyltrifluoropropylpolysiloxanes blocked at both ends with dimethylvinylsiloxy groups, dimethylsiloxane-methyltrifluoropropylsiloxane copolymers blocked at both ends with dimethylvinylsiloxy groups, dimethylsiloxane-methyltrifluoropropylsiloxane-methylmethyltri
- the viscosity of the alkenyl-containing organopolysiloxane as the base polymer (main component) at 23°C is preferably 100 to 500,000 mPa ⁇ s, and more preferably 700 to 100,000 mPa ⁇ s.
- the alkenyl-containing organopolysiloxane used as the base polymer (main component) may be used alone or in combination of two or more types.
- the organohydrogenpolysiloxane used as the crosslinking agent (curing agent) has, on average, at least 2, preferably at least 3, more preferably an upper limit of 500, even more preferably an upper limit of 200, and particularly preferably an upper limit of 100 hydrogen atoms bonded to silicon atoms (SiH groups) in the molecule, and preferably has no aliphatic unsaturated bonds in the molecule.
- the silicon-bonded organic group other than the silicon-bonded hydrogen atom is not particularly limited, but examples include unsubstituted or substituted monovalent hydrocarbon groups having typically 1 to 10, and preferably 1 to 6, carbon atoms. Specific examples include the same groups as those exemplified as silicon-bonded organic groups other than the silicon-bonded alkenyl groups in the description of the alkenyl-group-containing organopolysiloxane, as well as alkenyl groups such as vinyl groups and allyl groups. Preferred are unsubstituted monovalent hydrocarbon groups that do not have aliphatic unsaturated bonds, such as alkyl groups and aryl groups, and more preferably methyl groups and phenyl groups.
- the number of silicon atoms in the molecule is preferably 2 to 300, particularly 3 to 150, and especially 4 to 100, and is liquid at room temperature.
- the hydrogen atoms bonded to the silicon atoms may be located at either the ends of the molecular chain or in the middle of the molecular chain (non-terminal), or may be located at both.
- the molecular structure of the organohydrogenpolysiloxane may be linear, cyclic, branched, or three-dimensional mesh.
- the degree of polymerization (or the number of repetitions of the diorganosiloxane units constituting the main chain, which is a measure of the number of silicon atoms in the molecule) can be determined as the number average degree of polymerization (or number average molecular weight) converted into polystyrene in gel permeation chromatography (GPC) analysis using, for example, toluene as a developing solvent.
- GPC gel permeation chromatography
- organohydrogenpolysiloxanes examples include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris(hydrogendimethylsiloxy)methylsilane, tris(hydrogendimethylsiloxy)phenylsilane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane-dimethylsiloxane cyclic copolymer, methylhydrogenpolysiloxane blocked at both ends with trimethylsiloxy groups, dimethylsiloxane-methylhydrogensiloxane copolymer blocked at both ends with trimethylsiloxy groups, dimethylpolysiloxane blocked at both ends with dimethylhydrogensiloxy groups, dimethylsiloxane blocked at both ends with dimethylhydrogensiloxy groups, and dimethylsiloxane blocked at both ends with dimethylhydrogensiloxy groups.
- the organohydrogenpolysiloxane of component (G) having at least two silicon-bonded hydrogen atoms in the molecule is clearly distinguished from the adhesion promoter of component (I) described below in that it does not have functional groups such as epoxy groups or alkoxysilyl groups as silicon-bonded organic groups other than silicon-bonded hydrogen atoms in the molecule.
- Organohydrogenpolysiloxanes may be used alone or in combination of two or more.
- the amount of organohydrogenpolysiloxane added is an amount that provides 0.01 to 3 moles, preferably 0.05 to 2.5 moles, and more preferably 0.2 to 2 moles of silicon-bonded hydrogen atoms (SiH groups) per mole of alkenyl groups bonded to silicon atoms in the alkenyl-containing organopolysiloxane.
- Platinum group metal catalyst (hydrosilylation addition reaction catalyst) is used as a catalyst for promoting the addition reaction between silicon-bonded alkenyl groups in an alkenyl-group-containing organopolysiloxane and silicon-bonded hydrogen atoms in an organohydrogenpolysiloxane.
- Any known platinum group metal catalyst can be used. Specific examples include platinum-based catalysts such as platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, and complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, or acetylene alcohols.
- the amount of platinum group metal catalyst used may be an effective amount, which can be increased or decreased as appropriate depending on the desired curing speed, but is usually in the range of 0.01 to 1,000 ppm, preferably 0.1 to 500 ppm, and more preferably 1 to 300 ppm, calculated as the mass of platinum group metal atoms relative to the total amount of the alkenyl group-containing organopolysiloxane and organohydrogenpolysiloxane. If the amount is too high, the heat resistance of the resulting cured product may decrease.
- Component (I) is an adhesion promoter that imparts self-adhesiveness to the composition of the present invention. It is preferable that the self-adhesiveness is particularly good for metals and organic resins.
- the (I) component include organosilanes having at least one, preferably two or more functional groups selected from the group consisting of alkenyl groups such as vinyl groups, (meth)acryloxy groups, hydrosilyl groups (SiH groups), epoxy groups, alkoxysilyl groups, carbonyl groups, and phenyl groups; functional group-containing organosilicon compounds such as cyclic or linear organopolysiloxanes having 2 to 30, preferably about 4 to 20, silicon atoms (excluding components (F) and (G)); and non-silicon (i.e., no silicon atoms in the molecule) hydrocarbon compounds that contain 1 to 4, preferably 1 to 2, aromatic rings such as monovalent to tetravalent, preferably divalent to tetravalent phenylene structures in
- component (I) include the functional group-containing organoalkoxysilanes and functional group-containing organohydrogenpolysiloxanes exemplified below, and functional group-containing organosilicon compounds in which the total number of repeating bifunctional siloxane units in the functional group-containing linear organohydrogenpolysiloxanes in the exemplary compounds below is any positive integer within the range of 3 to 28, as well as bisphenol compounds (such as bisphenol F, bisphenol A, bisphenol AF) or their oligomers, in which the hydroxyl groups at both ends of the molecular chain are blocked with alkenyloxy groups or (meth)acryloxy-substituted alkyloxy groups.
- bisphenol compounds such as bisphenol F, bisphenol A, bisphenol AF
- Component (I) can be used alone or in combination of two or more types, but from the standpoint of adhesion to the substrate, it is preferable to use an organosilicon compound in combination with a non-silicon organic compound.
- the amount of component (I) that is blended is the amount that allows the composition of the present invention to obtain good self-adhesion to the adherend, particularly to metals and organic resins, and is, for example, 0.05 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and particularly preferably 0.5 to 10 parts by mass, per 100 parts by mass of component (F). If it is less than 0.05 parts by mass, sufficient adhesion may not be obtained, and if it exceeds 20 parts by mass, the obtained cured product may have poor weather resistance and mechanical properties.
- optional components can be added to the addition reaction curing liquid silicone adhesive as long as they do not impair the purpose of the present invention.
- optional components include reaction inhibitors, inorganic fillers similar to those exemplified in the above condensation curing liquid silicone adhesive (excluding hydroxide compounds whose decomposition temperature of component (A) is 180 to 600°C), organopolysiloxanes that do not contain silicon-bonded hydrogen atoms (SiH groups) or silicon-bonded alkenyl groups (so-called non-functional silicone oils), heat resistance additives, flame retardants, thixotropy agents, pigments, dyes, etc.
- the addition reaction curing liquid silicone adhesive can be prepared by uniformly mixing the above-mentioned components using a known mixer in a conventional manner.
- Addition reaction curing liquid silicone adhesives can be cured under the following conditions: 23 to 150°C, especially 23 to 100°C, for 10 minutes to 8 hours, especially 30 minutes to 5 hours.
- the ultraviolet-curable liquid silicone adhesive is a liquid silicone adhesive that contains, in addition to the above-mentioned (A) hydroxide compound having a decomposition temperature of 180 to 600°C, (J) an ultraviolet-reactive organopolysiloxane (base polymer) and (K) a photopolymerization initiator, and crosslinks upon irradiation with ultraviolet light to obtain a cured product.
- UV-curable liquid silicone adhesives include: (A) a hydroxide compound having a decomposition temperature of 180 to 600° C.: an amount of 25 to 80% by mass of the total adhesive; An easily dismantlable ultraviolet-curable liquid silicone-based adhesive is preferred, which contains (J) 100 parts by mass of an ultraviolet-reactive organopolysiloxane and (K) 0.01 to 10 parts by mass of a photopolymerization initiator, and in which the content of the material that generates heat by electromagnetic induction is 3% by mass or less.
- the UV-reactive organopolysiloxane of component (J) is not particularly limited as long as it acts as a base polymer in the UV-curable silicone composition, and is preferably an organopolysiloxane having at least two UV-reactive groups in one molecule, more preferably 2 to 20, and particularly preferably 2 to 10.
- the multiple UV-reactive groups present in this organopolysiloxane may all be the same or different.
- ultraviolet-reactive groups examples include alkenyl groups such as vinyl, allyl, and propenyl groups; alkenyloxy groups such as vinyloxy, allyloxy, propenyloxy, and isopropenyloxy groups; aliphatic unsaturated groups other than alkenyl groups such as acryloyl and methacryloyl groups; epoxy groups; and hydrosilyl groups.
- alkenyl groups such as vinyl, allyl, and propenyl groups
- alkenyloxy groups such as vinyloxy, allyloxy, propenyloxy, and isopropenyloxy groups
- aliphatic unsaturated groups other than alkenyl groups such as acryloyl and methacryloyl groups
- epoxy groups examples of ultraviolet-reactive groups
- hydrosilyl groups examples include alkenyl groups such as vinyl, allyl, and propenyl groups; alkenyloxy groups such as vinyloxy, allyloxy, propenyloxy, and isopropeny
- the organic group bonded to the silicon atom other than the silicon-bonded alkenyl group is not particularly limited as long as it does not have an aliphatic unsaturated bond, and examples thereof include unsubstituted or substituted monovalent hydrocarbon groups, excluding aliphatic unsaturated bonds, having usually 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms.
- Examples of the unsubstituted or substituted monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl, tolyl, xylyl, and naphthyl; aralkyl groups such as benzyl and phenethyl; and halogenated alkyl groups such as chloromethyl, 3-chloropropyl, and 3,3,3-trifluoropropyl, in which some or all of the hydrogen atoms of these groups are replaced with halogen atoms such as chlorine, fluorine, and bromine.
- alkyl groups and aryl groups and more preferably methyl and phenyl groups.
- organopolysiloxanes containing ultraviolet-reactive groups are dimethylpolysiloxanes blocked at both ends with dimethylvinylsiloxy groups, dimethylsiloxane-methylvinylsiloxane copolymers blocked at both ends with dimethylvinylsiloxy groups, dimethylsiloxane-diphenylsiloxane copolymers blocked at both ends with dimethylvinylsiloxy groups, dimethylpolysiloxanes blocked at both ends with dimethylacryloylsiloxy groups, dimethylsiloxane-methylvinylsiloxane copolymers blocked at both ends with dimethylacryloylsiloxy groups, dimethylsiloxane-diphenylsiloxane copolymers blocked at both ends with dimethylacryloylsiloxy groups, and dimethylsiloxane-diphenylsiloxane copolymers blocked at both ends with dimethylmethacryloylsiloxy groups.
- dimethylsiloxane/methylvinylsiloxane copolymers both ends blocked with dimethylmethacryloylsiloxy groups, dimethylsiloxane/diphenylsiloxane copolymers both ends blocked with dimethylmethacryloylsiloxy groups, dimethylpolysiloxanes both ends blocked with dimethylmercaptosiloxy groups, dimethylsiloxane/methylvinylsiloxane copolymers both ends blocked with dimethylmercaptosiloxy groups, dimethylsiloxane/diphenylsiloxane copolymers both ends blocked with dimethylmercaptosiloxy groups, dimethylpolysiloxanes both ends blocked with dimethylepoxysiloxy groups, dimethylsiloxane/methylvinylsiloxane copolymers both ends blocked with dimethylepoxysiloxy groups dimethylsiloxane copolymer, dimethylsiloxane-diphenylsiloxan
- the viscosity of the UV-reactive organopolysiloxane at 23°C is preferably 100 to 500,000 mPa ⁇ s, and more preferably 700 to 100,000 mPa ⁇ s.
- the ultraviolet-reactive organopolysiloxane may be used alone or in combination of two or more types.
- the photopolymerization initiator of the component (K) has the effect of promoting the photopolymerization of the ultraviolet-reactive group in the component (J).
- the component (K) is not particularly limited, and specific examples thereof include acetophenone, propiophenone, benzophenone, xanthol, fluorene, benzaldehyde, anthraquinone, triphenylamine, 4-methylacetophenone, 3-pentylacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4-chloro-4'-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoin, benzo
- preferred examples include benzophenone, 4-methoxyacetophenone, 4-methylbenzophenone, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, and 2-hydroxy-2-methyl-1-phenylpropan-1-one, and more preferred examples include diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, and 2-hydroxy-2-methyl-1-phenylpropan-1-one.
- These photopolymerization initiators may be used alone or in combination of two or more.
- the amount of component (K) added is not particularly limited, but is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 3 parts by mass, and even more preferably 0.5 to 3 parts by mass, per 100 parts by mass of component (J). If the amount of component (K) added is within this range, it is easy to control the curing of the UV-curable liquid silicone adhesive.
- UV-curable liquid silicone adhesive a liquid silicone adhesive that is both UV-curable and condensation-curable, or a liquid silicone adhesive that is both UV-curable and addition-curable, can also be used.
- a liquid silicone adhesive that is both UV-curable and condensation-curable uses the above-mentioned (A) hydroxide compound with a decomposition temperature of 180 to 600°C, as well as the above-mentioned (B) and (J) components as base polymers, the above-mentioned (C) component as a curing agent, and a component having both a substituent that reacts with UV light and a substituent that condenses, the above-mentioned (D) component as a condensation-curing catalyst, the above-mentioned (K) component as a UV-curing catalyst, and the above-mentioned (E) component as an adhesion-imparting component.
- a liquid silicone adhesive that is both UV-curable and addition-curable uses the above-mentioned (A) hydroxide compound with a decomposition temperature of 180 to 600°C, as well as the above-mentioned (F) and (J) components as base polymers, the above-mentioned (G) component as a curing agent, the above-mentioned (H) component as an addition-curing catalyst, the above-mentioned (K) component as a UV-curing catalyst, and the above-mentioned (I) component as an adhesion-imparting component.
- the ultraviolet-curing liquid silicone adhesive can be prepared by uniformly mixing the above-mentioned components using a known mixer in a conventional manner.
- the ultraviolet-curing liquid silicone adhesive is cured by irradiating it with ultraviolet light.
- ultraviolet light there are no particular limitations on the ultraviolet irradiation conditions, it is preferable to use an ultraviolet light-emitting diode having an emission wavelength of 365 nm, with an illuminance of 5 to 500 mW/ cm2 , preferably 10 to 200 mW/ cm2 , and a light quantity of 0.5 to 100 J/ cm2 , preferably 10 to 50 J/ cm2 .
- the bonded members are formed by bonding a plurality of members (particularly two members) including members having at least a portion of a bonding interface made of metal with a cured product (an adhesive member made of an adhesive silicone rubber cured product) obtained by curing a curable liquid silicone adhesive containing a specific amount of a hydroxide compound having a decomposition temperature of 180 to 600° C. and containing 3 mass % or less of a material that generates heat by electromagnetic induction.
- the members may be the same or different.
- one of the bonded members is a member having at least a portion of a bonding interface made of metal, and the other member can be selected from the same member (a member having at least a portion of a bonding interface made of metal), an organic resin member, and a metal member.
- At least the bonding interface is made of metal, and it may be made entirely of metal. Note that the metal at the bonding interface of the member only needs to have an area that can be sufficiently heated by electromagnetic induction.
- components in which at least a portion of the bonding interface is metal include automotive parts and electrical/electronic parts made of aluminum alloys such as A1050, A2017, A5052, A5083, A6061, and A1N30; aluminum alloy die castings such as ADC1, ADC3, ADC10, ADC12, and ADC14; carbon steels such as SPCC, SS400, and SAPH; stainless steels such as SUS304 and SUS430; and magnesium alloys such as AZ-91D and AM50A.
- aluminum alloys such as A1050, A2017, A5052, A5083, A6061, and A1N30
- aluminum alloy die castings such as ADC1, ADC3, ADC10, ADC12, and ADC14
- carbon steels such as SPCC, SS400, and SAPH
- stainless steels such as SUS304 and SUS430
- magnesium alloys such as AZ-91D and AM50A.
- the metals that make up the members and metal members whose joint interface is at least partially metal may be magnetic or non-magnetic as long as they are capable of generating heat through electromagnetic induction.
- Examples include pure metals such as aluminum, iron, and copper, and alloys that contain these (aluminum alloys (aluminum alloy die-casts such as Al-Cu-Si alloys (ADC12)), carbon steels (SPCC, SS400, SAPH, etc.), cast iron (Fe-Si-C ternary alloys), stainless steels (especially ferritic), copper alloys (brass, bronze, cupro-nickel), nichrome, magnesium alloys (AZ-91D, AM50A, etc.), titanium alloys, etc.).
- magnetic materials refer to metal materials whose relative magnetic permeability ( ⁇ / ⁇ 0), which is the ratio of the magnetic permeability in a vacuum ( ⁇ 0) to the initial magnetic permeability ( ⁇ ), is 5 or more, and even 50 or more.
- Organic resins that make up organic resin components include polybutylene terephthalate resin (PBT), polyphenylene sulfide resin (PPS), polyamide resins such as PA66 (nylon 66) and PA6 (nylon 6), and PC (polycarbonate resin).
- PBT polybutylene terephthalate resin
- PPS polyphenylene sulfide resin
- PA66 polyamide resin
- PA6 polyamide resin
- PC polycarbonate resin
- the above organic resins or metals constituting the components in which at least a portion of the bonding interface is metal, organic resin components, or metal components have a heat resistance temperature of 160°C or higher.
- a curable liquid silicone adhesive containing a hydroxide compound with a decomposition temperature of 180 to 600°C and containing 3% by mass or less of a material that generates heat by electromagnetic induction is applied to the surface of one of the components by hand or machine discharge in the shape of a joint (e.g., a gasket, etc.), and the other component is bonded and cured. It is then fixed with bolts, etc., as necessary.
- the curable liquid silicone adhesive of the present invention is a condensation curing type liquid silicone adhesive, it cures due to moisture in the air at room temperature, so if multiple components are combined and left to stand, the curing will proceed. If it is desired to increase the curing speed, it is effective to humidify.
- the curable liquid silicone adhesive of the present invention is an addition reaction curing type liquid silicone adhesive
- it cures due to addition reaction at a temperature of 23 to 150°C, so if multiple components are combined and left to stand or heated, the curing will proceed.
- the curable liquid silicone adhesive of the present invention is an ultraviolet curing type liquid silicone adhesive
- the photopolymerization initiator reacts by irradiation with ultraviolet light, and the curing reaction proceeds and the adhesive is cured.
- a secondary cure may be performed, and the temperature conditions at that time are preferably 120°C or higher, more preferably 150°C or higher, and lower than the decomposition temperature of the hydroxide compound and 250°C or lower.
- the curing time at this time is preferably 10 minutes to 48 hours, more preferably 30 minutes to 24 hours.
- joining members examples include automobile parts such as engines, transmissions, and automobile electrical components (ECUs (Electronic Control Units) and PCUs (Power Control Units)), as well as electric and electronic parts such as smartphones, tablets, liquid crystal displays, and batteries, with automobile parts and electric and electronic parts being preferred.
- ECUs Electronic Control Units
- PCUs Power Control Units
- electric and electronic parts such as smartphones, tablets, liquid crystal displays, and batteries, with automobile parts and electric and electronic parts being preferred.
- the above-mentioned joining members are designed to maintain their joined state when the operating environment temperature is 150°C or less, preferably between room temperature and 120°C.
- the above-mentioned joining members are preferably easily dismantled joining members that are joined with a certain degree of adhesive strength during normal use, and whose adhesive strength decreases to such an extent that the members can be separated after electromagnetic induction heating.
- the initial shear adhesive strength of the above-mentioned joining members is preferably 1.2 MPa or more, and in particular 1.5 MPa or more, and the shear adhesive strength of the joining members after electromagnetic induction heating is preferably 1 MPa or less.
- This shear adhesive strength is a value measured in accordance with the method specified in JIS K6850. Note that in order to set the initial and post-electromagnetic induction heating shear adhesive strengths within the above-mentioned ranges, this can be achieved by setting the composition of the curable liquid silicone adhesive to be within the specific ranges described above.
- the method of dismantling bonded members of the present invention involves heating the metal portion of the bonded interface of the bonded members by electromagnetic induction, and indirectly heating the cured product (cured adhesive silicone rubber) formed by curing the curable liquid silicone adhesive, which is the adhesive member, in contact with the metal or the entirety of the cured product to 160°C to 800°C, whereby the metal member naturally peels off, or the bonded members can be dismantled by peeling it off from the metal member by applying force to it by hand or using a tool such as a scraper. Also, the dismantled members can be recycled.
- the metal and adhesive member forming the bonding interface have a large difference in linear expansion coefficient. Therefore, when heated, the difference in thermal expansion causes a large thermal stress to be applied to the bonding interface. In addition, in the case of bonding members made of different materials, the difference in thermal expansion also causes thermal stress to be applied between the bonding members. Furthermore, when the metal at the bonding interface is heated by electromagnetic induction, the hydroxide compound of the component (A) in the cured product (cured adhesive silicone rubber product) obtained by curing the curable liquid silicone adhesive, which is the bonding member, is heated and decomposed to generate water, and the generated water is vaporized to foam and reduce the adhesive strength. As a result, the bonding members can be dismantled more quickly.
- the frequency, power, and time for electromagnetic induction heating are preferably such that the parts can be separated.
- the frequency can be selected within the range of 100 kHz to 500 kHz, and the power can be selected within the range of 500 W to 5 kW.
- the heating time by electromagnetic induction is not particularly limited, but is 2 minutes or less, preferably 1 minute or less, and more preferably 20 seconds or less.
- the present invention will be specifically explained by showing composition examples, composition comparison examples, and examples and comparison examples, but the present invention is not limited to the following examples.
- the room temperature is 23°C
- the viscosity is the value measured at 23°C using a rotational viscometer
- the average particle size is the value calculated as the cumulative weight average value D50 (or median size) using a particle size distribution measuring device using the laser light diffraction method.
- the BET specific surface area is a value calculated using the BET formula from an isothermal adsorption curve measured by the nitrogen gas adsorption method.
- composition 1 was obtained by uniformly mixing 70 parts by mass of dimethylpolysiloxane whose molecular chain terminals are blocked with trimethoxysilyl groups and have a viscosity of 30,000 mPa ⁇ s, 40 parts by mass of dimethylpolysiloxane whose molecular chain terminals are blocked with trimethylsilyl groups and have a viscosity of 100 mPa ⁇ s, 80 parts by mass of aluminum hydroxide whose average particle size is 10 ⁇ m and whose surface is untreated (amount in the entire composition is 31.0% by mass), 50 parts by mass of colloidal calcium carbonate whose BET specific surface area is 17 m2 /g and whose surface is treated with a fatty acid, 8 parts by mass of vinyltrimethoxysilane, 2 parts by mass of a compound represented by the following formula (1), and 0.8 parts by mass of diisopropoxytitan
- Composition Example 2 85 parts by mass of dimethylpolysiloxane whose molecular chain ends are capped with hydroxyl groups and whose viscosity is 20,000 mPa ⁇ s, 15 parts by mass of dimethylpolysiloxane whose molecular chain ends are capped with trimethylsilyl groups and whose viscosity is 100 mPa ⁇ s, 70 parts by mass of aluminum hydroxide whose average particle size is 10 ⁇ m and whose surface is untreated (amount in the entire composition is 31.9% by mass), 30 parts by mass of heavy calcium carbonate whose surface is treated with paraffin and whose BET specific surface area is 2.0 m2 /g, Composition 2 was obtained by uniformly mixing 9 parts by mass of fumed silica having a molecular weight of 1.0 to 1.0 g/g, 9.2 parts by mass of vinyltris(1-cyclopenten-1-yloxy)silane, 0.4 parts by mass of ⁇ -(N,N,N',N'-t
- Composition 3 was obtained by uniformly mixing 70 parts by mass of dimethylpolysiloxane whose molecular chain terminals are capped with trimethoxysilyl groups and have a viscosity of 30,000 mPa ⁇ s, 40 parts by mass of dimethylpolysiloxane whose molecular chain terminals are capped with trimethylsilyl groups and have a viscosity of 100 mPa ⁇ s, 80 parts by mass of aluminum hydroxide whose average particle size is 10 ⁇ m and whose surface is untreated (amount in the entire composition: 30.8% by mass), 50 parts by mass of colloidal calcium carbonate whose BET specific surface area is 17 m2 /g and whose surface is treated with a fatty acid, 2 parts by mass of iron powder whose average particle size is 30 ⁇ m (amount in the entire composition: 0.8% by mass), 8 parts by mass of vinyltrimethoxysilane, 2 parts by mass of the compound represented by the above formula (1), and 0.8 parts by
- Composition 4 was obtained by uniformly mixing 70 parts by mass of dimethylpolysiloxane whose molecular chain ends are blocked with trimethoxysilyl groups and whose viscosity is 30,000 mPa ⁇ s, 40 parts by mass of dimethylpolysiloxane whose molecular chain ends are blocked with trimethylsilyl groups and whose viscosity is 100 mPa ⁇ s, 5 parts by mass of fumed silica, 50 parts by mass of colloidal calcium carbonate whose BET specific surface area is 17 m2 /g and whose surface is treated with a fatty acid, 8 parts by mass of vinyltrimethoxysilane, 2 parts by mass of the compound represented by the above formula (1), and 0.8 parts by mass of diisopropoxytitanium bis(ethylacetoacetate).
- Composition 5 was obtained by uniformly mixing 70 parts by mass of dimethylpolysiloxane whose molecular chain terminals are capped with trimethoxysilyl groups and have a viscosity of 30,000 mPa ⁇ s, 40 parts by mass of dimethylpolysiloxane whose molecular chain terminals are capped with trimethylsilyl groups and have a viscosity of 100 mPa ⁇ s, 100 parts by mass of aluminum hydroxide whose average particle size is 10 ⁇ m and whose surface is untreated (amount in the entire composition: 30.5% by mass), 50 parts by mass of colloidal calcium carbonate whose BET specific surface area is 17 m2 /g and whose surface is treated with a fatty acid, 50 parts by mass of iron powder whose average particle size is 30 ⁇ m (amount in the entire composition: 15.2% by mass), 8 parts by mass of vinyltrimethoxysilane, 2 parts by mass of the compound represented by the above formula (1),
- the substrates used were an ADC12 (aluminum alloy die-cast) substrate measuring 25 mm wide and 50 mm long, and a PBT (polybutylene terephthalate resin, heat resistance temperature: 150°C or higher) substrate measuring 25 mm wide and 50 mm long. Any of the above compositions 1 to 5 was used as the curable liquid silicone adhesive.
- the ADC12 substrate and the PBT substrate were bonded together to a bond thickness of 0.5 mm and a bond area of 2.5 cm2, and the resulting bond was aged at 23°C/50% RH for 7 days to produce a bonded member bonded with a cured product of the curable liquid silicone adhesive (cured product of adhesive silicone rubber).
- Electromagnetic induction heating was performed at a frequency of 286 kHz and an output of 2.3 kW, and the metal part of the bonding interface was heated. Heating was continued until the bonding members were dismantled, and the time until dismantling was measured with a stopwatch. A time of 15 seconds or less was considered to be acceptable, and a time of more than 15 seconds was considered to be unacceptable. In all compositions, the bonding members were dismantled by heating alone.
- Examples 1 to 3 which are the methods for dismantling joined members of the present invention, enabled easy dismantling using electromagnetic induction heating in a short time of 12 to 14 seconds with little energy consumption, and further enabled recycling.
- Comparative Example 1 although it could be dismantled, the effect of foaming to reduce adhesive strength was not obtained because no hydroxide compound was added, and the time until dismantling was extended, but it was still recyclable.
- Comparative Example 2 because 15.2 mass% of metal powder was added to the composition, the adhesive was also heated and the PBT base material was dissolved, making it impossible to recycle.
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Abstract
Description
[1]
分解温度が180~600℃である水酸化化合物を25~80質量%含有し、かつ電磁誘導で発熱する材料の含有量が3質量%以下である硬化性液状シリコーン系接着剤を硬化させてなる硬化物で、接合界面の少なくとも一部が金属である部材を含む複数の部材同士が接合された接合部材について、電磁誘導によって接合界面の前記金属部分を加熱することにより、前記部材同士の内、前記金属を含む部材を分離して接合部材を解体する工程を含む接合部材の解体方法。
[2]
硬化性液状シリコーン系接着剤が、縮合硬化型液状シリコーン系接着剤、付加反応硬化型液状シリコーン系接着剤又は紫外線硬化型液状シリコーン系接着剤である[1]に記載の接合部材の解体方法。
[3]
分解温度が180~600℃である水酸化化合物が、水酸化アルミニウム、水酸化マグネシウム及び水酸化酸化アルミニウム(べーマイト)から選ばれる少なくとも1種である[1]又は[2]に記載の接合部材の解体方法。
[4]
電磁誘導加熱の周波数が、100kHz以上500kHz以下である[1]~[3]のいずれかに記載の接合部材の解体方法。
[5]
接合部材が自動車部品又は電気・電子部品である[1]~[4]のいずれかに記載の接合部材の解体方法。
[6]
[1]~[5]のいずれかに記載の接合部材の解体方法に用いられる下記(A)~(E)成分を含有し、電磁誘導で発熱する材料の含有量が3質量%以下である易解体性の縮合硬化型液状シリコーン系接着剤。
(A)分解温度が180~600℃である水酸化化合物:接着剤全体の25~80質量%となる量、
(B)ケイ素原子に結合した水酸基及び/又は加水分解性シリル基で分子鎖両末端が封鎖された直鎖状ジオルガノポリシロキサン:100質量部、
(C)ケイ素原子に結合した加水分解性基を分子中に3個以上有する加水分解性オルガノシラン化合物及び/又はその部分加水分解縮合物:0.1~40質量部、
(D)硬化触媒:0.001~20質量部、及び
(E)シランカップリング剤:0.05~20質量部。
[7]
[1]~[5]のいずれかに記載の接合部材の解体方法に用いられる下記(A)及び(F)~(H)成分を含有し、電磁誘導で発熱する材料の含有量が3質量%以下である易解体性の付加反応硬化型液状シリコーン系接着剤。
(A)分解温度が180~600℃である水酸化化合物:接着剤全体の25~80質量%となる量、
(F)ケイ素原子に結合したアルケニル基を分子鎖末端に有するアルケニル基含有オルガノポリシロキサン:100質量部、
(G)ケイ素原子に結合した水素原子を分子中に少なくとも2個有するオルガノハイドロジェンポリシロキサン:(F)成分中のケイ素原子に結合したアルケニル基1モルに対してケイ素原子結合水素原子が0.01~3モルとなる量、
(H)白金族金属触媒:(F)成分と(G)成分の合計量に対して白金族金属原子の質量換算で0.01~1,000ppm、及び
(I)接着性付与剤:0.05~20質量部。
[8]
[1]~[5]のいずれかに記載の接合部材の解体方法に用いられる下記(A)及び(J)、(K)成分を含有し、電磁誘導で発熱する材料の含有量が3質量%以下である易解体性の紫外線硬化型液状シリコーン系接着剤。
(A)分解温度が180~600℃である水酸化化合物:接着剤全体の25~80質量%となる量、
(J)紫外線反応性オルガノポリシロキサン:100質量部、及び
(K)光重合開始剤:0.01~10質量部。
本発明に使用される硬化性液状シリコーン系接着剤は、硬化して接合界面の少なくとも一部が金属である部材を含む複数の部材同士を接合する接着部材となるもので、分解温度が180~600℃である水酸化化合物(A)を含有し、電磁誘導で発熱する材料の含有量が3質量%以下であり、主鎖がシロキサン結合からなる高分子をベースポリマーに使用した接着剤であり、硬化タイプは、縮合硬化型、付加反応硬化型、紫外線硬化型が好ましい。
分解温度が180~600℃である水酸化化合物は、通常、金属の水酸化物又は酸化金属の水酸化物であることが好ましく、分解温度が180℃付近である水酸化アルミニウム、分解温度が300℃付近である水酸化マグネシウム、分解温度が500℃付近である水酸化酸化アルミニウム(べーマイト)を挙げることができる。なお、「分解温度」とは、水酸化化合物が分解して水を発生し始める温度である。
電磁誘導で発熱する材料としては、金属材料や、炭素繊維、カーボンブラックなどの炭素材料が例示できる。硬化性液状シリコーン系接着剤に用いる金属材料としては、アルミ粉末、鉄粉末、銅粉末、更にそれらの合金粉末などを挙げることができる。
縮合硬化型液状シリコーン系接着剤は、上述した(A)分解温度が180~600℃である水酸化化合物以外に、(B)ケイ素原子に結合した水酸基及び/又は加水分解性シリル基で分子鎖両末端が封鎖された直鎖状ジオルガノポリシロキサン(ベースポリマー)、(C)ケイ素原子に結合した加水分解性基を分子中に3個以上有する加水分解性オルガノシラン化合物及び/又はその部分加水分解縮合物(架橋剤)、(D)硬化触媒、及び(E)シランカップリング剤(接着性付与剤)を含み、室温において大気中の水分(湿気)による加水分解・縮合反応を利用して硬化物を得る液状シリコーン系接着剤である。
縮合硬化型液状シリコーン系接着剤としては、
(A)分解温度が180~600℃である水酸化化合物:接着剤全体の25~80質量%となる量、
(B)ケイ素原子に結合した水酸基及び/又は加水分解性シリル基で分子鎖両末端が封鎖された直鎖状ジオルガノポリシロキサン:100質量部、
(C)ケイ素原子に結合した加水分解性基を分子中に3個以上有する加水分解性オルガノシラン化合物及び/又はその部分加水分解縮合物:0.1~40質量部、
(D)硬化触媒:0.001~20質量部、及び
(E)シランカップリング剤:0.05~20質量部
を含有し、電磁誘導で発熱する材料の含有量が3質量%以下である易解体性の縮合硬化型液状シリコーン系接着剤が好ましい。
(A)成分以外の無機質充填剤を配合する場合、その配合量は、ケイ素原子に結合した水酸基及び/又は加水分解性シリル基で分子鎖両末端が封鎖された直鎖状ジオルガノポリシロキサン100質量部に対して0.1~800質量部であることが好ましく、より好ましくは0.5~600質量部である。
付加反応硬化型液状シリコーン系接着剤は、上述した(A)分解温度が180~600℃である水酸化化合物以外に、(F)ケイ素原子に結合したビニル基等のアルケニル基を分子鎖末端に有するアルケニル基含有オルガノポリシロキサン(ベースポリマー)、(G)ケイ素原子に結合した水素原子(SiH基)を分子中に少なくとも2個有するオルガノハイドロジェンポリシロキサン(架橋剤)、(H)白金族金属触媒(ヒドロシリル化付加反応触媒)、及び(I)接着性付与剤を含み、SiH基のビニル基への付加反応(ヒドロシリル化反応)により架橋し硬化物を得る液状シリコーン系接着剤である。
付加反応硬化型液状シリコーン系接着剤としては、
(A)分解温度が180~600℃である水酸化化合物:接着剤全体の25~80質量%となる量、
(F)ケイ素原子に結合したアルケニル基を分子鎖末端に有するアルケニル基含有オルガノポリシロキサン:100質量部、
(G)ケイ素原子に結合した水素原子を分子中に少なくとも2個有するオルガノハイドロジェンポリシロキサン:(F)成分中のケイ素原子に結合したアルケニル基1モルに対してケイ素原子結合水素原子が0.01~3モルとなる量、
(H)白金族金属触媒:(F)成分と(G)成分の合計量に対して白金族金属原子の質量換算で0.01~1,000ppm、及び
(I)接着性付与剤:0.05~20質量部
を含有し、電磁誘導で発熱する材料の含有量が3質量%以下である易解体性の付加反応硬化型液状シリコーン系接着剤が好ましい。
紫外線硬化型液状シリコーン系接着剤は、上述した(A)分解温度が180~600℃である水酸化化合物以外に、(J)紫外線反応性オルガノポリシロキサン(ベースポリマー)、(K)光重合開始剤を含み、紫外線の照射により架橋し硬化物を得る液状シリコーン系接着剤である。
紫外線硬化型液状シリコーン系接着剤としては、
(A)分解温度が180~600℃である水酸化化合物:接着剤全体の25~80質量%となる量、
(J)紫外線反応性オルガノポリシロキサン:100質量部、及び
(K)光重合開始剤:0.01~10質量部
を含有し、電磁誘導で発熱する材料の含有量が3質量%以下である易解体性の紫外線硬化型液状シリコーン系接着剤が好ましい。
これらの光重合開始剤は、1種単独で用いても2種以上を併用してもよい。
本発明の接合部材の解体方法において、接合部材は、分解温度が180~600℃である水酸化化合物を特定量含有し、電磁誘導で発熱する材料の含有量が3質量%以下である硬化性液状シリコーン系接着剤を硬化させてなる硬化物(接着性シリコーンゴム硬化物からなる接着部材)によって、接合界面の少なくとも一部が金属である部材を含む複数(特には2個)の部材同士が接合されたものである。該部材は同一であっても異種の部材であってもよい。
該接合部材において、接合された1つの部材は、接合界面の少なくとも一部が金属である部材を使用し、他の部材は、これと同じ部材(接合界面の少なくとも一部が金属である部材)、有機樹脂製部材及び金属製部材から選ばれるものを使用できる。
分解温度が180~600℃である水酸化化合物を含有し、電磁誘導で発熱する材料の含有量が3質量%以下である硬化性液状シリコーン系接着剤を、手又は機械吐出で片側の部材の表面に接合箇所(例えばガスケット等)の形状に塗布し、もう一方の部材を貼り合わせて接合し、硬化させる。その後必要に応じてボルトなどで固定する。
本発明の硬化性液状シリコーン系接着剤が縮合硬化型液状シリコーン系接着剤の場合、室温において空気中の湿分によって硬化するので、複数の部材を合体後、放置しておけば硬化が進行する。硬化速度を大きくしたい場合には加湿することが有効である。また、本発明の硬化性液状シリコーン系接着剤が付加反応硬化型液状シリコーン系接着剤の場合、23~150℃の温度において付加反応により硬化するので、複数の部材を合体後、放置又は加熱すれば硬化が進行する。本発明の硬化性液状シリコーン系接着剤が紫外線硬化型液状シリコーン系接着剤の場合、紫外線を照射することで、光重合開始剤が反応し、硬化反応が進行し、硬化する。また、必要に応じて2次キュアを行ってもよく、その際の温度条件としては好ましくは120℃以上、より好ましくは150℃以上、水酸化化合物の分解温度未満かつ250℃以下である。この際のキュア時間は好ましくは10分~48時間、更に好ましくは30分~24時間である。
本発明の接合部材の解体方法は、接合部材の内、接合界面の金属部分を電磁誘導によって加熱して、間接的に接着部材である硬化性液状シリコーン系接着剤を硬化させてなる硬化物(接着性シリコーンゴム硬化物)の金属と接している部分又は全部が160℃~800℃に加熱されることにより、金属部材が自然に剥離するか、あるいはこれに手で力を加えるか、又はスクレーパーなどの器具を使用して金属部材から剥離させることにより接合部材を解体することができる。また、解体した部材はリサイクルすることが可能である。
接合界面を形成している金属と接着部材は、線膨張係数差が大きい。このため、加熱されると熱膨張量の差により接着界面には大きな熱応力が掛かる。また、異種材料の接合部材の場合、熱膨張量の差により接合部材間にも熱応力が掛かる。更に、電磁誘導により接合界面の金属が加熱された際、接着部材である硬化性液状シリコーン系接着剤を硬化させてなる硬化物(接着性シリコーンゴム硬化物)中の(A)成分の水酸化化合物が加熱され、分解して水を発生、更に発生した水が気化することにより発泡し、接着力が低下する。その結果、より早く接合部材を解体することができる。
[組成物実施例1]
分子鎖両末端がトリメトキシシリル基で封鎖され、粘度が30,000mPa・sのジメチルポリシロキサン70質量部、分子鎖両末端がトリメチルシリル基で封鎖され、粘度が100mPa・sのジメチルポリシロキサン40質量部、平均粒子径が10μmであり、表面が未処理の水酸化アルミニウム80質量部(組成物全体中の含有量31.0質量%)、BET比表面積17m2/gであり、表面が脂肪酸で処理されたコロイダル炭酸カルシウム50質量部、ビニルトリメトキシシラン8質量部、下記式(1)で示される化合物2質量部、及びジイソプロポキシチタンビス(エチルアセトアセテート)0.8質量部を均一に混ぜ、組成物1を得た。
分子鎖両末端が水酸基で封鎖され、粘度が20,000mPa・sのジメチルポリシロキサン85質量部、分子鎖両末端がトリメチルシリル基で封鎖され、粘度が100mPa・sのジメチルポリシロキサン15質量部、平均粒子径が10μmであり、表面が未処理の水酸化アルミニウム70質量部(組成物全体中の含有量31.9質量%)、BET比表面積2.0m2/gであり、表面がパラフィンで処理された重質炭酸カルシウム30質量部、表面がジメチルジクロロシランで処理されたBET比表面積120m2/gの煙霧質シリカ9質量部、ビニルトリス(1-シクロペンテン-1-イルオキシ)シラン9.2質量部、γ-(N,N,N’,N’-テトラメチルグアニジル)プロピルトリメトキシシラン0.4質量部、上記式(1)で示される化合物0.4質量部、及びγ-アミノプロピルトリエトキシシラン0.4質量部を均一に混ぜ、組成物2を得た。
分子鎖両末端がトリメトキシシリル基で封鎖され、粘度が30,000mPa・sのジメチルポリシロキサン70質量部、分子鎖両末端がトリメチルシリル基で封鎖され、粘度が100mPa・sのジメチルポリシロキサン40質量部、平均粒子径が10μmであり、表面が未処理の水酸化アルミニウム80質量部(組成物全体中の含有量30.8質量%)、BET比表面積17m2/gであり、表面が脂肪酸で処理されたコロイダル炭酸カルシウム50質量部、平均粒子径が30μmである鉄粉末2質量部(組成物全体中の含有量0.8質量%)、ビニルトリメトキシシラン8質量部、上記式(1)で示される化合物2質量部、及びジイソプロポキシチタンビス(エチルアセトアセテート)0.8質量部を均一に混ぜ、組成物3を得た。
分子鎖両末端がトリメトキシシリル基で封鎖され、粘度が30,000mPa・sのジメチルポリシロキサン70質量部、分子鎖両末端がトリメチルシリル基で封鎖され、粘度が100mPa・sのジメチルポリシロキサン40質量部、煙霧質シリカ5質量部、BET比表面積17m2/gであり、表面が脂肪酸で処理されたコロイダル炭酸カルシウム50質量部、ビニルトリメトキシシラン8質量部、上記式(1)で示される化合物2質量部、及びジイソプロポキシチタンビス(エチルアセトアセテート)0.8質量部を均一に混ぜ、組成物4を得た。
分子鎖両末端がトリメトキシシリル基で封鎖され、粘度が30,000mPa・sのジメチルポリシロキサン70質量部、分子鎖両末端がトリメチルシリル基で封鎖され、粘度が100mPa・sのジメチルポリシロキサン40質量部、平均粒子径が10μmであり、表面が未処理の水酸化アルミニウム100質量部(組成物全体中の含有量30.5質量%)、BET比表面積17m2/gであり、表面が脂肪酸で処理されたコロイダル炭酸カルシウム50質量部、平均粒子径が30μmである鉄粉末50質量部(組成物全体中の含有量15.2質量%)、ビニルトリメトキシシラン8質量部、上記式(1)で示される化合物2質量部、及びジイソプロポキシチタンビス(エチルアセトアセテート)0.8質量部を均一に混ぜ、組成物5を得た。
基材として幅25mm、長さ50mmのADC12(アルミニウム合金ダイカスト)製基材と幅25mm、長さ50mmのPBT(ポリブチレンテレフタレート樹脂、耐熱温度:150℃以上)製基材を使用し、硬化性液状シリコーン系接着剤として上記組成物1~5のいずれかを使用し、接着厚みが0.5mm、接着面積が2.5cm2になるようにADC12製基材とPBT製基材を貼り合わせ、23℃/50%RHにて7日間養生することによって、硬化性液状シリコーン系接着剤の硬化物(接着性シリコーンゴム硬化物)で接合された接合部材を作製した。
[実施例1~3、比較例1、2]
上記で作製した接合部材を用いて、下記に示す評価方法により評価を行った。これらの結果を表1、図1、図2に示す。
上記で作製した接合部材を用いて、せん断接着力をJIS K6850に規定する方法に準じて測定した。
電磁誘導加熱にはアロニクス株式会社製EASYHEAT0224を使用した。電磁誘導加熱は、周波数286kHz、出力2.3kWで行い、接合界面の金属部分を加熱し、接合部材が解体されるまで加熱を続け、解体時の時間をストップウォッチで測定し、15秒以下を合格、15秒を超えるものを不合格とした。いずれの組成物でも接合部材は加熱のみで解体した。
解体されたADC12製基材の接合面の状態を株式会社キーエンス製デジタルマイクロスコープVHX8000で観察した。実施例1における電磁誘導加熱前の状態を図1に、電磁誘導加熱後の状態を図2に示した。また、PBT製基材側は残った接着剤をカッターナイフで削り、目視で表面状態を確認した。ADC12製基材とPBT製基材の電磁誘導加熱前後で表面状態の変化のないものを変化なしとした。
電磁誘導加熱により解体した部材のリサイクル性を確認した。ADC12製基材はそのまま使用し、PBT製基材側は接着剤をカッターナイフで削ったあと、シリコーン分解剤(シリコーンクリーナーX-100)で接着剤を完全除去後、水洗、乾燥した後に使用した。接合部材は上記と同じ方法で作製した。せん断接着力はJIS K6850に規定する方法に準じて測定した。
一方、比較例1では解体することができるものの、水酸化化合物が未添加のため、発泡による接着力低下の効果が得られず、解体までの時間が延びたが、リサイクルすることはできた。比較例2は金属粉末を組成物中に15.2質量%も添加しているため、接着剤も加熱され、PBT製基材が溶解し、リサイクルすることができなかった。
Claims (8)
- 分解温度が180~600℃である水酸化化合物を25~80質量%含有し、かつ電磁誘導で発熱する材料の含有量が3質量%以下である硬化性液状シリコーン系接着剤を硬化させてなる硬化物で、接合界面の少なくとも一部が金属である部材を含む複数の部材同士が接合された接合部材について、電磁誘導によって接合界面の前記金属部分を加熱することにより、前記部材同士の内、前記金属を含む部材を分離して接合部材を解体する工程を含む接合部材の解体方法。
- 硬化性液状シリコーン系接着剤が、縮合硬化型液状シリコーン系接着剤、付加反応硬化型液状シリコーン系接着剤又は紫外線硬化型液状シリコーン系接着剤である請求項1に記載の接合部材の解体方法。
- 分解温度が180~600℃である水酸化化合物が、水酸化アルミニウム、水酸化マグネシウム及び水酸化酸化アルミニウム(べーマイト)から選ばれる少なくとも1種である請求項1に記載の接合部材の解体方法。
- 電磁誘導加熱の周波数が、100kHz以上500kHz以下である請求項1に記載の接合部材の解体方法。
- 接合部材が自動車部品又は電気・電子部品である請求項1に記載の接合部材の解体方法。
- 請求項1~5のいずれか1項に記載の接合部材の解体方法に用いられる下記(A)~(E)成分を含有し、電磁誘導で発熱する材料の含有量が3質量%以下である易解体性の縮合硬化型液状シリコーン系接着剤。
(A)分解温度が180~600℃である水酸化化合物:接着剤全体の25~80質量%となる量、
(B)ケイ素原子に結合した水酸基及び/又は加水分解性シリル基で分子鎖両末端が封鎖された直鎖状ジオルガノポリシロキサン:100質量部、
(C)ケイ素原子に結合した加水分解性基を分子中に3個以上有する加水分解性オルガノシラン化合物及び/又はその部分加水分解縮合物:0.1~40質量部、
(D)硬化触媒:0.001~20質量部、及び
(E)シランカップリング剤:0.05~20質量部。 - 請求項1~5のいずれか1項に記載の接合部材の解体方法に用いられる下記(A)及び(F)~(H)成分を含有し、電磁誘導で発熱する材料の含有量が3質量%以下である易解体性の付加反応硬化型液状シリコーン系接着剤。
(A)分解温度が180~600℃である水酸化化合物:接着剤全体の25~80質量%となる量、
(F)ケイ素原子に結合したアルケニル基を分子鎖末端に有するアルケニル基含有オルガノポリシロキサン:100質量部、
(G)ケイ素原子に結合した水素原子を分子中に少なくとも2個有するオルガノハイドロジェンポリシロキサン:(F)成分中のケイ素原子に結合したアルケニル基1モルに対してケイ素原子結合水素原子が0.01~3モルとなる量、
(H)白金族金属触媒:(F)成分と(G)成分の合計量に対して白金族金属原子の質量換算で0.01~1,000ppm、及び
(I)接着性付与剤:0.05~20質量部。 - 請求項1~5のいずれか1項に記載の接合部材の解体方法に用いられる下記(A)及び(J)、(K)成分を含有し、電磁誘導で発熱する材料の含有量が3質量%以下である易解体性の紫外線硬化型液状シリコーン系接着剤。
(A)分解温度が180~600℃である水酸化化合物:接着剤全体の25~80質量%となる量、
(J)紫外線反応性オルガノポリシロキサン:100質量部、及び
(K)光重合開始剤:0.01~10質量部。
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