CN110869459B - Active energy ray-curable release adhesive composition - Google Patents

Active energy ray-curable release adhesive composition Download PDF

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CN110869459B
CN110869459B CN201880045675.4A CN201880045675A CN110869459B CN 110869459 B CN110869459 B CN 110869459B CN 201880045675 A CN201880045675 A CN 201880045675A CN 110869459 B CN110869459 B CN 110869459B
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acrylate
active energy
energy ray
adhesive composition
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CN110869459A (en
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冈部年孝
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Mitsubishi Chemical Corp
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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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

An active energy ray-curable release adhesive composition which can suppress the deterioration of a member to be processed and has an excellent pot life, wherein the active energy ray-curable release adhesive composition is an active energy ray-curable release adhesive composition comprising an acrylic resin (A), a urethane (meth) acrylate compound (B), an active energy ray polymerization initiator (C) and a crosslinking agent (D), the acrylic resin (A) is an acrylic resin obtained by polymerizing polymerization components including an alkyl (meth) acrylate monomer (a1), a hydroxyl group-containing monomer (a2) and a carboxyl group-containing monomer (a3), and the content ratio of the carboxyl group-containing monomer (a3) is 0.01 to 0.4 wt% of the polymerization components.

Description

Active energy ray-curable release adhesive composition
Technical Field
The present invention relates to an active energy ray-curable release adhesive composition used for an adhesive film for temporary surface protection when processing an electronic substrate, a semiconductor wafer, a glass processed product, a metal plate, a plastic plate, or the like.
Background
Conventionally, in a processing step such as cutting or drilling of an electronic component, an adhesive film for surface protection for temporarily protecting a surface has been used for the purpose of preventing contamination or damage of a member to be processed, and in recent years, the adhesive film for surface protection is used not only for the electronic component but also for processing various members.
Therefore, in recent years, a member to be processed is required to have an appropriate adhesive force for the reason of miniaturization of processing, thinning of a processed member, and the like, and on the other hand, it is required to peel off an adhesive film for surface protection after the action of surface protection is completed, and when peeling is performed, peeling with a light force without adhesive residue is required.
As an adhesive film or sheet for temporary surface protection, for example, patent document 1 discloses an adhesive sheet in which a pressure-sensitive adhesive layer composed of a pressure-sensitive adhesive and a radiation-polymerizable compound, which is an acrylic urethane oligomer having a weight-average molecular weight of 3000 to 10000, is applied to a substrate surface. It is described that the adhesive force with an adherend is drastically reduced by irradiation with ultraviolet rays when the sheet is peeled.
Patent document 2 discloses a removable adhesive agent which is obtained by using an acrylic adhesive agent having a weight average molecular weight of 20 ten thousand or more and a glass transition temperature of-60 to-30 ℃ and a urethane acrylate compound which is a reaction product of a hydroxyl group-containing acrylic compound having 3 or more acryloyl groups in the molecule and a diisocyanate compound, and which has little adhesive agent residue during removal.
Further, patent document 3 discloses a processing adhesive tape which is a semiconductor wafer or the like that can exhibit good pickup properties even when it is adhered to a wafer within several hours after grinding by controlling the content of a catalyst to 30 to 100ppm in an adhesive layer containing an isocyanate-based crosslinking agent, a polymer containing a functional group reactive with the isocyanate-based crosslinking agent, a urethane acrylate, and a catalyst.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 62-153376
Patent document 2: japanese laid-open patent publication No. 11-293201
Patent document 3: japanese patent laid-open publication No. 2013-152963
Disclosure of Invention
Problems to be solved by the invention
However, in the technique disclosed in patent document 1, although the adhesive strength of the releasable adhesive after curing is reduced, there are: the problems of adhesive remaining during peeling, chip scattering during cutting, and chip peeling and falling during spreading are still unsatisfactory.
Further, the technique disclosed in patent document 2 is intended to improve the description of the residual gum at the time of peeling, but when an acrylic resin containing a carboxyl group-containing monomer as a polymerization component is used, there is a concern that the member to be processed may be deteriorated due to the influence of the carboxyl group.
In the above patent document 3, a predetermined amount of catalyst is contained in order to exhibit good pickup properties even when the adhesive is adhered to an adherend within several hours after grinding, but there is a problem that the pot life in the adhesive application process is further shortened due to the influence of the catalyst.
Accordingly, in the present invention, in such a context, there is provided: an active energy ray-curable release adhesive composition which can suppress the deterioration of a member to be processed and has an excellent pot life of the adhesive composition, particularly an active energy ray-curable release adhesive composition used for an adhesive for temporarily protecting an adhesive film on the surface.
Means for solving the problems
Accordingly, the present inventors have made extensive studies in view of the above circumstances, and as a result, have found that: in an active energy ray-curable release adhesive composition containing an acrylic resin (A), a urethane (meth) acrylate compound (B), an active energy ray polymerization initiator (C) and a crosslinking agent (D), a small amount of an acid group is contained in the acrylic resin (A) in advance, whereby a member to be processed is not deteriorated and the pot life in the adhesive application process is also excellent.
That is, the present invention relates to an active energy ray-curable release adhesive composition comprising an acrylic resin (a), a urethane (meth) acrylate compound (B), an active energy ray polymerization initiator (C), and a crosslinking agent (D), wherein the acrylic resin (a) is an acrylic resin obtained by polymerizing polymerization components including an alkyl (meth) acrylate monomer (a1), a hydroxyl group-containing monomer (a2), and a carboxyl group-containing monomer (a3), and the content of the carboxyl group-containing monomer (a3) is 0.01 to 0.4% by weight of the polymerization components.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention is an active energy ray-curable release adhesive composition comprising an acrylic resin (a), a urethane (meth) acrylate compound (B), an active energy ray polymerization initiator (C), and a crosslinking agent (D), wherein the acrylic resin (a) is an acrylic resin obtained by polymerizing polymerization components including an alkyl (meth) acrylate monomer (a1), a hydroxyl group-containing monomer (a2), and a carboxyl group-containing monomer (a3), and the content ratio of the carboxyl group-containing monomer (a3) is 0.01 to 0.4 wt% of the polymerization components, and therefore, the composition has an excellent pot life. Further, the adhesive using the active energy ray-curable release adhesive composition of the present invention can suppress the deterioration of a member to be processed, and is particularly useful as an adhesive for an adhesive film for temporarily protecting a surface.
When the urethane (meth) acrylate compound (B) contains 1 to 1000ppm by weight of at least one of a metal compound and an amino group-containing compound, a more significant effect is exhibited.
When the urethane (meth) acrylate compound (B) has an ethylenically unsaturated group and the number of the ethylenically unsaturated groups is 3 to 20, the releasability after the irradiation with the active energy ray is excellent.
When the urethane (meth) acrylate compound (B) is a reaction product of a hydroxyl group-containing (meth) acrylate compound (B1) having 3 or more ethylenically unsaturated groups in the molecule and a polyisocyanate compound (B2), the releasability after irradiation with active energy rays is more excellent.
When the weight average molecular weight of the urethane (meth) acrylate compound (B) is 500 to 10000, the releasability after the irradiation with active energy rays is more excellent.
The acrylic resin (A) has a weight average molecular weight of 10 to 200 ten thousand and a glass transition point temperature of-80 to 50 ℃, has excellent adhesion and can prevent the member to be processed from being contaminated.
When the content of the urethane (meth) acrylate compound (B) is 25 to 100 parts by weight based on 100 parts by weight of the acrylic resin (a), the peelability after the irradiation with the active energy ray is more excellent.
Detailed Description
The mode for carrying out the present invention will be specifically described below, but the present invention is not limited to these examples.
In the present invention, "(meth) acrylic acid" means acrylic acid or methacrylic acid, "(meth) acryloyl" means acryloyl or methacryloyl, and "(meth) acrylate" means acrylate or methacrylate.
The "acrylic resin" refers to a resin obtained by polymerizing a polymerization component containing at least 1 type of (meth) acrylate monomer.
In the present invention, the "film" is not particularly distinguished from the "sheet" and the "tape", and is described as including these meanings.
The active energy ray-curable release adhesive composition of the present invention is generally used as an adhesive for an adhesive film on the premise that the composition is once stuck to a member to be processed and then released. The adhesive film is formed by applying an active energy ray-curable release adhesive composition to a substrate sheet, and after the adhesive film is adhered to a member to be processed, the adhesive is cured by irradiation with an active energy ray, whereby the adhesive strength is reduced and the adhesive film can be easily released from the member to be processed.
The active energy ray-curable release adhesive composition of the present invention contains an acrylic resin (a), a urethane (meth) acrylate compound (B), an active energy ray polymerization initiator (C), and a crosslinking agent (D).
[ acrylic resin (A) ]
The acrylic resin (a) used in the present invention is obtained by polymerizing polymerization components containing an alkyl ester (meth) acrylate monomer (a1), a hydroxyl group-containing monomer (a2), and a carboxyl group-containing monomer (a 3).
The alkyl ester of (meth) acrylic acid monomer (a1) has an alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 4 to 8 carbon atoms. If the carbon number is too large, the member to be processed tends to be easily contaminated.
Specific examples thereof include aliphatic alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-propyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth) acrylate; alicyclic (meth) acrylates such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate. These may be used alone, or 2 or more of them may be used in combination.
Among the alkyl ester of (meth) acrylic acid monomers (a1), methyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate are preferably used in terms of copolymerizability, adhesive properties, ease of handling, and ease of availability of raw materials.
The content of the alkyl ester of (meth) acrylate monomer (a1) in the polymerization component is usually 30 to 99% by weight, preferably 40 to 98% by weight, and more preferably 50 to 95% by weight. If the content is too small, the adhesive force before irradiation with active energy rays tends to be easily reduced, and if it is too large, the adhesive force before irradiation with active energy rays tends to be excessively increased.
The hydroxyl group-containing monomer (a2) is preferably a hydroxyl group-containing acrylate monomer, and specific examples thereof include: hydroxyalkyl acrylates such as 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyoctyl (meth) acrylate, caprolactone-modified monomers such as caprolactone-modified 2-hydroxyethyl (meth) acrylate, oxyalkylene-modified monomers such as diethylene glycol (meth) acrylate and polyethylene glycol (meth) acrylate, and primary hydroxyl group-containing monomers such as 2-acryloyloxyethyl-2-hydroxyethyl phthalate; secondary hydroxyl group-containing monomers such as 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-chloro-2-hydroxypropyl (meth) acrylate; and tertiary hydroxyl group-containing monomers such as 2, 2-dimethyl-2-hydroxyethyl (meth) acrylate. These may be used alone or in combination of 2 or more.
Among the above-mentioned hydroxyl group-containing monomers, a primary hydroxyl group-containing monomer is more preferable in terms of excellent reactivity with the crosslinking agent (D) described later, and 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are particularly preferable.
The content of the hydroxyl group-containing monomer (a2) in the polymerization component is preferably 0.1 to 40% by weight, particularly preferably 0.2 to 30% by weight, and further preferably 0.5 to 20% by weight. If the content is too large, crosslinking proceeds before the drying step, which tends to cause a problem in coating properties, and if it is too small, the degree of crosslinking decreases, which tends to increase staining properties of the workpiece.
Examples of the carboxyl group-containing monomer (a3) include: (meth) acrylic acid, acrylic acid dimer, crotonic acid, maleic anhydride, fumaric acid, citraconic acid, glutaconic acid, itaconic acid, acrylamide N-glycolic acid, cinnamic acid, and the like. Among them, (meth) acrylic acid is preferably used in terms of copolymerizability. These may be used alone or in combination of 2 or more.
In the present invention, the content of the carboxyl group-containing monomer (a3) in the polymerization component is 0.01 to 0.4% by weight, preferably 0.03 to 0.4% by weight, more preferably 0.05 to 0.3% by weight, and particularly preferably 0.1 to 0.2% by weight. If the content is too large, the workpiece is deteriorated, or if the workpiece is made of metal, the metal is easily corroded, and if the content is too small, the pot life at the time of applying the adhesive is shortened.
The acrylic resin (a) used in the present invention may contain, as necessary, other copolymerizable monomer (a4) in the polymerization component. Examples of the other copolymerizable monomer (a4) include: acetoacetyl group-containing monomers such as 2- (acetoacetoxy) ethyl (meth) acrylate and allyl acetoacetate; glycidyl group-containing monomers such as glycidyl (meth) acrylate and allyl glycidyl (meth) acrylate; vinyl carboxylate monomers such as vinyl acetate, vinyl propionate, vinyl stearate, and vinyl benzoate; aromatic ring-containing monomers such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyldiethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, styrene, and α -methylstyrene; a (meth) acrylate monomer having a diphenoxy structure such as diphenoxyethyl (meth) acrylate; (meth) acrylamide monomers such as ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, (meth) acryloylmorpholine, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, dimethylaminopropylacrylamide, and N-methylol (meth) acrylamide; alkoxy or oxyalkylene group-containing monomers such as 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, and polypropylene glycol mono (meth) acrylate; acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyl toluene, vinyl pyridine, vinyl pyrrolidone, dialkyl itaconate, dialkyl fumarate, allyl alcohol, acryloyl chloride, methyl vinyl ketone, allyl trimethyl ammonium chloride, dimethyl allyl vinyl ketone, and the like. These may be used alone or in combination of 2 or more.
The content of the other copolymerizable monomer (a4) in the polymerization component is preferably 40% by weight or less, particularly preferably 30% by weight or less, and more preferably 25% by weight or less. When the amount of the other copolymerizable monomer (a4) is too large, the adhesive properties tend to be deteriorated.
In the present invention, the (meth) acrylic resin (a) is produced by polymerizing the alkyl ester (meth) acrylate monomer (a1), the hydroxyl group-containing monomer (a2), the carboxyl group-containing monomer (a3), and if necessary, another copolymerizable monomer (a4) as copolymerization components, and the polymerization method can be preferably performed by conventionally known methods such as solution radical polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization. Among these, the production by solution radical polymerization is preferable in that the (meth) acrylic resin (a) can be produced safely and stably with an arbitrary monomer composition.
In the solution radical polymerization, for example, a monomer component including the alkyl ester (meth) acrylate monomer (a1), the hydroxyl group-containing monomer (a2), the carboxyl group-containing monomer (a3), and if necessary, another copolymerizable monomer (a4) and a polymerization initiator are mixed or dropped in an organic solvent, and polymerization is performed under reflux or at a temperature of usually 50 to 98 ℃ for about 0.1 to 20 hours.
Examples of the organic solvent used in the polymerization reaction include: aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, esters such as ethyl acetate and butyl acetate, aliphatic alcohols such as n-propanol and isopropanol, and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone.
As the polymerization initiator, a general radical polymerization initiator, that is, an azo-based polymerization initiator such as azobisisobutyronitrile or azobisdimethylvaleronitrile, a peroxide-based polymerization initiator such as benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide or cumene hydroperoxide, and the like can be used as specific examples.
The acrylic resin (a) preferably has a predetermined weight average molecular weight and a predetermined glass transition temperature.
The weight average molecular weight of the acrylic resin (a) is usually 10 to 200 ten thousand, preferably 15 to 150 ten thousand, particularly preferably 20 to 120 ten thousand, and particularly preferably 30 to 100 ten thousand. If the weight average molecular weight is too small, the stainability of the member to be processed tends to increase, and if it is too large, the coatability tends to decrease, or the cost tends to be unfavorable.
The dispersion degree (weight average molecular weight/number average molecular weight) of the acrylic resin (a) is preferably 20 or less, particularly preferably 10 or less, further preferably 7 or less, and particularly preferably 5 or less. If the dispersion degree is too high, the contamination of the workpiece tends to increase. The lower limit of the degree of dispersion is usually 1.1 from the viewpoint of the limit of production.
The weight average molecular weight is a weight average molecular weight obtained by conversion of a standard polystyrene molecular weight, and is obtained by subjecting 3 columns to high performance liquid chromatography (manufactured by japan Waters corporation, "Waters 2695 (main body)" and "Waters 2414 (detector)"): shodex GPC KF-806L (exclusion limit molecular weight: 2X 10)7And separation range: 100 to 2 x 107Theoretical plate number: 10000 sections/root, filler material: styrene-divinylbenzene copolymer, filler particle diameter: 10 μm) in series, and the number average molecular weight can be determined by the same method. The degree of dispersion is determined from the weight average molecular weight and the number average molecular weight.
Further, the glass transition temperature (Tg) of the acrylic resin (A) is preferably-80 to 50 ℃, particularly preferably-70 to 30 ℃, and further preferably-50 to 20 ℃. If the glass transition temperature is too high, the adhesiveness tends to be lowered, and if it is too low, the staining property of the workpiece tends to be increased.
The glass transition temperature is calculated from the following Fox equation.
[ formula 1]
Figure BDA0002359315240000091
Tg: glass transition temperature (K) of acrylic resin (A)
Tga: glass transition temperature (K) of homopolymer of monomer A
Wa: weight fraction of monomer A
Tgb: glass transition temperature (K) of homopolymer of monomer B
Wb: weight fraction of monomer B
Tgn: glass transition temperature (K) of homopolymer of monomer N
Wn: weight fraction of monomer N
(Wa+Wb+…+Wn＝1)
That is, the glass transition temperature of the acrylic resin (a) is calculated by substituting the glass transition temperature and the weight fraction of each monomer constituting the acrylic resin (a) as a homopolymer into the above Fox expression.
The glass transition temperature when the monomer constituting the acrylic resin (A) is a homopolymer is usually measured by a Differential Scanning Calorimeter (DSC), and can be measured by a method in accordance with JIS K7121-.
The viscosity of the acrylic resin (A) at 25 ℃ is preferably 1000 to 100000 mPas, particularly preferably 1500 to 50000 mPas. When the viscosity is outside the above range, the coating property tends to be easily lowered. The viscosity can be measured by an E-type viscometer.
[ urethane (meth) acrylate compound (B) ]
The urethane (meth) acrylate compound (B) used in the present invention is a compound having a urethane bond and a (meth) acryloyl group.
The urethane (meth) acrylate compound (B) may be a urethane (meth) acrylate compound (B1) obtained by reacting a hydroxyl group-containing (meth) acrylate compound (B1) with a polyvalent isocyanate compound (B2), or a urethane (meth) acrylate compound (B2) obtained by reacting a hydroxyl group-containing (meth) acrylate compound (B1), a polyvalent isocyanate compound (B2) and a polyol compound (B3). Among them, in the present invention, in terms of peelability after irradiation with active energy rays, it is preferable to use the urethane (meth) acrylate compound (B1).
In the present invention, only 1 kind of the urethane (meth) acrylate compound (B) may be used, or 2 or more kinds may be used in combination.
The hydroxyl group-containing (meth) acrylate compound (b1) is preferably a compound having 1 hydroxyl group, and examples thereof include: hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and 6-hydroxyhexyl (meth) acrylate, 2-hydroxyethyl acryloyl phosphate and 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, hydroxyl group-containing (meth) acrylate compounds having 1 ethylenically unsaturated group such as caprolactone-modified 2-hydroxyethyl (meth) acrylate, dipropylene glycol (meth) acrylate, fatty acid-modified glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate; hydroxyl group-containing (meth) acrylate compounds having 2 ethylenically unsaturated groups such as diglycerol di (meth) acrylate and 2-hydroxy-3-acryloyl-oxypropyl methacrylate; hydroxyl group-containing (meth) acrylate compounds having 3 or more ethylenically unsaturated groups, such as pentaerythritol tri (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, ethylene oxide-modified pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, and ethylene oxide-modified dipentaerythritol penta (meth) acrylate.
The hydroxyl group-containing (meth) acrylate compound (b1) may be used singly or in combination of 2 or more.
Among them, hydroxyl group-containing (meth) acrylate compounds containing 3 or more ethylenically unsaturated groups are preferable, and pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are particularly preferable, from the viewpoint of excellent reactivity and general usability.
Examples of the polyisocyanate-based compound (b2) include: aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate and lysine triisocyanate; alicyclic polyisocyanates such as hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, and 1, 3-bis (isocyanatomethyl) cyclohexane; or trimer compounds or polymer compounds of these polyisocyanates, allophanate polyisocyanates, biuret polyisocyanates, and water-dispersible polyisocyanates (for example, "AQUANATE 100", "AQUANATE 110", "AQUANATE 200", and "AQUANATE 210" manufactured by Nippon Polyurethane Industry Co., Ltd.), and the like.
Among them, in terms of excellent reactivity and versatility, aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, and alicyclic diisocyanates such as 1, 3-bis (isocyanatomethyl) cyclohexane are preferable, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, and hexamethylene diisocyanate are particularly preferable, and isophorone diisocyanate and hexamethylene diisocyanate are further preferable.
The polyol compound (b3) may be a compound containing 2 or more hydroxyl groups, and examples thereof include: aliphatic polyols, alicyclic polyols, polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polybutadiene polyols, polyisoprene polyols, (meth) acrylic polyols, polysiloxane polyols, and the like.
Examples of the aliphatic polyol include: aliphatic alcohols having 2 hydroxyl groups such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1, 3-propanediol, dimethylolpropane, neopentyl glycol, 2-diethyl-1, 3-propanediol, 2-butyl-2-ethyl-1, 3-propanediol, 1, 4-tetramethylene glycol, 1, 3-tetramethylene glycol, 2-methyl-1, 3-trimethylene glycol, 1, 5-pentamethylene glycol, 1, 6-hexamethylene glycol, 3-methyl-1, 5-pentamethylene glycol, 2, 4-diethyl-1, 5-pentamethylene glycol, pentaerythritol diacrylate, 1, 9-nonanediol, 2-methyl-1, 8-octanediol, etc, Sugar alcohols such as xylitol and sorbitol, and aliphatic alcohols having 3 or more hydroxyl groups such as glycerin, trimethylolpropane and trimethylolethane, and these may be used in 1 type or in combination of 2 or more.
Examples of the alicyclic polyol include: 1 or 2 or more kinds of cyclohexane diols such as 1, 4-cyclohexanediol and cyclohexyldimethanol, hydrogenated bisphenols such as hydrogenated bisphenol A, and tricyclodecanedimethanol may be used in combination.
Examples of the polyether polyol include: polyether polyols containing an alkylene structure such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polypentamethylene glycol, and polyhexamethylene glycol, and random or block copolymers of these polyalkylene glycols. These may be used alone or in combination of 2 or more.
Examples of the polyester polyol include: polycondensates of polyols with polycarboxylic acids; ring-opening polymers of cyclic esters (lactones); and a reaction product obtained from 3 components of a polyhydric alcohol, a polycarboxylic acid and a cyclic ester.
Examples of the polyol include: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1, 3-propanediol, 1, 4-tetramethylene glycol, 1, 3-tetramethylene glycol, 2-methyl-1, 3-trimethylene glycol, 1, 5-pentamethylene glycol, neopentyl glycol, 1, 6-hexamethylene glycol, 3-methyl-1, 5-pentamethylene glycol, 2, 4-diethyl-1, 5-pentamethylene glycol, glycerin, trimethylolpropane, trimethylolethane, cyclohexanediols (1, 4-cyclohexanediol, etc.), bisphenols (bisphenol a, etc.), sugar alcohols (xylitol, sorbitol, etc.), and the like.
Examples of the polycarboxylic acid include: aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; alicyclic dicarboxylic acids such as 1, 4-cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, 2, 6-naphthalenedicarboxylic acid, p-phenylenedicarboxylic acid, and trimellitic acid.
Examples of the cyclic ester include: propiolactone, beta-methyl-delta-valerolactone, epsilon-caprolactone and the like.
Examples of the polycarbonate polyol include: a reactant of a polyhydric alcohol and phosgene, a ring-opened polymer of a cyclic carbonate (alkylene carbonate, etc.), and the like.
Examples of the polyol include the polyols exemplified in the description of the polyester polyol, and examples of the alkylene carbonate include: ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, and the like.
The polycarbonate polyol may have an ester bond together with a carbonate bond as long as it has a carbonate bond in the molecule and a hydroxyl group at the terminal.
Examples of the polyolefin polyol include: polyolefin polyols having a saturated hydrocarbon skeleton of a homopolymer or copolymer of ethylene, propylene, butene, or the like and having a hydroxyl group at a molecular terminal thereof.
Examples of the polybutadiene-based polyol include those having a copolymer of butadiene as a hydrocarbon skeleton and having a hydroxyl group at a molecular terminal thereof.
The polybutadiene-based polyol may also be a hydrogenated polybutadiene polyol in which all or a part of the ethylenically unsaturated groups contained in the structure thereof has been hydrogenated.
The polyisoprene polyol includes a copolymer of isoprene as a hydrocarbon skeleton and having a hydroxyl group at a molecular terminal thereof.
The polyisoprene-based polyol may also be a hydrogenated polyisoprene polyol in which all or a part of the ethylenically unsaturated groups contained in the structure thereof is hydrogenated.
Examples of the (meth) acrylic polyol include: examples of the (meth) acrylate having at least 2 hydroxyl groups in the molecule include: and alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, and octadecyl (meth) acrylate.
Examples of the polysiloxane polyol include: dimethylpolysiloxane polyols, methylphenylpolysiloxane polyols, and the like.
Among them, aliphatic polyols and alicyclic polyols are preferably used in terms of cost, and polyester polyols, polyether polyols and polycarbonate polyols are preferably used in terms of general usability.
The weight average molecular weight of the polyol compound (b3) is preferably 60 to 3000, particularly preferably 100 to 1000, and further preferably 150 to 800. If the weight average molecular weight of the polyol compound (B3) is too large, the resulting urethane (meth) acrylate compound (B2) and acrylic resin (a) tend to be difficult to be uniformly mixed, and the adhesive residue tends to be generated in the member to be processed. If the weight average molecular weight of the polyol compound (b3) is too small, cracks tend to be easily generated in the pressure-sensitive adhesive layer after irradiation with active energy rays.
The urethane (meth) acrylate compound (B) can be produced by reacting the above components by a known reaction means.
In general, in the case of producing the urethane (meth) acrylate compound (B1), the hydroxyl group-containing (meth) acrylate compound (B1) and the polyisocyanate compound (B2) may be put together or separately into a reactor and subjected to a urethanation reaction by a known reaction means, and in the case of producing the urethane (meth) acrylate compound (B2), the polyol compound (B3) may be further added. In addition, in the case of producing the urethane (meth) acrylate compound (B2), a useful method is: the polyol-based compound (b3) and the polyisocyanate-based compound (b2) were reacted in advance to obtain a reaction product, and then the obtained reaction product was reacted with the hydroxyl group-containing (meth) acrylate-based compound (b 1).
In the urethanization reaction, the reaction is terminated when the residual isocyanate group content of the reaction system becomes 0.5 wt% or less, whereby the urethane (meth) acrylate compound (B) can be obtained.
In the urethanization reaction, a catalyst is preferably used for the purpose of promoting the reaction, and examples of the catalyst include a metal compound and an amino group-containing compound.
Examples of the metal-based compound include: organic metal compounds such as dibutyltin dilaurate, dibutyltin diacetate, trimethyltin hydroxide, tetra-n-butyltin, zinc bisacetylacetonate, zirconium tris (acetylacetonate) ethylacetoacetate, zirconium tetraacetylacetonate, and the like, organic metal compounds such as tin octylate, zinc caproate, zinc caprylate, zinc stearate, zirconium 2-ethylhexanoate, cobalt naphthenate, stannous chloride, tin chloride, potassium acetate, bismuth nitrate, bismuth bromide, bismuth iodide, bismuth sulfide, and the like, organic bismuth compounds such as dibutyltin dilaurate, dioctylbutyltin dilaurate, and the like, bismuth 2-ethylhexanoate, bismuth naphthenate, bismuth isodecanoate, bismuth neodecanoate, bismuth laurate, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth dineodecanoate, bismuth disalicylate, bismuth digallate, and the like.
Examples of the amino group-containing compound include: triethylamine, triethylenediamine, benzyldiethylamine, 1, 4-diazabicyclo [2,2,2] octane, 1, 8-diazabicyclo [5,4,0] undecene, N' -tetramethyl-1, 3-butanediamine, N-methylmorpholine, N-ethylmorpholine and the like.
Among these catalysts, dibutyltin dilaurate and 1, 8-diazabicyclo [5,4,0] undecene are suitable. These catalysts may be used alone or in combination of 2 or more.
In the urethanization reaction, an organic solvent having no functional group reactive to an isocyanate group may be used, and for example: esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aromatic solvents such as toluene and xylene.
In addition, the reaction temperature is usually 30 to 90 ℃, preferably 40 to 80 ℃, and the reaction time is usually 2 to 10 hours, preferably 3 to 8 hours.
The urethane (meth) acrylate compound (B) used in the present invention preferably has 3 to 20 ethylenically unsaturated groups, more preferably 4 to 18, and particularly preferably 6 to 15 groups, from the viewpoint of peelability after irradiation with active energy rays.
If the number of the ethylenically unsaturated groups is too large, the crosslinking density after irradiation with active energy rays tends to become too large, and cracks tend to be easily generated in the pressure-sensitive adhesive layer, and if it is too small, a sufficient crosslinking density cannot be obtained, and therefore, the peelability after irradiation with active energy rays tends to be easily reduced.
The weight average molecular weight of the urethane (meth) acrylate compound (B) used in the present invention is preferably 500 to 10000, particularly preferably 750 to 5000, and further preferably 1000 to 4000. If the weight average molecular weight is too high, the viscosity of the composition increases, and the urethane (meth) acrylate compound (B) and the acrylic resin (a) are difficult to be uniformly mixed, and the adhesive residue tends to be generated easily on the member to be processed. If the weight average molecular weight is too low, the urethane (meth) acrylate compound (B) tends to easily bleed out from the pressure-sensitive adhesive sheet, and adhesive residue tends to easily occur.
The weight average molecular weight is a weight average molecular weight obtained by conversion of a standard polystyrene molecular weight, and in high performance liquid chromatography (showa electric corporation, "Shodex GPC system-11 type"), 3 columns: shodex GPC KF-806L (exclusion limit molecules)Quantity: 2X 107And separation range: 100 to 2 x 107Theoretical plate number: 10000 steps/root, filler material: styrene-divinylbenzene copolymer, filler particle diameter: 10 μm) was used in series, and the measurement was possible.
The viscosity of the urethane (meth) acrylate compound (B) used in the present invention at 60 ℃ is preferably 1000 to 100000 mPas, and particularly preferably 1500 to 50000 mPas. When the viscosity is outside the above range, the coating property tends to be easily lowered. The viscosity can be measured by an E-type viscometer.
The urethane (meth) acrylate compound (B) obtained in the above-mentioned manner usually contains at least one of a metal compound derived from a catalyst and an amino group-containing compound, which are used for the purpose of promoting the urethane reaction. Since the pot life of the active energy ray-curable release adhesive composition containing the urethane (meth) acrylate compound (B) and the crosslinking agent (D) described later tends to be shortened, in the present invention, it is important to contain a small amount of an acid group (carboxyl group) in the acrylic resin (a) as described above in order to improve the pot life.
In the present invention, when the urethane (meth) acrylate compound (B) contains at least one of a metal compound and an amino group-containing compound in an amount of usually 1 to 1000ppm, particularly 5 to 500ppm by weight, a significant effect is obtained.
In the present invention, the content of the urethane (meth) acrylate compound (B) is preferably 25 to 100 parts by weight, more preferably 30 to 90 parts by weight, and particularly preferably 40 to 80 parts by weight, based on 100 parts by weight of the acrylic resin (a). If the content of the urethane (meth) acrylate compound (B) is too small, the peelability after the irradiation with the active energy ray tends to be easily reduced, and if too large, the pressure-sensitive adhesive layer tends to be easily cracked after the irradiation with the active energy ray.
[ active energy ray polymerization initiator (C) ]
The active energy ray polymerization initiator (C) may be any initiator as long as it generates radicals by the action of light, and examples thereof include: diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzildimethylketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) one, 1-hydroxycyclohexylphenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone oligoester Acetophenones such as acetophenone compounds; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenones such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyl-diphenylsulfide, 3 ', 4,4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone, 2,4, 6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl ] benzylammonium bromide, and (4-benzoylbenzyl) trimethylammonium chloride; thioxanthones such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3, 4-dimethyl-9H-thioxanthone-9-one meso (meso) chloride, and the like; acylphosphine oxides such as 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethyl-pentylphosphine oxide, and bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide; and the like. Among them, acetophenones are preferable, and 1-hydroxycyclohexyl phenyl ketone is particularly preferable. These active energy ray polymerization initiators (C) may be used alone or in combination of 2 or more.
Further, as the auxiliary agent for the active energy ray polymerization initiator (C), for example, triethanolamine, triisopropanolamine, 4 ' -dimethylaminobenzophenone (michler's ketone), 4 ' -diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate (n-butoxy) ester, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone, and the like can be used in combination. These auxiliaries may be used alone or in combination of 2 or more.
The content of the active energy ray polymerization initiator (C) is preferably 0.1 to 20 parts by weight, particularly preferably 0.5 to 15 parts by weight, and particularly preferably 1 to 10 parts by weight, based on 100 parts by weight of the acrylic resin (a).
If the content of the active energy ray polymerization initiator (C) is too small, the peelability after the active energy ray irradiation tends to be easily reduced, and if too large, the pressure-sensitive adhesive layer tends to be easily cracked after the active energy ray irradiation.
[ crosslinking agent (D) ])
Examples of the crosslinking agent (D) include: isocyanate-based crosslinking agents, epoxy-based crosslinking agents, aziridine-based crosslinking agents, oxazoline-based crosslinking agents, melamine-based crosslinking agents, aldehyde-based crosslinking agents, and amine-based crosslinking agents. Among these, an isocyanate-based crosslinking agent is preferably used in terms of improving adhesiveness to a base material and reactivity with the acrylic resin (a).
These crosslinking agents (D) may be used alone, or 2 or more kinds may be used in combination.
Examples of the isocyanate-based crosslinking agent include: 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, hydrogenated tolylene diisocyanate, 1, 3-xylylene diisocyanate, 1, 4-xylylene diisocyanate, hexamethylene diisocyanate, diphenylmethane-4, 4-diisocyanate, isophorone diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, tetramethylxylylene diisocyanate, 1, 5-naphthalene diisocyanate, triphenylmethane triisocyanate, and adducts of these polyisocyanate compounds with polyol compounds such as trimethylolpropane, biuret bodies and isocyanurate bodies of these polyisocyanate compounds, and the like.
Among them, in terms of chemical resistance and reactivity with functional groups, isocyanurate bodies of hexamethylene diisocyanate, 2, 4-tolylene diisocyanate, adducts of 2, 4-tolylene diisocyanate and 2, 6-tolylene diisocyanate with trimethylolpropane, isocyanurate bodies of 2, 4-tolylene diisocyanate and 2, 6-tolylene diisocyanate, and adducts of tetramethylxylylene diisocyanate with trimethylolpropane are preferable.
Examples of the epoxy crosslinking agent include: bisphenol a-epichlorohydrin type epoxy resins, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol triglycidyl ether, 1, 6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl erythritol, diglycerol polyglycidyl ether, 1,3 '-bis (N, N-diglycidylaminomethyl) cyclohexane, N' -tetraglycidyl-m-xylylenediamine, and the like.
Examples of the aziridine-based crosslinking agent include: tetramethylolmethane-tris- β -aziridinylpropionate, trimethylolpropane-tris- β -aziridinylpropionate, N ' -diphenylmethane-4, 4 ' -bis (1-aziridinecarboxamide), N ' -hexamethylene-1, 6-bis (1-aziridinecarboxamide), and the like.
Examples of the oxazoline-based crosslinking agent include: aliphatic or aromatic bisoxazoline compounds such as 2, 2' -bis (2-oxazoline), 1, 2-bis (2-oxazoline-2-yl) ethane, 1, 4-bis (2-oxazoline-2-yl) butane, 1, 8-bis (2-oxazoline-2-yl) butane, 1, 4-bis (2-oxazoline-2-yl) cyclohexane, 1, 2-bis (2-oxazoline-2-yl) benzene and 1, 3-bis (2-oxazoline-2-yl) benzene, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, And 1 or 2 or more kinds of addition polymerizable oxazoline such as 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline.
Examples of the melamine-based crosslinking agent include: hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine, hexapentoxymethylmelamine, hexahexoxymethylmelamine, melamine resins, and the like.
Examples of the aldehyde-based crosslinking agent include: glyoxal, malonaldehyde, succinaldehyde, malealdehyde, glutaraldehyde, formaldehyde, acetaldehyde, benzaldehyde, and the like.
Examples of the amine-based crosslinking agent include: hexamethylenediamine, triethyldiamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethyltetramine, isophoronediamine, amino resins, polyamides, and the like.
The content of the crosslinking agent (D) is usually 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, and more preferably 1 to 15 parts by weight, based on 100 parts by weight of the acrylic resin (A). If the amount of the crosslinking agent (D) is too small, the adhesive tends to have a low cohesive force and to cause adhesive residue, and if it is too large, flexibility and adhesive force tend to be reduced, and therefore, the crosslinking agent (D) tends to float with respect to a member to be processed.
[ other Components ]
The active energy ray-curable release adhesive composition of the present invention may further contain, for example, a small amount of additives such as a polyfunctional monomer, a monofunctional monomer, an antistatic agent, an antioxidant, a plasticizer, a filler, a pigment, a diluent, an antioxidant, an ultraviolet absorber, an ultraviolet stabilizer, and a tackifier resin, within a range not to impair the effects of the present invention. These additives may be used singly in 1 kind or in combination of 2 or more kinds. In particular, the antioxidant is effective for maintaining the stability of the adhesive layer. The content of the antioxidant in the case of blending is not particularly limited, and is preferably 0.01 to 5% by weight. In addition to the additive, a small amount of impurities and the like contained in a raw material for producing a constituent component of the active energy ray-curable release adhesive composition may be contained.
In this manner, the active energy ray-curable release adhesive composition of the present invention can be obtained.
In the present invention, the active energy ray-curable release adhesive composition containing the acrylic resin (a), the urethane (meth) acrylate compound (B), the active energy ray polymerization initiator (C), and the crosslinking agent (D) is crosslinked by the crosslinking agent (D) to exhibit the performance as an adhesive, and then the urethane (meth) acrylate compound (B) is polymerized by irradiation with active energy rays to cure the adhesive, thereby causing a decrease in adhesive strength and exhibiting releasability.
The active energy ray-curable release adhesive composition of the present invention is preferably used as an adhesive for a protective adhesive film for temporarily protecting a surface when a member to be processed such as an electronic substrate, a semiconductor wafer, a glass processed product, a metal plate, or a plastic plate is processed.
The adhesive film will be described below.
The above adhesive film generally has: a substrate sheet, a pressure-sensitive adhesive layer formed from the active energy ray-curable release pressure-sensitive adhesive composition of the present invention, and a release film. As a method for producing the adhesive film, first, the active energy ray-curable release adhesive composition of the present invention is directly applied to a release film or a substrate sheet, or the concentration of the composition is adjusted by using an appropriate organic solvent. Then, the adhesive film is dried by, for example, heat treatment at 80 to 105 ℃ for 0.5 to 10 minutes, and then is bonded to a substrate sheet or a release film to obtain an adhesive film. In addition, in order to obtain a balance of adhesive properties, curing may be further performed after drying.
The viscosity of the active energy ray-curable release adhesive composition at 25 ℃ is preferably 500 to 50000 mPas, particularly preferably 1000 to 25000 mPas. When the viscosity is outside the above range, the coating property tends to be easily lowered. The viscosity can be measured by an E-type viscometer.
Examples of the substrate sheet include: polyester resins such as polyethylene naphthalate, polyethylene terephthalate, polybutylene terephthalate, and polyethylene terephthalate/ethylene isophthalate copolymers; polyolefin resins such as polyethylene, polypropylene and polymethylpentene; polyvinyl fluoride resins such as polyvinyl fluoride, polyvinylidene fluoride, and polyvinyl fluoride; polyamides such as nylon 6 and nylon 6, 6; vinyl polymers such as polyvinyl chloride, polyvinyl chloride/vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, vinylon and the like; cellulose resins such as triacetylcellulose and cellophane; acrylic resins such as polymethyl methacrylate, polyethyl acrylate, and polybutyl acrylate; polystyrene; a polycarbonate; a polyarylate; a sheet made of synthetic resin such as polyimide, a metal foil of aluminum, copper or iron, a fine paper, a paper such as cellophane, a woven fabric or a nonwoven fabric made of glass fiber, natural fiber or synthetic fiber. These substrate sheets may be used in the form of a single body or a laminate in which 2 or more kinds of multilayer bodies are laminated. Among them, a sheet made of synthetic resin is preferable in terms of weight reduction and the like.
Further, as the release film, for example, there can be used: the release film obtained by subjecting various synthetic resin sheets, paper, woven fabric, nonwoven fabric, and the like exemplified as the substrate sheet to release treatment.
The method of applying the active energy ray-curable release adhesive composition is not particularly limited as long as it is a usual application method, and examples thereof include: roll coating, die coating, gravure coating, comma coating, screen printing, and the like.
The thickness of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film is preferably 10 to 200 μm, and more preferably 15 to 100 μm.
As the active energy ray, generally, there can be used: electromagnetic waves such as far ultraviolet rays, near ultraviolet rays, infrared rays, etc., X rays, gamma rays, etc.; and electron beams, proton beams, neutron beams, and the like, and curing by ultraviolet rays is advantageous in terms of curing speed, ease of obtaining an irradiation device, price, and the like.
The cumulative dose of the ultraviolet rays is usually 50 to 3000mJ/cm2Preferably 100 to 1000mJ/cm2. The irradiation time varies depending on the type of the light source, the distance between the light source and the adhesive layer, the thickness of the adhesive layer, and other conditions, and is usually several seconds, and in some cases, may be several fractions of a second.
The adhesive force of the adhesive film varies depending on the type of the substrate sheet, the type of the member to be processed, and the like, and is preferably 0.1 to 30N/25mm, more preferably 0.5 to 20N/25mm before the irradiation with the active energy ray. The adhesive strength after irradiation with active energy rays is preferably 0.01 to 1N/25mm, more preferably 0.05 to 0.5N/25 mm.
According to the active energy ray-curable release adhesive composition of the present invention, for example, an adhesive film using the composition as an adhesive is stuck to a member to be processed to temporarily protect the surface of the member to be processed, and then the adhesive is cured by irradiation with active energy rays as necessary to reduce the adhesive strength, so that the adhesive composition can be easily released from the member to be processed.
Examples
The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples as long as the invention does not depart from the gist thereof. In the following, "%" and "part(s)" are based on weight.
< preparation of acrylic resin (A) solution >
[ acrylic resin (A-1) ]
In a reactor equipped with a temperature controller, a thermometer, a stirrer, a dropping funnel and a reflux condenser, 29 parts of ethyl acetate was charged, and at the stage where the internal temperature was stabilized at 78 ℃ by raising the temperature with stirring, a mixture in which 77.3 parts of n-butyl acrylate (a1), 17.5 parts of methyl methacrylate (a1), 4 parts of 2-hydroxyethyl methacrylate (a2), 0.2 part of acrylic acid (a3) and 0.037 part of Azobisisobutyronitrile (AIBN) were dissolved was added dropwise over 2 hours and reacted under reflux. Then, after 3 hours from the start of the reaction, 7 parts of ethyl acetate and 0.7 part of 2-hydroxyethyl methacrylate (a2) were charged, and after 3.5 hours from the start of the reaction, a liquid in which 1.5 parts of ethyl acetate and 0.025 parts of AIBN were dissolved was added. Further, 5 hours after the start of the reaction, 20 parts of toluene and 0.3 part of 2-hydroxyethyl methacrylate (a2) were charged, and 5.5 hours after the start of the reaction, a liquid in which 4 parts of toluene and 0.05 part of AIBN were dissolved was added. 7.5 hours after the start of the reaction, 87.5 parts of ethyl acetate and 101 parts of toluene were charged to complete the reaction, thereby obtaining an acrylic resin (A-1) solution (having a weight-average molecular weight of 52 ten thousand, a glass transition temperature of-32 ℃, a resin content of 40%, and a viscosity of 9100 mPas (25 ℃).
[ acrylic resin (A-2) ]
An acrylic resin (A-2) solution (having a weight-average molecular weight of 48 ten thousand, a glass transition temperature of-17 ℃, a resin component of 40%, and a viscosity of 12400 mPas (25 ℃) was obtained in the same manner as in the acrylic resin (A-1) except that 64.85 parts of n-butyl acrylate and 30 parts of methyl methacrylate were used as the component (a1), 5 parts of 2-hydroxyethyl methacrylate was used as the component (a2), and 0.15 parts of acrylic acid was used as the component (a3) in the acrylic resin (A-1).
[ acrylic resin (A' -1) ]
An acrylic resin (A' -1) solution (weight average molecular weight: 39 ten thousand, glass transition temperature-35 ℃, resin component: 40%, viscosity: 8100 mPas (25 ℃) was obtained in the same manner as the acrylic resin (A-1) except that 81.9 parts of n-butyl acrylate and 10 parts of methyl methacrylate were used as the component (a1), 0.1 part of 2-hydroxyethyl methacrylate was used as the component (a2), and 8 parts of acrylic acid was used as the component (a3) in the acrylic resin (A-1).
[ acrylic resin (A' -2) ]
A solution of the acrylic resin (A' -2) (weight-average molecular weight: 62 ten thousand, glass transition temperature-34 ℃, resin component: 40%, viscosity: 6600 mPas (25 ℃) was obtained in the same manner as the acrylic resin (A-1), except that 62 parts of n-butyl acrylate and 10 parts of methyl methacrylate were used as the component (a1), 28 parts of 2-hydroxyethyl methacrylate was used as the component (a2), and the component (a3) was not used in the acrylic resin (A-1).
The urethane (meth) acrylate compound (B) was prepared as follows.
< preparation of urethane (meth) acrylate-based Compound (B) >
[ urethane acrylate (B1-1) ]
6.6 parts of isophorone diisocyanate, 93.4 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value: 48mgKOH/g), 0.06 part of 2, 6-di-t-butylcresol as a polymerization inhibitor, and 0.02 part of dibutyltin dilaurate as a reaction catalyst were put into a four-necked flask equipped with a temperature controller, a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port, and reacted at 60 ℃ to complete the reaction when the residual isocyanate group became 0.3% or less, thereby obtaining a urethane acrylate (B1-1) (weight average molecular weight: 2000) mixture. The content of the metal compound in the urethane acrylate (B1-1) was 200 ppm.
Next, each of the following compounding ingredients was prepared.
[ active energy ray polymerization initiator (C-1) ]
IRGACURE 184 (manufactured by BASF corporation)
[ crosslinking agent (D-1) ]
CORONATE L-55E (isocyanate-based crosslinking agent, available from Tosoh corporation)
< example 1 >
[ preparation of adhesive composition ]
100 parts of the acrylic resin (A-1) solution (40 parts of resin component) obtained above, 20 parts of urethane acrylate (B1-1), 1.4 parts of an active energy ray polymerization initiator (C-1), 2 parts of a crosslinking agent (D-1), and 30 parts of toluene as a diluent solvent were mixed to obtain an active energy ray-curable release adhesive composition.
[ production of adhesive film ]
The obtained active energy ray-curable release adhesive composition was applied to an easy-to-bond polyethylene terephthalate film (thickness: 50 μm) (manufactured by Toray corporation, "Lumiror T60") as a base sheet with an applicator, dried at 80 ℃ for 3 minutes, attached to a release film (manufactured by Mitsui Chemicals Tohcello. Inc., "SP-PET 3801-BU"), and cured at 40 ℃ for 3 days to obtain an adhesive film (thickness of adhesive layer: 25 μm).
The following evaluation was performed using the obtained adhesive film.
[ adhesive force: before ultraviolet irradiation)
From the adhesive film obtained in the above, a test piece having a size of 25mm × 100mm was prepared, and after peeling the release film, a rubber roll having a mass of 2kg was reciprocated 2 times in an atmosphere of 23 ℃ and a relative humidity of 50%, and pressure-bonded to a stainless steel plate (SUS304BA plate), and after leaving in the same atmosphere for 30 minutes, the 180-degree peel strength (N/25mm) was measured at a peel speed of 300 mm/minute.
[ adhesive force: after ultraviolet irradiation)
A25 mm × 100mm test piece was prepared from the adhesive film obtained above, after the release film was peeled off, a rubber roll having a mass of 2kg was reciprocated 2 times in an atmosphere of 23 ℃ and a relative humidity of 50%, and pressure-bonded to a stainless steel plate (SUS304BA plate), and after leaving in the same atmosphere for 30 minutes, ultraviolet irradiation was performed at a belt speed of 5.1 m/min from a height of 18cm using a high-pressure mercury lamp of 80W and 1 lamp (cumulative irradiation amount 200 mJ/cm/min)2). Further, after the sheet was left to stand at 23 ℃ under an atmosphere having a relative humidity of 50% for 30 minutes, the peel strength at 180 degrees (N/25mm) was measured at a peel rate of 300 mm/min.
[ corrosiveness of copper plate ]
An adhesive film was adhered to the surface-ground copper plate, and the plate was left at 85 ℃ under an atmosphere of relative temperature and humidity of 85% for 3 days. The discoloration of the copper plate after the test was visually confirmed. The evaluation criteria are as follows.
(evaluation criteria)
O. copper plate has no discoloration at all
Color change or corrosion of copper plate
[ pot life: viscosity change after preparation of adhesive composition ]
An adhesive composition was prepared by mixing 100 parts of an acrylic resin (A-1) solution, 20 parts of a urethane acrylate (B1-1), 1.4 parts of an active energy ray polymerization initiator (C-1), 2 parts of a crosslinking agent (D-1), and 30 parts of toluene as a diluting solvent. Then, the viscosity at 25 ℃ from immediately after the preparation of the adhesive composition to 24 hours later was measured with an E-type viscometer with time. The evaluation criteria are as follows.
(evaluation criteria)
O. · [ viscosity after 24 hours of preparation ]/[ viscosity immediately after preparation ] · below 3 and the compounded liquid was transparent after 24 hours
Δ · · viscosity after 24 hours of preparation ]/[ viscosity just after preparation ] · less than 3, but clouding of the compounded liquid occurred after 24 hours
X. [ viscosity after 24 hours of preparation ]/[ viscosity immediately after preparation ]: 3 or more
< example 2 >
An active energy ray-curable release adhesive composition was obtained in the same manner as in example 1 except that an acrylic resin (a-2) solution was added instead of the acrylic resin (a-1) solution, and the same evaluation as in example 1 was performed.
< example 3 >
An active energy ray-curable release adhesive composition was obtained in the same manner as in example 2 except that 12 parts of the urethane acrylate (B1-1) was used, and the same evaluation as in example 1 was performed.
< comparative example 1 >
An active energy ray-curable release adhesive composition was obtained in the same manner as in example 1 except that an acrylic resin (a' -1) solution was added instead of the acrylic resin (a-1) solution, and the same evaluation as in example 1 was performed.
< comparative example 2 >
An active energy ray-curable release adhesive composition was obtained in the same manner as in example 1 except that an acrylic resin (a' -2) solution was added instead of the acrylic resin (a-1) solution, and the same evaluation as in example 1 was performed.
The evaluation results of the examples and comparative examples are shown in table 1 below. Table 2 below shows changes with time in viscosity after the production of the adhesives of examples and comparative examples.
[ Table 1]
Figure BDA0002359315240000261
[ Table 2]
Figure BDA0002359315240000262
-: cannot measure
The active energy ray-curable release adhesive compositions of examples 1 to 3 had excellent pot life. Further, the adhesive films using the active energy ray-curable release adhesive compositions of examples 1 to 3 were not corrosive to copper plates, and had good adhesive strength before and after ultraviolet irradiation.
In contrast, the active energy ray-curable release adhesive composition of comparative example 1 in which the amount of the carboxyl group-containing monomer in the polymerized component of the acrylic resin (a) is larger than the specific range had a poor pot life. Further, the adhesive film using the active energy ray-curable release adhesive composition of comparative example 1 was corrosive to a copper plate, had high adhesive force before ultraviolet irradiation, and was not suitable for practical use.
In addition, the active energy ray-curable release adhesive composition of comparative example 2, which contained no carboxyl group-containing monomer in the polymerization component of the acrylic resin (a), was cured 3 hours after the preparation, and the pot life was very short.
The above embodiments are merely examples and are not to be construed as limiting the present invention. Various modifications obvious to those skilled in the art are considered to be within the scope of the present invention.
Industrial applicability
The active energy ray-curable release adhesive composition of the present invention can be suitably used as a temporary surface-protecting adhesive film for processing an electronic substrate, a semiconductor wafer, a glass processed product, a metal plate, a plastic plate, or the like.

Claims (8)

1. An active energy ray-curable release adhesive composition comprising an acrylic resin (A), a urethane (meth) acrylate compound (B), an active energy ray polymerization initiator (C) and a crosslinking agent (D), wherein the acrylic resin (A) is obtained by polymerizing a polymerization component comprising an alkyl (meth) acrylate monomer (a1), a hydroxyl group-containing monomer (a2) and a carboxyl group-containing monomer (a3), the content of the hydroxyl group-containing monomer (a2) is 5 to 40 wt%, the content of the carboxyl group-containing monomer (a3) is 0.01 to 0.15 wt% of the polymerization component, and the glass transition temperature of the acrylic resin (A) is-50 to 50 ℃.
2. The active energy ray-curable release adhesive composition according to claim 1, wherein the urethane (meth) acrylate compound (B) contains 1 to 1000ppm by weight of at least one of a metal compound and an amino group-containing compound.
3. The active energy ray-curable release adhesive composition according to claim 1 or 2, wherein the urethane (meth) acrylate compound (B) has an ethylenically unsaturated group, and the number of the ethylenically unsaturated groups is 3 to 20.
4. The active energy ray-curable release adhesive composition according to claim 1 or 2, wherein the urethane (meth) acrylate compound (B) is a reaction product of a hydroxyl group-containing (meth) acrylate compound (B1) having 3 or more ethylenically unsaturated groups in a molecule and a polyisocyanate compound (B2).
5. The active energy ray-curable release adhesive composition according to claim 1 or 2, wherein the weight average molecular weight of the urethane (meth) acrylate compound (B) is 500 to 10000.
6. The active energy ray-curable release adhesive composition according to claim 1 or 2, wherein the acrylic resin (a) has a weight average molecular weight of 10 to 200 ten thousand and a glass transition point temperature of-80 to 50 ℃.
7. The active energy ray-curable release adhesive composition according to claim 1 or 2, wherein the content of the urethane (meth) acrylate compound (B) is 25 to 100 parts by weight with respect to 100 parts by weight of the acrylic resin (a).
8. The active energy ray-curable release adhesive composition according to claim 1 or 2, which is used for an adhesive for a protective adhesive film for temporarily protecting a surface.
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