CN111465670A - Active energy ray-curable release adhesive composition and release adhesive sheet - Google Patents

Active energy ray-curable release adhesive composition and release adhesive sheet Download PDF

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Publication number
CN111465670A
CN111465670A CN201880079190.7A CN201880079190A CN111465670A CN 111465670 A CN111465670 A CN 111465670A CN 201880079190 A CN201880079190 A CN 201880079190A CN 111465670 A CN111465670 A CN 111465670A
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meth
acrylate
compound
ethylenically unsaturated
urethane
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竹田俊之
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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
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—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
    • 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]

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

An active energy ray-curable release adhesive composition having excellent adhesive properties and contamination resistance, which comprises: acrylic resin (A), urethane (meth) acrylate compound (B), and urethane (meth) acrylate other than the aboveAn ethylenically unsaturated compound (C) other than the acid ester compound (B), a photopolymerization initiator (D) and a crosslinking agent (E), wherein the acrylic resin (A) has an SP value of 9.9 (cal/cm) in the solubility parameter3)1/2The urethane (meth) acrylate compound (B) has 2 to 20 ethylenically unsaturated groups, the ethylenically unsaturated compound (C) has 2 to 10 ethylenically unsaturated groups, and the total content of the urethane (meth) acrylate compound (B) and the ethylenically unsaturated compound (C) is 20 to 100 parts by weight based on 100 parts by weight of the acrylic resin (A).

Description

Active energy ray-curable release adhesive composition and release adhesive sheet
Technical Field
The present invention relates to: an active energy ray-curable release adhesive composition and a release adhesive sheet used for an adhesive layer of a release adhesive sheet for temporary surface protection when a member to be processed such as a semiconductor wafer, a printed circuit board, a glass processed product, a metal plate, or a plastic plate is processed.
Background
Conventionally, in a processing step such as fabrication or drilling of an integrated circuit from the semiconductor wafer, an adhesive sheet for surface protection for temporarily protecting a surface of a member to be processed has been used for the purpose of preventing contamination or damage of the member to be processed. In recent years, for the reasons of miniaturization of processing techniques and thinning of a processed member, a suitable adhesive force is required for the processed member, and on the other hand, it is necessary to peel off the adhesive sheet for surface protection after the surface protection function is completed, and it is required to peel off the adhesive sheet with a light force without adhesive residue. In recent years, adhesive sheets for surface protection have been used not only for semiconductor wafers but also for processing various members.
Patent document 1 describes the following adhesive sheet for semiconductor wafer processing: the adhesive exhibits excellent adhesive force to a semiconductor wafer and has stable adhesive properties. In the examples of patent document 1, a resin composition is disclosed as an adhesive layer of an adhesive sheet for processing a semiconductor wafer, the resin composition being mixed with: an acrylic resin obtained by copolymerizing 50 parts by weight of 2-ethylhexyl acrylate, 10 parts by weight of butyl acrylate, 37 parts by weight of vinyl acetate, and 3 parts by weight of 2-hydroxyethyl methacrylate; 2-4 functional urethane acrylate having a molecular weight of 5000 or more; at least 1 or more 3-6 functional acrylate monomers having a molecular weight of 1000 or less.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 10-310748
Disclosure of Invention
Problems to be solved by the invention
The resin composition disclosed in patent document 1 is insufficient in adhesion before ultraviolet irradiation, and further improvement is required. In addition, the resin composition tends to have the following characteristics: further improvement is required because the pressure-sensitive adhesive layer remaining on the workpiece side when the pressure-sensitive adhesive sheet is peeled off contaminates the workpiece.
Means for solving the problems
Accordingly, the present inventors have made intensive studies in view of the above circumstances, and as a result, have found that: an active energy ray-curable release adhesive composition which contains an acrylic resin having a solubility parameter in which the SP value is a specific value or more, a urethane (meth) acrylate compound having a specific number of ethylenically unsaturated groups, an ethylenically unsaturated compound, a photopolymerization initiator, and a crosslinking agent, and in which the total amount of the urethane (meth) acrylate compound and the ethylenically unsaturated compound is in a specific range, is excellent in adhesion characteristics before and after irradiation with an active energy ray, and is excellent in stain resistance to a workpiece member.
That is, the invention of claim 1 is an active energy ray-curable release adhesive composition containing: an acrylic resin (A), a urethane (meth) acrylate compound (B), an ethylenically unsaturated compound (C) other than the urethane (meth) acrylate compound (B), a photopolymerization initiator (D), and a crosslinking agent (E), wherein the SP value in the solubility parameter of the acrylic resin (A) is 9.9 (cal/cm)3)1/2The urethane (meth) acrylate compound (B) is in the range of 2 to20 ethylenically unsaturated groups, wherein the ethylenically unsaturated compound (C) has 2 to 10 ethylenically unsaturated groups, and the total content of the urethane (meth) acrylate compound (B) and the ethylenically unsaturated compound (C) is 20 to 100 parts by weight based on 100 parts by weight of the acrylic resin (A). The release adhesive sheet according to claim 2 includes an adhesive layer obtained by crosslinking the active energy ray-curable release adhesive composition according to claim 1 with a crosslinking agent (E).
ADVANTAGEOUS EFFECTS OF INVENTION
The active energy ray-curable release adhesive composition of the present invention contains: an acrylic resin (A), a urethane (meth) acrylate compound (B), an ethylenically unsaturated compound (C) other than the urethane (meth) acrylate compound (B) (hereinafter simply referred to as "ethylenically unsaturated compound (C)"), a photopolymerization initiator (D), and a crosslinking agent (E), wherein the SP value in the solubility parameter of the acrylic resin (A) is 9.9 (cal/cm)3)1/2The urethane (meth) acrylate compound (B) has 2 to 20 ethylenically unsaturated groups, the ethylenically unsaturated compound (C) has 2 to 10 ethylenically unsaturated groups, and the total content of the urethane (meth) acrylate compound (B) and the ethylenically unsaturated compound (C) is 20 to 100 parts by weight based on 100 parts by weight of the acrylic resin (A). Accordingly, the acrylic resin (a) has excellent compatibility with the urethane (meth) acrylate compound (B) and the ethylenically unsaturated compound (C), and therefore, the respective components are uniformly mixed in the active energy ray-curable release adhesive composition. When a pressure-sensitive adhesive obtained by crosslinking the active energy ray-curable release pressure-sensitive adhesive composition with a crosslinking agent (E) is used as the pressure-sensitive adhesive layer of the release pressure-sensitive adhesive sheet, the following effects are exhibited: the adhesive properties before and after irradiation with active energy rays are excellent, and the stain resistance to a workpiece member is excellent.
In the present invention, particularly, when the glass transition temperature of the acrylic resin (A) is-50 to 20 ℃, the adhesive property when used as an adhesive layer is more excellent, and the stain resistance to a member to be processed is more excellent.
Further, in the present invention, in particular, if the weight content ratio (B: C) of the urethane (meth) acrylate compound (B) to the ethylenically unsaturated compound (C) is 99.9: 0.1-0.1: 99.9, the pressure-sensitive adhesive layer has more excellent pressure-sensitive adhesive properties and is more excellent in stain resistance to a workpiece member.
In the present invention, particularly, if the urethane (meth) acrylate compound (B) is a reaction product of a hydroxyl group-containing (meth) acrylate compound (B1) and a polyisocyanate compound (B2), the adhesive properties after irradiation with active energy rays are more excellent.
In the present invention, particularly, if the crosslinking agent (E) is an isocyanate-based crosslinking agent, the adhesive property when used as an adhesive layer is more excellent, and the stain resistance to a member to be processed is more excellent.
Detailed Description
Hereinafter, embodiments for carrying out the present invention will be specifically described, but the present invention is not limited to these.
In the present invention, "(meth) acrylic acid" means acrylic acid or methacrylic acid, "(meth) acryloyl group" means acryloyl group or methacryloyl group, and "(meth) acrylate" means acrylate or methacrylate, respectively.
The acrylic resin is a resin obtained by polymerizing a polymerization component containing at least 1 type of (meth) acrylate monomer.
In the present invention, "sheet" is described as including "film" and "tape" without any particular distinction.
The active energy ray-curable release adhesive composition of the present invention is generally used as an adhesive layer of a release adhesive sheet that is peeled off after being once stuck to a member to be processed. The release-type pressure-sensitive adhesive sheet is used in a state in which an active energy ray-curable release-type pressure-sensitive adhesive composition is applied to a base sheet, and after the sheet is adhered to a member to be processed, the pressure-sensitive adhesive layer is cured by irradiation with an active energy ray, the adhesive strength is reduced, and the sheet 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 ethylenically unsaturated compound (C), a photopolymerization initiator (D), and a crosslinking agent (E). Hereinafter, each component will be described.
[ acrylic resin (A) ]
In general, an acrylic resin refers to a thermoplastic resin obtained by polymerizing an alkyl ester (meth) acrylate monomer with a monomer copolymerizable therewith.
The acrylic resin (A) used in the present invention is characterized in that the SP value in the solubility parameter is 9.9 (cal/cm)3)1/2The above.
In the present invention, the SP value of the acrylic resin (a) is set to a specific value or more and is close to the SP values of the urethane (meth) acrylate compound (B) and the ethylenically unsaturated compound (C), and therefore, the compatibility between them is excellent. Therefore, the active energy ray-peelable composition is in a state in which the respective components are uniformly mixed, and exhibits an effect of excellent adhesive properties when forming an adhesive layer and excellent contamination resistance to a member to be processed.
The SP value in the solubility parameter of the acrylic resin (A) was 9.9 (cal/cm)3)1/2The above. Preferably 9.95 (cal/cm)3)1/2Above, more preferably 9.99 (cal/cm)3)1/2Above, particularly preferably 10 (cal/cm)3)1/2The above. The upper limit of the SP value is usually 20 (cal/cm)3)1/2Preferably 18 (cal/cm)3)1/2Particularly preferably 15 (cal/cm)3)1/2. If the SP value is too low, the compatibility with the urethane (meth) acrylate compound (B) and the ethylenically unsaturated compound (C) becomes low, and the adhesive properties when forming an adhesive become low. In addition, when the SP value is too lowThe stain resistance to the workpiece member is low, and the effects of the present invention cannot be obtained.
The SP value in the solubility parameter can be determined from the evaporation energy (Δ E) and the molar volume (Δ V) and the molar ratio of the alkyl (meth) acrylate monomer and the copolymerizable monomer constituting the acrylic resin (a), and specifically can be determined from the following formula (1).
SP value (cal/cm)3)1/2＝(ΔE/ΔV)1/2(1)
ΔE＝(x×ΔEx/Mx)+(y×ΔEy/My)+…(n×ΔEn/Mn)×(1/C)
ΔV＝(x×ΔVx/Mx)+(y×ΔVy/My)+…(n×ΔVn/Mn)×(1/C)
C＝(x/Mx)+(y/My)+····(n/Mn)
x: content of monomer X in the copolymerization component (% by weight)
Δ Ex: energy of evaporation of monomer X
Δ Vx: molar volume of monomer X
Mx: molecular weight of monomer X
y: content of monomer Y in the copolymerization component (% by weight)
Δ Ey: evaporation energy of monomer Y
Δ Vy: molar volume of monomer Y
My: molecular weight of monomer Y
n: content of monomer N in the copolymerization component (% by weight)
Δ En: evaporation energy of monomer N
Δ Vn: molar volume of monomer N
Mn: molecular weight of monomer N
C: molar ratio of acrylic resin (A)
The glass transition temperature (Tg) of the acrylic resin (A) used in the present invention is preferably-50 to 20 ℃, more preferably-40 to 10 ℃, still more preferably-30 to 0 ℃, and particularly preferably-20 to 0 ℃. If the glass transition temperature is too high, the adhesive properties tend to be lowered, and if it is too low, the contamination of the workpiece tends to increase.
The glass transition temperature (Tg) is a value calculated by substituting the glass transition temperature and the weight fraction when each monomer constituting the acrylic resin (a) is a homopolymer into the following Fox formula.
The glass transition temperature when the monomer constituting the acrylic resin (A) is formed into a homopolymer is usually measured by a Differential Scanning Calorimeter (DSC), and can be measured by a method in accordance with JIS K7121-.
Figure BDA0002528264870000061
Tg: glass transition temperature (K) of acrylic resin (A)
Tgx: glass transition temperature (K) of a homopolymer of monomer X
Wx: weight fraction of monomer X
Tgy: glass transition temperature (K) of a homopolymer of monomer Y
Wy: weight fraction of monomer Y
Tgn: glass transition temperature (K) of homopolymer of monomer N
Wn: weight fraction of monomer N
(Wx+Wy+…+Wn＝1)
The weight average molecular weight of the acrylic resin (a) is usually 1 to 250 ten thousand, preferably 10 to 200 ten thousand, particularly preferably 15 to 150 ten thousand, and particularly preferably 20 to 120 ten thousand. If the weight average molecular weight is too small, the stain resistance to the workpiece member tends to be low, and if it is too large, the coatability tends to be easily lowered, and the cost tends to be disadvantageous.
Further, the degree of dispersion (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 calculated based on the molecular weight of standard polystyrene, and is determined by high performance liquid chromatography (Japanese Water)"Waters 2695 (Main)" and "Waters 2414 (Detector)" manufactured by s Corp.) Cascade column Shodex GPC KF-806L (exclusion limit molecular weight: 2 × 10)7The separation range is 100-2 × 107Theoretical plate number: 10000 grades/root, filler material: styrene-divinylbenzene copolymer, filler particle diameter: 10 μm) of 3, and the number average molecular weight can be obtained by the same method.
The acrylic resin (a) having the above characteristics can be obtained by adjusting the type and content of the alkyl ester (meth) acrylate monomer and the copolymerizable monomer as the polymerization components so that the SP value becomes a specific value or more, and polymerizing them.
The alkyl ester of (meth) acrylic acid monomer 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 releasability tends to decrease, and the member to be processed tends to be easily contaminated.
Specific examples thereof include aliphatic alkyl (meth) acrylates such as methyl (meth) acrylate (SPa: 10.560, SPma: 9.933), ethyl (meth) acrylate, n-butyl (meth) acrylate (SPa: 9.769, SPma: 9.447), isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-propyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate (SPa: 9.221), 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 kinds may be used in combination. In this specification, Spa in () represents the SP value of acrylate and SPma represents the SP value of methacrylate, respectively, and the unit is (cal/cm)3)1/2。
Among the alkyl ester (meth) acrylate monomers, methyl (meth) acrylate and n-butyl (meth) acrylate are preferably used in terms of copolymerizability, adhesive properties, ease of handling, and ease of raw material availability.
The content of the alkyl acrylate monomer in the polymerization component is preferably 10 to 99% by weight, particularly preferably 20 to 98% by weight, and further preferably 30 to 95% by weight. If the content is too small, the adhesive force before irradiation with active energy rays tends to be reduced, and if it is too large, the adhesive force before irradiation with active energy rays tends to be too high.
Examples of the copolymerizable monomer include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other copolymerizable monomers.
The hydroxyl group-containing monomer is preferably a hydroxyl group-containing acrylate monomer, and specific examples thereof include a primary hydroxyl group-containing monomer such as 2-hydroxyethyl (meth) acrylate (SPa: 13.470), 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, hydroxyalkyl acrylates such as 8-hydroxyoctyl (meth) acrylate, caprolactone-modified monomers such as caprolactone-modified 2-hydroxyethyl (meth) acrylate, alkylene oxide-modified monomers such as diethylene glycol (meth) acrylate and polyethylene glycol (meth) acrylate, and 2-acryloyloxyethyl-2-hydroxyethylphthalate; 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 2 or more kinds may be used in combination.
Among the above-mentioned hydroxyl group-containing monomers, a primary hydroxyl group-containing monomer is preferable in terms of excellent reactivity with the crosslinking agent (E) described later, and 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are particularly preferable.
The content of the hydroxyl group-containing monomer in the polymerizable component is usually 0.1 to 40% by weight, preferably 0.2 to 30% by weight, more preferably 0.5 to 20% by weight. If the content is too large, crosslinking proceeds before the drying step, and a problem tends to occur in coating properties, and if it is too small, the degree of crosslinking tends to decrease, and staining properties to the member to be processed tends to increase.
Examples of the carboxyl group-containing monomer include (meth) acrylic acid (SPa: 14.040), acrylic acid dimer, crotonic acid, maleic anhydride, fumaric acid, citraconic acid, glutaconic acid, itaconic acid, acrylamide-N-glycolic acid, and cinnamic acid. Among them, (meth) acrylic acid is preferably used in terms of copolymerizability. These may be used alone, or 2 or more kinds may be used in combination.
The content of the carboxyl group-containing monomer in the polymerization component is usually 0.01 to 30% by weight, preferably 0.03 to 20% by weight, and more preferably 0.05 to 10% by weight. If the content is too large, the workpiece tends to be easily deteriorated, and if it is too small, the pot life at the time of coating tends to be shortened.
The acrylic resin (a) used in the present invention may suitably contain other copolymerizable monomers as copolymerizable monomers in addition to the above-mentioned hydroxyl group-containing monomer and carboxyl group-containing monomer.
Examples of the other copolymerizable monomers 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, (meth) acrylate monomers containing an aromatic ring 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, (meth) acrylate monomers containing a diphenoxy structure such as diphenoxy ethyl (meth) acrylate, (meth) acrylamide monomers such as ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, (meth) acryloylmorpholine, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, dimethylaminopropylacrylamide, (meth) acrylamide, N-methylol (meth) acrylamide, vinyl chloride-containing monomers such as 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxyethoxyethyl (meth) acrylate, allyl methacrylate, vinyl chloride, vinyl.
The content of the other copolymerizable monomer in the polymerization component is usually 40% by weight or less, preferably 30% by weight or less, and more preferably 25% by weight or less. When the amount of the other copolymerizable monomer is too large, the adhesive properties tend to be deteriorated.
By appropriately selecting the alkyl ester (meth) acrylate monomer and the polymerizable monomer and polymerizing them, the acrylic resin (a) having an SP value of a specific value or more can be obtained. Among these, it is preferable to select each monomer having no radical polymerizable group in the side chain, from the viewpoint of stability in polymerization of the acrylic resin, for the acrylic resin (a).
The polymerization method for obtaining the acrylic resin (a) can be suitably performed by a conventionally known method such as solution radical polymerization, suspension polymerization, bulk polymerization, or emulsion polymerization. Among these, solution radical polymerization is preferable because the acrylic resin (a) can be produced safely and stably with an arbitrary monomer composition.
In the solution radical polymerization, for example, the following procedure may be used: a monomer component such as an alkyl ester (meth) acrylate monomer and a copolymerizable monomer and a polymerization initiator are mixed or dropped in an organic solvent and polymerized in a reflux state or usually at 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, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone.
Specific examples of the polymerization initiator include azo polymerization initiators such as azobisisobutyronitrile and azobisdimethylvaleronitrile, which are common radical polymerization initiators, and peroxide polymerization initiators such as benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide and cumene hydroperoxide.
In this manner, the acrylic resin (a) used in the present invention can be obtained.
[ urethane (meth) acrylate-based 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) which is a reaction product of the hydroxyl group-containing (meth) acrylate compound (B1) and the polyisocyanate compound (B2), or may be a urethane (meth) acrylate compound (B2) which is a reaction product of the hydroxyl group-containing (meth) acrylate compound (B1), the polyisocyanate compound (B2) and the 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-based compound (b1) preferably has 1 hydroxyl group, and examples thereof include hydroxyl group-containing (meth) acrylate-based compounds having 2 ethylenically unsaturated groups such as glycerol di (meth) acrylate and 2-hydroxy-3-acryloyloxypropyl 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. These hydroxyl group-containing (meth) acrylate compounds (b1) may be used alone or in combination of 2 or more.
Among them, the hydroxyl group-containing (meth) acrylate-based compound (b1) having 3 or more ethylenically unsaturated groups is preferable in terms of excellent reactivity and versatility, and pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are particularly preferable.
Examples of the polyisocyanate compound (b2) include aromatic polyisocyanates such as toluene 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 and norbornene diisocyanate, and 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., L td.), and these polyisocyanate compounds (b2) can be used alone or in combination of 2 or more.
Among them, in terms of excellent reactivity and versatility, aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate, and alicyclic diisocyanates such as hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and norbornene diisocyanate are preferable, and 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, and polysiloxane polyols.
Examples of the aliphatic polyol include aliphatic alcohols having 2 hydroxyl groups such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 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., and aliphatic alcohols having 2 hydroxyl groups such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, and the like, Sugar alcohols such as xylitol and sorbitol, and aliphatic alcohols having 3 or more hydroxyl groups such as glycerin, trimethylolpropane and trimethylolethane.
Examples of the alicyclic polyol include 1, 4-cyclohexanediol, cyclohexanediols such as cyclohexyldimethanol, hydrogenated bisphenols such as hydrogenated bisphenol A, and tricyclodecanedimethanol.
Examples of the polyether polyol include polyether polyols having 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.
Examples of the polyester polyol include polycondensates of a polyol and a polycarboxylic acid; ring-opening polymers of cyclic esters (lactones); reaction products of 3 components of polyhydric alcohol, polycarboxylic acid and cyclic ester, and the like.
Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 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 and the like), bisphenols (bisphenol a and the like), sugar alcohols (xylitol, sorbitol and the like), 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, terephthalic acid, and trimellitic acid.
Examples of the cyclic ester include propiolactone, β -methyl-valerolactone, and caprolactone.
These polyhydric alcohols, polycarboxylic acids and cyclic esters may be used in 1 kind individually or in combination of 2 or more kinds.
Examples of the polycarbonate-based polyol include a reaction product of a polyol and phosgene; ring-opening polymers of cyclic carbonates (alkylene carbonates, 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, and hexamethylene carbonate.
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: having a homopolymer or copolymer of ethylene, propylene, butene, or the like as a saturated hydrocarbon skeleton and having a hydroxyl group at a molecular terminal thereof.
Examples of the polybutadiene-based polyol include: 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 have been hydrogenated.
Examples of the polyisoprene polyol include: a copolymer having 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 are hydrogenated.
Examples of the (meth) acrylic polyol include those having at least 2 hydroxyl groups in the molecule of a polymer or copolymer of a (meth) acrylic ester, and examples of the (meth) acrylic ester include 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 polyol and methylphenylpolysiloxane polyol.
The polyol compounds (b3) may be used singly or in combination of 2 or more.
Among them, aliphatic polyols and alicyclic polyols are preferable in terms of cost, and polyester polyols, polyether polyols and polycarbonate polyols are preferable in terms of versatility.
The weight average molecular weight of the polyol compound (b3) is usually 60 to 10000, preferably 100 to 8000, and more preferably 150 to 6000. If the weight average molecular weight of the polyol compound (B3) is too large, the resulting urethane (meth) acrylate compound (B2) and the acrylic resin (a) are not easily mixed uniformly, and a residual adhesive tends to be formed on 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 the urethane (meth) acrylate compound (B1), the hydroxyl group-containing (meth) acrylate compound (B1) and the polyisocyanate compound (B2) are simultaneously or separately charged into a reactor and a urethanization reaction is carried out by a known reaction means, and in the case of the urethane (meth) acrylate compound (B2), the hydroxyl group-containing (meth) acrylate compound (B1), the polyisocyanate compound (B2), and further the polyol compound (B3) are simultaneously or separately charged into a reactor and a urethanization reaction is carried out by a known reaction means.
In addition, in the case of producing the urethane (meth) acrylate compound (B2), a method of reacting a reaction product obtained by reacting the polyol compound (B3) and the polyisocyanate compound (B2) in advance with the hydroxyl group-containing (meth) acrylate compound (B1) is useful in terms of stability of the urethane-forming reaction, reduction in by-products, and the like.
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 reaction of the hydroxyl group-containing (meth) acrylate compound (b1) and the polyvalent isocyanate compound (b2), a reaction catalyst is preferably used for the purpose of promoting the reaction, and examples of the reaction catalyst include organic metal compounds such as dibutyltin dilaurate, trimethyltin hydroxide and tetra-N-butyltin, metal salts such as zinc octenate, tin octenoate, tin octylate, cobalt naphthenate, stannous chloride and tin chloride, metal salts such as triethylamine, benzyldiethylamine, 1, 4-diazabicyclo [2,2,2] octane, 1, 8-diazabicyclo [5,4,0] undecene, N, N, N ', N' -tetramethyl-1, 3-butanediamine and N-ethylmorpholine, amine catalysts such as bismuth nitrate, bismuth bromide, bismuth iodide and bismuth sulfide, examples thereof include bismuth-based catalysts such as organic bismuth compounds such as dibutyl bismuth dilaurate and dioctyl bismuth dilaurate, bismuth salts of 2-ethylhexanate, bismuth naphthenate, bismuth isodecanoate, bismuth neodecanoate, bismuth laurate, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth bisneodecanoate, bismuth disalicylate, and bismuth digallate, zirconium-based catalysts such as inorganic zirconium, organic zirconium, and zirconium simple substance, and 2-zinc ethylhexanate/zirconium tetraacetylacetonate, in which 2 or more kinds of catalysts are used in combination. These catalysts may be used in combination of 1 or 2 or more.
Of these catalysts, dibutyltin dilaurate and 1, 8-diazabicyclo [5,4,0] undecene are suitable.
In the above-mentioned urethanization reaction, there may be used: examples of the organic solvent having no functional group reactive with an isocyanate group include 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) obtained in this way must have 2 to 20 ethylenically unsaturated groups in terms of peelability after irradiation with active energy rays. Preferably 2 to 18, more preferably 4 to 15.
If the number of the ethylenically unsaturated groups is too large, the crosslinking density after irradiation with active energy rays becomes too large, and cracks are likely to occur in the pressure-sensitive adhesive layer, and if the number is too small, a sufficient crosslinking density cannot be obtained, and therefore, peeling after irradiation with active energy rays is unlikely to occur.
The urethane (meth) acrylate compound (B) has a weight average molecular weight of usually 500 to 10000, preferably 750 to 8000, and more preferably 1000 to 6000. If the weight average molecular weight is too high, the orientation is as follows: the urethane (meth) acrylate compound (B) has a high viscosity, and the compatibility with the acrylic resin (a) is lowered, so that a residue (residual glue) tends to be generated in the part of the pressure-sensitive adhesive layer of the workpiece member. 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 cause adhesive residue.
The weight average molecular weight is determined by converting the weight average molecular weight based on the molecular weight of standard polystyrene, and using, in series, 4 columns of ACQUITY APC XT450 × 1, ACQUITY APC XT 200 × 1 and ACQUITY APC XT45 × 2 on a high performance liquid chromatograph (manufactured by Waters, Inc. 'ACQUITY APC system').
The solubility parameter of the urethane (meth) acrylate compound (B) is usually 9 to 15 (cal/cm) in terms of SP value3)1/2Preferably 9.5 to 13 (cal/cm)3)1/2Particularly preferably 10 to 12 (cal/cm)3)1/2. When the SP value is not within the above range, the compatibility with the acrylic resin (a) and the ethylenically unsaturated compound (C) tends to be lowered, and the adhesive properties in forming the adhesive layer tend to be lowered. The SP value of the urethane (meth) acrylate compound (B) can be determined by Fedors-based calculation from the molecular structure.
The absolute value (| (a) - (B) |) of the difference between the SP values of the acrylic resin (a) and the urethane (meth) acrylate compound (B) is usually 3 or less, preferably 2 or less, more preferably 1 or less, and particularly preferably 0.8 or less. When the absolute value of the difference in SP values is not within the above range, the compatibility with the acrylic resin (a) tends to be lowered, and the adhesive properties in forming the adhesive layer tend to be lowered.
The viscosity of the urethane (meth) acrylate compound (B) used in the present invention at 60 ℃ is preferably 500 to 100000 mPas, and particularly preferably 1000 to 50000 mPas. When the viscosity is outside the above range, the coatability tends to be lowered. The viscosity can be measured by an E-type viscometer.
In the present invention, the content of the urethane (meth) acrylate compound (B) is usually 5 to 100 parts by weight, preferably 10 to 80 parts by weight, and particularly preferably 20 to 60 parts by weight, based on 100 parts by weight of the acrylic resin (a). When the content of the urethane (meth) acrylate compound (B) is too small, the adhesive layer tends to be less likely to peel off after irradiation with active energy rays, and when the content of the urethane (meth) acrylate compound (B) is too large, the adhesive layer tends to be cracked easily after irradiation with active energy rays.
[ ethylenically unsaturated Compound (C) ]
The ethylenically unsaturated compound (C) used in the present invention is preferably a (meth) acrylate-based compound, and any compound having an ethylenically unsaturated group can be used without particular limitation. The ethylenically unsaturated compound (C) used in the present invention does not include the urethane (meth) acrylate compound (B).
The ethylenically unsaturated compound (C) must have 2 to 10 ethylenically unsaturated groups in order to have excellent peeling characteristics after irradiation with active energy rays. Preferably 3 to 9, particularly preferably 4 to 8. If the number of the ethylenically unsaturated groups is too large, the crosslinking density after irradiation with active energy rays becomes too large, and cracks are likely to occur in the pressure-sensitive adhesive layer, and if the number is too small, a sufficient crosslinking density cannot be obtained, and therefore, peeling after irradiation with active energy rays is unlikely to occur.
The above ethylenically unsaturated compound (C) has an SP value of usually 8 to 12 (cal/cm) in the solubility parameter3)1/2Preferably 9 to 11.5 (cal/cm)3)1/2Particularly preferably 9.5 to 11 (cal/cm)3)1/2. When the SP value is not within the above range, the compatibility with the acrylic resin (a) and the urethane (meth) acrylate compound (B) tends to be lowered, and the adhesive properties when forming an adhesive tend to be lowered. The above-mentioned olefinic unsaturationThe SP value of the compound (C) and the SP value of the compound (C) can be determined by Fedors-based method calculation according to the molecular structure.
The absolute value (| (a) to |) of the difference in SP values between the acrylic resin (a) and the ethylenically unsaturated compound (C) is usually 3 or less, preferably 1 or less, more preferably 0.7 or less, and particularly preferably 0.5 or less. When the absolute value of the difference in SP values is not within the above range, the compatibility with the acrylic resin (a) tends to be lowered, and the adhesive properties in forming the adhesive layer tend to be lowered.
Examples of the ethylenically unsaturated compound (C) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide-modified bisphenol A type di (meth) acrylate, propylene oxide-modified bisphenol A type di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, ethoxylated cyclohexanedimethanol di (meth) acrylate, dimethyloldicyclopentane di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, and 1, compounds having 2 ethylenically unsaturated groups such as 6-hexanediol di (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, hydroxypivalic acid-modified neopentyl glycol di (meth) acrylate, and ethylene oxide isocyanurate-modified diacrylate; compounds having 3 ethylenically unsaturated groups such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (meth) acryloyloxyethoxyethoxytrimethylolpropane, isocyanuric acid ethylene oxide-modified triacrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, ethylene oxide-modified pentaerythritol tri (meth) acrylate, and ethoxylated glycerol triacrylate; and compounds having 4 or more ethylenically unsaturated groups such as pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol polyglycidyl ether poly (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, ethylene oxide-modified dipentaerythritol penta (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, and ethylene oxide-modified pentaerythritol tetra (meth) acrylate.
Further, as the ethylenically unsaturated compound (C), a michael adduct of (meth) acrylic acid or a 2- (meth) acryloyloxyethyl dicarboxylic acid monoester may be used in combination, and as the michael adduct of (meth) acrylic acid, there may be mentioned a (meth) acrylic acid dimer, a (meth) acrylic acid trimer, a (meth) acrylic acid tetramer, and the like.
The 2- (meth) acryloyloxyethyl dicarboxylic acid monoester is a carboxylic acid having a specific substituent, and examples thereof include 2- (meth) acryloyloxyethyl succinic acid monoester, 2- (meth) acryloyloxyethyl phthalic acid monoester, and 2- (meth) acryloyloxyethyl hexahydrophthalic acid monoester. Further, oligoester acrylates may be mentioned.
The above ethylenically unsaturated compounds (C) may be used singly or in combination of 2 or more.
Among these, from the viewpoint of excellent adhesive properties after irradiation with active energy rays, ethylenically unsaturated compounds having no hydroxyl group are preferable, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, and ethylene oxide-modified pentaerythritol tetra (meth) acrylate are more preferable, and pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate are particularly preferable.
In the present invention, it is preferable that the skeleton of the compound obtained by removing (meth) acrylic acid from the ethylenically unsaturated compound (C) is the same as the skeleton of the compound obtained by removing (meth) acrylic acid from the hydroxyl group-containing (meth) acrylate compound (B1) of the urethane (meth) acrylate compound (B) in terms of excellent compatibility and adhesive properties.
The content of the ethylenically unsaturated compound (C) is usually 5 to 100 parts by weight, preferably 10 to 80 parts by weight, and particularly preferably 20 to 60 parts by weight, based on 100 parts by weight of the acrylic resin (A). If the content of the ethylenically unsaturated compound (C) is too small, the material tends to be less likely to peel off after irradiation with active energy rays, and if it is too large, the material tends to have reduced stain resistance to the member to be processed after peeling off.
In the present invention, from the viewpoint of excellent adhesion before irradiation with active energy rays and excellent peelability after irradiation, it is important that: the total content of the urethane (meth) acrylate compound (B) and the ethylenically unsaturated compound (C) is 20 to 100 parts by weight based on 100 parts by weight of the acrylic resin (A). Preferably 25 to 90 parts by weight, particularly preferably 30 to 80 parts by weight. When the total content is too small, the adhesive force is not easily reduced even when the active energy ray is irradiated, and when the total content is too large, the stain resistance to the workpiece member after the active energy ray irradiation is low.
The weight content ratio of the urethane (meth) acrylate compound (B) to the ethylenically unsaturated compound (C) [ (B): (C) preferably 99.9: 0.1-0.1: 99.9, more preferably 99: 1-1: 99. further preferably 90: 10-10: 90. particularly preferably 80: 20-20: 80. if the weight content ratio of the urethane (meth) acrylate compound (B) to the ethylenically unsaturated compound (C) is not within the above range, the adhesive properties when forming the adhesive layer tend to decrease.
[ photopolymerization initiator (D) ]
The photopolymerization initiator (D) used in the present invention may be any one that generates a radical 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) ketone, 1-hydroxycyclohexylphenylketone, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-2-morpholinyl (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butanone, and, Acetophenones such as 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone oligomer; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenones such as benzophenone, o-benzoylbenzoic acid methyl group, 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 ] benzylbromide amine, and (4-benzoylbenzyl) trimethylammonium chloride; thioxanthones such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and 2- (3-dimethylamino-2-hydroxy) -3, 4-dimethyl-9H-thioxanthone-9-one methylchloride; 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. Among them, acetophenones are preferable, and 1-hydroxycyclohexyl phenyl ketone is particularly preferable. These photopolymerization initiators (D) may be used alone or in combination of 2 or more.
Further, as the auxiliary agent of the photopolymerization initiator (D), 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 photopolymerization initiator (D) 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 total of the acrylic resin (a), the urethane (meth) acrylate compound (B), and the ethylenically unsaturated compound (C). If the content of the photopolymerization initiator (D) is too small, the peelability after the irradiation with the active energy ray tends to be easily reduced, and if it is too large, the stain resistance to the workpiece member after the irradiation with the active energy ray tends to be low.
[ crosslinking agent (E) ]
Examples of the crosslinking agent (E) include isocyanate crosslinking agents, epoxy crosslinking agents, aziridine crosslinking agents, oxazoline crosslinking agents, melamine crosslinking agents, aldehyde crosslinking agents, and amine crosslinking agents. Among these, an isocyanate-based crosslinking agent is preferably used in terms of improving adhesiveness between the release-type pressure-sensitive adhesive sheet and the base sheet and reactivity with the acrylic resin (a).
These crosslinking agents (E) may be used alone or in combination of 2 or more.
Examples of the isocyanate-based crosslinking agent include 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, hydrogenated xylene diisocyanate, hexamethylene diisocyanate, diphenylmethane-4, 4-diisocyanate, isophorone diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, tetramethylxylene diisocyanate, 1, 5-naphthalene diisocyanate, triphenylmethane triisocyanate, adducts of these polyisocyanate compounds with polyol compounds such as trimethylolpropane, biuret and isocyanurate 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, 6-tolylene diisocyanate and trimethylolpropane, isocyanurate bodies of 2, 4-tolylene diisocyanate and 2, 6-tolylene diisocyanate, and adducts of tetramethylxylene diisocyanate and 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, and, And 1 or 2 or more kinds of addition polymerizable oxazoline such as 2-vinyl-5-methyl-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, and benzaldehyde.
Examples of the amine-based crosslinking agent include hexamethylenediamine, triethyldiamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethyltetramine, isophoronediamine, amine resins, and polyamides.
The content of the crosslinking agent (E) is usually preferably 0.1 to 30 parts by weight, particularly preferably 0.2 to 20 parts by weight, and further preferably 0.3 to 15 parts by weight, based on 100 parts by weight of the total of the acrylic resin (a), the urethane (meth) acrylate compound (B), and the ethylenically unsaturated compound (C). If the amount of the crosslinking agent (E) is too small, the adhesive tends to have a low cohesive force and to cause adhesive residue, and if the amount of the crosslinking agent (E) is too large, flexibility and adhesive force tend to be low and floating between the member to be processed tends to occur.
[ other ingredients ]
The active energy ray-curable release adhesive composition of the present invention may further contain, within a range not to impair the effects of the present invention: for example, small amounts of additives such as monofunctional monomers, antistatic agents, antioxidants, plasticizers, fillers, pigments, diluents, antioxidants, ultraviolet absorbers, and ultraviolet stabilizers can be used, and these additives may be used alone in 1 kind or in combination with 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 with respect to the active energy ray-curable release adhesive composition.
The active energy ray-curable release adhesive composition of the present invention may contain, in addition to the above-described additives, 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.
The active energy ray-curable release adhesive composition of the present invention preferably does not contain a tackifier resin such as a terpene resin, a rosin resin, a chroman resin, a phenol resin, a styrene resin, or a petroleum resin, from the viewpoint of reducing contamination resistance to a workpiece member after irradiation with an active energy ray.
In this manner, the active energy ray-curable release adhesive composition of the present invention can be obtained by mixing the acrylic resin (a), the urethane (meth) acrylate compound (B), the ethylenically unsaturated compound (C), the photopolymerization initiator (D), the crosslinking agent (E), and other components as necessary.
The active energy ray-curable release adhesive composition of the present invention can be suitably used as an adhesive layer of a release adhesive sheet by crosslinking with the crosslinking agent (E). After the release-type pressure-sensitive adhesive sheet is attached to a member to be processed, the urethane (meth) acrylate compound (B) and the ethylenically unsaturated compound (C) are polymerized by irradiation with active energy rays to cure the pressure-sensitive adhesive layer, which causes a decrease in adhesive strength and exhibits releasability. By utilizing this characteristic, when various members to be processed are processed, the surface of the members to be processed can be temporarily protected.
Hereinafter, a description will be given of a peelable pressure-sensitive adhesive sheet.
Examples of the member to be processed protected by the release adhesive sheet include a semiconductor wafer, a printed circuit board, a glass processed product, a metal plate, and a plastic plate.
The release-type pressure-sensitive adhesive sheet 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 above-mentioned release adhesive sheet, first, the active energy ray-curable release adhesive composition of the present invention is directly subjected to concentration adjustment, or subjected to concentration adjustment with an appropriate organic solvent, and then applied directly onto a release film or a substrate sheet. Thereafter, the release sheet can be obtained by drying the sheet by, for example, heat treatment at 80 to 105 ℃ for 0.5 to 10 minutes, and then adhering the sheet to a substrate sheet or a release film. In addition, in order to obtain a balance of adhesive properties, curing may be further performed after drying.
Examples of the substrate sheet include polyester resins selected from 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 (pvdf), polyvinylidene fluoride (pvdf), and polytetrafluoroethylene (polytetrafluoroethylene); polyamides such as nylon 6 and nylon 6, 6; polyvinyl chloride, polyvinyl chloride/vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, vinylon and other ethylene polymers; cellulose resins such as cellulose triacetate and cellophane; acrylic resins such as polymethyl methacrylate, polyethyl acrylate, and polybutyl acrylate; polystyrene; a polycarbonate; a polyarylate; a sheet made of at least one synthetic resin selected from the group consisting of polyimide and the like; metal foils of aluminum, copper, iron, and the like; paper such as coated paper and cellophane paper; woven fabrics and nonwoven fabrics made of glass fibers, natural fibers, synthetic fibers, and the like. These substrate sheets may be used as a single layer or as a multilayer in which 2 or more kinds are stacked. Among these, sheets made of synthetic resins are preferable in terms of weight reduction and the like.
Further, as the release film, for example, those obtained by subjecting various synthetic resin sheets, paper, woven fabric, nonwoven fabric, and the like exemplified as the base sheet to release treatment can be used.
The method for applying the active energy ray-curable release adhesive composition is not particularly limited as long as it is a general 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 in the above-mentioned release type pressure-sensitive adhesive sheet is preferably 1 to 200 μm, and more preferably 10 to 100 μm.
As the active energy ray, in general, in addition to light such as far ultraviolet rays, near ultraviolet rays, and infrared rays, electromagnetic waves such as X rays and γ rays, electron beams, proton beams, neutron beams, and the like can be used, but in view of curing speed, easiness of obtaining an irradiation apparatus, cost, and the like, it is advantageous to use ultraviolet rays.
The cumulative dose of the ultraviolet rays is usually 50 to 3000mJ/cm2Preferably 100 to 1000mJ/cm2. In additionThe irradiation time varies depending on the type of the light source, the distance between the light source and the pressure-sensitive adhesive layer, the thickness of the pressure-sensitive adhesive layer, and other conditions, and is usually several seconds, or in some cases, may be an extremely short time of less than 1 second.
The adhesive strength of the peelable adhesive sheet varies depending on the type of the substrate sheet, the type of the member to be processed, and the like, and is preferably 1 to 30N/25mm, more preferably 1 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.
The adhesive force after the irradiation with the active energy ray is preferably 1/5 or less, more preferably 1/50 or less, of the adhesive force before the irradiation with the active energy ray.
The release adhesive sheet using the active energy ray-curable release adhesive composition of the present invention as an adhesive layer is adhered to a workpiece to temporarily protect the surface of the workpiece, and then irradiated with active energy rays to cure the adhesive layer and reduce the adhesive strength, so that the release adhesive sheet can be easily released from the workpiece.
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded. In the following, "%" and "part(s)" are based on weight.
The active energy ray-curable release adhesive compositions of examples and comparative examples contain the following components.
The composition of the acrylic resin is shown in table 1 described below.
N-butyl acrylate
[ SP value: 9.769 (cal/cm)3)1/2Molecular weight: 128.2)
2-ethylhexyl acrylate
[ SP value: 9.221 (cal/cm)3)1/2Molecular weight: 184.3)
Acrylic acid methyl ester
[ SP value: 10.560 (cal/cm)3)1/2Molecular weight: 86.1)
Methyl methacrylate
[ SP value: 9.933 (cal/cm)3)1/2Molecular weight: 100.1)
2-hydroxyethyl acrylate
[ SP value: 14.480 (cal/cm)3)1/2Molecular weight: 116.1)
2-hydroxyethyl methacrylate
[ SP value: 13.470 (cal/cm)3)1/2Molecular weight: 144.2)
Acrylic acid
[ SP value: 14.040 (cal/cm)3)1/2Molecular weight: 72.1)
< acrylic resin >
[ 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 a stage where the internal temperature was stable at 78 ℃ while stirring and temperature was raised, a mixture in which 91.9 parts of n-butyl acrylate, 0.1 part of 2-hydroxyethyl methacrylate, 8 parts of acrylic acid and 0.037 part of Azobisisobutyronitrile (AIBN) were dissolved was added dropwise and mixed over 2 hours, and the mixture was reacted under reflux. Then, 3.5 hours after the start of the reaction (after reflux), a liquid in which 1.5 parts of ethyl acetate and 0.025 parts of AIBN were dissolved was added. Further, 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, 57.5 parts of ethyl acetate and 100 parts of toluene were charged to complete the reaction, thereby obtaining an acrylic resin (A-1) [ SP value: 10.057 (cal/cm)3)1/2Weight average molecular weight: 80 ten thousand, glass transition temperature (Tg): -48.2 ℃, resin composition: 35.0%, viscosity: 8000 mPas (25 ℃).
[ acrylic resin (A-2) ]
A solution-like acrylic resin (a-2) [ SP value: 11.065 (cal/cm)3)1/2Weight average molecular weight: 70 ten thousand, glass transition temperature: -45.1 ℃, resin composition: 35.0%, viscosity: 6000 mPas (25 ℃ C.) ].
[ acrylic resin (A-3) ]
A solution-like acrylic resin (a-3) was obtained in the same manner except that the polymerization components of the acrylic resin (a-1) were changed to 69 parts of n-butyl acrylate, 30 parts of methyl acrylate, and 1 part of 2-hydroxyethyl acrylate (SP value: 10.033 (cal/cm)3)1/2Weight average molecular weight: 60 ten thousand, glass transition temperature: -39.6 ℃, resin composition: 35.0%, viscosity: 5000 mPas (25 ℃ C.).
[ acrylic resin (A-4) ]
A solution-like acrylic resin (a-4) was obtained in the same manner as in the case of the acrylic resin (a-1) except that the polymerization components were changed to 59 parts of n-butyl acrylate, 40 parts of methyl acrylate, and 1 part of 2-hydroxyethyl acrylate (SP value: 10.110 (cal/cm)3)1/2Weight average molecular weight: 70 ten thousand, glass transition temperature: -33.6 ℃, resin composition: 35.0%, viscosity: 6000 mPas (25 ℃ C.) ].
[ acrylic resin (A-5) ]
A solution-like acrylic resin (a-5) was obtained in the same manner except that the polymerization components in the acrylic resin (a-1) were changed to 70 parts of n-butyl acrylate, 20 parts of methyl methacrylate, 0.1 part of 2-hydroxyethyl methacrylate, and 9.9 parts of acrylic acid (SP value: 10.163 (cal/cm)3)1/2Weight average molecular weight: 50 ten thousand, glass transition temperature: -24.2 ℃, resin composition: 35.0%, viscosity: 8000 mPas (25 ℃).
[ acrylic resin (A-6) ]
A solution-like acrylic resin (a-6) was obtained in the same manner except that the polymerization components in the acrylic resin (a-1) were changed to 69.8 parts of n-butyl acrylate, 25 parts of methyl methacrylate, 0.2 part of 2-hydroxyethyl methacrylate, and 5 parts of acrylic acid (SP value: 9.995 (cal/cm)3)1/2Weight average molecular weight: 45 ten thousand, glass transition temperature: -24.0 ℃, resin composition: 35.0Percent, viscosity: 6000 mPas (25 ℃ C.) ].
[ acrylic resin (A-7) ]
A solution-like acrylic resin (a-7) was obtained in the same manner as in the case of the acrylic resin (a-1) except that the polymerization components were changed to 39 parts of n-butyl acrylate, 60 parts of methyl acrylate, and 1 part of 2-hydroxyethyl acrylate (SP value: 10.270 (cal/cm)3)1/2Weight average molecular weight: 70 ten thousand, glass transition temperature: -21.0 ℃, resin composition: 35.0%, viscosity: 10000 mPas (25 ℃).
[ acrylic resin (A-8) ]
A solution-like acrylic resin (a-8) was obtained in the same manner as in the case of the acrylic resin (a-1) except that the polymerization components were changed to 64.85 parts of n-butyl acrylate, 30 parts of methyl methacrylate, 5 parts of 2-hydroxyethyl methacrylate and 0.15 part of acrylic acid (SP value: 9.996 (cal/cm)3)1/2Weight average molecular weight: 45 ten thousand, glass transition temperature: -19.1 ℃, resin composition: 35.0%, viscosity: 6000 mPas (25 ℃ C.) ].
[ acrylic resin (A' -1) ]
A solution-like acrylic resin (a' -1) was obtained in the same manner except that the polymerization component of the acrylic resin (a-1) was changed to 92.8 parts of 2-ethylhexyl acrylate, 7 parts of 2-hydroxyethyl acrylate, and 0.2 part of acrylic acid (SP value: 9.550 (cal/cm)3)1/2Weight average molecular weight: 100 ten thousand, glass transition temperature: -66.7 ℃, resin composition: 35.0%, viscosity: 4000 mPas (25 ℃ C.).
[ acrylic resin (A' -2) ]
A solution-like acrylic resin (a' -2) was obtained in the same manner as in the acrylic resin (a-1) except that the polymerization components were changed to 91.9 parts of 2-ethylhexyl acrylate, 0.1 part of 2-hydroxyethyl methacrylate, and 8 parts of acrylic acid (SP value: 9.530 (cal/cm)3)1/2Weight average molecular weight: 60 ten thousand, glass transition temperature: -62.1 ℃, resin composition: 35.0%, viscosity: 2000 mPas (25 ℃ C.).
[ acrylic resin (A' -3) ]
A solution-like acrylic resin (a' -3) [ SP value: 9.770 (cal/cm)3)1/2Weight average molecular weight: 95 ten thousand, glass transition temperature: -59.6 ℃, resin composition: 35.0%, viscosity: 3000 mPas (25 ℃ C.) ].
[ acrylic resin (A' -4) ]
A solution-like acrylic resin (a' -4) [ SP value: 9.787 (cal/cm)3)1/2Weight average molecular weight: 55 ten thousand, glass transition temperature: -55.4 ℃, resin composition: 35.0%, viscosity: 1500 mPas (25 ℃ C.).
[ Table 1]
Figure BDA0002528264870000291
< urethane (meth) acrylate-based Compound and ethylenically unsaturated Compound >
[ composition of urethane acrylate (B-1) and dipentaerythritol hexaacrylate (C-1) ]
8.7 parts of isophorone diisocyanate, 91.3 parts of an acrylic acid adduct of dipentaerythritol (hydroxyl value: 48mgKOH/g), 0.06 part of 2, 6-di-t-butylcresol as a polymerization inhibitor, and 0.01 part of dibutyltin dilaurate as a reaction catalyst were put into a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen-blowing port, and reacted at 60 ℃ to complete the reaction when the residual isocyanate group became 0.3% or less, thereby obtaining composition I (weight average molecular weight 2300). The composition I comprises 45 parts of urethane acrylate (B-1) and 55 parts of dipentaerythritol hexaacrylate (C-1).
[ urethane acrylate (B-1) ]
IsophoroneReaction product of diisocyanate and dipentaerythritol pentaacrylate [ ethylenically unsaturated group: 10, SP value: 10.64 (cal/cm)3)1/2〕
[ ethylenically unsaturated Compound (C-1) ]
Dipentaerythritol hexaacrylate [ ethylenically unsaturated group: 6, SP value: 10.40 (cal/cm)3)1/2〕
[ composition of urethane acrylate (B-2) and pentaerythritol tetraacrylate (C-2) ]
19.2 parts of isophorone diisocyanate and 80.8 parts of an acrylic acid adduct of pentaerythritol (hydroxyl value: 120mgKOH/g) were put into a flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen-blowing port, 0.06 part of 2, 6-di-t-butylcresol as a polymerization inhibitor and 0.01 part of dibutyltin dilaurate as a reaction catalyst were put into the flask, and a reaction was carried out at 60 ℃ to complete the reaction when the residual isocyanate group became 0.3% or less, thereby obtaining a composition II (weight average molecular weight: 1600). The composition II comprises 65 parts of urethane acrylate (B-2) and 35 parts of pentaerythritol tetraacrylate (C-2).
[ urethane acrylate (B-2) ]
Reaction product of isophorone diisocyanate with pentaerythritol triacrylate [ ethylenically unsaturated groups: 6, SP value: 10.73 (cal/cm)3)1/2〕
[ ethylenically unsaturated Compound (C-2) ]
Pentaerythritol tetraacrylate [ ethylenically unsaturated group: 4, SP value: 10.34 (cal/cm)3)1/2〕
[ composition of urethane acrylate (B-3) and dipentaerythritol hexaacrylate (C-1) ]
16.3 parts of isophorone diisocyanate, 83.7 parts of an acrylic acid adduct of dipentaerythritol (hydroxyl value: 98mgKOH/g), 0.06 part of 2, 6-di-t-butylcresol as a polymerization inhibitor, and 0.01 part of dibutyltin dilaurate as a reaction catalyst were put into a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen-blowing port, and reacted at 60 ℃ to complete the reaction when the residual isocyanate group became 0.3% or less, thereby obtaining composition III (weight-average molecular weight 5300). The composition III contained 37.5 parts of urethane acrylate (B-3) and 12.5 parts of dipentaerythritol hexaacrylate (C-1).
[ urethane acrylate (B-3) ]
Reaction product of isophorone diisocyanate with dipentaerythritol pentaacrylate [ ethylenically unsaturated group: 10, SP value: 10.64 (cal/cm)3)1/2〕
[ ethylenically unsaturated Compound (C-1) ]
Dipentaerythritol hexaacrylate [ ethylenically unsaturated group: 6, SP value: 10.40 (cal/cm)3)1/2〕
< photopolymerization initiator >
[ photopolymerization initiator (D-1) ]
Omnirad 184 (manufactured by IGM RESIN Co., Ltd.)
< crosslinking agent >
[ crosslinking agent (E-1) ]
CORONATE L-55E (isocyanate crosslinking agent, manufactured by Tosoh corporation)
< example 1>
[ preparation of active energy ray-curable Release adhesive composition ]
286 parts of the acrylic resin (A-1) (resin component 35%), 50 parts of the composition I [ 22.5 parts of urethane acrylate (B-1), 27.5 parts of ethylenically unsaturated compound (C-1) ], 2.1 parts of photopolymerization initiator (D-1), 9.7 parts of crosslinking agent (E-1) (5.4 parts in terms of active ingredient), and 30 parts of toluene as a diluting solvent were mixed to obtain an active energy ray-curable release adhesive composition.
[ production of peelable pressure-sensitive adhesive sheet ]
The obtained active energy ray-curable release adhesive composition was applied to an easy-to-bond polyethylene terephthalate film (film thickness 50 μm) (manufactured by Toray corporation, L umiror T60 ") as a base sheet using an applicator, dried at 100 ℃ for 3 minutes, and attached to a release film (manufactured by Mitsui Chemicals Tohcello. Inc.;" SP-PET 3801-BU ") and cured at 40 ℃ for 3 days to obtain a release adhesive sheet (adhesive layer thickness 25 μm).
Using the obtained release-type pressure-sensitive adhesive sheet, the following evaluations were carried out.
[ adhesive force: before Ultraviolet (UV) irradiation)
From the thus obtained releasable adhesive sheet, a test piece having a size of 25mm × 100mm was prepared, and after peeling the release film, a rubber roller having a mass of 2kg was reciprocated 2 times and pressed and stuck on a stainless steel plate (SUS304BA plate) in an atmosphere of 23 ℃ and a relative humidity of 50%, and after leaving to stand in the same atmosphere for 30 minutes, 180-degree peel strength (N/25mm) was measured at a peel speed of 300 mm/minute.
(evaluation criteria)
◎ … 10N/25mm or more
○ … 5N/25mm or more and less than 10N/25mm
△ … 1N/25mm or more and less than 5N/25mm
× … less than 1N/25mm, or residual gum
[ adhesive force: after Ultraviolet (UV) irradiation)
A test piece 25mm × 100mm in size was prepared from the above-obtained releasable adhesive sheet, and after peeling the release film, a rubber roller 2kg in mass was pressed and stuck to a stainless steel plate (SUS304BA plate) in an atmosphere of 23 ℃ and 50% relative humidity for 2 times in a reciprocating manner, and after leaving the sheet in the same atmosphere for 30 minutes, the sheet was irradiated with ultraviolet rays (cumulative irradiation dose 200 mJ/cm/min) from a height of 18cm at a conveyor speed of 5.1 m/min using a high-pressure mercury lamp of 80W and a lamp 12). Further, after the sheet was left to stand at 23 ℃ under an atmosphere of 50% relative humidity for 30 minutes, the 180-degree peel strength (N/25mm) was measured at a peel speed of 300 mm/minute.
(evaluation criteria)
◎ … below 0.2N/25mm
○ … 0.2N/25mm or more and less than 0.5N/25mm
△ … 0.5 above 0.5N/25mm and below 1N/25mm
× … 1N/25mm or generating adhesive residue
[ contamination resistance: before Ultraviolet (UV) irradiation)
The obtained release adhesive sheet was stuck to the surface of a 4-inch square stainless steel plate (SUS304BA plate) to which no foreign matter had adhered, and after standing still for 1 hour at 23 ℃ in an atmosphere of 65% relative humidity, the release adhesive sheet was released from the surface of the stainless steel plate, and the stainless steel plate after release was evaluated visually as follows.
(evaluation criteria)
○ … no adhesive residue
△ … slight residual glue
× … with residual glue
[ contamination resistance: after Ultraviolet (UV) irradiation)
The above-obtained peelable adhesive sheet was stuck to the surface of a 4-inch square stainless steel plate (SUS304BA plate) to which no foreign matter had adhered, and left to stand at 23 ℃ under an atmosphere of 65% relative humidity for 1 hour, and then irradiated with ultraviolet rays (cumulative dose of irradiation: 200 mJ/cm/cumulative dose) at a conveyor speed of 5.1 m/min from a height of 18cm using a high-pressure mercury lamp of 80W and a lamp 12). After that, the peelable adhesive sheet was peeled from the surface of the stainless steel plate, and the peeled stainless steel plate was evaluated visually as follows.
(evaluation criteria)
○ … no adhesive residue
△ … slight residual glue
× … with residual glue
[ haze value ]
The diffusive light transmittance and the total light transmittance of the release-type pressure-sensitive adhesive sheet from which the release film was peeled were measured by using a HAZE matrix NDH2000 (manufactured by japan electro-color industries, ltd.), and the obtained values of the diffusive light transmittance and the total light transmittance were substituted into the following formulas to obtain a HAZE value. The higher the haze value, the more uneven the respective components in the active energy ray-curable release adhesive composition. In addition, the haze value is a value including the substrate sheet.
Haze value (%) - (diffuse transmittance/total transmittance) × 100
(evaluation criteria)
◎ … is less than 1%
○ … 1% or more and less than 2%
△ … 2% or more and less than 3%
× … 3% or more
< examples 2 to 14 and comparative examples 1 to 9 >)
An active energy ray-curable release adhesive composition was obtained in the same manner as in example 1 except that the components were blended as shown in tables 2 and 3 below. The active energy ray-curable release adhesive compositions of examples 2 to 14 and comparative examples 1 to 9 thus obtained were evaluated in the same manner as in example 1. The evaluation results of examples 2 to 14 and comparative examples 1 to 9 are shown in table 4 below together with the evaluation result of example 1.
[ Table 2]
Figure BDA0002528264870000351
[ Table 3]
Figure BDA0002528264870000361
[ Table 4]
Figure BDA0002528264870000371
As shown in table 4, it can be seen that: the active energy ray-curable release adhesive compositions of examples 1 to 14, which contained the acrylic resin (a) having an SP value of a specific value or more among solubility parameters, the urethane (meth) acrylate compound (B) and the ethylenically unsaturated compound (C) having a specific number of ethylenically unsaturated groups, the photopolymerization initiator (D), the crosslinking agent (E), and the total content of the urethane (meth) acrylate compound (B) and the ethylenically unsaturated compound (C) in a specific range, exhibited low haze values when formed into the adhesive layer of the release adhesive sheet, and therefore, the components were in a uniform state in the active energy ray-curable release adhesive composition. Further, the release adhesive sheets using the active energy ray-curable release adhesive compositions of examples 1 to 14 were excellent in adhesive properties before and after irradiation with active energy rays, and further excellent in contamination resistance to a workpiece member.
On the other hand, the active energy ray-curable release adhesive compositions of comparative examples 1 to 4 using acrylic resins having SP values of solubility parameters lower than a specific value had high haze values, and therefore, the respective components were not in a uniform state, and the release adhesive sheets using the compositions had poor adhesive properties and poor contamination resistance to the members to be processed.
Further, the release adhesive sheets using the active energy ray-curable release adhesive compositions of comparative examples 5 to 9 in which the total content of the urethane (meth) acrylate compound (B) and the ethylenically unsaturated compound (C) was not within a specific range were poor in adhesive properties and stain resistance to the member to be processed.
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 intended 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 for a temporary surface-protecting adhesive film for processing a semiconductor wafer, a printed circuit board, a glass processed product, a metal plate, a plastic plate, or the like.

Claims (6)

1. An active energy ray-curable release adhesive composition characterized by containing: an acrylic resin (A), a urethane (meth) acrylate compound (B), an ethylenically unsaturated compound (C) other than the urethane (meth) acrylate compound (B), a photopolymerization initiator (D), and a crosslinking agent (E), wherein the SP value in the solubility parameter of the acrylic resin (A) is 9.9 (cal/cm)3)1/2The urethane (meth) acrylate compound (B) has 2 to 20 ethylenically unsaturated groups, and the ethylenically unsaturated compound (C) has 2 to 10 ethylenically unsaturated groupsAnd the total content of the urethane (meth) acrylate compound (B) and the ethylenically unsaturated compound (C) is 20 to 100 parts by weight based on 100 parts by weight of the acrylic resin (A).
2. The active energy ray-curable release adhesive composition according to claim 1, wherein the glass transition temperature of the acrylic resin (A) is-50 to 20 ℃.
3. The active energy ray-curable release adhesive composition according to claim 1 or 2, wherein the weight content ratio (B: C) of the urethane (meth) acrylate compound (B) to the ethylenically unsaturated compound (C) is 99.9: 0.1-0.1: 99.9.
4. the active energy ray-curable release adhesive composition according to any one of claims 1 to 3, wherein the urethane (meth) acrylate compound (B) is a reaction product of a hydroxyl group-containing (meth) acrylate compound (B1) and a polyvalent isocyanate compound (B2).
5. The active energy ray-curable release adhesive composition according to any one of claims 1 to 4, wherein the crosslinking agent (E) is an isocyanate-based crosslinking agent.
6. A releasable adhesive sheet comprising an adhesive layer obtained by crosslinking the active energy ray-curable releasable adhesive composition according to any one of claims 1 to 5 with a crosslinking agent (E).
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