TWI817964B - Active energy ray curable peel-off adhesive composition and peel-off adhesive sheet - Google Patents

Abstract

In terms of an active energy ray-curable peel-off adhesive composition having excellent adhesive properties and contamination resistance, the present invention provides an active energy ray-curable peel-off adhesive composition containing an acrylic resin (A), amine methyl Acid ester (meth)acrylate compound (B), ethylenically unsaturated compound (C) other than the above-mentioned urethane (meth)acrylate compound (B), photopolymerizable initiator (D) and a cross-linking agent (E), the SP value in the solubility parameter of the above-mentioned acrylic resin (A) is 9.9 (cal/cm ³ ) ^1/2 or more, and the above-mentioned urethane (meth)acrylate compound (B) ) has 2 to 20 ethylenically unsaturated groups, the above-mentioned ethylenically unsaturated compound (C) has 2 to 10 ethylenically unsaturated groups, and the above-mentioned urethane acid is The total content of the ester (meth)acrylate compound (B) and the ethylenically unsaturated compound (C) is 20 to 100 parts by weight.

Description

Active energy ray curable peel-off adhesive composition and peel-off adhesive sheet

The present invention relates to active energy rays used in the adhesive layer of peel-off adhesive sheets used temporarily to protect the surface of processed components such as semiconductor wafers, printed circuit boards, glass products, metal plates, plastic plates, etc. Hardening peelable adhesive composition and peelable adhesive sheet.

In the past, in order to prevent contamination or damage to the processed components during processing steps such as manufacturing integrated circuits or drilling holes from the above-mentioned semiconductor wafers, surface protection adhesives were used to temporarily protect the surfaces of the above-mentioned processed components. piece. However, in recent years, due to the miniaturization of processing technology or the thinning of processed components, it is required to have appropriate adhesion to the processed components. On the other hand, after the surface protection function is completed, it is necessary to peel off the surface protective film. The adhesive sheet requires light force to be peeled off without leaving any adhesive residue when peeling off. In addition, in recent years, adhesive sheets for surface protection are also used in the processing of not only semiconductor wafers but also various components.

Patent Document 1 describes an adhesive sheet for semiconductor wafer processing that exhibits excellent adhesive force to semiconductor wafers and has stable adhesive properties. However, the example of Patent Document 1 discloses a resin composition containing 50 parts by weight of 2-ethylhexyl acrylate and 10 parts by weight of butyl acrylate as an adhesive layer of an adhesive sheet for semiconductor wafer processing. , vinyl acetate 37 parts by weight, 2-hydroxyethyl methacrylate 3 Weight parts of copolymerized acrylic resin, 2 to 4 functional urethane acrylates with a molecular weight of 5,000 or more, and at least one or more 3 to 6 functional acrylate monomers with a molecular weight of 1,000 or less. Mixed.

[Prior technical literature]

[Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 10-310748

The adhesive force of the resin composition disclosed in the above-mentioned Patent Document 1 before ultraviolet irradiation is unsatisfactory, and there is a need for further improvement. In addition, with regard to the above-mentioned resin composition, when the adhesive sheet is peeled off, there is a tendency that the adhesive layer remains on the side of the processed member, causing the processed member to be contaminated, and there is a need for further improvement.

As a result of conducting a series of studies in view of these circumstances, the inventor of this case discovered an active energy ray-curable peel-off adhesive composition containing an acrylic resin whose SP value in the solubility parameter is a specific value or more, and has a specific number of A urethane (meth)acrylate compound with an ethylenically unsaturated group, an ethylenically unsaturated compound, a photopolymerizable initiator, a cross-linking agent, and the above urethane (meth)acrylate compound The total blending amount of ethylenically unsaturated compounds and ethylenically unsaturated compounds is within a specific range. The active energy ray curable peel-off adhesive composition has excellent adhesive properties before and after active energy ray irradiation. In addition, it has excellent resistance to the processed components. Excellent pollution resistance.

That is, the first gist of the present invention is an active energy ray curable peel-off adhesive composition containing an acrylic resin (A), a urethane (meth)acrylate compound (B), and the above-mentioned urethane resin. Ethylenically unsaturated compounds (C) other than the acid ester (meth)acrylate compound (B), photopolymerizable initiator (D) and cross-linking agent (E), solubility of the above-mentioned acrylic resin (A) The SP value in the parameters is 9.9 (cal/cm ³ ) ^{1/2 or} more. The above-mentioned urethane (meth)acrylate compound (B) has 2 to 20 ethylenically unsaturated groups, and the above-mentioned ethylenically unsaturated groups The saturated compound (C) has 2 to 10 ethylenically unsaturated groups, and the above-mentioned urethane (meth)acrylate compound (B) and the ethylenically unsaturated group are The total content of unsaturated compounds (C) is 20 to 100 parts by weight. Furthermore, a second gist of the present invention is a peelable adhesive sheet having an adhesive layer in which the active energy ray-curable peelable adhesive composition of the first gist is crosslinked by a crosslinking agent (E).

The active energy ray curable peel-off adhesive composition of the present invention contains an acrylic resin (A), a urethane (meth)acrylate compound (B), and the above-mentioned urethane (meth)acrylate. It is an ethylenically unsaturated compound (C) other than compound (B) [hereinafter referred to as "ethylenically unsaturated compound (C)"], a photopolymerizable initiator (D) and a cross-linking agent (E), and the above-mentioned acrylic acid The SP value in the solubility parameter of the resin (A) is 9.9 (cal/cm ³ ) ^1/2 or more, and the above-mentioned urethane (meth)acrylate compound (B) has 2 to 20 ethylenically unsaturated group, the above-mentioned ethylenically unsaturated compound (C) has 2 to 10 ethylenically unsaturated groups, and relative to 100 parts by weight of the above-mentioned acrylic resin (A), the above-mentioned urethane (meth)acrylate compound ( The total content of B) and the ethylenically unsaturated compound (C) is 20 to 100 parts by weight. Therefore, the acrylic resin (A) has excellent compatibility with the urethane (meth)acrylate compound (B) and the ethylenically unsaturated compound (C) and becomes an active energy ray-curable peel-off type. The state in which the ingredients in the adhesive composition are evenly mixed. However, when the adhesive obtained by cross-linking the active energy ray-curable peel-off adhesive composition with the cross-linking agent (E) is used as the adhesive layer of the peel-off adhesive sheet, it can exert an active energy ray-curable peel-off adhesive composition. It has excellent adhesion properties before and after irradiation. In addition, it has an excellent effect on the contamination resistance of the processed components.

In addition, in the present invention, in particular, if the glass transition temperature of the acrylic resin (A) is -50 to 20°C, the adhesive properties when used as an adhesive layer will be more excellent. In addition, the acrylic resin (A) will have better adhesion properties to the processed member. Those with better contamination resistance.

In addition, in the present invention, in particular, if the weight content ratio (B:C) of the above-mentioned urethane (meth)acrylate compound (B) and the ethylenically unsaturated compound (C) is 99.9:0.1~0.1 : 99.9, it has better adhesion properties when used as an adhesive layer. In addition, it has better contamination resistance to the processed components.

In the present invention, in particular, if the above-mentioned urethane (meth)acrylate compound (B) is a combination of a hydroxyl-containing (meth)acrylate compound (b1) and a polyvalent isocyanate compound (b2) The reaction product becomes one with better adhesive properties after irradiation with active energy rays.

In addition, in the present invention, especially if the cross-linking agent (E) is an isocyanate-based cross-linking agent, the adhesive properties when used as an adhesive layer are more excellent, and the contamination resistance of the processed member is better. Excellent ones.

Hereinafter, the embodiments for implementing the present invention will be described in detail, but the present invention is not limited to And so on.

In the present invention, "(meth)acrylic acid" means acrylic acid or methacrylic acid, "(meth)acrylyl" means acrylic acid or methacrylic acid, and "(meth)acrylate" means Acrylate or methacrylate.

In addition, the acrylic resin refers to a resin obtained by polymerizing a polymerization component containing at least one kind of (meth)acrylic acid ester monomer.

In addition, in the present invention, "sheet" is not particularly distinguished from "film" or "strip" and includes these meanings.

The active energy ray-curable peelable adhesive composition of the present invention is usually used as the adhesive layer of a peelable adhesive sheet based on the premise that it is first bonded to the member to be processed and then peeled off. The above-mentioned peel-off adhesive sheet is used in a state where an active energy ray-curable peel-off adhesive composition is coated on a base sheet. After being bonded to the workpiece, the adhesive layer is hardened and adhered by irradiating active energy rays. The force is reduced and can be easily peeled off from the processed component.

The active energy ray curable peel-off adhesive composition of the present invention contains an acrylic resin (A), a urethane (meth)acrylate compound (B), an ethylenically unsaturated compound (C), and a photopolymerizable Sexual initiator (D) and cross-linking agent (E). Each component is explained below.

[Acrylic resin (A)]

Generally, an acrylic resin is a thermoplastic resin obtained by polymerizing a (meth)acrylic acid alkyl ester monomer and a copolymerizable monomer.

The characteristic of the acrylic resin (A) used in the present invention is that the SP value in the solubility parameter is 9.9 (cal/cm ³ ) ^1/2 or more.

In the present invention, the SP value of the acrylic resin (A) is equal to or higher than a specific value and is close to the SP value of the urethane (meth)acrylate compound (B) and the ethylenically unsaturated compound (C). Become those with excellent compatibility with each other. Therefore, the components in the active energy ray exfoliating composition are in a state of being uniformly mixed, and the active energy ray exfoliating composition exhibits excellent adhesion properties when used as an adhesive layer and excellent contamination resistance for the member to be processed.

The SP value among the solubility parameters of the acrylic resin (A) is 9.9 (cal/cm ³ ) ^1/2 or more. It is preferably 9.95 (cal/cm ³ ) ^1/2 or more, more preferably 9.99 (cal/cm ³ ) ^{1/2 or} more, especially 10 (cal/cm ³ ) ^1/2 or more. In addition, the upper limit of the above-mentioned SP value is usually 20 (cal/cm ³ ) ^1/2 , preferably 18 (cal/cm ³ ) ^1/2 , and particularly preferably 15 (cal/cm ³ ) ^1/2 . When 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 made into an adhesive are reduced. In addition, when the SP value is too low, the contamination resistance of the processed member becomes low, and the effects of the present invention cannot be obtained.

The SP value in the above solubility parameter can be determined by the evaporation energy (△E) and molar volume (△V) of the (meth)acrylic acid alkyl ester monomer and copolymerizable monomer constituting the acrylic resin (A) and It can be obtained in Molbiform. Specifically, it can be obtained by the following formula (1).

[Number 1] SP value (cal/cm ³ ) ^1/2 = (△E/△V) ^1/2 (1)

△E=(x×△Ex/Mx)+(y×△Ey/My)+‧‧‧(n×△En/Mn)×(1/C)

△V=(x×△Vx/Mx)+(y×△Vy/My)+‧‧‧(n×△Vn/Mn)×(1/C)

C=(x/Mx)+(y/My)+‧‧‧‧(n/Mn)

x: Content of monomer X relative to copolymerized components (weight %)

△Ex: Evaporation energy of monomer X

△Vx: molar volume of monomer X

Mx: molecular weight of monomer X

y: Content of monomer Y relative to copolymerized components (weight %)

△Ey: evaporation energy of monomer Y

△Vy: Molar volume of monomer Y

My: molecular weight of monomer Y

n: Content of monomer N relative to copolymerized components (weight %)

△En: evaporation energy of monomer N

△Vn: molar volume of monomer N

Mn: molecular weight of monomer N

C: Mol ratio of acrylic resin (A)

The glass transition temperature (Tg) of the acrylic resin (A) used in the present invention is preferably -50~20°C, more preferably -40~10°C, further preferably -30~0°C, especially -20~ 0℃. If the glass transition temperature is too high, the adhesive properties tend to decrease, and if it is too low, the contamination of the processed member tends to increase.

In addition, the above-mentioned glass transition temperature (Tg) is a value calculated by substituting the glass transition temperature and weight fraction of each monomer constituting the acrylic resin (A) into a homopolymer into the following Fox's formula.

Here, the glass transition temperature when the monomer constituting the acrylic resin (A) is converted into a homopolymer is usually measured by a differential scanning calorimeter (DSC). It can be determined by following JIS K 7121-1987 Or measure according to the method of JIS K 6240.

Tg: Glass transition temperature (K) of acrylic resin (A)

Tgx: Glass transition temperature of homopolymer of monomer X (K)

Wx: weight fraction of monomer X

Tgy: Glass transition temperature (K) of homopolymer of monomer Y

Wy: weight fraction of monomer Y

Tgn: glass transition temperature of homopolymer of monomer N (K)

Wn: weight fraction of monomer N

(Wx+Wy+‧‧‧+Wn=1)

The weight average molecular weight of the acrylic resin (A) is usually 10,000 to 2,500,000, preferably 100,000 to 2,000,000, further preferably 150,000 to 1,500,000, and particularly preferably 200,000 to 1,200,000. If the weight average molecular weight is too small, the contamination resistance to the member to be processed will tend to be low, and if it is too large, the coating properties will tend to decrease, or it will tend to be disadvantageous in terms of cost.

In addition, the dispersion degree (weight average molecular weight/number average molecular weight) of the acrylic resin (A) is preferably 20 or less, more preferably 10 or less, further preferably 7 or less, especially 5 or less. If the dispersion is too high, the contamination of the member to be processed will tend to increase. In addition, the lower limit of the dispersion degree takes into account the manufacturing limit and is usually 1.1.

The above-mentioned weight average molecular weight is the weight average molecular weight converted from the standard polystyrene molecular weight, using a high performance liquid chromatograph (manufactured by Japan Waters Co., Ltd., "Waters 2695 (main body)" and "Waters 2414 (detector)"). ), using three columns in series: Shodex GPC KF-806L (exclusion limit molecular weight: 2×10 ⁷ , separation range: 100~2×10 ⁷ , number of theoretical plates: 10,000 plates/column, filler material: styrene - Divinylbenzene copolymer, filler particle size: 10 μm), the number average molecular weight can also be obtained by the same method.

The acrylic resin (A) having the above characteristics can be obtained by adjusting the types of (meth)acrylic acid alkyl ester monomers and copolymerizable monomers that are polymerization components so that the SP value becomes a specific value or more. Or content and polymerization to obtain.

Regarding the above-mentioned (meth)acrylic acid alkyl ester monomer, the carbon number of the alkyl group is usually 1 to 20, preferably 1 to 12, more preferably 1 to 8, especially 4 to 8. 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 include 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, hard (meth)acrylate Aliphatic (meth)acrylic alkyl esters such as fatty esters and isostearyl (meth)acrylate; alicyclic (meth)acrylic acid esters such as cyclohexyl (meth)acrylate and isocamphenyl (meth)acrylate ) acrylate, etc. These may be used individually or 2 or more types may be used together. In addition, in this specification, SPa in ( ) represents the SP value of acrylate, and SPma represents the SP value of methacrylate, and the unit is (cal/cm ³ ) ^1/2 .

Among the above-mentioned alkyl (meth)acrylate monomers, methyl (meth)acrylate and normal (meth)acrylate are preferably used from the viewpoints of copolymerizability, adhesive properties, ease of handling, and ease of acquisition of raw materials. butyl ester.

The content of the above-mentioned alkyl acrylate monomer in the polymerization component is usually 10 to 99% by weight, more preferably 20 to 98% by weight, and further preferably 30 to 95% by weight. If the content is too small, the adhesive force before active energy ray irradiation tends to decrease. If it is too large, the adhesive force before active energy ray irradiation tends to become too high.

Examples of the copolymerizable monomer include hydroxyl group-containing monomers, carboxyl group-containing monomers, other copolymerizable monomers, and the like.

The above-mentioned hydroxyl-containing monomer is preferably a hydroxyl-containing acrylate monomer. Specific examples thereof include 2-hydroxyethyl (meth)acrylate (SPa: 13.470) and 4-(meth)acrylate. Hydroxybutyl acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate and other hydroxyalkyl acrylates, caprolactone modified Caprolactone-modified monomers such as 2-hydroxyethyl (meth)acrylate, oxyalkylene-modified monomers such as diethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate, etc. monomers containing primary hydroxyl groups such as 2-propenyloxyethyl-2-hydroxyethylphthalic acid; (meth)acrylic acid-2-hydroxypropyl, (meth)acrylic acid-2-hydroxybutyl , (meth)acrylic acid-3-chloro-2-hydroxypropyl and other monomers containing 2-level hydroxyl groups; (meth)acrylic acid-2,2-dimethyl-2-hydroxyethyl and other monomers containing 3-level hydroxyl groups Monomer etc. These may be used individually or 2 or more types may be used together.

Among the above-mentioned hydroxyl group-containing monomers, from the viewpoint of excellent reactivity with the cross-linking agent (E) described below, a primary hydroxyl group-containing monomer is preferred, and (meth)acrylic acid-2-hydroxyethyl is particularly preferred. , (meth)acrylic acid-4-hydroxybutyl ester.

The content of the above-mentioned hydroxyl-containing monomer in the polymerization component is usually 0.1~40% by weight, preferably 0.2~30% by weight, and more preferably 0.5~20% by weight. If the content is too high, cross-linking will occur before the drying step, which may easily cause problems with coatability. If it is too low, the degree of cross-linking will decrease and contamination of the member to be processed will tend to increase.

Examples of the carboxyl group-containing monomer include (meth)acrylic acid (SPa: 14.040), acrylic acid dimer, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, and pentene. Diacid, itaconic acid, acrylamide-N-glycolic acid, cinnamic acid, etc. Among them, (meth)acrylic acid is preferably used from the viewpoint of copolymerizability. These may be used individually or 2 or more types may be used together.

The content of the above-mentioned carboxyl group-containing monomer in the polymerization component is usually 0.01~30% by weight, preferably 0.03~20% by weight, and more preferably 0.05~10% by weight. If the content is too high, the material to be processed will tend to deteriorate easily, while if it is too low, the pot life during coating will tend to be shortened.

The acrylic resin (A) used in the present invention may appropriately contain other copolymerizable monomers in addition to the above-mentioned hydroxyl group-containing monomer and carboxyl group-containing monomer as polymerizable monomers.

啉、二甲基(甲基)丙烯醯胺、二乙基(甲基)丙烯醯胺、二甲基胺基丙基丙烯醯胺、(甲基)丙烯醯胺-N-羥甲基(甲基)丙烯醯胺等(甲基)丙烯醯胺系單體；(甲基)丙烯酸-2-甲氧基乙酯、(甲基)丙烯酸-2-乙氧基乙酯、甲氧基二乙二醇(甲基)丙烯酸酯、乙氧基二乙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、聚丙二醇單(甲基)丙烯 酸酯等含有烷氧基或氧伸烷基之單體；丙烯腈、甲基丙烯腈、氯乙烯、氯化亞乙烯、烷基乙烯醚、乙烯基甲苯、乙烯基吡啶、乙烯基吡咯啶酮、伊康酸二烷基酯、富馬酸二烷基酯、烯丙醇、丙烯醯氯、甲基乙烯酮、烯丙基三甲基氯化銨、二甲基烯丙基乙烯基酮等。此等可單獨使用也可併用2種以上。 Examples of the above-mentioned other copolymerizable monomers include acetyl acetyl group-containing monomers such as 2-(acetyl acetyloxy)ethyl (meth)acrylate and allyl acetyl acetate; (Meth)glycidyl acrylate, (meth)allylglycidyl acrylate and other glycidyl-containing monomers; vinyl acetate, vinyl propionate, vinyl stearate, vinyl benzoate Ester and other carboxylic acid vinyl ester monomers; phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenyl diethylene glycol (meth)acrylate, (meth)acrylate Monomers containing aromatic rings such as 2-hydroxy-3-phenoxypropyl methacrylate, styrene, α-methylstyrene; biphenyloxyethyl (meth)acrylate, etc. containing biphenyl (meth)acrylate monomers with base oxygen structure; ethoxymethyl (meth)acrylamide, n-butoxymethyl (meth)acrylamide, (meth)acrylamide

Phinoline, dimethyl(meth)acrylamide, diethyl(meth)acrylamide, dimethylaminopropylacrylamide, (meth)acrylamide-N-hydroxymethyl(meth)acrylamide (meth)acrylamide-based monomers such as acrylamide; 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, methoxydiethyl Glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, polypropylene glycol mono(meth)acrylate, etc. contain alkoxylates Monomers with alkyl or oxyalkylene groups; acrylonitrile, methacrylonitrile, vinyl chloride, vinylene chloride, alkyl vinyl ether, vinyl toluene, vinyl pyridine, vinyl pyrrolidone, itaconic acid diane ester, dialkyl fumarate, allyl alcohol, acrylic acid chloride, methyl ketene, allyltrimethylammonium chloride, dimethylallyl vinyl ketone, etc. These may be used individually or in combination of 2 or more types.

The content of the above-mentioned other copolymerizable monomers 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. If there are too many other copolymerizable monomers, the adhesive properties tend to be easily reduced.

By appropriately selecting and polymerizing the alkyl (meth)acrylate monomer and polymerizable monomer, an acrylic resin (A) having an SP value equal to or higher than a specific value can be obtained. However, in the acrylic resin (A), from the viewpoint of stability during polymerization of the acrylic resin, it is preferable to select each monomer so that the side chain does not contain a radically polymerizable group.

The polymerization method for obtaining the above-mentioned acrylic resin (A) can usually be appropriately performed by conventional methods such as solution radical polymerization, suspension polymerization, block polymerization, and emulsion polymerization. Among them, solution radical polymerization is preferable because the acrylic resin (A) can be produced safely and stably with any monomer composition.

The above-mentioned solution free radical polymerization, for example, (meth)acrylic acid alkyl ester monomers, copolymerizable monomers and other monomer components and polymerization initiators are mixed or added dropwise to an organic solvent, in a reflux state or usually 50~98℃, polymerization takes about 0.1~20 hours.

Examples of the organic solvent used in the above polymerization reaction include aromatic solvents such as toluene and xylene. Hydrocarbons, aliphatic hydrocarbons such as hexane, esters such as ethyl acetate and butyl acetate, aliphatic alcohols such as n-propanol and isopropanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketones etc.

Examples of the polymerization initiator include azo-based polymerization initiators such as azobisisobutyronitrile and azobisdimethylvaleronitrile, which are common radical polymerization initiators, and benzyl peroxide. Specific examples include peroxide polymerization initiators such as lauryl peroxide, di-tert-butyl peroxide, and cumene hydroperoxide.

In this way, the acrylic resin (A) used in the present invention can be obtained.

[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)acrylyl group.

The above-mentioned urethane (meth)acrylate compound (B) may be a urethane (B) which is a reaction product of a hydroxyl-containing (meth)acrylate compound (b1) and a polyisocyanate compound (b2). The meth)acrylate compound (B1) may also be an amine that is a reaction product of a hydroxyl-containing (meth)acrylate compound (b1), a polyisocyanate compound (b2), and a polyol compound (b3). Formate (meth)acrylate compound (B2). Among them, in the present invention, the urethane (meth)acrylate compound (B1) is preferably used from the viewpoint of releasability after irradiation with active energy rays.

In addition, only one type of the urethane (meth)acrylate compound (B) in the present invention may be used, or two or more types may be used in combination.

The hydroxyl-containing (meth)acrylate compound (b1) is preferably one having one hydroxyl group, and examples thereof include glycerol di(meth)acrylate, 2-hydroxy-3-acrylyl- Oxypropyl methacrylate, etc. contain 2 Ethylenically unsaturated hydroxyl-containing (meth)acrylate compounds; neopentylerythritol tri(meth)acrylate, caprolactone-modified neopenterythritol tri(meth)acrylate, ethylene oxide Alkane modified neopenterythritol tri(meth)acrylate, dineopenterythritol penta(meth)acrylate, caprolactone modified dipenterythritol penta(meth)acrylate, ethylene oxide Modified dipenterythritol penta(meth)acrylate and other hydroxyl-containing (meth)acrylate compounds containing more than three ethylenically unsaturated groups. These hydroxyl-containing (meth)acrylate compounds (b1) can be used alone or in combination of two or more kinds.

Among these, from the viewpoint of excellent reactivity and versatility, the hydroxyl-containing (meth)acrylate compound (b1) containing three or more ethylenically unsaturated groups is preferred, and neopentyl tetracycline is particularly preferred. Alcohol tri(meth)acrylate, dipenterythritol penta(meth)acrylate.

Examples of the polyvalent isocyanate compound (b2) include toluene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, and diisocyanate diisocyanate. Aromatic polyisocyanates such as xylene, tetramethylxylylene diisocyanate, phenylene diisocyanate, naphthylene diisocyanate; hexamethylene diisocyanate, diisocyanate Aliphatic polyisocyanates such as trimethylhexamethylene, lysine diisocyanate, and lysine triisocyanate; hydrogenated diphenylmethane diisocyanate, hydrogenated diphenylene diisocyanate, and isophorone diisocyanate , alicyclic polyisocyanates such as norbornene diisocyanate; or trimer compounds or polymer compounds of these polyisocyanates, allophanate type polyisocyanates, biuret type polyisocyanates , water-dispersed polyisocyanates (such as "AQUANATE 100", "AQUANATE: 110", "AQUANATE 200", "AQUANATE 210" manufactured by Nippon Polyurethane Industry Co., Ltd.), etc. These polyvalent isocyanate compounds (b2) can be used alone or in combination of two or more types.

Among these, from the viewpoint of excellent reactivity and versatility, hexamethylene diisocyanate and diisocyanate are preferred. Aliphatic diisocyanates such as trimethylhexamethylene cyanate and lysate diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated diphenylene diisocyanate, isophorone diisocyanate, norbornene Alicyclic diisocyanates such as diisocyanate are particularly preferably isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated diphenylene diisocyanate, and hexamethylene diisocyanate, and further preferably Isophorone diisocyanate, hexamethylene diisocyanate.

The polyol compound (b3) may be a compound containing two 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, etc.

Examples of the aliphatic polyol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, dimethylolpropane, neopentyl glycol, and 2,2-diethyl glycol. -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, neopentylerythritol diacrylate, 1,9-nonanediol, 2-methyl-1,8-octanediol, etc. contain 2 hydroxyl groups Aliphatic alcohols, sugar alcohols such as xylitol or sorbitol, aliphatic alcohols containing more than three hydroxyl groups such as glycerin, trimethylolpropane, trimethylolethane, etc.

Examples of the alicyclic polyol include cyclohexanediols such as 1,4-cyclohexanediol and cyclohexanedimethanol, hydrogenated bisphenols such as hydrogenated bisphenol A, and tricyclodecanediol. Methanol etc.

Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, polypentamethylene glycol, polyhexamethylene glycol, and the like. There are many polyether systems containing alkylene structures. Alcohols, or random or block copolymers of these polyalkylene glycols, etc.

Examples of the polyester polyol include condensation polymers of polyols and polycarboxylic acids; ring-opened polymers of cyclic esters (lactones); polymers derived from polyols, polycarboxylic acids, and cyclic esters. Reaction products of 3 ingredients, etc.

Examples of the polyol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene glycol, and 1,3-tetramethylene glycol. Alcohol, 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 or sorbitol, etc.), etc.

Examples of the polycarboxylic acid include malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid. Aliphatic dicarboxylic acids such as acid; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, Aromatic dicarboxylic acids such as terephthalic acid and trimellitic acid.

Examples of the cyclic ester include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone.

These polyhydric alcohols, polycarboxylic acids, and cyclic esters may be used individually by 1 type or 2 or more types may be used together.

Examples of the polycarbonate-based polyol include reaction products of polyol and phosgene; ring-opening polymers of cyclic carbonates (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, and tetramethylene carbonate. Ester, hexamethylene carbonate, etc.

In addition, the polycarbonate polyol only needs to be a compound having a carbonate bond in the molecule and a hydroxyl group at the end, and may have both a carbonate bond and an ester bond.

Examples of the polyolefin-based polyol include those having a homopolymer or copolymer of ethylene, propylene, butene, etc. as a saturated hydrocarbon skeleton and having a hydroxyl group at the molecular terminal.

Examples of the polybutadiene-based polyol include a copolymer having butadiene as a hydrocarbon skeleton and having a hydroxyl group at its molecular terminal.

The polybutadiene polyol may also be a hydrogenated polybutadiene polyol obtained by hydrogenating all or part of the ethylenically unsaturated groups contained in its structure.

Examples of the polyisoprene-based polyol include a copolymer having isoprene as a hydrocarbon skeleton and having a hydroxyl group at its molecular terminal.

The polyisoprene polyol may also be a hydrogenated polyisoprene polyol obtained by hydrogenating all or part of the ethylenically unsaturated groups contained in its structure.

Examples of the above-mentioned (meth)acrylic polyols include polymers or copolymers of (meth)acrylate having at least two hydroxyl groups in the molecule. Regarding the (meth)acrylate, Examples include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, and octyl (meth)acrylate. , 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate and other alkyl (meth)acrylates, etc.

Examples of the polysiloxane polyol include dimethylpolysiloxane polyol, methylphenylpolysiloxane polyol, and the like.

The above-mentioned polyol-based compound (b3) can be used alone or in combination of two or more types.

Among them, from the viewpoint of cost, aliphatic polyols and alicyclic polyols are preferably used, and from the viewpoint of versatility, polyester polyols, polyether polyols, and polycarbonate polyols are preferably used.

The weight average molecular weight of the polyol compound (b3) is usually 60 to 10,000, preferably 100 to 8,000, more preferably 150 to 6,000. If the weight average molecular weight of the polyol compound (b3) is too large, it may be difficult to uniformly mix the obtained urethane (meth)acrylate compound (B2) and the acrylic resin (A), and the processed member may be easily Tendency to produce residual glue. In addition, if the weight average molecular weight of the polyol compound (b3) is too small, cracks tend to easily occur in the adhesive layer after irradiation with active energy rays.

The urethane (meth)acrylate compound (B) can be produced by reacting the above-mentioned components with a known reaction method.

Usually, in the case of the urethane (meth)acrylate compound (B1), the above-mentioned hydroxyl-containing (meth)acrylate compound (b1) and the polyvalent isocyanate compound (b2) can be combined at once or Each compound is added to the reactor and is produced by performing a urethanation reaction by a known reaction method. In the case of the urethane (meth)acrylate compound (B2), a polyol compound is added. Compound (b3).

In addition, when producing the urethane (meth)acrylate compound (B2), a reaction product obtained by reacting the polyol compound (b3) and the polyisocyanate compound (b2) in advance is mixed with a hydroxyl-containing compound. The method of reacting the (meth)acrylate compound (b1) is useful from the viewpoint of stability of the urethanization reaction and reduction of by-products.

In the above urethanation reaction, the residual isocyanate group content in the reaction system becomes The reaction is terminated at a time point of 0.5% by weight or less, and the urethane (meth)acrylate compound (B) can be obtained.

啉等胺系觸媒、硝酸鉍、溴化鉍、碘化鉍、硫化鉍等，此外還可列舉二月桂酸二丁基鉍、二月桂酸二辛基鉍等有機鉍化合物、或2-乙基己酸鉍鹽、環烷酸鉍鹽、異癸酸鉍鹽、新癸酸鉍鹽、月桂酸鉍鹽、馬來酸鉍鹽、硬脂酸鉍鹽、油酸鉍鹽、亞油酸鉍鹽、乙酸鉍鹽、雙新癸酸鉍、二水楊酸鉍鹽、二沒食子酸鉍鹽等有機酸鉍鹽等鉍系觸媒、無機鋯、有機鋯、鋯單體等鋯系觸媒、2-乙基己酸鋅/四乙醯丙酮鋯等併用2種以上之觸媒者。此外，此等觸媒可使用1種或組合2種以上來使用。 In the reaction between the hydroxyl-containing (meth)acrylate compound (b1) and the polyisocyanate compound (b2), a reaction catalyst is preferably used for the purpose of accelerating the reaction. As the reaction catalyst, for example, Organometallic compounds such as dibutyltin dilaurate, trimethyltin hydroxide, tetra-n-butyltin, zinc octenoate, tin octenoate, tin octoate, cobalt naphthenate, tin (II) chloride, tin chloride ( IV) and other metal salts, triethylamine, benzyldiethylamine, 1,4-diazabicyclo[2,2,2]octane, 1,8-diazabicyclo[5,4,0]ten Monene, N,N,N',N'-tetramethyl-1,3-butanediamine, N-ethyl

Amine-based catalysts such as phosphine, bismuth nitrate, bismuth bromide, bismuth iodide, bismuth sulfide, etc. In addition, organic bismuth compounds such as dibutylbismuth dilaurate, dioctylbismuth dilaurate, or 2-ethyl Bismuth hexanoate, bismuth naphthenate, bismuth isodecanate, bismuth neodecanoate, bismuth laurate, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate Bismuth-based catalysts such as organic acid bismuth salts such as bismuth acetate salt, bismuth bis-neodecanate, bismuth disalicylate salt, and bismuth digallate salt, inorganic zirconium, organic zirconium, and zirconium monomers Catalysts, zinc 2-ethylhexanoate/zirconium tetraethyl acetonate, etc. are used in combination with two or more catalysts. In addition, these catalysts can be used alone or in combination of two or more types.

Among these catalysts, dibutyltin dilaurate and 1,8-diazabicyclo[5,4,0]undecene are suitable.

In the urethanization reaction, organic solvents that do not have functional groups that react with isocyanate groups can be used, such as esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, toluene, Organic solvents such as xylene and other aromatic solvents.

In addition, the reaction temperature is usually 30~90°C, preferably 40~80°C, and the reaction time is usually 2~10 hours, preferably 3~8 hours.

The urethane (meth)acrylate compound (B) obtained in this manner must have 2 to 20 ethylenically unsaturated groups from the viewpoint of peelability after active energy ray irradiation. The number is preferably 2 to 18, and more preferably 4 to 15.

If the number of ethylenically unsaturated groups is too large, the cross-linking density after irradiation with active energy rays will be too high and cracks will easily occur in the adhesive layer. If it is too small, sufficient cross-linking density will not be obtained and the active energy rays will become too high. It is not easy to peel off after irradiation.

The weight average molecular weight of the above-mentioned urethane (meth)acrylate compound (B) is usually 500 to 10,000, preferably 750 to 8,000, more preferably 1,000 to 6,000. If the weight average molecular weight is too high, the viscosity of the urethane (meth)acrylate compound (B) will increase, the compatibility with the acrylic resin (A) will decrease, and a partial adhesive layer will easily form. The tendency for residue (residual glue) to be left on the component being processed. If the weight average molecular weight is too low, the urethane (meth)acrylate compound (B) tends to bleed out from the adhesive sheet, resulting in adhesive residue.

In addition, the weight average molecular weight mentioned above is the weight average molecular weight calculated by converting the standard polystyrene molecular weight, and can be achieved by using 4 columns in series with a high performance liquid chromatograph ("ACQUITY APC system" manufactured by Waters Corporation): ACQUITY APC XT 450 × 1 piece, ACQUITY APC XT 200 × 1 piece, ACQUITY APC XT 45 × 2 pieces for measurement.

The SP value in the solubility parameter of the above-mentioned urethane (meth)acrylate compound (B) is usually 9 to 15 (cal/cm ³ ) ^1/2 , preferably 9.5 to 13 (cal/cm ³ ) ^{1 /2} , especially 10~12(cal/cm ³ ) ^1/2 . When the SP value is outside the above range, the compatibility with the acrylic resin (A) and the ethylenically unsaturated compound (C) tends to decrease, and the adhesive properties when it is formed into an adhesive layer tend to decrease. In addition, the SP value of the above-mentioned urethane (meth)acrylate compound (B) can be obtained by calculation according to the Fedors method from the molecular structure.

In addition, the absolute value of the difference in SP value (|(A)-(B)|) between the acrylic resin (A) and the urethane (meth)acrylate compound (B) is preferably 3 or less. It is 2 or less, more preferably 1 or less, especially 0.8 or less. When the absolute value of the difference in SP values is outside the above range, the compatibility with the acrylic resin (A) tends to decrease, and the adhesive properties when forming an adhesive layer tend to decrease.

The viscosity of the urethane (meth)acrylate compound (B) used in the present invention at 60°C is preferably 500~100,000mPa‧s, especially 1,000~50,000mPa‧s. When the viscosity is outside the above range, the coating properties tend to decrease. In addition, viscosity can be measured with an E-type viscometer.

The content of the urethane (meth)acrylate compound (B) in the present invention is usually 5 to 100 parts by weight, preferably 10 to 80 parts by weight relative to 100 parts by weight of the acrylic resin (A). In particular, it is preferably 20 to 60 parts by weight. If the content of the urethane (meth)acrylate compound (B) is too small, it will tend to be difficult to peel off after irradiation with active energy rays. If the urethane (meth)acrylate compound (B) If the content is too high, there is a tendency for cracks to easily occur in the adhesive layer 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 compound, but any compound having an ethylenically unsaturated group can be used without any particular limitation. In addition, the ethylenically unsaturated compound (C) used in the present invention excludes the above-mentioned urethane (meth)acrylate compound (B).

From the viewpoint of excellent peeling properties after irradiation with active energy rays, the ethylenically unsaturated compound (C) must have 2 to 10 ethylenically unsaturated groups. The number should be 3 to 9, especially 4 to 8. If the If the number of ethylenically unsaturated groups is too large, the cross-linking density after irradiation with active energy rays will become too large and cracks will easily occur in the adhesive layer. If it is too small, sufficient cross-linking density will not be obtained and the cross-linking density will become too high after irradiation with active energy rays. Not easy to peel off.

The SP value in the solubility parameter of the above-mentioned ethylenically unsaturated compound (C) is usually 8~12 (cal/cm ³ ) ^1/2 , preferably 9~11.5 (cal/cm ³ ) ^1/2 , especially 9.5 ~11(cal/cm ³ ) ^1/2 . When the SP value is outside the above range, the compatibility with the acrylic resin (A) and the urethane (meth)acrylate compound (B) tends to decrease, and the adhesive properties when made into an adhesive tend to decrease. In addition, the SP value of the above-mentioned ethylenically unsaturated compound (C) can be obtained by calculation based on the Fedors method from the molecular structure.

Furthermore, the absolute value (|(A)-(C)|) of the difference in SP value between the acrylic resin (A) and the ethylenically unsaturated compound (C) is usually 3 or less, preferably 1 or less, and more preferably 0.7 or less, preferably 0.5 or less. When the absolute value of the difference in SP values is outside the above range, the compatibility with the acrylic resin (A) tends to decrease, and the adhesive properties when forming an adhesive layer tend to decrease.

Examples of the ethylenically unsaturated compound (C) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and 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, butylene glycol di(meth)acrylate Acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide modified bisphenol A type di(meth)acrylate, ethylene oxide modified bisphenol A type di(meth)acrylate, Cyclohexane dimethanol di(meth)acrylate, ethoxylated cyclohexanedimethanol di(meth)acrylate, dimethylol dicyclopentane di(meth)acrylate, tricyclodecane Dimethanol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, glycerol di(meth)acrylate, neopentylerythritol di(meth)acrylate, ethylene glycol Alcohol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, Diepoxypropyl phthalate di(meth)acrylate, hydroxytrimethylacetic acid modified neopentyl glycol di(meth)acrylate, isocyanuric acid ethylene oxide modified diacrylate, etc. Compounds with 2 ethylenically unsaturated groups; trimethylolpropane tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, tri(meth)acryloxyethoxytrimethylol propane, isocyanuric acid ethylene oxide modified triacrylate, caprolactone modified neopenterythritol tri(meth)acrylate, ethylene oxide modified neopenterythritol tri(meth)acrylate Acrylates, ethoxylated glycerol triacrylate and other compounds with three ethylenically unsaturated groups; neopentylerythritol tetra(meth)acrylate, dineopenterythritol penta(meth)acrylate, Dineopenterythritol hexa(meth)acrylate, glycerol polyepoxypropyl ether poly(meth)acrylate, caprolactone modified dipenterythritol penta(meth)acrylate, caprolactone Ester-modified dipenterythritol hexa(meth)acrylate, caprolactone-modified dipenterythritol tetra(meth)acrylate, ethylene oxide-modified dipenterythritol penta(meth)acrylate Compounds with more than 4 ethylenically unsaturated groups, such as ester, ethylene oxide-modified dipenterythritol hexa(meth)acrylate, ethylene oxide-modified neopenterythritol tetra(meth)acrylate, etc. wait.

In addition, as the ethylenically unsaturated compound (C), a Michael adduct of (meth)acrylic acid or 2-(meth)acryloxyethyldicarboxylic acid monoester may be used in combination. , examples of the wheat adduct of (meth)acrylic acid include (meth)acrylic acid dimer, (meth)acrylic acid trimer, (meth)acrylic acid tetramer, and the like.

The above-mentioned 2-(meth)acryloxyethyldicarboxylic acid monoester is a carboxylic acid having a specific substituent, and examples thereof include 2-(meth)acryloxyethylsuccinic acid monoester, 2- (Meth)acryloxyethyl phthalic acid monoester, 2-(meth)acryloxyethyl hexahydrophthalic acid monoester, etc. In addition, other oligoester acrylates can also be cited.

The said ethylenically unsaturated compound (C) can be used individually or in combination of 2 or more types.

Among these, considering the excellent adhesive properties after irradiation with active energy rays, it is appropriate not to have The ethylenically unsaturated compound of the hydroxyl group is more preferably neopentyritol tetra(meth)acrylate, dineopenterythritol hexa(meth)acrylate, or caprolactone-modified neopenterythritol tetra(meth)acrylate. Acrylate, ethylene oxide modified dipenterythritol hexa(meth)acrylate, ethylene oxide modified neopenterythritol tetra(meth)acrylate, especially neopenterythritol tetra(meth)acrylate. acrylate, dineopenterythritol hexa(meth)acrylate.

Furthermore, in the present invention, from the viewpoint of excellent compatibility and adhesive properties, the skeleton of the compound obtained by removing (meth)acrylic acid from the ethylenically unsaturated compound (C) is the same as that obtained from the above-mentioned urethane (meth)acrylate. It is preferable that the skeletons of the compounds obtained by removing (meth)acrylic acid from the hydroxyl-containing (meth)acrylate compound (b1) of the compound (B) are the same.

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 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, it will tend to be difficult to peel off after irradiation with active energy rays. If it is too large, the contamination resistance of the processed member after peeling will tend to decrease.

In the present invention, from the viewpoint of excellent adhesion before irradiation with active energy rays and excellent peelability after irradiation with active energy rays, urethane (meth)acrylate is used relative to 100 parts by weight of acrylic resin (A). It is important that the total content of the compound (B) and the ethylenically unsaturated compound (C) is 20 to 100 parts by weight. It is preferably 25 to 90 parts by weight, especially 30 to 80 parts by weight. If the total content is too small, it will be difficult to reduce the adhesive force even if active energy rays are irradiated. If the total content is too high, the contamination resistance of the processed member after irradiation of active energy rays will decrease.

In addition, the weight content ratio of the urethane (meth)acrylate compound (B) and the ethylenically unsaturated compound (C) [(B): (C)] is preferably 99.9:0.1~0.1:99.9, more preferably It is suitable to be 99:1~1:99, and further suitable The time is 90:10~10:90, especially 80:20~20:80. If the weight content ratio of the urethane (meth)acrylate compound (B) and the ethylenically unsaturated compound (C) is outside the above range, the adhesive properties tend to decrease when the adhesive layer is formed.

[Photopolymerizable initiator (D)]

啉基(4-硫代甲基苯基)丙-1-酮、2-芐基-2-二甲基胺基-1-(4-

啉基苯基)丁酮、2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙酮寡聚物等苯乙酮類；安息香(benzoin)、安息香甲醚、安息香乙醚、安息香異丙醚、安息香異丁醚等安息香類；二苯甲酮、鄰苯甲醯基苯甲酸甲酯、4-苯基二苯甲酮、4-苯甲醯基-4’-甲基-二苯基硫醚、3,3’,4,4’-肆(第三丁基過氧化羰基)二苯甲酮、2,4,6-三甲基二苯甲酮、4-苯甲醯基-N,N-二甲基-N-[2-(1-氧基-2-丙烯基氧基)乙基]苯甲基溴化銨、(4-苯甲醯基苄基)三甲基氯化銨等二苯甲酮類；2-異丙基-9-氧硫

、4-異丙基-9-氧硫

、2,4-二乙基-9-氧硫

、2,4-二氯-9-氧硫

、1-氯-4-丙氧基-9-氧硫

、2-(3-二甲基胺基-2-羥基)-3,4-二甲基-9H-硫

-9-酮甲氯化物等9-氧硫

(thioxanthone)類；2,4,6-三甲基苯甲醯基-二苯基氧化膦、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基-戊基氧化膦、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦等醯基氧化膦類等。其中，宜為苯乙酮類，尤其宜為1-羥基環己基苯基酮。此外，此等光聚合性起始劑(D)可單獨使用或併用2種以上。 The photopolymerizable initiator (D) used in the present invention may be one that generates free radicals by the action of light, and examples thereof include diethoxyacetophenone, 2-hydroxy-2-methyl-1 -Phenylpropan-1-one, benzildimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxy Cyclohexyl phenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-2-

Phylyl(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-

Phylinophenyl)butanone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone oligomer and other acetophenones; benzoin, benzoin methyl Ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoins; benzophenone, o-benzoylbenzoic acid methyl ester, 4-phenylbenzophenone, 4-benzoyl-4 '-Methyl-diphenyl sulfide, 3,3',4,4'-(tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4-Benzyl-N,N-dimethyl-N-[2-(1-oxy-2-propenyloxy)ethyl]benzyl ammonium bromide, (4-benzyl Benzyl)trimethylammonium chloride and other benzophenones; 2-isopropyl-9-oxosulfide

, 4-isopropyl-9-oxosulfide

, 2,4-diethyl-9-oxosulfide

,2,4-dichloro-9-oxosulfide

,1-Chloro-4-propoxy-9-oxosulfide

, 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-sulfide

-9-ketomethyl chloride and other 9-oxysulfur

(thioxanthone) type; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl -Pentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and other acylphosphine oxides. Among them, acetophenones are preferred, and 1-hydroxycyclohexyl phenyl ketone is particularly preferred. Moreover, these photopolymerizable initiators (D) can be used individually or in combination of 2 or more types.

、2,4-二異丙基-9-氧硫

等。此等助劑可單獨使用或併用2種以上。 In addition, as an auxiliary agent of the photopolymerizable initiator (D), for example, triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michelle ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzene (n-Butoxy)ethyl formate, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester, 2,4-diethyl-9-oxo sulfur

, 2,4-diisopropyl-9-oxosulfide

wait. These additives can be used alone or in combination of two or more types.

Content of photopolymerizable initiator (D) based on 100 parts by weight of the total of acrylic resin (A), urethane (meth)acrylate compound (B) and ethylenically unsaturated compound (C) It is preferably 0.1 to 20 parts by weight, especially 0.5 to 15 parts by weight, especially 1 to 10 parts by weight. If the content of the photopolymerizable initiator (D) is too small, the peelability after irradiation with active energy rays will tend to be reduced. If it is too much, the contamination resistance of the workpiece after irradiation with active energy rays will be reduced. tendency.

[Crosslinking agent (E)]

唑啉(Oxazoline)系交聯劑、三聚氰胺系交聯劑、醛系交聯劑、胺系交聯劑等。此等之中，考慮改善剝離型黏著片與基材片之黏接性之觀點或與丙烯酸系樹脂(A)之反應性的觀點，宜使用異氰酸酯系交聯劑。 Examples of the cross-linking agent (E) include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, aziridine-based cross-linking agents,

Oxazoline cross-linking agent, melamine cross-linking agent, aldehyde cross-linking agent, amine cross-linking agent, etc. Among these, it is preferable to use an isocyanate cross-linking agent from the viewpoint of improving the adhesion between the peelable adhesive sheet and the base sheet or the reactivity with the acrylic resin (A).

In addition, these cross-linking agents (E) may be used alone, or two or more types may be used in combination.

Examples of the isocyanate cross-linking agent include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hydrogenated toluene diisocyanate, and hydrogenated diisocyanate. Toluene, hexamethylene diisocyanate, diphenylmethane-4,4-diisocyanate, isophorone diisocyanate, 1,3-bis(methylisocyanato)cyclohexane, diisocyanato Tetramethylxylylene cyanate, 1,5-naphthyl diisocyanate, triphenylmethane triisocyanate, and adducts of these polyisocyanate compounds and polyol compounds such as trimethylolpropane, this wait Biuret body or isocyanurate body of polyisocyanate compound.

Among these, from the viewpoint of chemical resistance or reactivity with functional groups, the isocyanurate form of hexamethylene diisocyanate, 2,4-tolyl diisocyanate, and 2,4-diisocyanate are preferred. -Toluene diisocyanate, adduct of 2,6-toluene diisocyanate and trimethylolpropane, 2,4-toluene diisocyanate and 2,6-toluene diisocyanate It is an adduct of isocyanurate, tetramethylxylylene diisocyanate and trimethylolpropane.

Examples of the above-mentioned epoxy cross-linking agent include bisphenol A. Epichlorohydrin type epoxy resin, ethylene glycol diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, glycerin diepoxypropyl ether, glycerin triepoxypropyl ether, 1,6 -Hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, neopentyl erythritol polyglycidyl butanetetraol , Diglycerol polyepoxypropyl ether, 1,3'-bis(N,N-diepoxypropylaminomethyl)cyclohexane, N,N,N',N'-tetraepoxy Propyl m-xylenediamine, etc.

Examples of the aziridine-based crosslinking agent include tetramethylolmethane-tris-β-aziridinylpropionate and trimethylolpropane-tris-β-aziridinylpropionate. , N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxyamide), N,N'-hexamethylene-1,6-bis(1-aziridinecarboxylic acid) amide) etc.

唑啉系交聯劑而言，可舉例如2,2’-雙(2-

唑啉)、1,2-雙(2-

唑啉-2-基)乙烷、1,4-雙(2-

唑啉-2-基)丁烷、1,8-雙(2-

唑啉-2-基)丁烷、1,4-雙(2-

唑啉-2-基)環己烷、1,2-雙(2-

唑啉-2-基)苯、1,3-雙(2-

唑啉-2-基)苯等包含脂肪族或芳香族之雙

唑啉化合物、2-乙烯基-2-

唑啉、2-乙烯基-4-甲基-2-

唑啉、2-乙烯基-5-甲基-2-

唑啉、2-異丙烯基-2-

唑啉、2-異丙烯基-4-甲基-2-

唑啉、2-異丙烯基-5-乙基-2-

唑啉等加成聚合性

唑啉中之1種或2種以上的聚合物等。 As for the above

Examples of the oxazoline cross-linking agent include 2,2'-bis(2-

oxazoline), 1,2-bis(2-

Zozolin-2-yl)ethane, 1,4-bis(2-

Oxazolin-2-yl)butane, 1,8-bis(2-

Oxazolin-2-yl)butane, 1,4-bis(2-

oxazolin-2-yl)cyclohexane, 1,2-bis(2-

Zozolin-2-yl)benzene, 1,3-bis(2-

oxazolin-2-yl) benzene, etc. containing aliphatic or aromatic bis

Oxazoline compound, 2-vinyl-2-

Oxazoline, 2-vinyl-4-methyl-2-

Oxazoline, 2-vinyl-5-methyl-2-

Oxazoline, 2-isopropenyl-2-

Oxazoline, 2-isopropenyl-4-methyl-2-

Oxazoline, 2-isopropenyl-5-ethyl-2-

Addition polymerizability of oxazoline etc.

One or more polymers of oxazoline, etc.

Examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine, and hexapentoxymethylmelamine. Melamine, hexahexyloxymethylmelamine, melamine resin, etc.

Examples of the aldehyde cross-linking agent include glyoxal, malondialdehyde, succinic aldehyde, maleic dialdehyde, glutaraldehyde, formaldehyde, acetaldehyde, benzaldehyde, and the like.

Examples of the amine cross-linking agent include hexamethylenediamine, triethyldiamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, and triethyltetramine. Amine, isophorone diamine, amine resin, polyamide, etc.

Usually, the content of the cross-linking agent (E) is 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). It is preferably 0.1 to 30 parts by weight, more preferably 0.2 to 20 parts by weight, and further preferably 0.3 to 15 parts by weight. If there is too little cross-linking agent (E), the cohesive force of the adhesive will decrease, which tends to cause residual glue. If there is too much cross-linking agent (E), the flexibility and adhesion will decrease, causing a gap between the adhesive and the component to be processed. Tendency to float.

[Other ingredients]

The active energy ray curable peel-off adhesive composition of the present invention may further contain, for example, a small amount of monofunctional monomer, antistatic agent, antioxidant, plasticizer, filler within the scope that does not impair the effect of the present invention. Agents, pigments, thinners, anti-aging agents, ultraviolet absorbers, ultraviolet stabilizers and other additives. These additives can be used alone or in combination of two or more. Antioxidants, in particular, are effective in maintaining the stability of the adhesive layer. The content of antioxidants when blended is not particularly limited, but is preferably 0.01 to 5% by weight relative to the active energy ray curable peel-off adhesive composition.

In addition, the active energy ray-curable peelable adhesive composition of the present invention may contain, in addition to the above-mentioned additives, a small amount of impurities contained in the manufacturing raw materials of the constituent components of the active energy ray-curable peelable adhesive composition. wait.

In addition, considering the reduction in the contamination resistance of the workpiece after irradiation with active energy rays, the active energy ray curable peel-off adhesive composition of the present invention preferably does not contain terpene-based resins, rosin-based resins, and chromanes. Tackiness-imparting resins such as (Chromane) resin, phenol resin, styrene resin, petroleum resin, etc.

Therefore, by mixing an acrylic resin (A), a urethane (meth)acrylate compound (B), an ethylenically unsaturated compound (C), a photopolymerizable initiator (D), and a crosslinking agent (E). The active energy ray curable peel-off adhesive composition of the present invention can be obtained by adding other components according to the demand.

The active energy ray-curable peel-off adhesive composition of the present invention is cross-linked by the above-mentioned cross-linking agent (E), and can be suitably used as an adhesive layer of a peel-off adhesive sheet. After the peel-off adhesive sheet is bonded to the member to be processed, the urethane (meth)acrylate compound (B) and the ethylenically unsaturated compound (C) are polymerized by irradiation with active energy rays. Causes the adhesive layer to harden, reduces adhesion, and exerts peelability. Utilizing this characteristic, it is used to temporarily protect the surface of various types of processed components when the components being processed are processed.

The peel-off adhesive sheet will be described below.

Examples of the components to be processed protected by the peelable adhesive sheet include semiconductor wafers, printed circuit boards, glass processed products, metal plates, plastic plates, and the like.

The above-mentioned peelable adhesive sheet usually has a base material sheet, an adhesive layer composed of the active energy ray curable peelable adhesive composition of the present invention, and a release film. As for the production method of the peel-off adhesive sheet, first, the active energy ray-curable peel-off adhesive composition of the present invention itself or the concentration is adjusted with an appropriate organic solvent, and then directly coated on the release film or the base material Chip. Thereafter, the adhesive sheet is dried by performing a heat treatment at 80 to 105° C. for 0.5 to 10 minutes, and then affixed to a base material sheet or a release film to obtain a release-type adhesive sheet. In addition, in order to achieve a balance of adhesive properties, aging can be performed after drying.

Examples of the base sheet include polyethylene naphthalate, polyethylene terephthalate, polybutylene terephthalate, and polyethylene terephthalate. Polyester resins such as /isophthalate copolymer; polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; polyvinyl fluoride, polyvinylidene difluoride, Polyfluorinated vinyl resins such as polytetrafluoroethylene; polyamides such as nylon 6, nylon 6,6; polyvinyl chloride, polyvinyl chloride/vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene- Ethylene polymers such as vinyl alcohol copolymer, polyvinyl alcohol, and vinylon; cellulose-based resins such as cellulose triacetate and cellophane; polymethyl methacrylate, polyethyl methacrylate, Sheets made of at least one synthetic resin from the group consisting of polyethyl acrylate, polybutyl acrylate and other acrylic resins; polystyrene; polycarbonate; polyarylate; polyimide; aluminum, copper , iron and other metal foils; high-quality paper, cellophane and other papers; fabrics or non-woven fabrics composed of glass fiber, natural fiber, synthetic fiber, etc. These base material sheets can be used in the form of a single layer or in the form of laminating two or more types of multilayers. Among these, from the viewpoint of lightweighting, etc., a sheet made of synthetic resin is preferable.

In addition, as the release film, for example, those obtained by subjecting various synthetic resin sheets, paper, woven fabrics, non-woven fabrics, etc. exemplified in the above-mentioned base material sheet to a release treatment can be used.

In addition, the coating method of the above-mentioned active energy ray curable peel-off adhesive composition is not particularly limited as long as it is a general coating method, and examples thereof include roll coating, die coating, gravure coating, notched wheel coating, Screen printing and other methods.

The thickness of the adhesive layer in the peel-off adhesive sheet is usually 1 to 200 μm, and more preferably 10 to 100 μm.

For active energy rays, light such as far ultraviolet, ultraviolet, near ultraviolet, and infrared rays, electromagnetic waves such as Considering the ease of obtaining the device, price, etc., it is advantageous to use the ultraviolet system.

The cumulative exposure dose of the above-mentioned ultraviolet rays is usually 50~3,000mJ/ ^cm2 , preferably 100~1,000mJ/ ^cm2 . In addition, the irradiation time depends on the type of light source, the distance between the light source and the adhesive layer, the thickness of the adhesive layer, and other conditions. It is usually a few seconds, but it can also be a very short time of less than 1 second depending on the situation.

The adhesive force of the above-mentioned peel-off adhesive sheet varies depending on the type of base material sheet, the type of components to be processed, etc. Before irradiation with active energy rays, it is preferably 1~30N/25mm, and more preferably 1~20N/25mm. In addition, the adhesion force after irradiation with active energy rays should be 0.01~1N/25mm, and more preferably 0.05~0.5N/25mm.

However, the adhesive force after irradiation with active energy rays is preferably 1/5 or less of the adhesive force before irradiation with active energy rays, and more preferably 1/50 or less.

The active energy ray curable peel-off adhesive composition of the present invention is used as an adhesive layer. The peel-off adhesive sheet obtained is attached to the workpiece to temporarily protect the surface of the workpiece. By irradiating active energy rays, the adhesive layer will harden and the adhesion will be reduced, so it can be easily removed. The processed components are peeled off.

[Example]

Hereinafter, the present invention will be described in more detail using examples. However, the present invention is not limited to the following examples unless the gist of the invention is exceeded. In addition, the following "%" and "part" are based on weight.

Each component contained in the active energy ray curable peelable adhesive composition of the Examples and Comparative Examples is as follows.

In addition, the composition of the acrylic resin is shown in Table 1 mentioned later.

‧n-Butyl acrylate

[SP value: 9.769 (cal/cm ³ ) ^1/2 , molecular weight: 128.2]

‧2-ethylhexyl acrylate

[SP value: 9.221 (cal/cm ³ ) ^1/2 , molecular weight: 184.3]

‧Methyl acrylate

[SP value: 10.560 (cal/cm ³ ) ^1/2 , molecular weight: 86.1]

‧Methyl methacrylate

[SP value: 9.933 (cal/cm ³ ) ^1/2 , molecular weight: 100.1]

‧2-hydroxyethyl acrylate

[SP value: 14.480 (cal/cm ³ ) ^1/2 , molecular weight: 116.1]

‧2-hydroxyethyl methacrylate

[SP value: 13.470 (cal/cm ³ ) ^1/2 , molecular weight: 144.2]

‧acrylic acid

[SP value: 14.040 (cal/cm ³ ) ^1/2 , molecular weight: 72.1]

<Acrylic resin>

[Acrylic resin (A-1)]

In a reactor equipped with a temperature regulator, a thermometer, a stirrer, a dropping funnel and a reflux cooler, add 29 parts of ethyl acetate and raise the temperature while stirring. When the internal temperature stabilizes at 78°C, add it dropwise over 2 hours. A mixture of 91.9 parts of n-butyl acrylate, 0.1 part of 2-hydroxyethyl methacrylate, 8 parts of acrylic acid, and 0.037 parts of azobisisobutyronitrile (AIBN) was mixed and dissolved, and the mixture was reacted under reflux. Then, a liquid in which 1.5 parts of ethyl acetate and 0.025 parts of AIBN were dissolved was added 3.5 hours after the start of the reaction (after reflux). In addition, 5.5 hours after the start of the reaction, a liquid in which 4 parts of toluene and 0.05 parts 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 added to terminate the reaction and obtain a solution of acrylic resin (A-1) [SP value: 10.057 (cal/cm ³ ) ^{1/ 2} , weight average molecular weight: 800,000, glass transition temperature (Tg): -48.2℃, resin composition: 35.0%, viscosity: 8,000mPa‧s (25℃)].

[Acrylic resin (A-2)]

A solution-form acrylic resin (A) was obtained in the same manner except that the polymerized components in the acrylic resin (A-1) were changed to 70 parts of n-butyl acrylate and 30 parts of 2-hydroxyethyl acrylate. -2) [SP value: 11.065 (cal/cm ³ ) ^1/2 , weight average molecular weight: 700,000, glass transition temperature: -45.1℃, resin composition: 35.0%, viscosity: 6,000mPa‧s (25℃)] .

[Acrylic resin (A-3)]

A solution was obtained in the same manner except that the polymerized components in 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. Acrylic resin (A-3) [SP value: 10.033 (cal/cm ³ ) ^1/2 , weight average molecular weight: 600,000, glass transition temperature: -39.6°C, resin composition: 35.0%, viscosity: 5,000mPa‧s (25℃)].

[Acrylic resin (A-4)]

A solution was obtained in the same manner except that the polymerized components in the acrylic resin (A-1) were changed to 59 parts of n-butyl acrylate, 40 parts of methyl acrylate, and 1 part of 2-hydroxyethyl acrylate. Acrylic resin (A-4) [SP value: 10.110 (cal/cm ³ ) ^1/2 , weight average molecular weight: 700,000, glass transition temperature: -33.6°C, resin composition: 35.0%, viscosity: 6,000mPa‧s (25℃)].

[Acrylic resin (A-5)]

The polymerized components in the above-mentioned 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. , acrylic resin (A-5) in solution was obtained in the same manner [SP value: 10.163 (cal/cm ³ ) ^1/2 , weight average molecular weight: 500,000, glass transition temperature: -24.2°C, resin composition: 35.0 %, viscosity: 8,000mPa‧s (25℃)].

[Acrylic resin (A-6)]

The polymerized components in the acrylic resin (A-1) were changed to 69.8 parts of n-butyl acrylate, 25 parts of methyl methacrylate, 0.2 parts of 2-hydroxyethyl methacrylate, and 5 parts of acrylic acid. , obtain a solution of acrylic resin (A-6) in the same manner [SP value: 9.995 (cal/cm ³ ) ^1/2 , weight average molecular weight: 450,000, glass transition temperature: -24.0°C, resin composition: 35.0 %, viscosity: 6,000mPa‧s (25℃)].

[Acrylic resin (A-7)]

A solution was obtained in the same manner except that the polymerized components in the acrylic resin (A-1) were changed to 39 parts of n-butyl acrylate, 60 parts of methyl acrylate, and 1 part of 2-hydroxyethyl acrylate. Acrylic resin (A-7) [SP value: 10.270 (cal/cm ³ ) ^1/2 , weight average molecular weight: 700,000, glass transition temperature: -21.0°C, resin composition: 35.0%, viscosity: 10,000mPa‧s (25℃)].

[Acrylic resin (A-8)]

The polymerized components in the acrylic resin (A-1) were changed to 64.85 parts of n-butyl acrylate, 30 parts of methyl methacrylate, 5 parts of 2-hydroxyethyl methacrylate, and 0.15 parts of acrylic acid. , obtain solution acrylic resin (A-8) in the same manner [SP value: 9.996 (cal/cm ³ ) ^1/2 , weight average molecular weight: 450,000, glass transition temperature: -19.1°C, resin composition: 35.0 %, viscosity: 6,000mPa‧s (25℃)].

[Acrylic resin (A’-1)]

A solution was obtained in the same manner except that the polymerization components in the acrylic resin (A-1) were changed to 92.8 parts of 2-ethylhexyl acrylate, 7 parts of 2-hydroxyethyl acrylate, and 0.2 part of acrylic acid. Acrylic resin (A'-1) [SP value: 9.550 (cal/cm ³ ) ^1/2 , weight average molecular weight: 1 million, glass transition temperature: -66.7°C, resin composition: 35.0%, viscosity: 4,000 mPa‧s(25℃)].

[Acrylic resin (A’-2)]

The same procedure was carried out except that the polymerized components in the acrylic resin (A-1) were changed to 91.9 parts of 2-ethylhexyl acrylate, 0.1 part of 2-hydroxyethyl methacrylate, and 8 parts of acrylic acid. Obtained solution acrylic resin (A'-2) [SP value: 9.530 (cal/cm ³ ) ^1/2 , weight average molecular weight: 600,000, glass transition temperature: -62.1°C, resin composition: 35.0%, viscosity :2,000mPa‧s(25℃)].

[Acrylic resin (A’-3)]

The polymerization components in the acrylic resin (A-1) were changed to 59 parts of n-butyl acrylate, 36 parts of 2-ethylhexyl acrylate, and 5 parts of 2-hydroxyethyl acrylate. Method to obtain solution acrylic resin (A'-3) [SP value: 9.770 (cal/cm ³ ) ^1/2 , weight average molecular weight: 950,000, glass transition temperature: -59.6°C, resin composition: 35.0%, Viscosity: 3,000mPa‧s (25℃)].

[Acrylic resin (A’-4)]

The polymerized components in the above-mentioned acrylic resin (A-1) were changed to 45.9 parts of n-butyl acrylate, 46 parts of 2-ethylhexyl acrylate, 0.1 part of 2-hydroxyethyl methacrylate, and 8 parts of acrylic acid. Otherwise, a solution-like acrylic resin (A'-4) was obtained in the same manner [SP value: 9.787 (cal/cm ³ ) ^1/2 , weight average molecular weight: 550,000, glass transition temperature: -55.4°C, Resin composition: 35.0%, viscosity: 1500mPa‧s (25℃)].

BA: n-butyl acrylate, 2EHA: 2-ethylhexyl acrylate, MA: methyl acrylate, MMA: methyl methacrylate

HEA: 2-hydroxyethyl acrylate, HEMA: 2-hydroxyethyl methacrylate, AAc: propylene acid

<Urethane (meth)acrylate compounds and ethylenically unsaturated compounds>

[Composition of urethane acrylate (B-1) and dipenterythritol hexaacrylate (C-1)]

In a 4-neck flask equipped with a thermometer, a mixer, a water-cooled condenser, and a nitrogen blowing inlet, add 8.7 parts of isophorone diisocyanate and 91.3 parts of dipenterythritol's acrylic acid adduct (hydroxyl value 48 mgKOH/g), as 0.06 parts of 2,6-di-tert-butylcresol as a polymerization inhibitor and 0.01 part of dibutyltin dilaurate as a reaction catalyst were reacted at 60°C, and the reaction was terminated when the residual isocyanate group became less than 0.3% to obtain Composition I (weight average molecular weight 2,300). This composition I contains 45 parts of urethane acrylate (B-1) and 55 parts of dipenterythritol hexaacrylate (C-1).

[Urethane acrylate (B-1)]

‧Reaction product of isophorone diisocyanate and dineopenterythritol pentaacrylate [ethylenically unsaturated groups: 10, SP value: 10.64 (cal/cm ³ ) ^1/2 ]

[Ethylenically unsaturated compound (C-1)]

‧Dipenterythritol hexaacrylate [ethylenically unsaturated groups: 6, SP value: 10.40 (cal/cm ³ ) ^1/2 ]

[Composition of urethane acrylate (B-2) and neopentyl tetraacrylate (C-2)]

In a flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen blowing inlet, add 19.2 parts of isophorone diisocyanate and 80.8 parts of neopentylerythritol's acrylic acid adduct (hydroxyl value: 120 mgKOH/g) as a polymerization inhibitor. 0.06 parts of 2,6-di-tert-butylcresol and 0.01 part of dibutyltin dilaurate as a reaction catalyst were reacted at 60°C. The reaction was terminated when the residual isocyanate group became less than 0.3%, and composition II was obtained. (Weight average molecular weight 1,600). This composition II contains 65 parts of urethane acrylate (B-2) and 35 parts of neopentyl tetraacrylate (C-2).

[Urethane acrylate (B-2)]

‧Reaction product of isophorone diisocyanate and neopentylerythritol triacrylate [ethylenically unsaturated groups: 6, SP value: 10.73 (cal/cm ³ ) ^1/2 ]

[Ethylenically unsaturated compound (C-2)]

‧Neopenterythritol tetraacrylate [ethylenically unsaturated groups: 4, SP value: 10.34 (cal/cm ³ ) ^1/2 ]

[Composition of urethane acrylate (B-3) and dipenterythritol hexaacrylate (C-1)]

In a 4-neck flask equipped with a thermometer, a mixer, a water-cooled condenser, and a nitrogen blowing inlet, add 16.3 parts of isophorone diisocyanate and 83.7 parts of dipenterythritol's acrylic acid adduct (hydroxyl value: 98 mgKOH/g), as 0.06 parts of 2,6-di-tert-butylcresol as a polymerization inhibitor and 0.01 part of dibutyltin dilaurate as a reaction catalyst were reacted at 60°C, and the reaction was terminated when the residual isocyanate group became less than 0.3% to obtain Composition III (weight average molecular weight 5300). This composition III contains 37.5 parts of urethane acrylate (B-3) and 12.5 parts of dineopenterythritol hexaacrylate (C-1).

[Urethane acrylate (B-3)]

‧Reaction product of isophorone diisocyanate and dineopenterythritol pentaacrylate [ethylenically unsaturated groups: 10, SP value: 10.64 (cal/cm ³ ) ^1/2 ]

[Ethylenically unsaturated compound (C-1)]

‧Dipenterythritol hexaacrylate [ethylenically unsaturated groups: 6, SP value: 10.40 (cal/cm ³ ) ^1/2 ]

<Photopolymerization initiator>

[Photopolymerizable initiator (D-1)]

‧Omnirad 184 (made by IGM RESIN)

<Cross-linking agent>

[Crosslinking agent (E-1)]

‧CORONATE L-55E (isocyanate cross-linking agent, manufactured by Tosoh Corporation)

<<Example 1>>

[Preparation of active energy ray curable peel-off adhesive composition]

Mix 286 parts of the above-mentioned acrylic resin (A-1) (resin component 35%), 50 parts of composition I [22.5 parts of urethane acrylate (B-1), 27.5 parts of ethylenically unsaturated compound (C-1) parts], 2.1 parts of photopolymerizable initiator (D-1), 9.7 parts of cross-linking agent (E-1) (5.4 parts in terms of active ingredients), and 30 parts of toluene as a diluent solvent to obtain active energy ray hardening Sexually peelable adhesive composition.

[Production of peel-off adhesive sheets]

The obtained active energy ray-curable peel-off adhesive composition was applied to an easy-adhesive polyethylene terephthalate film (film thickness: 50 μm) (manufactured by Tosoh Corporation, "Lumirror T60") as a base sheet using an applicator. "), dried at 100°C for 3 minutes, attached to a release film ("SP-PET 38 01-BU" manufactured by Mitsui Chemicals Tohcello. Inc.), and aged at 40°C for 3 days to obtain Peel-off adhesive sheet (the thickness of the adhesive layer is 25 μm).

The following evaluation was performed using the obtained peelable adhesive sheet.

[Adhesion: Before ultraviolet (UV) irradiation]

A test piece with a size of 25 mm × 100 mm was made from the peel-off adhesive sheet obtained above. After peeling off the release film, it was rolled back and forth twice with a rubber roller with a mass of 2 kg in an environment of 23°C and 50% relative humidity. It is attached to a stainless steel plate (SUS304BA plate) under pressure, and after being left in the same environment for 30 minutes, the 180-degree peel strength (N/25mm) is measured at a peeling speed of 300mm/min.

(evaluation criteria)

◎‧‧‧10N/25mm or more

○‧‧‧More than 5N/25mm, less than 10N/25mm

△‧‧‧1N/25mm or more, less than 5N/25mm

×‧‧‧ does not reach 1N/25mm, or residual glue may be produced

[Adhesion: after ultraviolet (UV) irradiation]

A test piece with a size of 25 mm × 100 mm was made from the peel-off adhesive sheet obtained above. After peeling off the release film, it was rolled back and forth twice with a rubber roller with a mass of 2 kg in an environment of 23°C and 50% relative humidity. Pressurize and attach to the stainless steel plate (SUS304BA plate). After leaving it in the same environment for 30 minutes, use an 80W high-pressure mercury lamp to irradiate ultraviolet light from a height of 18cm at a conveyor belt speed of 5.1m/min (cumulative irradiation dose 200mJ/ cm ² ). After placing it in an environment of 23°C and 50% relative humidity for 30 minutes, measure the 180-degree peel strength (N/25mm) at a peeling speed of 300mm/min.

(evaluation criteria)

◎‧‧‧Less than 0.2N/25mm

○‧‧‧0.2N/25mm or more, less than 0.5N/25mm

△‧‧‧0.5N/25mm or more, less than 1N/25mm

×‧‧‧1N/25mm or more or residual glue may be produced

[Contamination resistance: Before ultraviolet (UV) irradiation]

Attach the above-obtained peel-off adhesive sheet to the surface of a 4-inch square stainless steel plate (SUS304BA plate) with no foreign matter attached. After leaving it for 1 hour at 23°C and a relative humidity of 65%, remove it from the surface of the stainless steel plate. For peel-off type adhesive sheets, the stainless steel plate after peeling is visually evaluated according to the following standards.

(evaluation criteria)

○‧‧‧No glue residue

△‧‧‧Only a little glue residue

×‧‧‧There is glue residue

[Contamination resistance: After ultraviolet (UV) irradiation]

Attach the above-obtained peel-off adhesive sheet to the surface of a 4-inch square stainless steel plate (SUS304BA plate) with no foreign matter attached. After leaving it for 1 hour at 23°C and a relative humidity of 65%, use an 80W A high-pressure mercury lamp was used to irradiate ultraviolet rays from a height of 18cm at a conveyor speed of 5.1m/min (cumulative irradiation dose 200mJ/cm ² ). Thereafter, the release-type adhesive sheet was peeled off from the surface of the stainless steel plate, and the peeled stainless steel plate was visually evaluated based on the following criteria.

(evaluation criteria)

○‧‧‧No glue residue

△‧‧‧Only a little glue residue

×‧‧‧There is glue residue

[Haze value]

The diffusion transmittance and total light transmittance of the release-type adhesive sheet after peeling off the release film were measured using HAZE MATER NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), and the obtained diffusion transmittance and total light transmittance were measured Substitute the value into the following formula to obtain the haze value. In addition, the higher the haze value is, the more uneven each component in the active energy ray-curable peelable adhesive composition is. In addition, the haze value includes the value of the base material sheet.

Haze value (%) = (diffusion transmittance/total light transmittance) × 100

(evaluation criteria)

◎‧‧‧Less than 1%

○‧‧‧More than 1%, less than 2%

△‧‧‧More than 2%, less than 3%

×‧‧‧3% or more

<<Examples 2~14, Comparative Examples 1~9>>

An active energy ray curable release-type adhesive composition was obtained in the same manner as in Example 1, except that each component was blended as shown in Tables 2 and 3 below. In addition, the active energy ray curable peelable adhesive compositions obtained in Examples 2 to 14 and Comparative Examples 1 to 9 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 described below together with the evaluation results of Example 1.

※1以樹脂換算的形式，※2胺甲酸酯(甲基)丙烯酸酯系化合物(B)與乙烯性不飽和化合物(C)之合計含量，※3以有效成分換算的形式 【Table 2】

※1 In terms of resin conversion, ※2 Total content of urethane (meth)acrylate compound (B) and ethylenically unsaturated compound (C), ※3 In terms of active ingredient conversion

※1以樹脂換算的形式，※2胺甲酸酯(甲基)丙烯酸酯系化合物(B)與乙烯性不飽和化合物(C)之合計含量，※3以有效成分換算的形式

※1 In terms of resin conversion, ※2 Total content of urethane (meth)acrylate compound (B) and ethylenically unsaturated compound (C), ※3 In terms of active ingredient conversion

【Table 4】

As shown in Table 4 above, it can be seen that an acrylic resin (A) having an SP value of a solubility parameter or more than a specific value and a urethane (meth)acrylate compound having a specific number of ethylenically unsaturated groups are included. (B) and an ethylenically unsaturated compound (C), a photopolymerizable initiator (D) and a cross-linking agent (E), and the urethane (meth)acrylate compound (B) is not an ethylenically unsaturated compound. The total content of the saturated compound (C) is within a specific range of the active energy ray-curable peel-off adhesive compositions of Examples 1 to 14 because the haze value when made into the adhesive layer of the peel-off adhesive sheet is low. , so each component is in a uniform state in the active energy ray curable peel-off adhesive composition. However, the peelable adhesive sheets obtained by using the active energy ray-curable peelable adhesive compositions of Examples 1 to 14 have excellent adhesive properties before and after irradiation of active energy rays, and are suitable for being processed. The components have excellent contamination resistance.

On the other hand, the active energy ray-curable peel-off adhesive compositions of Comparative Examples 1 to 4 using an acrylic resin whose SP value in the solubility parameter does not reach a specific value have high haze values, so each component has no In a uniform state, the peel-off adhesive sheet obtained by using this has poor adhesive properties and poor resistance to contamination of the member to be processed.

In addition, active energy ray-curable peel-off adhesives were used in Comparative Examples 5 to 9 in which the total content of the urethane (meth)acrylate compound (B) and the ethylenically unsaturated compound (C) was outside the specific range. The peel-off adhesive sheet obtained from the agent composition has poor adhesive properties or poor contamination resistance to the components being processed.

Although the specific forms of the present invention have been shown in the above-mentioned embodiments, the above-mentioned embodiments are merely examples and have no limiting meaning. Various changes that are obvious to those with ordinary skill in this technical field are intended to be included within the scope of the present invention.

[Industrial applicability]

The active energy ray-curable peel-off adhesive composition of the present invention can be suitably used as an adhesive film for temporarily protecting the surface of semiconductor wafers, printed circuit boards, glass processed products, metal plates, plastic plates, etc. middle.

Claims (5)

An active energy ray curable peel-off adhesive composition contains an acrylic resin (A), a urethane (meth)acrylate compound (B), and the urethane (meth)acrylate compound Ethylenically unsaturated compound (C), photopolymerizable initiator (D) and cross-linking agent (E) other than compound (B), characterized by: SP value in the solubility parameter of the acrylic resin (A) It is 9.9 (cal/cm ³ ) ^1/2 or more, and the urethane (meth)acrylate compound (B) is a hydroxyl-containing (meth)acrylate compound (b1) and a polyisocyanate compound ( The reaction product of b2), the polyvalent isocyanate compound (b2) is at least one of an aliphatic diisocyanate and an alicyclic diisocyanate, and the urethane (meth)acrylate compound (B) has The ethylenically unsaturated compound (C) has 2 to 20 ethylenically unsaturated groups and has a weight average molecular weight of 500 to 10,000, and the ethylenically unsaturated compound (C) has 2 to 10 ethylenically unsaturated groups, and the acrylic resin (A) weighs 100 parts, the total content of the urethane (meth)acrylate compound (B) and the ethylenically unsaturated compound (C) is 20 to 100 parts by weight. For example, in the active energy ray-curable peel-off adhesive composition of item 1 of the patent application, the glass transition temperature of the acrylic resin (A) is -50~20°C. For example, the active energy ray curable peel-off adhesive composition in the patent scope 1 or 2 of the application, wherein the urethane (meth)acrylate compound (B) and the ethylenically unsaturated compound (C) are The weight content ratio (B:C) is 99.9:0.1~0.1:99.9. For example, the active energy ray curable peel-off adhesive composition in Item 1 or 2 of the patent scope, among which: The cross-linking agent (E) is an isocyanate-based cross-linking agent. A peel-off adhesive sheet, characterized by having an active energy ray-curable peel-off adhesive composition cross-linked by a cross-linking agent (E) as in any one of items 1 to 4 of the patent application. Adhesive layer.