CN108307635A - Work pieces process adhesive tape - Google Patents

Work pieces process adhesive tape Download PDF

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Publication number
CN108307635A
CN108307635A CN201680023562.5A CN201680023562A CN108307635A CN 108307635 A CN108307635 A CN 108307635A CN 201680023562 A CN201680023562 A CN 201680023562A CN 108307635 A CN108307635 A CN 108307635A
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CN
China
Prior art keywords
methyl
adhesive tape
acrylate
compound
work pieces
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Granted
Application number
CN201680023562.5A
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Chinese (zh)
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CN108307635B (en
Inventor
小升雄朗
小升雄一朗
藤本泰史
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Lintec Corp
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Lintec 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • 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
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Abstract

The work pieces process adhesive tape of the present invention has base material and is set to the adhesive phase of a surface side of the base material, wherein, described adhesive layer includes urethane based resin (A) and energy ray-curable compound (B), the energy ray-curable compound (B) is not reacted with the urethane based resin (A) and with optical polymerism unsaturated bond, molecular weight 35,000 or less.

Description

Work pieces process adhesive tape
Technical field
The present invention relates to work pieces process adhesive tapes, more particularly in order to protect carry convex block semiconductor wafer surface And the semiconductor wafer surface protection adhesive tape used.
Background technology
The slimming of information terminal apparatus, miniaturization, multifunction fast development process in, wherein mounted half Conductor device similarly requires slimming, densification, it is also desirable to the slimming of semiconductor wafer.Currently, in order to cope with this It is expected that carrying out implementing grinding and the research of slimming to the back side of semiconductor wafer.In addition, in recent years, for semiconductor For chip, the convex block by formation such as solders of 30~100 μm or so of height is formed in wafer surface sometimes.To such band In the case of thering is the semiconductor wafer of convex block to carry out back side grinding, in order to protect convex portion, sometimes in the crystalline substance for being formed with convex block Piece surface mount surface protective plate.
In the past, as surface protective plate, it is known to comprising the storage modulus of 25 DEG C and 60 DEG C is adjusted to particular range The surface protective plate of resin layer (for example, referring to patent document 1).The surface protective plate be equipped with room temperature (25 DEG C) storage modulus with There are the resin layers of gap for the storage modulus of high temperature (60 DEG C), as a result, by being pasted on the crystalline substance with concavo-convex portion at high temperature Piece surface, makes resin layer soften, and absorbs the bumps of wafer surface, reduces the difference of height of wafer surface.
In addition, as surface protective plate, it is known in order to make that adaptation and fissility are good and being arranged on base material has 2 resin layers of given tensile modulus of elasticity, and in 2 resin layers, the resin layer of surface side is pasted by polystyrene type bullet Property the thermoplastic elastomer (TPE)s such as body, ethylene octane copolymer, polyurethane elastomer and polyester elastomer be formed by surface guarantor Bluff piece (with reference to patent document 2).
In addition, as surface protective plate, it is known to be equipped with the adhesive tape of middle layer and adhesive phase in the one side of base material. In the adhesive tape, in order to improve concave-convex absorbability, 25 DEG C of storage modulus of middle layer is set as 30~1000kPa or so, and And adhesive phase (for example, referring to patent document 3) is formed by energy line solidification type adhesive.As described in Patent Document 3 in table When using energy line solidification type adhesive in the screening glass of face, it is easy to make stickup and fissility to semiconductor wafer to become good It is good.It should be noted that it is previous, for ease of adjustment cementability and it is easy to ensure the imbedibility of convex block, in surface protective plate The energy line solidification type adhesive used has mainly used the adhesive of acrylic compounds.
Existing technical literature
Patent document
Patent document 1：No. 4603578 bulletins of Japanese Patent No.
Patent document 2：No. 4918181 bulletins of Japanese Patent No.
Patent document 3：No. 4367769 bulletins of Japanese Patent No.
Invention content
The subject that the invention solves
However, recently as further densification, the miniaturization of semiconductor device, there are what bump height increased to incline To studying the convex block with 200 μm or more height.But bump height is increased and difference of height is made to increase Semiconductor wafer for, if using the surface protective plate of the acrylic compounds described in patent document 3, have when piece is removed When adhesive residue (residual paste) is largely generated on convex block.This is because the cohesion of the energy line solidification type adhesive of acrylic compounds Power, mechanical strength are relatively low.
On the other hand, such as in patent document 1,2, polyurethanes elasticity is used for the adhesive surface in surface protective plate Material other than the acrylic adhesives such as body is studied.But in patent document 1,2, do not exist to these materials Application in energy line solidification type adhesive is studied, in order to ensure the imbedibility of cementability, fissility and convex block, need into The improvement of one step.
The present invention is completed in view of above actual conditions, and the issue of the present invention is to provide a kind of work pieces process use Adhesive tape not only makes the surface shape to workpiece to the adhesiveness, fissility and adhesive phase of the workpiece such as semiconductor wafer Followability become good (using the imbedibility of convex block as representative), and even if the surface shape of workpiece to be pasted is uneven, The residual paste of workpiece surface is also few.
The method to solve the problem
The inventors of the present invention have made intensive studies, as a result, it has been found that, by using carbamates adhesive as bonding It agent and is formed and is set as specifically forming, the above subject can be solved, so as to complete the present invention below.The present invention The work pieces process adhesive tape of (1) below~(16) is provided.
(1) a kind of work pieces process adhesive tape has base material and is set to the adhesive phase of a surface side of the base material, Wherein,
Described adhesive layer includes urethane based resin (A) and energy ray-curable compound (B), the energy line Curability compound (B) does not react with the urethane based resin (A) and with optical polymerism unsaturated bond, molecular weight It is 35,000 or less.
(2) the work pieces process adhesive tape described in above-mentioned (1), wherein the energy ray-curable compound (B) be selected from It is at least one kind of in (methyl) acrylate monomer (B1) and carbamate (methyl) acrylate (B2).
(3) the work pieces process adhesive tape described in above-mentioned (2), wherein the energy ray-curable compound (B) is at least wrapped Containing (methyl) acrylate monomer (B1), and (methyl) acrylate monomer (B1) is multifunctional (methyl) acrylate, The multifunctional (methyl) acrylate is the complete carboxylate of polyalcohol and (methyl) acrylic acid.
(4) the work pieces process adhesive tape described in any one of above-mentioned (1)~(3), wherein the energy ray-curable Close object (B) has 2 or more (methyl) acryloyl groups in 1 molecule.
(5) the work pieces process adhesive tape described in any one of above-mentioned (1)~(4), wherein the carbamates tree Fat (A) has optical polymerism unsaturated bond.
(6) the work pieces process adhesive tape described in any one of above-mentioned (1)~(5), wherein described adhesive layer is by least Include the adhesive composition shape of urethane polymer (A '), the energy ray-curable compound (B) and crosslinking agent (C) At,
The urethane based resin (A) is to be crosslinked urethane polymer (A ') using the crosslinking agent (C) Made of.
(7) the work pieces process adhesive tape described in above-mentioned (6), wherein the crosslinking agent (C) includes to contain optical polymerism not The crosslinking agent (C1) of saturated bond.
(8) the work pieces process adhesive tape described in above-mentioned (6) or (7), wherein the urethane polymer (A ') with The crosslinking agent (C) is bonded by urethane bond.
(9) the work pieces process adhesive tape described in any one of above-mentioned (6)~(8), wherein described adhesive composition is also Containing compound (D), the compound (D) has optical polymerism unsaturated bond and can be reacted with the crosslinking agent (C) Reactive functional groups.
(10) the work pieces process adhesive tape described in above-mentioned (9), wherein the compound (D) is multifunctional (methyl) third Olefin(e) acid ester, the multifunctional (methyl) acrylate are the partial esterification objects of polyalcohol and (methyl) acrylic acid.
(11) the work pieces process adhesive tape described in any one of above-mentioned (1)~(10), wherein described adhesive layer is shining It is 2.5MPa or more to penetrate the fracture strength after energy line.
(12) the work pieces process adhesive tape described in any one of above-mentioned (1)~(11), wherein in the base material and described There is middle layer between adhesive phase.
(13) the work pieces process adhesive tape described in above-mentioned (12), wherein the thickness of the middle layer is 10~600 μm.
(14) the work pieces process adhesive tape described in above-mentioned (12) or (13), wherein the middle layer is surveyed at frequency 1Hz Loss angle tangent at fixed 50 DEG C is 1.0 or more.
(15) the work pieces process adhesive tape described in any one of above-mentioned (1)~(14), the bonding after irradiation energy line Power is 2000mN/25mm or less.
(16) the work pieces process adhesive tape described in any one of above-mentioned (1)~(15) is that semiconductor wafer surface is protected Shield adhesive tape.
The effect of invention
The present invention can provide a kind of followability change making adhesiveness, fissility and adhesive phase to the surface shape of workpiece Well and the few work pieces process adhesive tape of the residual paste of workpiece surface.
Specific implementation mode
In the following record, " weight average molecular weight (Mw) " is scaled by what gel permeation chromatography (GPC) method measured The value of polystyrene, specifically, being the value measured based on the method described in embodiment.
In addition, in record in the present specification, such as " (methyl) acrylate " as indicating " acrylate " and " first The term of both base acrylate " and use, other similar terms are similarly handled.
Hereinafter, using embodiment, the present invention will be described.
The work pieces process adhesive tape of the present invention has base material and is set to base material (hereinafter, also referred to as " adhesive tape ") The adhesive phase of one surface side.In addition, adhesive tape can have middle layer between the base material and adhesive phase.Adhesive tape can be as It is made of 2 layers or 3 layers described in upper, other layers can also be set.For example, stripping material can further be arranged over the binder layer Material.
Hereinafter, being described in detail to each component for constituting adhesive tape.
＜ base materials ＞
Base material used in adhesive tape is not particularly limited, preferably resin film.Compared with paper, non-woven fabrics, resin film production Raw dust is few, is consequently adapted to the tooling member of electronic unit, and is easy to get, therefore preferably.Base material can be by one The monofilm that resin film is formed, can also be multilayer film made of the multiple resin films of lamination.
As the resin film as base material, can enumerate for example：Polyolefins film, vinyl halide polymers class film, propylene Acid resin class film, rubber film, cellulose family film, polyesters film, polycarbonate-based film, polystyrene type film, polyphenylene sulfide ethers Film, cyclic olefin polymerization species film etc..
In these, from by grinding wafer to it is very thin when can also stably keep chip viewpoint and be thickness From the viewpoint of film with high accuracy, preferably polyesters film, in polyesters film, from the sight being easy to get and thickness and precision is high Point consideration, preferably polyethylene terephthalate film.
In addition, the thickness of base material is not particularly limited, preferably 10~200 μm, more preferably 25~150 μm.
It should be noted that from the viewpoint of improving cementability of the base material to adhesive phase or middle layer, can use On the surface of resin film, further lamination has the base material of adhesive layer or adhesive phase.In addition, not damaging effect of the present invention Can also contain in the base material that uses in range, in the present invention filler, colorant, antistatic agent, antioxidant, organic lubricant, Catalyst etc..In addition, base material can be transparent, and it can also be according to coloring be desired with, preferably transmission can make adhesive phase The base material of the energy line of cured sufficient degree.
＜ middle layers ＞
For the adhesive tape of the present invention, middle layer can be equipped in the one side of base material.By the gluing for making the present invention Band has middle layer, in the case where the difference of height for being equipped with the workpiece surfaces bumps such as convex block on workpiece is big, can also be embedded to protrusion Thus adhesive phase and middle layer are easy making adhesive tape flat with the holding of face opposite side that is being pasted on workpiece face.The present invention (hereinafter, also referred to as, " loss angle is just for loss angle tangent (tan δ) at used middle layer measured with frequency 1Hz 50 DEG C Cut ") it is preferably 1.0 or more.
If the loss angle tangent of middle layer is such value, work pieces process is being pasted on adhesive tape with convex block Chip etc. when having irregular workpiece, middle layer is sufficiently deformed, and can easily follow bumps.It is fully absorbed from middle layer The bumps of convex block etc., for example from the viewpoint of obtaining the good sticking state to the wafer surface with convex block, middle layer Loss angle tangent is more preferably 1.5 or more, further preferably 1.65 or more, is still more preferably 1.8 or more.
In addition, from the viewpoint of mobility when heating middle layer is adjusted to proper range, the loss angle of middle layer Tangent is preferably 5.0 hereinafter, more preferably 4.0 or less.
It should be noted that more specifically, the loss angle tangent of above-mentioned middle layer is based on the implementation described below Method described in example and the value that measures.
In addition, the thickness of middle layer can suitably be adjusted according to the state by adhesive surface for being pasted with adhesive tape, from energy From the viewpoint of the convex block for enough absorbing high height, preferably 10~600 μm, more preferably 25~550 μm, further preferably 35~500 μm.
Middle layer is formed using middle layer resin combination.In addition, middle layer is preferably comprised with resin combination Carbamate (methyl) acrylate.
(carbamate (methyl) acrylate (X))
Carbamate (methyl) acrylate (X) is at least change with (methyl) acryloyl group and urethane bond Object is closed, and with the property polymerizeing by irradiation by energy line.It should be noted that energy line refers to electromagnetic wave or charged particle The ray with the quanta of energy (energy quanta), refers to ultraviolet light isoreactivity light or electron ray etc. in beam.
(methyl) acryloyl group quantity in carbamate (methyl) acrylate (X) can be simple function, 2 functions or More than 3 functions, for ease of making loss angle tangent be 1.0 or more, middle layer preferably comprises mono-functional amine with resin combination Formic acid esters (methyl) acrylate.This is because, mono-functional amine's formic acid esters (methyl) acrylate and the shape in paradigmatic structure It is unrelated at three-dimensional net structure, it is not easy to form three-dimensional net structure in middle layer, to be easy to improve loss angle tangent.
As carbamate (methyl) acrylate (X) used in middle layer resin combination, such as can make Compound with (methyl) acryloyl group is reacted with terminal isocyanate carbamate prepolymer to be obtained, and the end is different Cyanate carbamate prepolymer is obtained from so that polyol compound is reacted with polyisocyanate compound.Carbamic acid Ester (methyl) acrylate (X) can use a kind, or two or more is applied in combination.
(polyol compound)
As long as polyol compound has the compound of 2 or more hydroxyls, it is not particularly limited.
As specific polyol compound, can enumerate for example：Aklylene glycol, polyether polyol, polyester-type are more First alcohol, polycarbonate polyol etc..
Wherein, preferred, polyethers type polyalcohol.
It should be noted that as polyol compound, can be the glycol of 2 functions, the trihydroxylic alcohol of 3 functions, 4 functions with On any one of polyalcohol, consider from viewpoints such as easiness in obtaining, versatility, reactivity, preferably the glycol of 2 functions, more Preferred, polyethers type glycol.
The compound that the preferred following formula of polyether glycol (1) indicates.
[chemical formula 1]
In above-mentioned formula (1), R is the alkyl of divalent, preferably alkylidene, the alkylidene of more preferable carbon atom number 1~6.In carbon original In the alkylidene of subnumber 1~6, preferably ethylidene, propylidene, tetramethylene, more preferably propylidene, tetramethylene.
In addition, n is the number of repeat unit of oxyalkylene, preferably 10~250, more preferably 25~205, further preferably 40~185.When n is above range, the urethane bond of carbamate (methyl) acrylate that can make is dense Degree is appropriate, easily prepared middle layer and loss angle tangent is made to meet above-mentioned important document.
In above-mentioned formula (1) compound represented, preferably polyethylene glycol, polypropylene glycol, polytetramethylene glycol, more preferably Polypropylene glycol, polytetramethylene glycol.
By reacting for polyether glycol and polyisocyanate compound, generation has imported ehter bond portion (- (- R-O-) n-) Terminal isocyanate carbamate prepolymer.By using such polyether glycol, carbamate (methyl) acrylic acid Ester contains the structural unit derived from polyether glycol.
Polyester polyol is as obtained from polyol component and polyacid constituent polycondensation.As polyol component, It can enumerate：Ethylene glycol, diethylene glycol, triethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1,3 butylene glycol, 1,4- fourths two Alcohol, neopentyl glycol, pentanediol, 3- methyl-1s, 5- pentanediols, 2,2,4- trimethyl -1,3- pentanediols, hexylene glycol, ethohexadiol, 2, 2- diethyl -1,3- propylene glycol, 2- ethyl -2- butyl -1,3- propylene glycol, 1,4 cyclohexane dimethanol, bisphenol-A ethylene glycol or Various glycols etc. well known to propylene glycol addition product etc..
As the polyacid constituent of the manufacture for polyester polyol, it can use and be conventionally known as the polynary of polyester The compound of sour component.
As specific polyacid constituent, can enumerate for example：Adipic acid, maleic acid, succinic acid, oxalic acid, fumaric acid, third The binary acid such as diacid, glutaric acid, pimelic acid, azelaic acid, decanedioic acid, suberic acid；Phthalic acid, M-phthalic acid, to benzene two The aromatic polyvalents such as the polyacids such as the binary acid such as formic acid, 2,6 naphthalene dicarboxylic acid, trimellitic acid, Pyromellitic Acid acid, these sour institutes Corresponding acid anhydrides, its derivative and dimeric dibasic acid, hydrogenated dimer acids etc..Wherein, from the viewpoint for forming the film with appropriate hardness Consider, optimization aromatic polyacid.In the esterification for manufacturing polyester polyol, it can use as needed various Well known catalyst.
It as polycarbonate polyol, is not particularly limited, glycols and alkylene carbonate as escribed above can be enumerated The reactant etc. of base ester.
As the calculated number-average molecular weight of hydroxyl value by polyol compound, preferably 1,000~10,000, more preferably It is 2,000~9,000, further preferably 3,000~7,000.The number-average molecular weight be 1,000 or more when, can to avoid because The generation of excessive urethane bond and cause be difficult to control middle layer viscoelastic property the case where, therefore preferably.It is another Aspect, when the number-average molecular weight is 10,000 or less, the middle layer that can be prevented is overbated, therefore preferably.
It should be noted that being by (polynary alcohol functional group by the calculated number-average molecular weight of hydroxyl value of polyol compound Number) × 56.11 × 1000/ (hydroxyl value (unit：MgKOH/g)) calculated value.
(polyisocyanate compound)
As polyisocyanate compound, can enumerate for example：Tetramethylene diisocyanate, hexa-methylene diisocyanate The aliphatic polyisocyantes such as ester, trimethyl hexamethylene diisocyanate；Isophorone diisocyanate, norbornane two are different Cyanate, dicyclohexyl methyl hydride -4,4 '-diisocyanate, dicyclohexyl methyl hydride -2,4 '-diisocyanate, ω, ω '-two are different The alicyclic diisocyanates class such as cyanate dimethyl cyclohexane；4,4 '-methyl diphenylene diisocyanates, toluene diisocynate Ester, benzene dimethylene diisocyanate, tolidine diisocyanate (tolidine diisocyanate), tetramethylene two Aromatic diisocyanates classes such as toluene di-isocyanate(TDI), naphthalene -1,5- diisocyanate etc..
Wherein, from the viewpoint of operability, preferably isophorone diisocyanate, hexamethylene diisocyanate, benzene Dimethylene diisocyanate.
{ compound with (methyl) acryloyl group }
As the compound with (methyl) acryloyl group, (methyl) acrylate with hydroxyl can be enumerated.As (methyl) acrylate with hydroxyl, as long as the compound with hydroxyl and (methyl) acryloyl group at least in 1 molecule , it is not particularly limited.
As specific (methyl) acrylate with hydroxyl, can enumerate for example：(methyl) acrylic acid 2- hydroxyl second Ester, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 4- hydroxybutyls, (methyl) acrylic acid 4- hydroxycyclohexyls, (first Base) acrylic acid 5- hydroxyl rings monooctyl ester, (methyl) acrylic acid 2- hydroxyl -3- phenoxy-propyls, pentaerythrite three (methyl) acrylic acid (methyl) hydroxyalkyl acrylates such as ester, polyethyleneglycol (methyl) acrylate, (methyl) acrylic acid 2- hydroxy methacrylates； N- methylols (methyl) acrylamide etc. hydroxyls (methyl) acrylamide；Make (methyl) acrylic acid and vinyl alcohol, vinyl benzene Phenol, bisphenol-A 2-glycidyl ester reaction obtained from reactant etc..
In these, preferred (methyl) hydroxyalkyl acrylates, more preferable (methyl) acrylic acid 2- hydroxy methacrylates.
Thus obtained carbamate (methyl) acrylate (X's) for middle layer resin combination divides equally again Son amount preferably 1,000~100,000, more preferably 3,000~80,000, further preferably 5,000~65,000.This is heavy When average molecular weight is 1,000 or more, formed with the polymerizable monomer described below in carbamate (methyl) acrylate It, can be to centre due to coming from the molecular separating force of the structure of carbamate (methyl) acrylate to each other in polymer Layer assigns the hardness of appropriateness, therefore preferably.
The use level of carbamate (methyl) acrylate (X) in middle layer resin combination is with total composition On the basis of count, preferably 20~70 mass %, more preferably 25~60 mass %, further preferably 30~50 mass %, more Further preferably 33~47 mass %.When the use level of carbamate (methyl) acrylate is the range, it is easily formed The high middle layer of loss angle tangent.
Middle layer resin combination other than above-mentioned carbamate (methyl) acrylate (X) also contain for example containing Mercapto compound (Y) or polymerizable monomer (Z) preferably comprise both above-mentioned.
(sulfur-bearing alcohol-based compounds (Y))
As sulfur-bearing alcohol-based compounds (Y), as long as the compound at least one mercapto in molecule, does not have Especially limitation, from the viewpoint of being easy to raising loss angle tangent, preferably polyfunctional sulfur-bearing alcohol-based compounds, more preferably The sulfur-bearing alcohol-based compounds of 4 functions.
As specific sulfur-bearing alcohol-based compounds (Y), can enumerate for example：Nonyl mercaptan, 1- lauryl mercaptans, 1,2- second Two mercaptan, 1,3- dimercaptopropanes, triazine thiol, two mercaptan of triazine, three mercaptan of triazine, trithioglycerin, tetraethylene glycol are double (3-thiopropionate), trimethylolpropane tris (3-thiopropionate), pentaerythrite four (3-thiopropionate), pentaerythrite Four mercaptoacetates, dipentaerythritol six (3-thiopropionate), three [(3- sulfydryls acyloxy) ethyl] isocyanuric acid esters, 1, Bis- (the 3- sulfydryls butyryl acyloxy) butane of 4-, pentaerythrite four (3- mercaptobutylates), 1,3,5- tri- (3- sulfydryls butoxyethyl group)- 1,3,5- triazines -2,4,6- (1H, 3H, 5H)-triketone etc..
It should be noted that these sulfur-bearing alcohol-based compounds (Y) can use a kind, or two or more is applied in combination.
The molecular weight of sulfur-bearing alcohol-based compounds (Y) is preferably 200~3,000, more preferably 300~2, and 000.The molecular weight For above range when, it is good with the compatibility of carbamate (methyl) acrylate (X), film forming can be made to become good.
100 matter of total relative to carbamate (methyl) acrylate (X) and the polymerizable monomer (Z) described below Part is measured, the use level of sulfur-bearing alcohol-based compounds (Y) is preferably 1.0~4.9 mass parts, more preferably 1.5~4.8 mass parts.
When the use level is 1.0 mass parts or more, it is easily formed the high middle layer of loss angle tangent, convex block suction can be improved The property received.On the other hand, when which is 4.9 below mass part, the exudation etc. of the middle layer when being rolled into a roll can be inhibited.
(polymerizable monomer (Z))
From the viewpoint of improving film forming, preferably further contain in middle layer resin combination used in the present invention There is polymerizable monomer (Z).Polymerizable monomer (Z) is the polymerism other than above-mentioned carbamate (methyl) acrylate (X) Object is closed, is that can irradiate the compound polymerizeing with other ingredients by energy line.Wherein, polymerizable monomer (Z) refers to removing resin Substance other than ingredient.Polymerizable monomer (Z) the preferably compound at least one (methyl) acryloyl group.
It should be noted that in the present specification, " resin component " refer to oligomer in structure with repetitive structure or Polymer substance is the compound that weight average molecular weight is 1,000 or more.
As polymerizable monomer (Z), can enumerate for example：(methyl) acrylic acid of alkyl with carbon atom number 1~30 Arrcostab, (methyl) acrylate with functional groups such as hydroxyl, amide groups, amino, epoxy groups, with the (first of alicyclic structure Base) acrylate, (methyl) acrylate with aromatic structure, (methyl) acrylate with heterocycle structure, benzene second Alkene, hydroxyethyl vinylethers, hydroxy butyl vinyl ether, N- vinyl formamides, n-vinyl pyrrolidone, N- vinyl are in oneself Vinyl compounds such as amide, allyl glycidyl ether etc..
As (methyl) alkyl acrylate of the alkyl with carbon atom number 1~30, can enumerate for example：(methyl) third E pioic acid methyl ester, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) acrylic acid N-butyl, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid n-pentyl ester, (methyl) acrylic acid Just own ester, (methyl) 2-EHA, (methyl) n-octyl, (methyl) acrylic acid nonyl ester, (methyl) propylene Sour last of the ten Heavenly stems ester, (methyl) acrylic acid hendecane base ester, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) acrylic acid tetradecane base ester, (methyl) aliphatic acrylate, (methyl) octadecyl acrylate, (methyl) third Olefin(e) acid eicosane base ester etc..
As (methyl) acrylate with functional group, can enumerate for example：(methyl) Hydroxyethyl Acrylate, (first Base) hydroxyls (methyl) acrylate such as hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate；(methyl) acrylamide, N, N- dimethyl (methyl) acrylamide, N- butyl (methyl) acrylamide, N- methylols (methyl) acrylamide, N- methylols Propane (methyl) acrylamide, N- methoxies (methyl) acrylamide, N- butoxymethyls (methyl) acrylamide etc. contain Amido compounds；Containing primary amino group (methyl) acrylate, containing secondary amino group (methyl) acrylate, tertiary-amino-containing (methyl) propylene Acid esters etc. contains amino (methyl) acrylate；(methyl) glycidyl acrylate, (methyl) acrylic acid methylglycidyl esters Deng containing epoxy group (methyl) acrylate etc..
As (methyl) acrylate with alicyclic structure, can enumerate for example：(methyl) isobornyl acrylate, (methyl) acrylic acid dicyclopentenyl ester, (methyl) dicyclopentanyl acrylate, (methyl) acrylic acid dicyclopentenyl oxygroup ester, (methyl) Cyclohexyl acrylate, (methyl) acrylic acid Buddha's warrior attendant alkyl ester etc..
As (methyl) acrylate with aromatic structure, can enumerate for example：(methyl) phenylethyl hydroxyl Propyl ester, (methyl) benzyl acrylate, (methyl) acrylic acid 2- hydroxyl -3- phenoxy-propyls etc..
As (methyl) acrylate with heterocycle structure, can enumerate for example：(methyl) tetrahydrofurfuryl acrylate, (methyl) acrylic acid morpholine ester etc..
In these, from from the viewpoint of the compatibility of above-mentioned carbamate (methyl) acrylate (X), preferably With large volume of group, more specifically, (methyl) acrylate preferably with alicyclic structure, with aromatic structure (methyl) acrylate, (methyl) acrylate with heterocycle structure, more preferably with alicyclic structure (methyl) propylene Acid esters.In addition, from being easy to from the viewpoint of making loss angle tangent be 1.0 or more, as polymerizable monomer, preferably comprise with official (methyl) acrylate that can be rolled into a ball and (methyl) acrylate with alicyclic structure more preferably include hydroxyl (methyl) propylene Acid esters and (methyl) isobornyl acrylate.
Consider from above-mentioned viewpoint, the cooperation of (methyl) acrylate with alicyclic structure in middle layer resin combination Amount counts preferably 32~53 mass %, more preferably 35~51 mass %, further preferably 37 on the basis of total composition ~48 mass % are still more preferably 40~47 mass %.
In addition, considering from above-mentioned viewpoint, relative to the total of the polymerizable monomer (Z) contained in middle layer resin combination The use level of amount, (methyl) acrylate with alicyclic structure is preferably 52~87 mass %, more preferably 55~85 matter %, further preferably 60~80 mass % are measured, are still more preferably 65~77 mass %.(methyl) with alicyclic structure When the use level of acrylate is the range, it is easy to that loss angle tangent is made to be 1.0 or more.
In addition, middle layer is preferably 30~80 mass % with the use level of the polymerizable monomer (Z) in resin combination, more Preferably 40~75 mass %, further preferably 50~70 mass % are still more preferably 53~67 mass %.Polymerism When the use level of monomer (Z) is the range, the motility for the part that polymerizable monomer (Z) is polymerized in middle layer is high, therefore Middle layer has the tendency for becoming soft, it is easier to form the middle layer that loss angle tangent meets above-mentioned important document.
In addition, from the viewpoint of identical, carbamate (methyl) acrylate (X) in middle layer resin combination Mass ratio (carbamate (methyl) acrylate/polymerizable monomer) with polymerizable monomer (Z) is preferably 20/80~60/ 40, more preferably 30/70~50/50, further preferably 35/65~45/55.
(energy line polymerization initiator (R))
Middle layer resin combination preferably further contains energy line polymerization initiator (R).It is poly- by containing energy line Initiator (R) is closed, ultraviolet light Isoenergetical line can be utilized more easily middle layer to be made to be cured with resin combination.Energy line polymerize Initiator (R) is also generally referred to as " Photoepolymerizationinitiater initiater ", and therefore, in the present specification, hereinafter also referred to as " photopolymerization causes Agent ".
As Photoepolymerizationinitiater initiater, can enumerate for example：Benzoin compound, acetophenone compound, acylphosphine oxide Photosensitizers such as Photoepolymerizationinitiater initiaters, amine or the quinones such as object, cyclopentadiene titanium compound, thioxanthone compounds, peroxide compound etc. are closed, more Specifically, can enumerate for example：1- hydroxycyclohexylphenylketones, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone, benzene are even Relation by marriage, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, 2,2- dimethoxy -1,2- diphenylethane -1- ketone etc..
These Photoepolymerizationinitiater initiaters can use a kind, or two or more is applied in combination.
Relative to 100 mass parts of total of carbamate (methyl) acrylate and polymerizable monomer, photopolymerization causes The use level of agent is preferably 0.05~15 mass parts, more preferably 0.1~10 mass parts, further preferably 0.3~5 mass Part.
(other additives)
Within the scope of the effect of the invention, middle layer resin combination can contain other additives.As Other additives can be enumerated for example：Crosslinking agent, antioxidant, softening agent (plasticizer), filler, antirust agent, pigment, dyestuff Deng.In the case where coordinating these additives, the total relative to carbamate (methyl) acrylate and polymerizable monomer The use level of 100 mass parts, other additives is preferably 0.01~6 mass parts, more preferably 0.1~3 mass parts.
It should be noted that within the scope of the effect of the invention, in addition to carbamate (methyl) acrylate In addition, middle layer resin combination can also contain the resin component other than carbamate (methyl) acrylate, but excellent Choosing only contains carbamate (methyl) acrylate as resin component.
Resin component other than carbamate (methyl) acrylate contained in middle layer resin combination contains Amount be preferably 5 mass % hereinafter, more preferably 1 mass % hereinafter, further preferably 0.1 mass % hereinafter, further it is excellent It is selected as 0 mass %.
In addition, middle layer can also be formed by the middle layer containing other resin components with resin combination, thus carry out generation It is formed for by carbamate (methyl) acrylate (X).For example, middle layer can be used comprising non-reacted carbamic acid The solidification compound of ester polymer or oligomer and polymerizable monomer, the composition comprising ethene-alpha-olefin copolymer carry out shape At.Non-reacted urethane polymer or oligomer can use well known substance that can make as polymerizable monomer With monomer same as described above.Such solidification compound can contain above-mentioned energy line polymerization initiator.
Ethene-alpha-olefin copolymer is obtained from polymerizeing ethylene with 'alpha '-olefin monomers.It, can be with as 'alpha '-olefin monomers It enumerates：Ethylene, 1- butylene, 2-methyl-1-butene alkene, 2- Methyl-1-pentenes, 1- hexenes, 2,2- dimethyl -1- butylene, 2- methyl - 1- hexenes, 4-methyl-1-pentene, 1- heptene, 3- methyl-1s-hexene, 2,2- dimethyl -1- amylenes, 3,3- dimethyl -1- penta Alkene, 2,3- dimethyl -1- amylenes, 3- ethyl -1- amylenes, 2,2,3- trimethyl -1- butylene, 1- octenes, 2,2,4- trimethyls -1- Octene etc..These 'alpha '-olefin monomers can be used alone, or two or more is applied in combination.
In addition, ethene-alpha-olefin copolymer can be copolymerized made of ethylene, 'alpha '-olefin monomers and other monomer polymerizations Object.As other monomer components, can enumerate for example：Vinyl acetate, styrene, acrylonitrile, methacrylonitrile, vinyl ketone Equal vinyl compounds；The unsaturated carboxylic acids such as acrylic acid, methacrylic acid；Methyl acrylate, ethyl acrylate, acrylic acid positive third The esters of unsaturated carboxylic acids such as ester, methyl methacrylate, ethyl methacrylate, n propyl methacrylate；Acrylamide, methyl Unsaturated carboxylic acids amide such as acrylamide etc..These monomers can be used alone, or two or more is applied in combination.
＜ adhesive phases ＞
Adhesive phase is set on base material, in addition, equipped with middle layer, is set in the middle layer.This hair Bright adhesive phase includes at least urethane based resin (A) and energy ray-curable compound (B), the energy line curing Property compound (B) do not reacted with urethane based resin (A) and molecular weight be 35,000 or less.
In the present invention, by making adhesive phase contain urethane based resin (A), the cohesiveness and machine of adhesive phase Tool intensity improves, and therefore, when removing adhesive tape from workpiece after energy line curing, is not easy to generate in workpiece surfaces such as convex blocks Residual paste.In addition, by least containing energy ray-curable compound (B), it can make adhesive phase that there is energy ray-curable.Cause This, stripping performance when can make to remove adhesive tape from workpiece is good.In addition, by making energy line curability compound (B) To be non-reacted, the storage modulus of adhesive phase can be reduced as hereinafter described, be easy to ensure the bumps to workpiece surface Followability.
Fracture strength of the adhesive phase after energy line irradiation is preferably 2.5MPa or more.When fracture strength be 2.5MPa with When upper, mechanical strength is enough values, is easy to reduce above-mentioned residual paste.In addition, from inhibiting residual paste and being easy to carry high-crowned bury Entering property, adhesive phase cementability and fissility from the viewpoint of, above-mentioned fracture strength is preferably 2.8~30MPa, more preferably 3.0~25MPa.It should be noted that fracture strength is measured according to the method described in the embodiment described below.
It should be noted that fracture strength can be adjusted by changing the type of urethane based resin (A). Alternatively, it is also possible to be adjusted by the amount of the optical polymerism unsaturated bond described below, existing makes to contain in adhesive phase The amount of the optical polymerism unsaturated bond tendency that fracture strength reduces when fracture strength increases, reduces when increasing.Likewise it is possible to It is adjusted by the amount of the crosslinker component described below, there is fracture strength when the amount of crosslinker component being made to increase and increase The tendency that fracture strength reduces when greatly, reducing.
Adhesive phase is energy ray-curable, can be softer quality in energy line pre-irradiation, adhesive phase is easy therefore In following the bumps for being formed in workpiece surface.In addition, for adhesive tape, cured by irradiation energy line, can be made Bonding force reduces, and is easy to remove from workpiece.
From the viewpoint of residual paste when adhesive tape being inhibited to remove, bonding force of the adhesive tape after energy line irradiation is preferably 2000mN/25mm or less.It is prominent greatly with convex block etc. especially surface to be pasted in the adhesive tape for the present invention that there will be middle layer In the case of the workpiece for playing (such as 200 μm of height or more), it is generally in protrusion and is glued in the adhesive tape of workpiece surface The state that interbed is absorbed.Therefore, although from residual paste is easy tod produce when removing adhesive tape thereon, by the way that bonding force to be set as 2000mN/25mm is hereinafter, can be easy to prevent such residual paste.Adhesive tape energy line irradiation after bonding force be preferably 50~1750mN/25mm, more preferably 100~1500nN/25mm.
In addition, adhesive tape is greater than 2000mN/25mm in the bonding force of energy line pre-irradiation, preferably 3000~ 30000mN/25mm, more preferably 3500~9000mN/m.When the bonding force of energy line pre-irradiation is the range, to workpiece surface Cementability it is good, the protective value of workpiece is good.
It should be noted that the bonding force of adhesive tape be by the adhesive level of adhesive tape be pasted on silicon mirror chip, in It is measured in the environment of 23 DEG C, when being removed with 180 ° of peel angle, 300mm/ points of peeling rate, specifically according to rear What the method described in the embodiment of face narration measured.
Bonding force can by change type etc. of urethane based resin (A), energy ray-curable compound (B) come It is adjusted.In addition, energy line irradiation after bonding force can by the amount of the optical polymerism unsaturated bond described below come into Row adjustment, it is viscous when bonding force is reduced, reduced when increasing there are the amount of the optical polymerism unsaturated bond contained in adhesive composition The tendency that resultant force increases.In addition, the bonding force after energy line irradiation can also contain optical polymerism by cooperation as hereinafter described Crosslinking agent (C1), the compound (D) of unsaturated bond and easily reduce.
(urethane based resin (A))
Urethane based resin (A) is the polymer containing at least one of urethane bond and urea bond.In addition, The adhesive phase of the present invention is by including at least the amino first of urethane polymer (A ') and energy ray-curable compound (B) Esters of gallic acid adhesive composition (hereinafter, also referred to as " adhesive composition ") is formed, urethane based resin (A) at least by Urethane polymer (A ') as host agent is constituted.In addition, carbamates adhesive composition can be as needed Further contain crosslinking agent (C), compound (D) etc..
Urethane based resin (A) can utilize resin made of crosslinking agent (C) crosslinking.In addition, as described above, ammonia Carbamate class adhesive composition can also contain direct or indirect as compound (D) etc. other than crosslinking agent (C) The chemical combination that ground is bonded to urethane polymer (A '), is integrally formed urethane based resin (A) within the adhesive layer Object.
It should be noted that it is poly- to be directly or indirectly bonded to carbamate as crosslinking agent (C) and compound (D) It closes object (A '), be integrally formed urethane based resin (A) within the adhesive layer together with urethane polymer (A ') Compound be generically and collectively referred to as " host agent reactive compounds ".
In the present invention, coordinate the ingredient (B) described below in order to ensure the adhesiveness of adhesive phase and with amount appropriate ~(E), relative to adhesive composition total amount, the use level of urethane polymer (A ') is preferably 30~85 mass %, More preferably 35~80 mass %, further preferably 37~77 mass %.In addition, relative to adhesive composition total amount, it is main It is preferably 40~95 mass % that the use level of agent reactive compounds and urethane polymer (A '), which amounts to, and more preferably 45 ~94 mass %, further preferably 50~93 mass %.
Urethane based resin (A) preferably has optical polymerism unsaturated bond.Have in urethane based resin (A) When optical polymerism unsaturated bond, in the adhesive phase of work pieces process adhesive tape, urethane based resin (A) and energy line Curability compound (B) all has optical polymerism unsaturated bond.Therefore, by adhesive phase irradiation energy line, utilizing polymerization Reaction bonding between urethane based resin (A) and energy ray-curable compound (B), it is easier to reduce energy line irradiation The bonding force of adhesive tape afterwards, fissility when making to remove adhesive tape from workpiece become good.And then it can be further The residual paste that reduction generates when removing adhesive tape from workpiece.In addition, carrying out base with merely with energy ray-curable compound (B) It is compared in the case where adhesive phase solidification of energy line irradiation, there are what the intensity of the adhesive phase after energy line irradiation increased to incline To, it is easier to inhibit the generation of residual paste.
It is not particularly limited to the method for importing optical polymerism unsaturated bond in urethane based resin (A).For example, Optical polymerism unsaturated bond import before urethane polymer (A ') there is hydroxyl in the case of, can make to have can be with The compound of the functional group of hydroxyl reaction and functional group comprising optical polymerisms unsaturated bonds such as (methyl) acryloyl groups with it is above-mentioned Hydroxyl reaction, to import optical polymerism unsaturated bond.As it is above-mentioned have can with the functional group of hydroxyl reaction and include light The compound of the functional group of polyunsaturated bond can be enumerated for example：Methacryloxyethyl isocyanates etc..In this way Compound it can be made to be reacted with urethane polymer (A ') in advance, it can also be made to be contained in adhesive phase in advance In, so that it is reacted with urethane polymer (A ') when forming adhesive phase.
In addition, as it is explained in detail hereinafter, as crosslinking agent (C), it is right using the crosslinking agent (C1) with optical polymerism unsaturated bond Urethane polymer (A ') is crosslinked, it is possible thereby to import optical polymerism insatiable hunger into urethane based resin (A) And key.Furthermore it is also possible to import optical polymerism not into urethane based resin (A) using the compound (D) described below Saturated bond.
＜ urethane polymers (A ') ＞
Urethane polymer (A ') can enumerate the polymerization containing at least one of urethane bond and urea bond Object, can specifically enumerate end obtained from making polyalcohol and polyisocyanate compound react has the polyurethane of hydroxyl polynary Alcohol.In addition, urethane polymer (A ') can use so that polyalcohol and polyisocyanate compound is reacted obtained from end End is the urethane polymer of isocyanates.
As polyalcohol used in urethane polymer (A '), polyester polyol and polyether polyols can be enumerated Alcohol.
As polyester polyol, well known polyester polyol can be used.Polyester polyol is sour component and diol component And the ester that at least one of polyol component is formed can be enumerated as sour component：Terephthalic acid (TPA), adipic acid, nonyl two Acid, decanedioic acid, phthalic anhydride, M-phthalic acid, trimellitic acid etc..In addition, as diol component, can enumerate：Second two Alcohol, propylene glycol, diethylene glycol, butanediol, 1,6-HD, 3- methyl-1s, 5- pentanediols, 3,3 '-dihydroxymethyl heptane, polyoxy Ethylene glycol, polyoxypropylene diols, 1,4-butanediol, neopentyl glycol, butyl ethyl pentanediol can be with as polyol component It enumerates：Glycerine, trimethylolpropane, pentaerythrite etc..
Alternatively, it is also possible to being by the lactones ring-opening polymerisation such as polycaprolactone, poly- (Beta-methyl-gamma-valerolactone), poly- valerolactone Obtained from polyester polyol etc..
In addition, as polyether polyol, well known polyether polyol can be used.It is, for example, possible to use following polyethers is more First alcohol, the polyether polyol are uses with low molecular weight polyols such as water, propylene glycol, ethylene glycol, glycerine, trimethylolpropanes As initiator, make the synthesis of epoxy compounds such as ethylene oxide, propylene oxide, epoxy butane, tetrahydrofuran obtained from, specifically It is 2 or more polyether polyol that the functional group numbers such as polypropylene glycol, polyethylene glycol, polytetramethylene glycol, which can be used,.
As polyisocyanate compound, can enumerate：Well known aromatic polyisocyanate, aliphatic polyisocyanic acid Ester, aromatic-aliphatic polyisocyanates, alicyclic polyisocyanates etc..As aromatic polyisocyanate, can enumerate：1,3- Phenylene diisocyanate, 4,4 '-biphenyl diisocyanates, 1,4- phenylene diisocyanates, 4,4 '-methyl diphenylene diisocyanates, 2,4 toluene diisocyanate, 2,6- toluene di-isocyanate(TDI)s, 4,4 '-toluidine diisocyanates, 2,4,6- triisocyanates Base toluene, 1,3,5- triisocyanate bases benzene, dianisidine diisocyanate (dianisidine diisocyanate), 4, 4 '-diphenyl ether diisocyanates, 4,4 ', 4 "-triphenylmethane triisocyanates etc..
As aliphatic polyisocyante, can enumerate：Trimethylene diisocyanate, tetramethylene diisocyanate, Hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2- trimethylene diisocyanates, 2,3- butylidene diisocyanates Ester, 1,3- tetramethylene diisocyanates, ten dimethylene diisocyanates, 2,4,4- trimethyl hexamethylene diisocyanates Deng.
As aromatic-aliphatic polyisocyanates, can enumerate：ω, ω '-diisocyanate ester group -1,3- dimethyl benzenes, ω, ω '-diisocyanate ester group -1,4- dimethyl benzenes, ω, ω '-diisocyanate ester group -1,4- diethylbenzenes, durol two Methylene -1,4- diisocyanate, tetramethylxylene -1,3- diisocyanate etc..
As alicyclic polyisocyanates, can enumerate：3- isocyanatomethyl -3,5,5- trimethylcyclohexyl isocyanides Acid esters, 1,3- pentamethylene diisocyanate, 1,3- cyclohexane diisocyanates, 1,4- cyclohexane diisocyanates, methyl -2,4- Cyclohexane diisocyanate, methyl -2,6- cyclohexane diisocyanates, 4,4 '-methylene two (cyclohexyl isocyanate), 1,4- Two (isocyanatomethyl) hexamethylenes, 1,4- bis- (isocyanatomethyl) hexamethylene etc..
In addition, the trihydroxy methyl third of above-mentioned polyisocyanate compound can be applied in combination in above-mentioned polyisocyanate compound Alkane addition product, reacted with water obtained from biuret body, 3 polymers etc. containing isocyanurate ring.
As polyisocyanate compound, preferably 4,4 '-methyl diphenylene diisocyanates, hexa-methylene diisocyanate Ester, 3- isocyanatomethyl -3,5,5- trimethylcyclohexylisocyanates (isophorone diisocyanate) etc..
In addition, polyurethane polyol can be other than polyalcohol and polyfunctional isocyanate also with ethylenediamine, N- ammonia Polyurethane polyol made of the diamine reactants such as ehtylethanolamine, isophorone diamine, benzene dimethylamine.In addition, as polyalcohol, Other than above-mentioned polyester polyol, polyether polyol, ethylene glycol, 1,4-butanediol, neopentyl glycol, butyl can also be used Ethyl pentanediol, glycerine, trimethylolpropane, pentaerythrite etc..
It should be noted that the reaction of polyalcohol and polyisocyanate compound is usually in tertiary amine compounds, You Jijin It is carried out in the presence of the catalyst such as category class compound.
As urethane polymer (A '), it is not limited to above-mentioned example, for example, can also be Michael's addition type Urethane polymer.
As Michael's addition type urethane polymer, it can be cited for example that (1) below, (2) such polymerization Object.
(1) polymer obtained from making amino-compound be reacted with carbamate prepolymer, the carbamate are pre- Polymers is obtained from so that above-mentioned polyalcohol is reacted with polyisocyanate compound, and end have isocyanate group (- NCO), the amino-compound is that polyamines is made to occur obtained from Michael addition reaction with unsaturated compound.
(2) make unsaturated compound that polymer obtained from Michael addition reaction, the poly- ammonia occur with polyurethane-urea Ester urea be above-mentioned polyalcohol, polyisocyanate compound and polyamines reaction obtained from, and end have primary amino group or parahelium Base.
As the polyamines used in Michael's addition type urethane polymer, well known polyamines, tool can be used Body can be enumerated：Ethylenediamine, propane diamine, trimethylene diamine, tetra-methylenedimine, five methylene diamine, hexamethylene diamine, Trien, diethylenetriamines, triaminopropane, 2,2,4- trimethylhexamethylenediamines, toluenediamine, hydrazine, piperazine The alicyclic polyamines such as the aliphatic polyamines such as piperazine, isophorone diamine, dicyclohexyl methyl hydride -4,4 '-diamines and phenylenediamine, benzene two The aromatic polyamines such as methylamine.Furthermore it is also possible to which using 2- hydroxyethyl ethylenediamine, N- (2- ethoxys) propane diamine, (2- ethoxys are sub- Propyl) diamines, (two -2- ethoxys ethylidene) diamines, (two -2- ethoxys propylidene) diamines, (2- hydroxypropyls ethylidene) two Diamines in amine, (two -2- hydroxypropyls ethylidene) diamines equimolecular with hydroxyl and be amino by the converting carboxylate groups of dimeric dibasic acid Dimer diamine, two ends there is propoxyl group amine and polyether polyols diamines etc. shown in following logical (2).
H2-NCH2-CH2-CH2-O(CnH2n-O)m-CH2-CH2-CH2-NH2 (2)
(it should be noted that in formula (2), n indicates that 2~4 arbitrary integer, m indicate 2~50 arbitrary integer.)
In addition, as polyamines, it can also use end that there is the dendritic of primary amino group or secondary amino group (dendrimer)。
In above-mentioned polyamines, from the viewpoint of being easy to control reaction, preferably isophorone diamine, 2,2,4- trimethyls Hexamethylene diamine, hexamethylene diamine.
In addition, in order to be modified to urethane polymer, Michael's addition type carbamate can be used poly- Close the unsaturated compound used in object.Therefore, unsaturated compound ready for use can arbitrarily be selected according to modified purpose Type.As unsaturated compound, can enumerate for example：(methyl) acrylic compounds unsaturated compound, amides are unsaturated Compound, fatty acid vinyl ester unsaturated compounds, vinyl ethers unsaturated compounds, alpha-olefines unsaturation chemical combination Object, allylic unsaturated compound, allyl acetate unsaturated compounds, vinyl cyanide unsaturated compounds, benzene second Alkene or vinyl benzene unsaturated compounds etc..
The type of unsaturated compound ready for use can be arbitrarily selected according to modified purpose, but is preferably conceived to not Functional group possessed by saturated compounds selects.As functional group possessed by such unsaturated compound, can be exemplified Go out alkyl, polyalkylene glycol base, alkoxy, phenoxy group, hydroxyl, carboxyl, perfluoroalkyl, alkoxysilyl, epoxy group, And nitrogen-containing groups such as amide groups, dialkyl amido, quaternary ammonium salt base etc., in order to make as described above in urethane polymer (A ') Containing hydroxyl, preferably there is hydroxyl.
It should be noted that the specific example as unsaturated compound, these compounds can use such as Japan special Open the compound described in 2002-121256 bulletins (Europe Publication EP1146061A1).
The weight average molecular weight of urethane polymer (A ') used in the present invention is preferably 10,000~300,000, More preferably 30,000~150,000.By make weight average molecular weight be 10,000 or more, the cohesiveness of adhesive phase can be improved, The higher effect for inhibiting residual paste can be obtained.In addition, by making weight average molecular weight for 300,000 hereinafter, there are following advantages： Being diluted or heated with solvent when forming adhesive phase by adhesive composition makes its melting, to not easily lead to viscosity It is increased to influence the degree of Technological adaptability.
(energy ray-curable compound (B))
Energy ray-curable compound (B) used in the present invention is not reacted and is had with urethane based resin (A) Optical polymerism unsaturated bond.
Here, it does not react and refers to, other than " optical polymerism unsaturated bond ", do not contain not only and urethane polymerization The functional group of object (A ') reaction, does not contain the functional group reacted with host agent reactive compounds yet, compound (B) be not with bonding The compound that urethane based resin (A) reacts in oxidant layer.
That is, energy ray-curable compound (B) is by making urethane polymer (A '), crosslinking agent (C) and root When forming adhesive phase according to needing other ingredients (such as (D) ingredient) to be used to be reacted, not with these (A '), (C), (D) compound of ingredient reaction.
As a result, energy ray-curable compound (B) as do not constituted in adhesive phase urethane based resin (A) at Divide and exists.For urethane polymer, usual cohesiveness is high and storage modulus is also high, in the case that individual difficult With protrusions such as the convex blocks that is embedded to workpiece surface, in the present invention, the energy of urethane polymer chain is not made up of cooperation Line curability compound (B) makes the storage modulus of adhesive phase reduce, and is easy to ensure the imbedibility to convex block.
It should be noted that in the present invention, optical polymerism unsaturated bond refers to being reacted not by energy line irradiates Saturated bond, typically olefinic double bond, the carbon-to-carbon double bond preferably contained in (methyl) acryloyl group.
The molecular weight of energy ray-curable compound (B) is 35,000 or less.When molecular weight is more than 35,000, it is difficult to make to glue The storage modulus of mixture layer reduces, it is difficult to ensure to the imbedibility of convex block.Additionally, there are with urethane based resin (A) The hidden danger of compatibility poor.The molecular weight of energy ray-curable compound (B) is preferably 150~35,000, further preferably 200~34,000.It should be noted that molecular weight refers to its formula weight when can determine formula weight, it is when not can determine that formula weight Refer to weight average molecular weight.
The use level of energy ray-curable compound (B) is different according to the compound used, relative to carbamate 100 mass parts of resinoid (A) are (that is, refer to 100 mass of total of urethane polymer (A ') and host agent reactive compounds Part, it is same as below), usually 1~120 mass parts, preferably 2~100 mass parts, more preferably 4~90 mass parts.Passing through will The use level of energy ray-curable compound (B) is set as such range, it is readily available have both to the followability of workpiece surface and Inhibit the adhesive phase of residual paste.
As the particular compound of energy ray-curable compound (B), the change with (methyl) acryloyl group can be enumerated Close object.(methyl) acryloyl group (optical polymerism unsaturated bond) functional group in one molecular energy line curability compound (B) is only To be 1 or more, preferably 2 or more, more preferably 2~12.
In addition, the specific example as energy ray-curable compound (B) used in the present invention, can enumerate and be selected from It is at least one kind of in (methyl) acrylate monomer (B1) and carbamate (methyl) acrylate (B2).
(methyl) acrylate monomer (B1) is the compound for having in the molecule (methyl) acryloyl group, (methyl) third The quantity of enoyl- is preferably 2 or more, more preferably 3~6.Especially do not have light in urethane based resin (A) In the case of polyunsaturated bond, preferably adhesive phase contains the quantity of (methyl) acryloyl group for 4 or more (methyl) Acrylate monomer (B1), to be easy to make the bonding force of adhesive tape to reduce after to adhesive phase irradiation energy line.
As (methyl) acrylate monomer (B1), whole hydroxyls and (methyl) propylene for example, polyalcohol can be enumerated Acid forms the multifunctional (methyl) acrylate of complete carboxylate obtained from ester.Here, the carbon atom number of polyalcohol is preferred It is 4~10.In addition, the molecular weight of (methyl) acrylate monomer (B1) is preferably 150~1000, more preferably 200~800.
As the particular compound of multifunctional (methyl) acrylate, can enumerate：Trimethylolpropane tris (methyl) third Olefin(e) acid ester, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, 1,4- butanediols two (methyl) Acrylate, 1,6- hexylene glycols two (methyl) acrylate etc., wherein preferred pentaerythrite four (methyl) acrylate.
It should be noted that (methyl) acrylate monomer (B1) can determine that structure, molecular weight refer to its formula weight.
(methyl) acrylate monomer (B1) can also prevent residual paste in less use level, and can pass through energy line Cure and making bonding force suitably reduces, therefore preferably.
In addition, specifically, relative to 100 mass parts of urethane based resin (A), (methyl) acrylate monomer (B1) use level is preferably 1~20 mass parts, more preferably 2~15 mass parts, further preferably 3~10 mass parts.It is logical It crosses and energy line curability compound (B) is set as such use level, can suitably prevent the residual paste of adhesive phase, and can be with It is irradiated by energy line by the bonding force of adhesive phase is made suitably to reduce.
Carbamate (methyl) acrylate (B2) is with urethane bond and end is with (methyl) acryloyl The polymer of base.As carbamate (methyl) acrylate (B2), can enumerate：Pass through polyol compound and polyisocyanate cyanogen The reaction of ester compound generates terminal isocyanate urethane polymer, and makes the functional group of its end and have (first Base) acryloyl group compound reaction obtained from compound etc..Such carbamate (methyl) acrylate (B2) by There is energy ray-curable in the effect of (methyl) acryloyl group.
It should be noted that carbamate (methyl) acrylate (B2) and the polyol that uses in order to obtain Object, polyisocyanate compound and can be from the carbamate of above-mentioned middle layer with the compound of (methyl) acryloyl group Polyol compound, polyisocyanate compound used in (methyl) acrylate (X) and with (methyl) acryloyl group Appropriate selection uses respectively in compound, omits it here and illustrates.
Carbamate (methyl) acrylate (B2) has (methyl) acryloyl group, (methyl) propylene in 1 molecule Acyl function is preferably 2 or more, more preferably 2~12, further preferably 2~10.As a result, by making its more official Energyization may be easy to make bonding force reduce by energy line curing.
In addition, the molecular weight of carbamate (methyl) acrylate (B2) be 35000 hereinafter, preferably 2000~ 35000, more preferably 5000~34000.It should be noted that the molecular weight of carbamate (methyl) acrylate (B2) is Refer to weight average molecular weight.By the way that the molecular weight of carbamate (methyl) acrylate is set as such range, adhesive can be made The storage modulus of layer reduces, and is easy to ensure the followability to workpiece surface bumps.It is additionally possible to suppress the amino in adhesive phase The movement of formic acid esters (methyl) acrylate (B2), improves the ageing stability of adhesive tape.
In the case where energy ray-curable compound (B) is carbamate (methyl) acrylate (B2), amino first The use level of acid esters (methyl) acrylate (B2) is preferably 30~120 relative to 100 mass parts of urethane based resin (A) Mass parts, more preferably 40~100 mass parts, further preferably 50~90 mass parts.By by carbamate (methyl) Acrylate (B2) is set as such use level, can keep the bond properties of adhesive phase well, and be easy to ensure imbedibility. In addition, bonding force can fully be reduced by energy line curing, and then it is easy to that residual paste is made to reduce.
(crosslinking agent (C))
The adhesive composition of the present invention preferably further contains crosslinking agent (C).Crosslinking agent (C) is poly- with carbamate Object (A ') is closed to react and make urethane polymer (A ') crosslinked substance.By making adhesive composition contain crosslinking agent (C), crosslink density can be improved, be easily formed the adhesive phase of high mechanical strength.In addition, when can also be easy to prevent stripping adhesive tape Residual paste etc..
Preferably there are 2 or more in the case where urethane polymer (A ') has hydroxyl as crosslinking agent (C) The crosslinking agent of isocyanate group, to be reacted with the hydroxyl.It should be noted that containing crosslinking agent in adhesive composition In the case of, usually it is crosslinked by heated after application.
In addition, conversely, can also be urethane polymer (A ') there is isocyanate group, crosslinking agent (C) to have hydroxyl Base.For urethane polymer (A '), from its manufacturing method for, usually have hydroxyl or isocyanate group, Therefore preferably urethane polymer (A ') is bonded with crosslinking agent (C) by urethane bond.
As the crosslinking agent (C) that can be used in the present invention, it is preferable to use the crosslinking agent containing optical polymerism unsaturated bond (C1)。
In addition, the crosslinking agent (C1) containing optical polymerism unsaturated bond be preferably with 2 or more isocyanate group and The compound of (methyl) acryloyl group, more preferably using carbamate (methyl) propylene at least with 2 isocyanate group Acid esters.
The weight average molecular weight of carbamate (methyl) acrylate is preferably 500~2000, more preferably 700~ 1000.In addition, in the case where a molecule cross-link agent (C1) has 2 or more optical polymerism unsaturated bonds, there are molecule friendships Optical polymerism unsaturated bond in connection agent (C1) is easy tendency polymerized together.Accordingly, it is difficult to which crosslinking agent (C1) is had Optical polymerism unsaturated bond and optical polymerism unsaturated bond possessed by other molecules react, sometimes through to adhesive phase Irradiation energy line and the effect that makes the bonding force of adhesive tape reduce is small.Therefore, as crosslinking agent (C1), have in a preferably molecule 1 optical polymerism unsaturated bond.In addition, as carbamate (methyl) acrylate that crosslinking agent (C1) uses, Ke Yilie Citing is such as：" EBECRYL 4150 " of DAICEL-ALLNEX companies manufacture.
In the present embodiment, by using the crosslinking agent (C1) with optical polymerism unsaturated bond, within the adhesive layer Make urethane based resin (A) that there is optical polymerism unsaturated bond.
As the crosslinking agent containing hydroxyl and optical polymerism unsaturated bond, can enumerate for example：Side chain have hydroxyl and The acrylate copolymer of (methyl) acryloyl group.In this case, carbamates made of being crosslinked using crosslinking agent (C1) Resin (A) becomes so-called propenoic methyl carbamate resin, also includes in this way in urethane based resin of the invention (A) Propenoic methyl carbamate resin.
Relative to 100 mass parts of urethane based resin (A), the crosslinking agent (C1) containing optical polymerism unsaturated bond Use level is preferably 5~60 mass parts, more preferably 10~50 mass parts, further preferably 15~45 mass parts.Passing through will Crosslinking agent (C1) is set as such use level, and the crosslink density of adhesive phase can be made to become good, and can be by appropriate amount Optical polymerism unsaturated bond imported into urethane based resin (A).
In addition, adhesive composition, which can also contain the crosslinking agent (C2) without optical polymerism unsaturated bond, is used as crosslinking agent (C).It can be from the above-mentioned use enumerated in the case where urethane polymer (A ') has hydroxyl as crosslinking agent (C2) Suitably selection uses in the polyisocyanate compound that synthesis of carbamates polymer (A ') uses.In addition, being crosslinked In the case that preceding polymer (A ') has isocyanate group, well known polyalcohol can be used as crosslinking agent (C2).Pass through So that adhesive composition is contained crosslinking agent (C2), can fully improve the crosslink density of adhesive phase.
Crosslinking agent (C) can be entirely the crosslinking agent (C1) with optical polymerism unsaturated bond, can also be entirely to be free of The crosslinking agent (C2) of optical polymerism unsaturated bond preferably comprises the crosslinking agent (C1) with optical polymerism unsaturated bond, more preferably Contain both crosslinking agent (C1) and crosslinking agent (C2).
Relative to 100 mass parts of urethane based resin (A), the crosslinking agent (C2) of optical polymerism unsaturated bond is free of Use level is preferably 0.2~15 mass parts, more preferably 0.5~10 mass parts.In addition, as described above, crosslinking is applied in combination In the case of agent (C1), the use level of the crosslinking agent (C2) without optical polymerism unsaturated bond can be less, relative to amino first 100 mass parts of acid esters resinoid (A), preferably 0.2~5 mass parts, more preferably 0.5~2 mass parts.
(compound (D))
In the case where adhesive composition contains crosslinking agent (C), preferably also contain compound (D), the compound (D) With optical polymerism unsaturated bond and the reactive functional groups that can be reacted with crosslinking agent (C).Change with reactive functional groups When conjunction object (D) reacts with crosslinking agent (C) in urethane polymer (A ') and forms urethane polymer chain, with crosslinking Agent (C) reacts.
When adhesive composition contains compound (D), using compound (D) into urethane based resin (A) Import optical polymerism unsaturated bond.Therefore, when making adhesive phase cure by energy line, the viscous of adhesive phase can easily be made Resultant force reduces, and can also be easily prevented from residual paste etc..In addition, also have the effect of being easy to make the performance of adhesive tape through when stablize.
As the reactive functional groups contained by compound (D), can enumerate：Isocyanate group, hydroxyl.In addition, conduct Compound (D) can enumerate (methyl) acrylate monomer with hydroxyl He (methyl) acryloyl group.1 molecular compound (D) In (methyl) acryloyl group (i.e. optical polymerism unsaturated bond) functional group quantity be preferably in 1 molecule contain 2 or more, more Preferably 2~5.
It is preferably 150~3 to use the molecular weight of (methyl) acrylate monomer as ingredient (D), and 000, more preferably It is 200~2,000.
Use (methyl) acrylate monomer that can enumerate the portion of polyalcohol and (methyl) acrylic acid as ingredient (D) Divide the multifunctional (methyl) acrylate of carboxylate.Here, the carbon atom number of polyalcohol is preferably 4~10.As specificization Object is closed, can be exemplified out：Pentaerythrite three (methyl) acrylate, dipentaerythritol four (methyl) acrylate, two seasons penta 4 Alcohol five (methyl) acrylate etc., wherein it is preferred that pentaerythrite three (methyl) acrylate.
Relative to 100 mass parts of urethane based resin (A), the use level of compound (D) is preferably 1~30 mass Part, more preferably 2~20 mass parts, further preferably 3~15 mass parts.By in such range fit compound (D), Harmful effect can not be caused to the bond properties of adhesive phase, be easy to reduce bonding force by the solidification of energy line, be also easy to Prevent residual paste.In addition, in the case where energy ray-curable compound (B) contains (methyl) acrylate monomer (B1), usually It is preferable to use compound (D).It, can be further as a result, when compound (D) and (methyl) acrylate monomer (B1) is applied in combination Play the effect of the present invention.
(energy line polymerization initiator (E))
Adhesive composition preferably also contains energy line polymerization initiator (E).It is poly- by making adhesive phase contain energy line Initiator (E) is closed, can easily be cured by energy line irradiation.It, can be from upper as energy line polymerization initiator (E) It states and suitably selects to use in the Photoepolymerizationinitiater initiater that the middle layer resin combination enumerated can use.
It is solid relative to urethane polymer (A '), crosslinking agent (C1), energy line with optical polymerism unsaturated bond 100 mass parts of total of the compound with optical polymerism unsaturated bond such as the property changed compound (B), compound (D), energy line are poly- The use level for closing initiator (E) is preferably 0.05~25 mass parts, more preferably 0.1~20 mass parts, further preferably 0.3 ~15 mass parts.
It should be noted that adhesive composition other can add containing what is used in carbamates adhesive in the past Add agent, fillers, colorant, antioxidant, antifoaming agent, the light stabilizers such as calcium carbonate, titanium oxide etc. can be contained.
The thickness of adhesive phase can be according to bump height of wafer surface etc., the surface for being attached face of stickup adhesive tape State and suitably adjust, preferably 2~150 μm, more preferably 5~100 μm, further preferably 8~50 μm.
＜ release liners ＞
The release liner used in the process of the release liner, the manufacturing method described below that are set on adhesive phase can Using having carried out the stripping film of single side lift-off processing, carried out the stripping film etc. of two-sided lift-off processing, can enumerate in stripping material The material release liner etc. that remover is coated on base material.
As release liner base material, can enumerate for example：Pet resin, poly terephthalic acid The polyolefin such as polyester resin films, acrylic resin, the polyvinyl resins such as butanediol ester resin, polyethylene naphthalate resin Plastic foils such as resin film etc..
As remover, can enumerate for example：Organic silicon resin, olefine kind resin, isoprene resin, butadiene The heat-resistant powder fillers such as resinoid, chain alkyl resinoid, alkyd based resin, fluorine-containing resinoid etc..
In addition, the thickness of release liner is not particularly limited, preferably 5~200 μm, more preferably 10~120 μm.
[manufacturing method of adhesive tape]
The manufacturing method of the adhesive tape of the present invention is not particularly limited, and can be manufactured by well known method.
Middle layer can for example be formed in the following manner：It is directly coated with middle layer resin combination in the one side of base material Solution and form coated film, be then dried as needed, and carry out curing process.In addition, middle layer can by with Under type is formed：It is coated with the solution of middle layer resin combination in the lift-off processing face of release liner and forms coated film, so It is dried as needed afterwards, carries out semi-solid preparation processing, thus form semi-solid preparation layer on release liner, which is glued It is affixed on base material, and semi-solid preparation layer is made to be fully cured.At this point it is possible to appropriate before semi-solid preparation layer is fully cured or after solidification Remove release liner.It should be noted that the solidification of middle layer preferably makes its polymerizing curable to coated film irradiation energy line, energy It is preferably ultraviolet light to measure line.In addition, when forming middle layer using olefines material, in being formed by extrusion molding etc. Interbed.
In addition, adhesive phase is preferably heated, is crosslinked to adhesive composition after coating adhesive composition and root It is dried and is formed according to needs.At this point, adhesive composition can be coated directly onto on middle layer or base material, can also be coated with In forming adhesive phase on the lift-off processing face of release liner, adhesive phase is then fitted in into shape in middle layer or base material At.The release liner of configuration over the binder layer can be removed as needed.
It, can be in middle layer resin combination or adhesive composition further when forming middle layer, adhesive phase Coordinate organic solvent, the dilution of middle layer resin combination or adhesive composition is made.As the organic solvent used, It can enumerate for example：Methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, twoAlkane, hexamethylene, n-hexane, toluene, dimethylbenzene, Normal propyl alcohol, isopropanol etc..
It should be noted that these organic solvents can directly use middle layer resin combination or adhesive composition In contain each ingredient synthesis when used organic solvent, a kind or more of organic solvent other than it can also be added.
Middle layer resin combination or adhesive composition can be coated by well known coating method.As painting Cloth method can be enumerated for example：Spin-coating method, spray coating method, stick coating method, scraper for coating method, rolling method, scraper plate rubbing method, die coating method, Gravure coating process etc..
[application method of adhesive tape]
The adhesive tape of the present invention is pasted on various workpiece, uses when processing the workpiece, is preferably pasted on concave-convex, protrusion Workpiece face use.
In addition, being more preferably pasted on semiconductor wafer surface, particularly foring the wafer surface of convex block, as semiconductor Wafer surface protection is used with adhesive tape.In addition, adhesive tape is further preferably pasted on semiconductor wafer surface, subsequent Chip back surface grinding when be formed in wafer surface as protection the back grinding tape of circuit use.In the adhesive tape of the present invention In the case of with middle layer, even if good if wafer surface has the difference of height imbedibility by formation such as convex blocks therefore brilliant The protective value on piece surface is good.In this case, adhesive tape is pasted on to the adhesive tape temperature when surface of semiconductor wafer For such as 40~80 DEG C or so, preferably 50~70 DEG C.
In the present invention, adhesive phase is energy-line solidifying type, is pasted on the adhesive tape of the workpiece surfaces such as semiconductor wafer After irradiation energy line has carried out energy line curing, removed from workpiece surface.Therefore, for adhesive tape, due to It is stripped after so that bonding force is reduced, therefore its fissility is good.In addition, when removing the adhesive tape after solidification as described above, do not allow Residual paste easily occurs.
It should be noted that adhesive tape when for semiconductor wafer purposes, is not limited to back of the body grinding, can be used for Other purposes.For example, it is also possible to adhesive tape is pasted on chip back surface, as the cutting sheet for keeping chip in cut crystal To use.In this case, chip can be workpiece for foring through electrode etc. chip back surface form the protrusions such as convex block, Concave-convex workpiece.
Embodiment
Hereinafter, the present invention is illustrated in further detail based on embodiment, but the present invention is not by these examples Limitation.
Assay method in the present invention, evaluation method is as follows described.
[weight average molecular weight (Mw), number-average molecular weight (Mn)]
Using gel permeation chromatography device (ProductName " HLC-8220 ", TOSOH Co., Ltd manufacture), under the following conditions It measures, uses the value for measuring and being converted into standard polystyren.
(determination condition)
Chromatographic column：“TSK guard column HXL-H”“TSK gel GMHXL(×2)”“TSK gel G2000HXL” (being TOSOH Co., Ltd's manufacture)
Column temperature：40℃
Eluting solvent：Tetrahydrofuran
Flow velocity：1.0mL/ point
[loss angle tangent (tan δ)]
The middle layer resin group that will be used in each Examples and Comparative Examples in a manner of jet flow die head (fountain die) It closes object and is coated on polyethylene terephthalate film class stripping film (Lindeke Co., Ltd's manufacture, ProductName " SP- 38 μm of PET381031 ", thickness) on, form film.Then, ultraviolet light is irradiated from film side, forms semi-solid preparation layer.
It should be noted that as ultraviolet lamp, conveyor type ultraviolet lamp is used (manufacture of Eyegraphics companies, ProductName " ECS-4011GX "), as ultraviolet source, uses high-pressure mercury-vapor lamp (manufacture of Eyegraphics companies, ProductName " H04-L41 "), as irradiation condition, in the illumination 112mW/ of optical wavelength 365nm cm2, light quantity 177mJ/cm2The item of (being measured using the ultraviolet gauge " UVPF-A1 " of Eyegraphics companies manufacture) Ultraviolet light irradiation has been carried out under part.
Polyethylene terephthalate film class stripping film (Lindeke Co., Ltd's system is laminated on the semi-solid preparation layer of formation Make, ProductName " SP-PET381031 ", 38 μm of thickness), and further carry out ultraviolet light irradiation and (irradiated using above-mentioned ultraviolet light Device, ultraviolet source, as irradiation condition, illumination 271mW/cm2, light quantity 1,200mJ/cm2), so that it is fully cured, forms Two sides is pasted with the middle layer of 200 μm of the thickness of stripping film.
Prepare 5 middle layers formed in this way, removes PET class stripping films, release surface is overlapped each other, successively lamination, by This is prepared for middle layer laminated body (1,000 μm of thickness).
Then, obtained middle layer laminated body is punched into the circle of diameter 10mm, has been obtained viscoelastic for measuring Sample.Frequency is applied to said sample using determination of viscoelasticity device (manufacture of TA Instruments companies, ProductName " ARES ") The strain of rate 1Hz, with the storage modulus (G ') of 4 DEG C/minute of determination of heating rate -50~150 DEG C, loss when having obtained 50 DEG C Angle tangent (tan δ).
[fracture strength]
It is prepared for two sides and is pasted with polyethylene terephthalate class stripping film (Lindeke Co., Ltd's manufacture, product Name " SP-PET381031 ") adhesive phase (200 μm of thickness).Here, using method identical with embodiment, comparative example one Thickness is formed on a stripping film being changed to 40 μm of adhesive phase, another stripping film is then pasted on adhesive phase.Prepare 5 A adhesive phase being clipped in such stripping film, the surface of adhesive phase for making one stripping film of stripping and exposing are right each other It sets, carries out lamination.The step is repeated, the adhesive phase of 200 μm of thickness made of 5 layers of adhesive phase lamination is resulted in.Make The UV irradiation units " RAD-2000m/12 " manufactured with Lindeke Co., Ltd in illumination 220mW/cm, irradiate speed 15mm/ seconds Under conditions of ultraviolet light is irradiated to the adhesive phase laminated body that is clipped between 2 stripping films, then by the solidfied material of adhesive phase It is cut into 15mm × 150mm.Then, the both ends parts 25mm will be pasted on for the label of film stretching, have made measure object part For the Rectangular samples of 15mm × 100mm.Determine " the Autograph AG- manufactured with Shimadzu Scisakusho Ltd Fracture strength when IS500N " is with 200mm/ points of measurement of tensile speed.
[bonding force of energy line pre-irradiation]
The adhesive tape of Examples and Comparative Examples is equably cut into 25mm width, and adhesive tape is temporarily positioned over as quilt On the silicon mirror chip of bur, make the roller round-trip 1 time on it of weight 1kg, is glued by applying the load that dead weight is brought Patch.After stickup, is taken care of in the environment of 23 DEG C, relative humidity 50% 1 hour, then use cupping machine (ORIENTEC Company manufactures, ProductName " TENSILON ") with 300mm/ points of 180 ° of peel angle, peeling rate stripping adhesive tapes, determine this When bonding force.
[bonding force after energy line irradiation]
The adhesive tape of Examples and Comparative Examples is equably cut into 25mm width, and adhesive tape is temporarily positioned over as quilt On the silicon mirror chip of bur, make the roller round-trip 1 time on it of weight 1kg, is glued by applying the load that dead weight is brought Patch.It after stickup, takes care of 1 hour in the environment of 23 DEG C, relative humidity 50%, is irradiated with the UV that Lindeke Co., Ltd manufactures Device " RAD-2000m/12 " irradiates ultraviolet light in 15mm/ seconds with illumination 220mW/cm, irradiation speed from adhesive tape side, then 23 DEG C, place in the environment of relative humidity 50% 5 minutes, then using cupping machine, (ORIENTEC companies manufacture, ProductName " TENSILON ") with 300mm/ points of 180 ° of peel angle, peeling rate stripping adhesive tapes, determine bonding force at this time.
[imbedibility evaluation]
The laminating machine " RAD-3510F/12 " manufactured using Lindeke Co., Ltd in Examples and Comparative Examples by what is made Adhesive tape is pasted on 250 μm of bump height, 500 μm of spacing, overlooking the chip of ball bumps of 300 μm of diameter, (Waltz is public Take charge of manufacture, 8 inch wafers, convex block specification Sn/Ag/Cu=96.5/3/0.5 mass %, wafer surface material SiO2).It needs It is bright, when pasting, the laminating bench of device and laminating roll are set as 60 DEG C.After laminating, using Lindeke Co., Ltd The UV irradiation units " RAD-2000m/12 " of manufacture irradiate purple in 15mm/ seconds with illumination 220mW/cm, irradiation speed from adhesive tape side Outside line.Using digit microscope (manufacture of KEYENCE companies, ProductName " VHX-1000 "), for being pasted with the glue obtained in this way The evaluation chip of adhesive tape determines the diameter of circular void caused by from substrate side to convex block periphery, calculates bury according to the following formula Entering property.
Diameter/bump diameter × 100 [%] in imbedibility=gap
Using calculated imbedibility have 110% less than 130% appropriate gap the case where as optimal, according to Evaluation criteria below is evaluated.
A：Imbedibility=110% is less than 130%
B：Imbedibility=130% is less than 140%
C：Imbedibility=be less than 110% or 140% or more
[the residual paste of convex block is evaluated]
In the environment of 23 DEG C, relative humidity 50%, using cupping machine, (ORIENTEC companies manufacture, ProductName " TENSILON "), adhesive tape is pasted with for 120mm/ points from what is made in the same manner as above-mentioned imbedibility evaluation test with tensile speed Evaluation chip on removed adhesive tape.After stripping, the electron microscope " VE-9800 " manufactured using KEYENCE companies is right The wafer view convex portion of chip, it is thus identified that whether there is or not residual paste.
[making of the base material with middle layer]
Coordinate 40 mass parts of mono-functional amine's formic acid esters acrylate, 45 mass parts of isobornyl acrylate (IBXA), third 15 mass parts of olefin(e) acid hydroxy propyl ester (HPA), pentaerythrite four (3- mercaptobutylates) (Showa Denko K. K, ProductName " Karenz MTPE1 ", the compound containing 4 secondary mercaptos, 100 mass parts % of solid component concentration) 3.5 mass parts, crosslinking 1.8 mass parts of agent and as Photoepolymerizationinitiater initiater 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone (BASF AG manufacture, ProductName " DAROCUR 1173 ", 100 mass parts % of solid component concentration) 1.0 mass parts, it is prepared for middle layer resin combination Object.The middle layer is coated on polyethylene terephthalate film class stripping film with resin combination in a manner of jet flow die head On (Lindeke Co., Ltd's manufacture, ProductName " SP-PET381031 ", 38 μm of thickness), film is formd.
Then, ultraviolet light is irradiated from film side, forms semi-solid preparation layer.It is filled it should be noted that being irradiated as ultraviolet light It sets, using conveyor type ultraviolet lamp (manufacture of Eyegraphics companies, ProductName " ECS-401GGX "), as purple Outer line source, using high-pressure mercury-vapor lamp (manufacture of Eyegraphics companies, ProductName " H04-L41 "), as irradiation condition, in light The illumination 112mW/cm of wavelength 365nm2, light quantity 177mJ/cm2(utilize the manufacture of Eyegraphics companies, ProductName " UVPF-A1 " Be measured) under conditions of carried out ultraviolet light irradiation.
Will by polyethylene terephthalate (PET) class film (Japan spin Co., Ltd. manufacture, ProductName " Cosmo 50 μm of Shine A4100 ", thickness) base material that is formed is laminated to and is formed by semi-solid preparation layer, further carried out from PET film side Ultraviolet light irradiation is (using above-mentioned ultraviolet lamp, ultraviolet source, as irradiation condition, illumination 271mW/cm2, light quantity 1200mJ/cm2), so that it is fully cured, form the middle layer of 300 μm of thickness on the PET film of base material, has obtained with centre The base material of layer.
It should be noted that with the loss angle tangent (tan δ) of the middle layer at 50 DEG C of frequency 1Hz measurement for 1.92.
It should be noted that in embodiment below, comparative example, each mass parts indicate to will be diluted with the value after liquid dilution It is scaled the value of solid constituent.
[embodiment 1]
As urethane polymer (A '), prepare the poly- ammonia with carbamate skeleton and with multiple hydroxyls Ester polyol (manufacture of TOYOCHEM companies, ProductName " SH-101 ", weight average molecular weight：100,000), poly- to the carbamate Close urethane acrylate with multiple isocyanate group of the addition as crosslinking agent (C1) in object (A ') 100 mass parts (manufacture of DAICEL-ALLNEX companies, ProductName " EBECRYL4150 ", weight average molecular weight：1,040) 32 mass parts, as energy Pentaerythritol tetraacrylate (the formula weight of line curability compound (B)：352) and as compound (D) pentaerythrite 3 third Olefin(e) acid ester (formula weight：298) mixture (mass ratio (C: D)=40: 60) (manufacture of the villages Xin Zhong Chemical Co., Ltd., ProductName " A- TMM-3LM-N ") 17 mass parts, the 2,2- dimethoxy -1,2- diphenylethane -1- ketone as energy line polymerization initiator (E) (BASF AG manufacture, ProductName " Irgacure651 ") 5 mass parts, as the polyisocyanate compound of crosslinking agent (C2) " T-501B " of manufacture (TOYOCHEM companies) 1 mass parts carry out stirring in 10 minutes, with dilution with toluene, be prepared for solid at Divide the adhesive composition of 40 mass % of concentration.
Then, the adhesive composition of preparation is coated on (Lin get Ke plants of polyethylene terephthalate class stripping film The manufacture of formula commercial firm, ProductName " SP-PET381031 ", 38 μm of thickness) on, it is heated 2 minutes at 100 DEG C, makes it dry, shelling From the adhesive phase for foring 10 μm of thickness on film.
Then, the stripping film on the base material with middle layer previously made is removed, by the adhesive phase on stripping film It fits in the middle layer of exposing, the unnecessary portion of the end in width direction is then cut into removing, obtained setting successively There is the adhesive tape of base material, middle layer, adhesive phase and stripping film.By the adhesive tape evaluation result is shown in table 1.
[embodiment 2]
Urethane polymer (A ') is changed to ProductName " SP-205 " (Weight-average molecular of TOYOCHEM companies manufacture Amount：98,000) it, is prepared for adhesive composition, in addition to this, adhesive tape has been made according to step same as Example 1.
[embodiment 3]
" A-TMM-3LM-N " 17 mass parts are changed to the carbamate third as energy ray-curable compound (B) Olefin(e) acid ester (Negami Chemical Ind Co., Ltd.'s manufacture, ProductName " UN-6200 ", 2 functional groups, weight average molecular weight 6,270) 100 mass Part, it is prepared for adhesive composition, in addition to this, adhesive tape has been made according to step same as Example 1.
[embodiment 4]
Urethane polymer (A ') is changed to the ProductName " SP-205 " of TOYOCHEM companies manufacture, is prepared for gluing Mixture composite has made adhesive tape according to step same as Example 3 in addition to this.
[embodiment 5]
" A-TMM-3LM-N " 17 mass parts are changed to the carbamate third as energy ray-curable compound (B) Olefin(e) acid ester (6 functions, weight average molecular weight 33,000) 100 mass parts make according to step same as Example 1 in addition to this Adhesive tape.
[comparative example 1]
Being prepared for addition has the acrylic copolymer (weight average molecular weight of methylacryloyl：900,000, solid content： 35 mass %), the acrylic copolymer is by 6 mass parts of 94 mass parts of 2-EHA and acrylic acid 2- hydroxy methacrylates Addition methacrylic acid 2- isocyanatoethyl methacrylate (Showa Denko K. K's systems in acrylic copolymer obtained from polymerization Make, ProductName " Karenz MOI "), and make the markup percentage in terms of molal quantity benchmark relative to the hydroxyl in acrylic copolymer It is 50%.1- hydroxycyclohexylphenylketones (the BASF AG of addition as Photoepolymerizationinitiater initiater into 00 mass parts of copolymer 1 Manufacture, ProductName " Irgacure184 ") 3 mass parts, polyisocyanate compound (the TOYOCHEM corporations as crosslinking agent Make, ProductName " BHS-8515 ") 0.8 mass parts, stirring in 30 minutes is carried out, acrylic pressure-sensitive adhesive compositions are prepared for.It will Obtained acrylic pressure-sensitive adhesive compositions are coated on polyethylene terephthalate class stripping film (Lindeke Co., Ltd's system Make, ProductName " SP-PET381031 ", 38 μm of thickness) on, it makes it dry, forms the adhesive phase of 10 μm of thickness.
Stripping film on the base material with middle layer previously made is removed, it will be in the middle layer and stripping film of exposing Adhesive phase be bonded, the unnecessary portion of the end in width direction is then cut into removings, obtained successively equipped with base material, in The adhesive tape of interbed, adhesive phase and stripping film.By the adhesive tape evaluation result is shown in table 1.
[comparative example 2]
The acrylic acid obtained from 90 mass parts of 2-EHA, the polymerization of 10 mass parts of acrylic acid 4- hydroxybutyls Addition methacrylic acid 2- isocyanatoethyl methacrylates (Showa Denko K. K's manufacture, ProductName " Karenz in copolymer MOI "), and so that in terms of molal quantity benchmark be 65% relative to the markup percentage of the hydroxyl in acrylic copolymer, to obtain Addition has the acrylic copolymer (weight average molecular weight of methylacryloyl：1,000,000, solid content：25 mass %).To 1- hydroxycyclohexylphenylketone (BASF AG manufacture, product of the addition as Photoepolymerizationinitiater initiater in 00 mass parts of copolymer 1 Name " Irgacure184 ") 3 mass parts, as crosslinking agent polyisocyanate compound (TOYOCHEM companies manufacture, ProductName " BHS-8515 ") 1.1 mass parts, stirring in 30 minutes is carried out, acrylic pressure-sensitive adhesive compositions are prepared for.In addition to this, it presses Adhesive tape has been made according to the step identical as comparative example 1.
[comparative example 3]
The acrylic acid obtained from 90 mass parts of 2-EHA, the polymerization of 10 mass parts of acrylic acid 4- hydroxybutyls Addition methacrylic acid 2- isocyanatoethyl methacrylates (Showa Denko K. K's manufacture, ProductName " Karenz in copolymer MOI "), and so that in terms of molal quantity benchmark be 75% relative to the hydroxyl in acrylic copolymer, having obtained addition has methyl-prop Acrylic copolymer (the weight average molecular weight of enoyl-：1,000,000, solid content：25 mass %).
1- hydroxycyclohexylphenylketone (BASF public affairs of the addition as Photoepolymerizationinitiater initiater into 00 mass parts of copolymer 1 Department manufacture, ProductName " Irgacure184 ") 5 mass parts, the polyisocyanate compound (ProductName as crosslinking agent The manufacture of TOYOCHEM companies, ProductName " BHS-8515 ") 1.2 mass parts, stirring in 30 minutes is carried out, it is viscous to be prepared for acrylic compounds Mixture composite.In addition to this, adhesive tape has been made according to the step identical as comparative example 1.
[comparative example 4]
Other than being not added with " A-TMM-3LM-N ", adhesive tape has been made according to step same as Example 1.
[table 1]
In above Examples 1 to 5, adhesive composition is carbamates, and in carbamates tree Contain nonreactive energy ray-curable compound (B) in fat (A), thus can making the imbedibility of convex block, (adhesive phase is to workpiece The followability of surface shape) become good, fracture strength increases, and can prevent residual paste when stripping.In addition, due to improving energy The bonding force after solidification can fully be reduced while amount line bonding force before curing, therefore fissility, excellent in adhesion.
On the other hand, in comparative example 1~3, adhesive composition is acrylic compounds, and fracture strength is low, can not be prevented residual Paste.In addition, for comparative example 4, although carbamates, energy ray-curable compound (B) is not contained, therefore The flexibility of adhesive phase is poor, and imbedibility is insufficient.

Claims (16)

1. a kind of work pieces process adhesive tape has base material and is set to the adhesive phase of a surface side of the base material, wherein
Described adhesive layer includes urethane based resin (A) and energy ray-curable compound (B), the energy line curing Property compound (B) do not reacted with the urethane based resin (A) and with optical polymerism unsaturated bond, molecular weight 35, 000 or less.
2. work pieces process adhesive tape according to claim 1, wherein the energy ray-curable compound (B) is choosing From at least one kind of in (methyl) acrylate monomer (B1) and carbamate (methyl) acrylate (B2).
3. work pieces process adhesive tape according to claim 2, wherein the energy ray-curable compound (B) is at least Including (methyl) acrylate monomer (B1), and (methyl) acrylate monomer (B1) is multifunctional (methyl) acrylic acid Ester, the multifunctional (methyl) acrylate are the complete carboxylates of polyalcohol and (methyl) acrylic acid.
4. work pieces process adhesive tape described in any one of claim 1 to 3, wherein the energy ray-curable Close object (B) has 2 or more (methyl) acryloyl groups in 1 molecule.
5. work pieces process adhesive tape according to any one of claims 1 to 4, wherein the carbamates tree Fat (A) has optical polymerism unsaturated bond.
6. work pieces process adhesive tape according to any one of claims 1 to 5, wherein described adhesive layer is by least Include the adhesive composition shape of urethane polymer (A '), the energy ray-curable compound (B) and crosslinking agent (C) At,
The urethane based resin (A) is to be crosslinked urethane polymer (A ') using the crosslinking agent (C) 's.
7. work pieces process adhesive tape according to claim 6, wherein the crosslinking agent (C) contains optical polymerism The crosslinking agent (C1) of unsaturated bond.
8. the work pieces process adhesive tape described according to claim 6 or 7, wherein the urethane polymer (A ') with The crosslinking agent (C) is bonded by urethane bond.
9. the work pieces process adhesive tape according to any one of claim 6~8, wherein described adhesive composition is also Containing compound (D), the compound (D) has optical polymerism unsaturated bond and can be reacted with the crosslinking agent (C) Reactive functional groups.
10. work pieces process adhesive tape according to claim 9, wherein the compound (D) is multifunctional (methyl) third Olefin(e) acid ester, the multifunctional (methyl) acrylate are the partial esterification objects of polyalcohol and (methyl) acrylic acid.
11. according to work pieces process adhesive tape according to any one of claims 1 to 10, wherein described adhesive layer is shining It is 2.5MPa or more to penetrate the fracture strength after energy line.
12. the work pieces process adhesive tape according to any one of claim 1~11, wherein in the base material and described There is middle layer between adhesive phase.
13. work pieces process adhesive tape according to claim 12, wherein the thickness of the middle layer is 10~600 μm.
14. work pieces process adhesive tape according to claim 12 or 13, wherein the middle layer is surveyed at frequency 1Hz Loss angle tangent at fixed 50 DEG C is 1.0 or more.
15. the work pieces process adhesive tape according to any one of claim 1~14, the bonding force after irradiation energy line For 2000mN/25mm or less.
16. the work pieces process adhesive tape according to any one of claim 1~15 is semiconductor wafer surface protection Use adhesive tape.
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