JP2011184603A - Self-adhesive tape and tape for processing semiconductor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a self-adhesive tape which can exfoliate a chip easily at a pickup time while keeping self-adhesive power enough to prevent the chip from flying at a dicing time and contamination of the self-adhesive layer with a bled-out component is also suppressed. <P>SOLUTION: The self-adhesive tape 12 is obtained by forming the self-adhesive layer 12b on a base film 12a. The self-adhesive layer 12b contains 100 parts weight of an acrylic copolymer compound, 0.01-20 parts weight of a fluorine-based graft copolymer having a siloxane bond in a side chain thereof, and 0.01-20 parts weight of a curing agent. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  INDUSTRIAL APPLICABILITY The present invention can be used for fixing a semiconductor wafer in a dicing process for dividing a semiconductor wafer into chip-like elements, and in a die bonding process or a mounting process for bonding a chip-chip or a chip-substrate after dicing. The present invention also relates to an adhesive tape and a semiconductor processing tape that can be used.

  In a manufacturing process of a semiconductor device such as an IC, a process of attaching a sticky and stretchable semiconductor processing tape to the back surface of a semiconductor wafer on which a circuit pattern is formed, and then cutting (dicing) the semiconductor wafer into chips. In addition, a process for picking up the cut chip, and a die bonding (mounting) process for bonding the picked-up chip to a lead frame, a package substrate, etc., or stacking and bonding semiconductor chips together in a stacked package Is done.

As a semiconductor processing tape used in the manufacturing process of the semiconductor device, there is a dicing die bonding film (for example, Patent Documents 1 to 3) in which an adhesive tape and a thermosetting adhesive film containing an epoxy resin component are laminated. Proposed.
The adhesive tape is a step of dicing a semiconductor wafer and fixing the wafer so that the cut chips are not scattered, and a step of picking up the chips is required while high adhesive force is required to strongly fix the wafer. Then, low adhesive strength that can be easily peeled off from the chip is required.
For example, in Patent Documents 1 and 2, by using an energy ray-curable adhesive for the adhesive tape, the viscosity of the adhesive layer is reduced by irradiation with energy rays after dicing, and then subjected to a pickup process, which is required during dicing. It has been proposed to satisfy both of the high adhesive force that is applied and the low adhesive force that is required during pickup. Further, for example, Patent Document 3 proposes that both a high adhesive force required at the time of dicing and a low adhesive force required at the time of pick-up can be achieved by adding a (meth) acrylic modified product of silicone resin. Yes.

JP 2002-226996 A JP 2005-303275 A Japanese Patent No. 2661950

In an assembly process of a semiconductor device such as an IC, a process of cutting and separating (dicing) a semiconductor wafer after pattern formation, a process of mounting the chip on a substrate, and a process of sealing with a resin or the like It is made up of. In the dicing step, the semiconductor wafer is previously attached and fixed to a semiconductor processing tape, and then dicing is performed along the chip shape. In the subsequent mounting process, the adhesive layer and the pressure-sensitive adhesive tape are configured to be peelable, and the chip with the adhesive is peeled off (pick-up) from the pressure-sensitive adhesive tape and fixed to the substrate or the like with the adhesive for fixing the adhesive attached to the chip. .
However, those described in Patent Documents 1 and 2 do not sufficiently satisfy the requirement that the wafer does not peel off when dicing and can be easily peeled off when picking up. It was. For this purpose, there is a method of adding a low molecular weight component to the pressure-sensitive adhesive layer for the purpose of reducing pick-up failure. However, the low molecular weight component is likely to be deposited on the surface of the pressure-sensitive adhesive by bleed-out and easily peel off from the ring frame. When dicing, a sufficient adhesive force that does not peel off the wafer cannot be maintained, and chip skipping may occur. Furthermore, the bleed-out low molecular weight component contaminates the adhesive layer, so that the reliability may be significantly impaired such as peeling from the substrate in a subsequent process.
On the other hand, in the pressure-sensitive adhesive tape described in Patent Document 3, since the (meth) acrylic modified product of silicone resin is not taken into the polymer, the adhesive layer may be contaminated and similarly peeled off from the substrate.

  Therefore, the main object of the present invention is that the chip can be easily peeled off during pick-up while maintaining sufficient adhesive strength to prevent chip skipping during dicing, and contamination of the adhesive layer due to bleed-out is also possible. It is providing the adhesive tape and semiconductor processing tape which can be suppressed.

In order to solve the above problems, according to one aspect of the present invention,
In the adhesive tape in which the adhesive layer is formed on the base film,
As a component of the pressure-sensitive adhesive layer,
For 100 parts by weight of the acrylic copolymer compound,
There is provided an adhesive tape comprising 0.01 to 20 parts by weight of a fluorine-based graft copolymer having a siloxane bond in the side chain and 0.01 to 20 parts by weight of a curing agent.

According to another aspect of the invention,
There is provided a semiconductor processing tape in which the pressure-sensitive adhesive tape and an adhesive film are laminated.

  According to the present invention, a fluorine-based graft copolymer having a siloxane bond in the side chain is contained as one component of the pressure-sensitive adhesive layer while maintaining sufficient adhesive strength to prevent chip skipping during dicing. Therefore, the chip can be easily peeled off during pick-up, and contamination of the adhesive layer due to bleed-out can be suppressed.

It is sectional drawing which shows schematic structure of a dicing die-bonding tape. It is drawing for demonstrating the rough usage method of a dicing die-bonding tape. FIG. 3 is a diagram for explaining a subsequent process of FIG. 2. FIG. 4 is a diagram for explaining a subsequent process of FIG. 3. FIG. 5 is a diagram for explaining a process subsequent to FIG. 4.

  Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings.

[Dicing die bonding tape]
As shown in FIG. 1, the dicing die bonding tape 10 is mainly composed of an adhesive tape 12 and an adhesive film 13. The dicing die bonding tape 10 is an example of a semiconductor processing tape, and may be cut into a predetermined shape (pre-cut) in advance in accordance with a use process or an apparatus, or may be cut for each semiconductor wafer. It may be a long roll shape.
The pressure-sensitive adhesive tape 12 includes a base film 12a and a pressure-sensitive adhesive layer 12b, and the pressure-sensitive adhesive layer 12b is formed on the base film 12a.
The adhesive film 13 is composed of a release liner 13 a and an adhesive layer 13 b, and the adhesive layer 13 b is provided on the adhesive layer 12 b of the adhesive tape 12. The release liner 13a covers the pressure-sensitive adhesive tape 12, and protects the pressure-sensitive adhesive layer 12b and the adhesive layer 13b.
Next, each component of the dicing die bonding tape 10 will be described in order.

[Base film (12a)]
The base film 12a is preferably radiolucent, and specifically, plastic or rubber is usually used and is not particularly limited as long as it transmits radiation, but radiation curing by ultraviolet irradiation. When the adhesive is cured, a material having good light transmission can be selected as the base material.

  Examples of polymers that can be selected as such a substrate include polyethylene, polypropylene, ethylene-propylene copolymer, polybutene-1, poly-4-methylpentene-1, ethylene-vinyl acetate copolymer, ethylene-acrylic. Homopolymer or copolymer of α-olefin such as ethyl acid copolymer, ethylene-methyl acrylate copolymer, ethylene-acrylic acid copolymer, ionomer, or a mixture thereof, polyethylene terephthalate, polycarbonate, polymethyl methacrylate Engineering plastics such as polyurethane, thermoplastic elastomers such as polyurethane, styrene-ethylene-butene or pentene copolymers, polyamide-polyol copolymers, and mixtures thereof.

In order to increase the gap between the elements, it is preferable that necking (occurrence of partial elongation due to poor propagation of force that occurs when the base film 12a is radially stretched) is as small as possible, including polyurethane, molecular weight, and styrene. Examples thereof include styrene-ethylene-butene or pentene copolymers with limited amounts, and it is effective to use a cross-linked base film 12a to prevent elongation or deflection during dicing. The thickness of the base film 12a is usually suitably from 30 to 300 μm from the viewpoint of strong elongation characteristics and radiation transparency.
In addition, when the surface opposite to the side on which the radiation curable pressure-sensitive adhesive layer 12b of the base film 12a is applied is textured or coated with a lubricant, blocking prevention, and the pressure-sensitive adhesive tape 12 and the jig at the time of radial stretching of the pressure-sensitive adhesive tape 12 Since there exists an effect of necking prevention of the base film 12a by reducing friction, it is preferable.

[Adhesive layer (12b)]
The pressure-sensitive adhesive layer 12b is composed of an acrylic pressure-sensitive adhesive (acrylic resin) whose main component is a compound (A) having a radiation curable carbon-carbon double bond having an iodine value of 0.5 to 20 in the molecule. Yes. Here, the radiation refers to light rays such as ultraviolet rays or ionizing radiations such as electron beams.
Specifically, the pressure-sensitive adhesive layer 12b is composed of 0.01 to 20 parts by weight of the fluorine-based graft copolymer (B) and 0.01 to 20 parts by weight of the curing agent (C) with respect to 100 parts by weight of the compound (A). Is contained.
In particular, the fluorine-based graft copolymer (B) has a siloxane bond in the side chain, and the curing agent (C) is a compound (C) selected from at least one selected from polyisocyanates, melamine / formaldehyde resins, and epoxy resins. And the fluorine-based graft copolymer (B) and the curing agent (C) are reactive.
Hereinafter, constituent materials (components) of the pressure-sensitive adhesive layer 12b, characteristics thereof, and the like will be described in order.

(1) Compound (A)
The amount of the radiation curable carbon-carbon double bond introduced into the compound (A) is 0.5 to 20, preferably 0.8 to 10, in terms of iodine value. If the iodine value is 0.5 or more, an effect of reducing the adhesive strength after irradiation can be obtained. If the iodine value is 20 or less, the fluidity of the adhesive after irradiation is sufficient and after stretching. Therefore, the problem that the image recognition of each element becomes difficult at the time of pick-up can be suppressed. Furthermore, the compound (A) itself is stable and easy to manufacture.

  The compound (A) preferably has a glass transition point of −70 ° C. to 0 ° C., more preferably −66 ° C. to −28 ° C. If the glass transition point (hereinafter also referred to as “Tg”) is −70 ° C. or higher, the heat resistance against heat associated with radiation irradiation is sufficient, and if it is 0 ° C. or lower, after dicing on a wafer having a rough surface state. The effect of preventing scattering of the element is sufficiently obtained.

  The compound (A) may be produced by any method, and has, for example, a radiation curable carbon-carbon double bond such as an acrylic copolymer or a methacrylic copolymer, and a functional group. A compound obtained by reacting a compound (A1) having a functional group with a compound (A2) having a functional group capable of reacting with the functional group is used.

  Among these, the compound (A1) having a radiation curable carbon-carbon double bond and a functional group is a monomer having a radiation curable carbon-carbon double bond such as an alkyl acrylate ester or an alkyl methacrylate ester. It can be obtained by copolymerizing (A1-1) and a monomer (A1-2) having a functional group.

  As the monomer (A1-1), hexyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, decyl acrylate, or a monomer having 5 or less carbon atoms may be used. There can be listed pentyl acrylate, n-butyl acrylate, isobutyl acrylate, ethyl acrylate, methyl acrylate, or similar methacrylates.

  Since a glass transition point becomes so low that a monomer with a large carbon number is used as the monomer (A1-1), a monomer having a desired glass transition point can be produced. In addition to the glass transition point, it is also possible to blend a low molecular compound having a carbon-carbon double bond such as vinyl acetate, styrene, acrylonitrile for the purpose of improving compatibility and various performances of the monomer (A1-1). It is possible within the range of 5% by weight or less of the total weight.

  Examples of the functional group of the monomer (A1-2) include a carboxyl group, a hydroxyl group, an amino group, a cyclic acid anhydride group, an epoxy group, and an isocyanate group. Specific examples of the monomer (A1-2) Examples include acrylic acid, methacrylic acid, cinnamic acid, itaconic acid, fumaric acid, phthalic acid, 2-hydroxyalkyl acrylates, 2-hydroxyalkyl methacrylates, glycol monoacrylates, glycol monomethacrylates, N-methylol. Acrylamide, N-methylol methacrylamide, allyl alcohol, N-alkylaminoethyl acrylates, N-alkylaminoethyl methacrylates, acrylamides, methacrylamides, maleic anhydride, itaconic anhydride, fumaric anhydride, phthalic anhydride, Glycidyl relay , Glycidyl methacrylate, allyl glycidyl ether, a portion of the isocyanate groups of the polyisocyanate compound a hydroxyl group or a carboxyl group and a radiation-curable carbon - can be enumerated those urethanization with a monomer having a carbon double bond and the like.

  In the compound (A2), the functional group used is a hydroxyl group or an epoxy group when the functional group of the compound (A1), that is, the monomer (A1-2) is a carboxyl group or a cyclic acid anhydride group. In the case of a hydroxyl group, a cyclic acid anhydride group and an isocyanate group can be mentioned. In the case of an amino group, an epoxy group and an isocyanate group can be mentioned. In the case of an epoxy group, a carboxyl group, a cyclic acid anhydride group, an amino group, and the like can be exemplified. Specific examples thereof are the same as those listed in the specific examples of the monomer (A1-2). Can be enumerated.

  In the reaction of the compound (A1) and the compound (A2), by leaving an unreacted functional group, what is prescribed in the present invention can be produced with respect to characteristics such as acid value or hydroxyl value.

  In the synthesis of the above compound (A), as the organic solvent when the reaction is carried out by solution polymerization, ketone, ester, alcohol, and aromatic solvents can be used, among which toluene, ethyl acetate , Isopropyl alcohol, benzene, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, etc., are generally good solvents for acrylic polymers, preferably having a boiling point of 60-120 ° C., and α, α′-azobis as a polymerization initiator A radical generator such as an azobis type such as isobutyl nitrile or an organic peroxide type such as benzoyl peroxide is usually used. At this time, a catalyst and a polymerization inhibitor can be used together as necessary, and the compound (A) having a desired molecular weight can be obtained by adjusting the polymerization temperature and the polymerization time. In terms of adjusting the molecular weight, it is preferable to use a mercaptan or carbon tetrachloride solvent. This reaction is not limited to solution polymerization, and other methods such as bulk polymerization and suspension polymerization may be used.

  As described above, the compound (A) can be obtained. In the present invention, the molecular weight of the compound (A) is preferably about 300,000 to 1,500,000. If it is less than 300,000, the cohesive force due to radiation irradiation becomes small, and when the wafer is diced, the device is likely to be displaced, and image recognition may be difficult. In order to prevent the deviation of the element as much as possible, the molecular weight is preferably 400,000 or more. Further, if the molecular weight exceeds 1,500,000, there is a possibility of gelation during synthesis and coating. In addition, the molecular weight in this invention is a weight average molecular weight of polystyrene conversion.

  In addition, it is preferable that the compound (A) has an OH group having a hydroxyl value of 5 to 100 mgKOH / g because the risk of pick-up mistakes can be further reduced by reducing the adhesive strength after radiation irradiation. Moreover, it is preferable that a compound (A) has a COOH group used as the acid value of 0.5-30 mgKOH / g.

  Here, if the hydroxyl value of the compound (A) is too low, the effect of reducing the adhesive strength after irradiation is not sufficient, and if it is too high, the fluidity of the adhesive after irradiation tends to be impaired. If the acid value is too low, the effect of improving the tape restoring property is not sufficient, and if it is too high, the fluidity of the pressure-sensitive adhesive tends to be impaired.

（式（１）中、Ｒ¹は水素原子又は炭素原子数１〜１０の炭化水素基であり、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、及びＲ⁶は互いに同一でも異なっていてもよい水素原子又は炭素原子数１〜１０の炭化水素基であり、ｎは２以上の整数である）で示される片末端ラジカル重合性ポリシロキサン及び／又は下記一般式（２）：

（式（２）中、Ｒ⁷は水素原子又は炭素原子数１〜１０の炭化水素基であり、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、及びＲ¹²は互いに同一でも異なっていてもよい水素原子又は炭素原子数１〜１０の炭化水素基であり、ｐは０〜１０の整数であり、ｑは２以上の整数である）で示される片末端ラジカル重合性ポリシロキサン、及び
（Ｂ３）ラジカル重合反応条件下において、前記のウレタン結合を介してラジカル重合性不飽和結合部分を有する有機溶剤可溶性フッ素樹脂（Ｂ１）〔すなわち、前記ラジカル重合性フッ素樹脂（Ｂ１）〕と、二重結合による重合反応以外には反応しないラジカル重合性単量体（以下、非反応性ラジカル重合性単量体と称することがある）を共重合したものである。 (2) Fluorine-based graft copolymer (B)
The fluorine-based graft copolymer (B) has a structure called a “branched polymer” in which the main chain is made of a fluororesin and has a siloxane bond in its side chain.
Specifically, the fluorine-based graft copolymer (B)
(B1) an organic solvent-soluble fluororesin having a radically polymerizable unsaturated bond moiety via a urethane bond (hereinafter sometimes simply referred to as a radically polymerizable fluororesin),
(B2) The following general formula (1):

(In the formula (1), R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon ^{atoms, R 2, R 3, R} 4, R 5, and R ⁶ may be the same or different A hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 2 or more) and / or the following general formula (2):

(In the formula (2), R ⁷ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² may be the same or different from each other. A hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, p is an integer of 0 to 10, and q is an integer of 2 or more, and (B3) Under radical polymerization reaction conditions, the organic solvent-soluble fluororesin (B1) having a radical polymerizable unsaturated bond moiety through the urethane bond (that is, the radical polymerizable fluororesin (B1)) and a double bond It is a copolymer of a radical polymerizable monomer that does not react other than the polymerization reaction (hereinafter sometimes referred to as a non-reactive radical polymerizable monomer).

  The weight ratio of each material of the radical polymerizable fluororesin (B1), the one-end radical polymerizable polysiloxane (B2), and the non-reactive radical polymerizable monomer (B3) is preferably a radical polymerizable fluororesin (B1). Is 2 to 70% by weight, the one-end radical polymerizable polysiloxane (B2) is 4 to 40% by weight, and the non-reactive radical polymerizable monomer (B3) is 15 to 94% by weight.

(2.1) Radical polymerizable fluororesin (B1)
The organic solvent-soluble fluororesin (B1) having a radical polymerizable unsaturated bond moiety through a urethane bond used in the present invention is, for example, an organic solvent-soluble fluororesin (B1-1) having a hydroxyl group and a radical having an isocyanate group. It can be obtained by reacting the polymerizable monomer (B1-2).

  The organic solvent-soluble fluororesin (B1-1) having a hydroxyl group is not particularly limited as long as it contains at least a hydroxyl group-containing monomer portion and a polyfluoroparaffin portion as its constituent components. As a repeating unit, the general formula (3):

[In Formula (3), R ²¹ and R ²² may be the same or different independently for each repeating unit, and may be a hydrogen atom, a halogen atom (for example, a fluorine atom or a chlorine atom), a carbon number 1 to 10 alkyl groups (for example, methyl group or ethyl group), aryl groups having 6 to 8 carbon atoms (for example, phenyl group), halogen atoms (for example, fluorine atom or chlorine atom) 1 to 10 alkyl groups (for example, trifluoromethyl group, 2,2,2-trifluoroethyl group, or trichloromethyl group), or one halogen atom (for example, fluorine atom or chlorine atom), A plurality of substituted aryl groups having 6 to 8 carbon atoms (for example, pentafluorophenyl group, x is an integer of 2 or more), and general formula (4):

[In the formula (4), R ²³ independently represents a hydrogen atom, a halogen atom (for example, a fluorine atom or a chlorine atom), an alkyl group having 1 to 10 carbon atoms (for example, a methyl group or ethyl, independently for each repeating unit) Group), an aryl group having 6 to 8 carbon atoms (for example, a phenyl group), an alkyl group having 1 to 10 carbon atoms substituted with one or more halogen atoms (for example, fluorine atom or chlorine atom) (for example, tri A fluoromethyl group, a 2,2,2-trifluoroethyl group, or a trichloromethyl group), or an aryl group having 6 to 8 carbon atoms substituted by one or more halogen atoms (for example, fluorine atom or chlorine atom) (e.g., pentafluorophenyl group), R ²⁴ represents independently for each repeating unit, a divalent group selected oR ^25a group, CH ₂ oR ^25b group, and COOR ^25c group, R ^25a R ^25b, and R ^25c represents an alkylene group having 1 to 10 carbon atoms (e.g., methylene group, ethylene group, trimethylene group, tetramethylene group, or hexamethylene group), a cycloalkylene group having 6 to 10 carbon atoms (e.g., A cyclohexylene group), an alkylidene group having 2 to 10 carbon atoms (for example, an isopropylidene group), and a divalent group selected from 6 to 10 carbon atoms, and y is an integer of 2 or more. It can contain repeating units.

  Furthermore, the organic solvent-soluble fluororesin (B1-1) having a hydroxyl group may be, for example, a general component (5):

[In the formula (5), R ²⁶ independently represents a hydrogen atom, a halogen atom (for example, a fluorine atom or a chlorine atom), an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, Or an ethyl group), an aryl group having 6 to 10 carbon atoms (for example, a phenyl group), an alkyl group having 1 to 10 carbon atoms substituted with one or more halogen atoms (for example, a fluorine atom or a chlorine atom) (for example, , A trifluoromethyl group, a 2,2,2-trifluoroethyl group, or a trichloromethyl group), or a halogen atom (for example, a fluorine atom or a chlorine atom) having 6 to 10 carbon atoms substituted with one or more An aryl group (for example, a pentafluorophenyl group), R ²⁷ is independently an OR ^28a group or an OCOR ^28b group for each repeating unit, and R ^28a and R ^28b are a hydrogen atom, a halogen atom Child (for example, fluorine atom or chlorine atom), alkyl group having 1 to 10 carbon atoms (for example, methyl group or ethyl group), aryl group having 6 to 10 carbon atoms (for example, phenyl group), 6 to 10 carbon atoms A cycloalkyl group (for example, a cyclohexyl group), an alkyl group having 1 to 10 carbon atoms (for example, a trifluoromethyl group, 2, 2) substituted with one or more halogen atoms (for example, a fluorine atom or a chlorine atom) , 2-trifluoroethyl group or trichloromethyl group), or an aryl group having 6 to 10 carbon atoms substituted with one or more halogen atoms (for example, fluorine atom or chlorine atom) (for example, pentafluorophenyl group) And z is an integer of 2 or more]
The repeating unit represented by these can be included. By including the repeating unit represented by the general formula (5), solubility in an organic solvent can be improved.

  The hydroxyl value of the organic solvent-soluble fluororesin (B1-1) having a hydroxyl group is preferably 5 to 250 mgKOH / g, more preferably 10 to 200 mgKOH / g, and 20 to 150 mgKOH / g. More preferably. When the hydroxyl value is less than 5 mgKOH / g, the amount of the radically polymerizable monomer (B1-2) having an isocyanate group is remarkably reduced, so that the reaction mixture tends to become cloudy. On the other hand, when the hydroxyl value exceeds 250 mgKOH / g, the compatibility with the below-mentioned one-end radical polymerizable polysiloxane [component (B2)] is deteriorated and graft copolymerization may not proceed. The organic solvent-soluble fluororesin (B1-1) having a hydroxyl group may have an acid value. That is, it can have a free carboxylic acid group. When it has a free carboxylic acid group, the reaction rate when combined with a curing agent such as melamine, isocyanate prepolymer, or blocked isocyanate prepolymer described later increases.

  As the organic solvent-soluble fluororesin (B1-1) having a hydroxyl group used in the present invention, a compound prepared by a known method can be used, or a commercially available product can also be used. Examples of commercially available products include vinyl ether fluoropolymers (Lumiflon LF-100, LF-200, LF-302, LF-400, LF-554, LF-600, LF-986N; manufactured by Asahi Glass Co., Ltd.), allyl ether Fluororesin (Cefalcoat PX-40, A606X, A202B, CF-803; manufactured by Central Glass Co., Ltd.), vinyl carboxylate / acrylic ester fluoropolymer (Zaflon FC-110, FC-220, FC-250, FC-275) , FC-310, FC-575, XFC-973; manufactured by Toagosei Co., Ltd.) or vinyl ether / vinyl carboxylate fluororesin (Fluonate; manufactured by Dainippon Ink & Chemicals, Inc.). The organic solvent-soluble fluororesin (B1-1) having a hydroxyl group can be used alone or in combination of two or more.

  The radical polymerizable monomer (B1-2) having an isocyanate group is not particularly limited as long as it is a monomer containing an isocyanate group and a portion having radical polymerization, but has an isocyanate group, It is preferable to use a radical polymer monomer having no other functional group (for example, a hydroxyl group or a polysiloxane chain). As a radically polymerizable monomer (B1-2) having a suitable isocyanate group, for example, general formula (6):

Wherein (6), R ³¹ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, for example, an alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, A pentyl group or a hexyl group), an aryl group having 6 to 10 carbon atoms (for example, a phenyl group), or a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclohexyl group, R ³² is an oxygen atom or a carbon atom) A linear or branched divalent hydrocarbon group having 1 to 10 atoms, for example, an alkylene group having 1 to 10 carbon atoms (for example, a methylene group, an ethylene group, a trimethylene group, or a tetramethylene group), a carbon atom; An alkylidene group having 2 to 10 carbon atoms (for example, isopropylidene group), an arylene group having 6 to 10 carbon atoms (for example, a phenylene group, a tolylene group, or a xylylene group), or a carbon atom Number 3-10 cycloalkylene group (e.g., cyclohexylene) a radical polymerizable monomer represented by a], or the general formula (7):

[In Formula (7), ^R41 is a hydrogen atom or a C1-C10 hydrocarbon group, for example, a C1-C10 alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, pentyl group, or hexyl group), an aryl group having 6 to 10 carbon atoms (e.g., phenyl group), or a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclohexyl group, R ⁴² is an oxygen atom or a carbon A linear or branched divalent hydrocarbon group having 1 to 10 atoms, for example, an alkylene group having 1 to 10 carbon atoms (for example, a methylene group, an ethylene group, a trimethylene group, or a tetramethylene group), a carbon atom; An alkylidene group having 2 to 10 carbon atoms (for example, isopropylidene group), an arylene group having 6 to 10 carbon atoms (for example, a phenylene group, a tolylene group, or a xylylene group), or a carbon atom Number 3-10 cycloalkylene group (e.g., cyclohexylene group) is preferable to use a radically polymerizable monomer represented by a].

  As the radical polymerizable monomer (B1-2) having an isocyanate group, one kind of methacryloyl isocyanate, 2-isocyanatoethyl methacrylate, or m- or p-isopropenyl-α, α-dimethylbenzyl isocyanate or Two or more are preferably used.

  In the reaction for preparing the radical polymerizable fluororesin (B1) from the organic solvent soluble fluororesin (B1-1) having the hydroxyl group and the radical polymerizable monomer (B1-2) having the isocyanate group, The radical polymerizable monomer (B1-2) having an isocyanate group is preferably 0.001 mol or more and 0.000 mol or more per 1 equivalent of the hydroxyl group of the organic solvent-soluble fluororesin (B1-1) having the hydroxyl group. The reaction is carried out in an amount of less than 1 mol, more preferably 0.01 mol or more and less than 0.08 mol. When the amount of the isocyanate group-containing radical polymerizable monomer (B1-2) is less than 0.001 mol, graft copolymerization becomes difficult, the reaction mixture becomes cloudy, and it is not preferable because the two layers are separated over time. Moreover, when it is 0.1 mol or more, gelation tends to occur during graft copolymerization, which is not preferable. The reaction between the organic solvent-soluble fluororesin having a hydroxyl group (B1-1) and the radical polymerizable monomer having an isocyanate group (B1-2) is carried out at room temperature to 80 ° C. in the absence of a catalyst or in the presence of a catalyst. Can do.

  The radical polymerizable fluororesin (B1) thus obtained is used in an amount of 2 to 70% by weight, preferably 4 to 60% by weight, based on the total amount of monomers used.

(2.2) One-end radical polymerizable polysiloxane (B2)
In the present invention, the monomer represented by the general formula (1) can be used as the one-end radical polymerizable polysiloxane (B2).
R ¹ in the general formula (1) is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. In this specification, a C1-C10 hydrocarbon group is a C1-C10 alkyl group (For example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group), carbon number, for example. A 6-10 aryl group (for example, a phenyl group) or a C3-C10 cycloalkyl group (for example, a cyclohexyl group) can be mentioned. R ¹ is preferably a hydrogen atom or a methyl group. In the general formula (1), R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ may be the same as or different from each other. R ² , R ³ , R ⁴ , and R ⁵ are each independently preferably a methyl group or a phenyl group, and R ⁶ is preferably a methyl group, a butyl group, or a phenyl group. Moreover, n in the said General formula (1) is an integer greater than or equal to 2, Preferably it is an integer greater than or equal to 10, More preferably, it is an integer greater than or equal to 30.

Moreover, in this invention, the monomer shown by the said General formula (2) can also be used as a one terminal radically polymerizable polysiloxane (B2).
In the general formula (2), R ⁷ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrogen atom or a methyl group. Moreover, R < ⁸ >, R < ⁹ >, R < ¹⁰ >, R <^11> , and R < ¹² > in the said General formula (2) may mutually be same or different. R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently preferably a methyl group or a phenyl group, and R ¹² is preferably a methyl group, a butyl group or a phenyl group. Moreover, p in the said General formula (2) is an integer of 0-10, Preferably it is 3. Moreover, q in the said General formula (2) is an integer greater than or equal to 2, Preferably it is an integer greater than or equal to 10, More preferably, it is an integer greater than or equal to 30.

  As such a one-terminal radical polymerizable polysiloxane (B2), a compound prepared by a known method can be used, or a commercially available product can be used. Examples of commercially available products include Silaplane FM-0711 (number average molecular weight 1,000, manufactured by Chisso Corporation), Silaplane FM-0721 (number average molecular weight 5,000, manufactured by Chisso Corporation), Silaplane FM-0725 ( Number average molecular weight 10,000, manufactured by Chisso Corporation), X-22-174DX (number average molecular weight 4,600, manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

  In the present invention, the single-end radical polymerizable polysiloxane represented by the general formula (1) is used alone or in combination of two or more, or the single-end radical polymerizable polysiloxane represented by the general formula (2). Siloxane can be used alone or in admixture of two or more kinds. Furthermore, one or more of the one-end radical polymerizable polysiloxanes represented by the general formula (1) and the general formula (2) can be used. One or more of the one-terminal radically polymerizable polysiloxanes represented can be mixed and used.

  These one-terminal radically polymerizable polysiloxane (B2) is used in an amount of 4 to 40% by weight, preferably 10 to 30% by weight, based on the total amount of monomers used.

(2.3) Non-reactive radically polymerizable monomer (B3)
The non-reactive radically polymerizable monomer (B3), that is, the radically polymerizable monomer that does not react other than the polymerization reaction with the radically polymerizable fluororesin (B1) under a radical polymerization reaction condition. Needless to say, (B3) is bonded to the radically polymerizable fluororesin (B1) by a double bond polymerization reaction under the radical polymerization reaction conditions at the double bond portion.
This non-reactive radically polymerizable monomer (B3) is a monomer having a substituent or not having a substituent, and the substituent is a functional group (excluding a double bond). Can be. However, this functional group (excluding the double bond) needs to be a group that does not react with the radical polymerizable fluororesin (B1) under the radical polymerization reaction conditions. Specific examples of the substituent containing such a functional group (excluding a double bond) include, for example, a halogen atom (for example, a fluorine atom, a chlorine atom, or a bromine atom), and an alkyl group having 1 to 20 carbon atoms. (For example, methyl group, ethyl group, propyl group, butyl group, hexyl group, lauryl group, or stearyl group), aryl group having 6 to 10 carbon atoms (for example, phenyl group, tolyl group, or xylyl group), or alkyl Aralkyl groups having 1 to 10 carbon atoms and 6 to 10 carbon atoms in the aryl portion (for example, benzyl group) [The above alkyl group, aryl group and aralkyl group are collectively referred to as “hydrocarbon group R” hereinafter. The hydrocarbon group R having one or more hydroxyl groups (for example, hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, hydroxy group) A thiol group, a 2,3-dihydroxypropyl group, a hydroxyphenyl group, or a 4-hydroxymethylphenyl group), the hydrocarbon group R having one or more nitrile groups (for example, a cyanoethyl group), one ether group or A plurality of hydrocarbon groups R (for example, methoxymethyl group, ethoxyethyl group, or methoxymethoxymethyl group), one or more ester groups (for example, acetoxymethyl group), The hydrocarbon group R having one or more 3-amino groups (for example, dimethylaminomethyl group or diethylaminoethyl group), the hydrocarbon group R having one or more epoxy groups (for example, glycidyl group, or 3,4-epoxycyclohexylmethyl group), the hydrocarbon group R having one or more amide groups, The hydrocarbon group R having one or more boxyl groups (for example, carboxymethyl group), the hydrocarbon group R having one or more urethane groups, the hydrocarbon group having one or more urea groups R, the hydrocarbon group R having one or more alkoxysilyl groups (for example, trimethoxysilylmethyl group or dimethoxymethylsilylmethyl group) and the like can be exemplified.

  On the other hand, examples of the substituent (functional group) that may react with the radical polymerizable fluororesin (B1) during the radical polymerization include, for example, acid halides (for example, carboxylic acid chlorides, carboxyls). Acid bromide, phosphate chloride, or sulfonate chloride), acid anhydrides (for example, maleic anhydride), isocyanate compounds, and the like. The non-reactive radical polymerizable monomer (B3) cannot have these functional groups, but has any functional group that does not react with the radical polymerizable fluororesin (B1) under the above conditions. Can have.

  Examples of the non-reactive radically polymerizable monomer (B3) that can be used in the present invention include styrene monomers such as styrene, p-methylstyrene, p-chloromethylstyrene, and vinyltoluene; (Meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, phenyl (meth) A Relate or (meth) acrylate monomers with hydrocarbon groups such as benzyl (meth) acrylate; replace the hydrogen atoms of these (meth) acrylate monomers with fluorine, chlorine or bromine atoms (Meth) acrylate monomers; vinyl ester monomers such as vinyl acetate, vinyl benzoate, or vinyl ester of branched monocarboxylic acid (Veoba; manufactured by Shell Chemical Co., Ltd.); acrylonitrile, or methacrylonitrile Acrylonitrile monomers such as; vinyl ether monomers such as ethyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, or cyclohexyl vinyl ether; acrylamides such as (meth) acrylamide, dimethyl (meth) acrylamide, or diacetone acrylamide Monomers; vinyl Pyridine, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, 4- (N, N-dimethylamino) styrene, or N- {2- (meth) acryloyloxyethyl} piperidine and other basic nitrogen-containing vinyl compound monomers; glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, or 3,4-epoxyvinylcyclohexane Epoxy group-containing vinyl compound monomers such as (meth) acrylic acid, angelic acid, crotonic acid, maleic acid, 4-vinylbenzoic acid, p-vinylbenzenesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid Or mono {2- (meth) acryloyloxyethyl} reed Acidic vinyl compound monomers such as copper phosphate; p-hydroxymethylstyrene, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meta ) Acrylate, 4-hydroxybutyl (meth) acrylate, di-2-hydroxyethyl fumarate, polyethylene glycol or polypropylene glycol mono (meth) acrylate, or an ε-caprolactone adduct thereof, α, β-ethylenically unsaturated carboxylic acid Hydroxyalkyl esters of acids, adducts of α, β-ethylenically unsaturated carboxylic acids and ε-caprolactone, such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid or citraconic acid, or Hydroxyl groups such as adducts of the above α, β-ethylenically unsaturated carboxylic acids and epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, and branched monocarboxylic acid glycidyl ester (Cardura E, manufactured by Shell Chemical Co., Ltd.) Containing vinyl compound monomer; Silane compound monomer such as vinyltrimethoxysilane, γ-methacryloxyethyltrimethoxysilane, γ-methacryloxyethylmethyldimethoxysilane; Olefin monomer such as ethylene or propylene A halogenated olefin monomer such as vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride, tetrafluoroethylene, or chlorotrifluoroethylene; and other maleimides, vinyl sulfones, and the like.

  As said non-reactive radically polymerizable monomer (B3), the said monomer may be used individually or may be used in mixture of 2 or more types, mainly from a viewpoint of copolymerizability ( A (meth) acrylate monomer is preferably used.

  The non-reactive radically polymerizable monomer (B3) is used in an amount of 15 to 94% by weight, preferably 30 to 70% by weight, based on the total amount of monomers used.

  In the present invention, the use weight of the radical polymerizable fluororesin (B1) with respect to the total use weight of the one-end radical polymerizable polysiloxane (B2) and the non-reactive radical polymerizable monomer (B3). The ratio [i.e., B1 / (B2 + B3); hereinafter may be referred to as “fluororesin / acrylic ratio”] is preferably in the range of 2/1 to 1/50.

(2.4) Preparation method, characteristics, etc. The radical polymerizable fluororesin (B1), the one-end radical polymerizable polysiloxane (B2), and the non-reactive radical polymerizable monomer (B3) In order to prepare the fluorine-based graft copolymer (B) using any of the above, any known and commonly used polymerization method can be used, and in particular, the solution radical polymerization method or the non-aqueous dispersion radical polymerization method is most used. It is simple and particularly preferred.

  Examples of the solvent used in the polymerization include aromatic hydrocarbon compounds such as toluene, xylene, or a mixture of aromatic hydrocarbons (Sorvesso 100, manufactured by Esso Petroleum Corporation); n-hexane, cyclohexane, octane, Aliphatic and alicyclic hydrocarbon compounds such as mineral spirits or kerosene; ester compounds such as ethyl acetate, n-butyl acetate, i-butyl acetate, or butyl cellosolve acetate; methanol, ethanol, n-propanol, i- Examples include alcohol compounds such as propanol, n-butanol, i-butanol, ethylene glycol, propylene glycol, ethyl cellosolve, and butyl cellosolve, and these solvents can be used alone or in combination of two or more. .

  The above polymerization can be carried out by a conventional method using various known and commonly used radical polymerization initiators, for example, azo compounds or peroxide radical polymerization initiators. The polymerization time is not particularly limited, but a range of 1 to 48 hours is usually selected. Moreover, superposition | polymerization temperature is 30-120 degreeC normally, Preferably it is 60-100 degreeC. The polymerization can be carried out by adding a known and commonly used chain transfer agent, for example, butyl mercaptan, dodecyl mercaptan, or α-methylstyrene dimer, if necessary.

  The molecular weight of the fluorine-based graft copolymer obtained by the above method is not particularly limited, but the weight average molecular weight is preferably about 5,000 to 2 by polystyrene conversion GPC (gel permeation chromatography). , 000,000 (more preferably about 10,000 to 1,000,000).

  The hydroxyl value of the fluorine-based graft copolymer obtained by the above method is one of the factors that influence the properties. The hydroxyl value can be adjusted by the hydroxyl value of the radical polymerizable fluororesin (B1) component, and the non-reactive radical polymerizable monomer (B3) component has a single hydroxyl group. When a monomer is included, it can be adjusted according to the amount of use.

(3) Curing agent (C)
The curing agent (C) is a compound (C) selected from at least one of polyisocyanates, melamine / formaldehyde resins, and epoxy resins, and can be used alone or in combination of two or more. As a result of this compound (C) acting as a crosslinking agent and reacting with the compound (A), a crosslinked structure is formed in the pressure-sensitive adhesive layer 12b, and the pressure-sensitive adhesive layer 12b has a three-dimensional network structure. In particular, the compound (C) is reactive with the fluorine-based graft copolymer (B), and the reacted cross-linking agent is taken into the polymer of the compound (A), and bleeding out in the pressure-sensitive adhesive layer 12b is suppressed. The In order for the compound (C) to react with the fluorine-based graft copolymer (B) and be easily incorporated into the polymer of the compound (A), the hydroxyl value of the fluorine-based graft copolymer (B) is preferably The acid value is preferably 0.1 mgKOH / g or more. At least one of the hydroxyl group value and acid value of the fluorine-based graft copolymer (B) may be 0.1 mgKOH / g or more.
Further, the compound (C) acts as a crosslinking agent as described above, and agglomeration of the pressure-sensitive adhesive mainly composed of the compounds (A) and (C) due to the crosslinked structure formed as a result of the reaction with the compound (A) or the substrate film 12a. The force can be improved after application of the adhesive.

The polyisocyanates are not particularly limited, and examples thereof include 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 '-[2,2-bis (4 -Phenoxyphenyl) propane] aromatic isocyanate such as diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate Lysine diisocyanate, lysine triisocyanate and the like. Specifically, Coronate L etc. can be used as a commercial item.
Further, as the melamine / formaldehyde resin, specifically, Nicalac MX-45 (manufactured by Sanwa Chemical Co., Ltd.), Melan (manufactured by Hitachi Chemical Co., Ltd.), etc. can be used as commercial products.
Furthermore, as the epoxy resin, TETRAD-X (registered trademark, manufactured by Mitsubishi Chemical Corporation) or the like can be used.
In the present invention, it is particularly preferable to use polyisocyanates.

  The addition amount of the compound (C) is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, with respect to 100 parts by weight of the compound (A). More preferably, the content is ˜3 parts by weight. If the amount is less than 0.01 parts by weight, the cohesive force improving effect tends to be insufficient. If the amount exceeds 20 parts by weight, the curing reaction proceeds rapidly during the blending and application of the adhesive, and a crosslinked structure is formed. Therefore, workability tends to be impaired.

(4) Photopolymerization initiator (D)
The pressure-sensitive adhesive layer 12b preferably contains a photopolymerization initiator (D).
There is no restriction | limiting in particular in a photoinitiator (D), A conventionally well-known thing can be used. For example, benzophenones such as benzophenone, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 4,4′-dichlorobenzophenone, acetophenones such as acetophenone and diethoxyacetophenone, 2-ethylanthraquinone, t- Examples include anthraquinones such as butylanthraquinone, 2-chlorothioxanthone, benzoin ethyl ether, benzoin isopropyl ether, benzyl, 2,4,5-triallylimidazole dimer (rophine dimer), and acridine compounds. These can be used alone or in combination of two or more.

  As addition amount of a photoinitiator (D), it is preferable to set it as 0.01-5 weight part with respect to 100 weight part of compounds (A), and it is more preferable to set it as 0.01-4 weight part.

  Furthermore, the radiation-curable pressure-sensitive adhesive used in the present invention can be blended with a tackifier, a tackiness modifier, a surfactant, etc., as required, or other modifiers and conventional components. The thickness of the pressure-sensitive adhesive layer 12b is not particularly limited, but is usually 2 to 50 μm.

(5) Properties, etc. The adhesive layer 12b preferably has a storage elastic modulus at 80 ° C. of 8 × 10 ⁴ to 1 × 10 ⁷ Pa in order to suppress cracking / chip (chipping) of the chip during dicing. Preferably it is 1 * 10 < ⁵ > -5 * 10 < ⁶ > Pa, The storage elastic modulus in 25 degreeC is also preferably 8 * 10 < ⁴ > -1 * 10 < ⁷ > Pa, More preferably, it is 1 * 10 < ⁵ > -5 * 10 < ⁶ > Pa. is there.
The elastic modulus at 25 ° C. or 80 ° C. of the pressure-sensitive adhesive layer 12b was measured from 0 ° C. using a viscoelasticity meter (manufactured by Rheometric Science Co., Ltd., trade name: ARES), and the heating rate was 5 ° C./min. The dynamic viscoelasticity was measured at a frequency of 1 Hz, and the storage elastic modulus when the temperature reached 25 ° C. or 80 ° C. was defined as each elastic modulus.
In addition, the adhesive layer 12b is provided by being cured after being coated on the base film 12a. For the pressure-sensitive adhesive layer 12b, it is preferable to use a material that is gradually cured by leaving it to stand at room temperature for about one week and has an elastic modulus in a preferable range.
As a method of hardening the pressure-sensitive adhesive layer 12b, an inorganic compound filler is added, which increases the glass transition point (Tg) of the pressure-sensitive adhesive component used as a main component, blends a large amount of the curing agent added to the pressure-sensitive adhesive layer 12b. However, it is not limited to this method. Moreover, it may be cured by radiation irradiation to adjust the hardness of the pressure-sensitive adhesive layer 12b.

[Adhesive film (13)]
The adhesive film 13 has a weight average molecular weight of 0.5 to 6% by weight of the epoxy resin (a), the phenol resin (b) having a hydroxyl group equivalent of 150 g / eq or more, glycidyl acrylate or glycidyl methacrylate with respect to the release liner 13a. The adhesive layer 13b is formed by a composition containing 10,000 or more epoxy group-containing acrylic copolymer (c), filler (d) and curing accelerator (e) (each constituting the adhesive layer 13b). Details of the components and characteristics of the adhesive film 13 are described in JP-A-2005-303275 (paragraphs 0034 to 0068, etc.).

  The adhesive layer 13b is prepared by dissolving or dispersing the material contained in the adhesive layer 13b in a solvent to form a varnish, and applying and heating the release liner 13a such as a polytetrafluoroethylene film or a polyethylene terephthalate film whose surface has been subjected to a release treatment. It is formed on the release liner 13a by drying and removing the solvent. As heating conditions in this case, for example, it is preferable that the temperature is about 80 to 250 ° C. and about 10 minutes to 20 hours.

  As the release liner 13a, a plastic film such as a polytetrafluoroethylene film, a polyethylene terephthalate film, a polyethylene film, a polypropylene film, a polymethylpentene film, or a polyimide film can be used. Can also be used.

  The adhesive film 13 can be peeled off the release liner 13a at the time of use to use only the adhesive layer 13b, or can be used together with the release liner 13a and removed later.

  As a method for applying the varnish to the release liner 13a, a known method can be used. Examples thereof include a knife coating method, a roll coating method, a spray coating method, a gravure coating method, a bar coating method, and a curtain coating method. .

  The thickness of the adhesive layer 13b is not particularly limited, but is preferably 3 to 300 μm, more preferably 5 to 250 μm, still more preferably 10 to 200 μm, and 20 to 100 μm. It is particularly preferred that If it is thinner than 3 μm, the stress relaxation effect tends to be poor, and if it is thicker than 300 μm, it is not economical.

  The solvent for varnishing is not particularly limited, but in consideration of volatility during film production, methyl ethyl ketone, acetone, methyl isobutyl ketone, 2-ethoxyethanol, toluene, xylene, butyl cellosolve, methanol, ethanol, It is preferable to use a solvent having a relatively low boiling point such as 2-methoxyethanol. For the purpose of improving the coating properties, a solvent having a relatively high boiling point such as dimethylacetamide, dimethylformamide, N-methylpyrrolidone, cyclohexanone can be added.

  In forming the adhesive layer 13b, it is preferable to use a raking machine, a three roll, a ball mill, a bead mill, or the like, particularly in consideration of the dispersibility of the filler (d). You can also. Moreover, the mixing time can be shortened by mixing the filler and the low molecular weight compound in advance and then blending the high molecular weight compound. In addition, after forming the varnish, it is preferable to remove bubbles in the varnish by vacuum degassing or the like. Moreover, in this invention, after mixing an epoxy resin (a) and a phenol resin (b), and a filler (d), an epoxy-group-containing acrylic copolymer (c) and a hardening accelerator (e) are added to those mixtures. It is preferable to employ a method for producing an adhesive composition by mixing. Further, two or more of the adhesive layers 13b of the present invention can be bonded together in order to obtain a desired thickness. In this case, the bonding is performed so that the adhesive layers 13b are not separated from each other.

[Manufacturing method of dicing die bonding tape]
In producing the pressure-sensitive adhesive tape 12, for example, the pressure-sensitive adhesive composition is directly applied onto the base film 12a and dried to form the pressure-sensitive adhesive layer 12b on the base film 12a. The application and drying can be performed in the same manner as the method for forming the adhesive layer 13b on the release liner 13a in the adhesive film 13.

Then, the adhesive film 13 (adhesive layer 13b) is laminated | stacked on the adhesive layer 12b.
In this case, for example, the release liner 13a (adhesive film 13) on which the adhesive layer 13b is formed in advance and the base film 12a (adhesive tape 12) on which the adhesive layer 12b is formed are bonded to the surface of the adhesive layer 12b. Lamination is performed so that the surface of the agent layer 13b is in contact. The laminating condition is preferably a linear pressure of 0.1 to 100 kgf / cm at 10 to 100 ° C.

[How to use dicing die bonding tape]
In manufacturing the semiconductor device, the dicing die bonding tape 10 can be used.
First, the release liner 13 a is removed from the dicing die bonding tape 10, and as shown in FIG. 2, the adhesive layer 13 b is attached to the semiconductor wafer 1 and the side portions of the adhesive tape 12 are fixed by the ring frame 20. The ring frame 20 is an example of a dicing frame. The adhesive film 13 (adhesive layer 13b) is laminated on the part of the adhesive tape 12 where the semiconductor wafer 1 is bonded. There is no adhesive film 13 at the part of the adhesive tape 12 that contacts the ring frame 20.
Thereafter, as shown in FIG. 3, the semiconductor wafer 1 is diced into a predetermined size by using the thin grindstone 21 while the lower surface of the adhesive tape 12 is sucked and fixed by the suction table 22 to manufacture a plurality of semiconductor chips 2.
Thereafter, as shown in FIG. 4, with the adhesive tape 12 fixed by the ring frame 20, the push-up member 30 is raised, the central portion of the adhesive tape 12 is bent upward, and radiation such as ultraviolet rays is applied to the adhesive tape 12 ( The pressure-sensitive adhesive layer 12b) is irradiated to weaken the pressure-sensitive adhesive force of the pressure-sensitive adhesive layer 12b.
Thereafter, as shown in FIG. 5, the push-up pin 31 is raised at a position corresponding to each semiconductor chip 2, and the semiconductor chip 2 is picked up by the suction collet 32.
Thereafter, the picked-up semiconductor chip 2 is bonded (die-bonded) to a support member such as a lead frame or another semiconductor chip 2, and a semiconductor device is obtained through steps such as attaching a gold wire and heat curing. It becomes.

According to the dicing die bonding tape 10 described above, when the semiconductor wafer 1 is cut into small element pieces (dice processing), the cut element (semiconductor chip 2) is sufficiently fixed to prevent chip jumping. Since the adhesive layer 12b has a three-dimensional network structure and has flexibility after irradiation, it has a stable low adhesion regardless of the surface properties of the semiconductor wafer 1. As a result, an excellent effect is obtained that a cut element (semiconductor chip 2) can always be easily picked up from the adhesive tape 12.
In particular, since a certain amount of the fluorine-based graft copolymer (B) is contained as a constituent component of the pressure-sensitive adhesive layer 12b,
(I) The pressure-sensitive adhesive layer 12b and the adhesive film 13 are easily peeled off, and the pickup performance of the semiconductor chip 2 can be improved. (Ii) The surface energy of the pressure-sensitive adhesive layer 12b is lowered, and the pressure-sensitive adhesive layer 12b is an adhesive film. (Iii) The fluorine-based graft copolymer (B) reacts with the curing agent (C) as the crosslinking agent, and the reacted crosslinking agent becomes the compound (A) as the polymer. It is taken in in a polymer by reacting with and it has the outstanding effect that the contamination of the adhesive tape 13 by bleed-out can be reduced.

(1) Sample preparation (1.1) Example 1
The compound having a radiation curable carbon-carbon double bond and a functional group is composed of 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate and methyl methacrylate, and has a mass average molecular weight of 700,000, a glass transition temperature of -60 ° C., and radiation curable carbon. -An acrylic copolymer compound having a carbon double bond amount of 0.9 meq / g was prepared.
Thereafter, with respect to 100 parts by weight of the copolymer compound, fluorine resin / siloxane graft polymer ZX-022 (trade name, manufactured by Fuji Kasei Kogyo Co., Ltd.) as a fluorine-based graft copolymer having a siloxane bond in the side chain. 1 part by weight, 3 parts by weight of polyisocyanate compound coronate L (manufactured by Nippon Polyurethane Co., Ltd., trade name) as a curing agent, and 5 parts by weight of Irgacure 184 (manufactured by Nippon Ciba-Geigy Corporation, trade name) as a photopolymerization initiator In addition, a radiation curable adhesive was obtained.

  On the other hand, a resin composition composed of a polypropylene resin and a hydrogenated styrene-butadiene copolymer was melt-kneaded and molded to obtain a base film having a thickness of 100 μm and a width of 300 mm.

  Then, an adhesive is applied to the base film with a gravure coater and dried in a hot air drying furnace to obtain an adhesive tape that is a laminate of the adhesive layer having a thickness of 10 μm after drying and the base film. It was. Thereafter, an adhesive film having a thickness of 20 μm prepared in advance as described later was bonded onto the adhesive layer of the adhesive tape to prepare a dicing die bonding tape. This dicing die bonding tape was used as a sample of “Example 1”.

  There are various types of adhesive films (die bond films), which may be manufactured in any way. Here, 100 parts by weight of an acrylic copolymer (glycidyl acrylate copolymer), 100 parts by weight of a cresol novolac type epoxy resin, 10 parts by weight of xylene novolac type phenol resin, 5 parts by weight of 2-phenylimidazole and 0.5 parts by weight of xylenediamine as an epoxy curing agent were blended and applied to a PET film, and then dried at 110 ° C. for 2 minutes, An adhesive film having a thickness of 20 μm was produced.

(1.2) Example 2
In sample preparation of Example 1, the addition amount of fluororesin / siloxane graft type polymer ZX-022 (trade name, manufactured by Fuji Kasei Kogyo Co., Ltd.) was changed to 3 parts by weight. Other than that, a dicing die-bonding tape was prepared in the same manner as described above, and this was used as a sample of “Example 2”.

(1.3) Example 3
In sample preparation of Example 1, the addition amount of fluororesin / siloxane graft type polymer ZX-022 (trade name, manufactured by Fuji Kasei Kogyo Co., Ltd.) was changed to 20 parts by weight. Other than that, a dicing die-bonding tape was prepared in the same manner as described above, and this was used as a sample of “Example 3”.

(1.4) Example 4
In the sample preparation of Example 1, the type of fluororesin / siloxane graft type polymer was changed to ZX-007C (trade name, manufactured by Fuji Kasei Kogyo Co., Ltd.), and 0.1 part by weight thereof was added. Other than that, a dicing die-bonding tape was prepared in the same manner as described above, and this was used as a sample of “Example 4”.

(1.5) Example 5
In the sample preparation of Example 1, the kind of fluororesin / siloxane graft type polymer was changed to ZX-007C (trade name, manufactured by Fuji Kasei Kogyo Co., Ltd.), and 3 parts by weight thereof was added. Other than that, a dicing die-bonding tape was prepared in the same manner as described above, and this was used as a sample of “Example 5”.

(1.6) Example 6
In the sample preparation of Example 1, the kind of fluororesin / siloxane graft type polymer was changed to ZX-212 (trade name, manufactured by Fuji Kasei Kogyo Co., Ltd.), and 3 parts by weight thereof was added. Other than that, a dicing die-bonding tape was prepared in the same manner as described above, and this was used as a sample of “Example 6”.

(1.7) Comparative Example 1
For comparison, in the sample preparation of Example 1, an adhesive tape and a dicing die bonding tape were prepared without adding any fluororesin / siloxane graft type polymer to the adhesive, and this was referred to as “Comparative Example 1”. A sample was used.

(1.8) Comparative Example 2
For comparison, in the sample preparation of Example 1, the addition amount of the fluororesin / siloxane graft type polymer ZX-022 was changed to 0.009 parts by weight to prepare an adhesive tape and a dicing die bonding tape. The sample was “Comparative Example 2”.

(1.9) Comparative Example 3
For comparison, in the sample preparation of Example 1, the addition amount of the fluororesin / siloxane graft type polymer ZX-022 was changed to 22 parts by weight to prepare an adhesive tape and a dicing die bonding tape. The sample of Example 3 was used.

(1.10) Comparative Example 4
For comparison, in the sample preparation of Example 1, the addition amount of the fluororesin / siloxane graft type polymer ZX-022 was changed to 30 parts by weight to prepare an adhesive tape and a dicing die bonding tape. The sample of Example 4 was used.

(1.11) Comparative Example 5
For comparison, in the sample preparation of Example 1, the fluororesin / siloxane graft type polymer ZX-022 was changed to Ebe1360 (silicone acrylate: Daicel Cytec) to prepare an adhesive tape and a dicing die bonding tape. This was used as a sample of “Comparative Example 5”.

(1.12) Comparative Example 6
For comparison, in the sample preparation of Example 1, the fluororesin / siloxane graft type polymer ZX-022 was changed to Ebe1360 (silicone acrylate: Daicel Cytec), and 3 parts by weight of this was added. A die bonding tape was prepared and used as a sample of “Comparative Example 6”.

(1.13) Comparative Example 7
For comparison, in the sample preparation of Example 1, the fluororesin / siloxane graft type polymer ZX-022 was changed to Alflow E-10 (oleic acid amide: NOF Corporation), and 3 parts by weight thereof was added. An adhesive tape and a dicing / die bonding tape were prepared and used as a sample of “Comparative Example 7”.

(2) Evaluation of sample (2.1) Measurement of adhesive strength Each sample was irradiated with ultraviolet rays, and the adhesive strength before and after the ultraviolet irradiation was measured based on JIS-Z0237. Measurement was performed at 90 ° peeling and a peeling speed of 50 mm / min. A high-pressure mercury lamp (80 mw / cm ² , irradiation distance 10 cm) was used as the ultraviolet lamp, and the irradiation intensity was 200 mJ / cm ² . The measurement results are shown in Table 1.

(2.2) Presence / absence of chip jumping Each sample was heat bonded to a wafer at 70 ° C. for 1 minute, and then the wafer was diced into 5 mm × 5 mm. Then, the chip | tip after dicing was observed and the presence or absence of the chip | tip jump at the time of dicing was observed. The observation results are shown in Table 1.

(2.3) Pickup property A silicon wafer having a thickness of 50 μm was bonded to each sample by heating at 70 ° C. for 10 seconds, and then diced to 10 mm × 10 mm.
Thereafter, the pressure-sensitive adhesive layer was irradiated with ultraviolet rays of 200 mJ / cm ² with an air-cooled high-pressure mercury lamp (80 mw / cm ² , irradiation distance 10 cm), and then a die bonder device (manufactured by NEC Machinery, trade name: 50 chips) in the center of the silicon wafer. A pickup test by CPS-100FM) was performed, and the success rate of pickup by the number of pickup chips was obtained.
At that time, in the picked-up element, the pick-up success rate was calculated by assuming that the pick-up was successful when the adhesive layer peeled from the pressure-sensitive adhesive layer was retained. The calculation results are shown in Table 1. In Table 1, the criteria for ◎, ○, △, × (pickup criteria) are as follows.

“◎”: The success rate of pick-up at a push-up height of 0.7 mm, 0.5 mm, and 0.3 mm by a push-up pin is 100%. “◯”: The success rate of pick-up at a push-up height of 0.7 mm and 0.5 mm is 100. %, And the success rate of pick-up at a push-up height of 0.3 mm is less than 100%. “△”: The success rate of pick-up at a push-up height of 0.7 mm is 100%, and the push-up height is 0.5 mm. .. Pickup success rate at 3 mm is less than 100% “X”: Pickup success rate at push-up heights of 0.7 mm, 0.5 mm, and 0.3 mm is less than 100%

(2.4) Package Reliability Each sample was heat bonded to a wafer at 70 ° C. for 1 minute, and then the wafer was diced to 10 mm × 10 mm. Thereafter, the adhesive layer was irradiated with ultraviolet rays of 200 mJ / cm ² by an air-cooled high-pressure mercury lamp (80 mW / cm ² , irradiation distance 10 cm), and then a pick-up test was performed with a die bonder device (trade name CPS-100FM, manufactured by NEC Machinery). A simulated element in which an aluminum wiring is formed on a silicon chip of a picked-up adhesive-attached chip is die-bonded on a silver-plated FR4 substrate via a sheet-like adhesive, and 175 ° C., 70 kgf / cm 2, molding time 120 20 BGA packages having a thickness of 1.0 mm were molded under the condition of seconds, and post-cured at 180 ° C. for 4 hours, and used as an evaluation package.
Then, after immersing the obtained package in a solder bath adjusted to 260 ° C. for 10 seconds in advance, the presence or absence of package cracks was confirmed by a transmission method using an ultrasonic exploration device (Hyper manufactured by Hitachi Construction Machinery Co., Ltd.). evaluated. The evaluation results are shown in Table 1. Here, the evaluation was made based on the number of cracked defective packages among the 20 evaluation packages.

(3) Summary From the results in Table 1, in the samples of Examples 1 to 6 in which the fluororesin / siloxane graft type polymer and the polyisocyanurate compound were used in combination with the adhesive composition, all had extremely high adhesive strength before UV irradiation. On the other hand, it exhibited an extremely low adhesive strength after UV irradiation, had no chip skipping, and was excellent in pick-up property and package reliability.
On the other hand, in the samples of Comparative Examples 1 and 2 in which the fluororesin / siloxane graft type polymer was not completely or hardly blended, the adhesive strength after ultraviolet irradiation was not sufficiently lowered, and the pickup property was inferior.
Further, in the samples of Comparative Examples 3 and 4 to which 22 and 30 parts by weight of the fluororesin / siloxane graft polymer were added, the chip strength occurred during dicing because the adhesive strength before ultraviolet irradiation was not sufficient.
Further, in the samples of Comparative Examples 5 and 6 using silicone acrylate and Comparative Example 7 using oleic acid amide, chip skipping occurred and the pick-up property and package reliability were remarkably lowered.
From the above, as a component of the pressure-sensitive adhesive layer, containing a certain amount of a fluorine-based graft copolymer having a siloxane bond in the side chain is useful at least in terms of prevention of chip skipping, pickup characteristics, and package reliability. It can be seen that it is.

DESCRIPTION OF SYMBOLS 1 Semiconductor wafer 2 Semiconductor chip 10 Dicing die-bonding tape 12 Adhesive tape 12a Base film 12b Adhesive layer 13 Adhesive film 13a Release liner 13b Adhesive layer 20 Ring frame 21 Thin grindstone 22 Adsorption table 30 Push-up member 31 Push-up pin 32 Adsorption Collet

Claims (10)

In the adhesive tape in which the adhesive layer is formed on the base film,
As a component of the pressure-sensitive adhesive layer,
For 100 parts by weight of the acrylic copolymer compound,
A pressure-sensitive adhesive tape comprising 0.01 to 20 parts by weight of a fluorine-based graft copolymer having a siloxane bond in a side chain and 0.01 to 20 parts by weight of a curing agent. In the adhesive tape according to claim 1,
The pressure-sensitive adhesive tape characterized in that the fluorine-based graft copolymer has a hydroxyl value of 0.1 mgKOH / g or more or an acid value of 0.1 mgKOH / g or more. In the adhesive tape according to claim 1 or 2,
The pressure-sensitive adhesive tape, wherein the fluorine-based graft copolymer and the curing agent are reactive. In the adhesive tape as described in any one of Claims 1-3,
The adhesive tape whose storage elastic modulus in 80 degreeC of the said adhesive layer is 8 * 10 < ⁴ > -1 * 10 < ⁷ > Pa. In the adhesive tape as described in any one of Claims 1-4,
The adhesive tape whose storage elastic modulus in 25 degreeC of the said adhesive layer is 8 * 10 < ⁴ > -1 * 10 < ⁷ > Pa. In the adhesive tape as described in any one of Claims 1-5,
The pressure-sensitive adhesive tape, wherein the pressure-sensitive adhesive layer is an acrylic resin having a three-dimensional network structure. In the adhesive tape as described in any one of Claims 1-6,
The pressure-sensitive adhesive tape, wherein the pressure-sensitive adhesive layer is obtained by applying a mixture containing at least an acrylic resin and a curing agent on a base film and then curing the mixture. In the adhesive tape as described in any one of Claims 1-7,
The pressure-sensitive adhesive layer is
A compound having a radiation-curable carbon-carbon double bond having an iodine value of 0.5 to 20 in the molecule;
A compound selected from at least one selected from polyisocyanates, melamine / formaldehyde resins and epoxy resins,
An adhesive tape characterized by containing.   The tape for semiconductor processing which laminated | stacked the adhesive tape and adhesive film as described in any one of Claims 1-8. The semiconductor processing tape according to claim 9,
When manufacturing a semiconductor device, a dicing die bonding tape that is fixed to a dicing frame at the time of dicing, fixed to a wafer and diced, and further used in an adhesion process for overlapping with a lead frame or a semiconductor chip,
The tape for semiconductor processing characterized by laminating | stacking the said adhesive film in the site | part by which the wafer is bonded on the base film, and not having the said adhesive film in the part bonded by the flame | frame for dicing.

Images