KR101362878B1 - Adhesive composition for dicing die bonding film - Google Patents

Abstract

The present invention is to provide an adhesive composition for dicing die bonding film comprising an acrylic copolymer having a phosphate group, to increase the adhesive force to the ring frame and to have an excellent pickup success rate.

Description

Adhesive composition for dicing die bonding film {Adhesive composition for dicing die bonding film}

The present invention relates to an adhesive composition for dicing die bonding film. More specifically, the present invention is to provide an adhesive composition for dicing die bonding film comprising an acrylic copolymer having a phosphate group to increase the adhesive force to a ring frame and has an excellent pickup success rate.

Dicing die bonding films used in semiconductor manufacturing processes are classified into photocurable films requiring ultraviolet irradiation and ultraviolet non-irradiating films that do not require ultraviolet irradiation. The photocurable film has excellent adhesive force before photocuring and is excellent in a cutting process. However, the photocurable film has a cumbersome process because it must additionally perform a step of irradiating ultraviolet rays in order to perform the pick-up step after the cutting step. In addition, when sufficient ultraviolet energy is not supplied, defects may occur in the pickup process.

On the contrary, the ultraviolet non-irradiated film does not have to perform the ultraviolet irradiation process separately. However, in the case of the conventionally developed dicing film, the adhesive strength to the ring frame is weak, and there is a need to additionally attach a strong adhesive film to a portion to which the ring frame is attached.

Therefore, the ultraviolet non-irradiation dicing die, which can solve the problem of additionally attaching a film having a strong adhesive force in the manufacture of the ultraviolet non-irradiation dicing film and reducing the cumbersome process of the semiconductor manufacturing process that must additionally perform the ultraviolet irradiation process. There is a need to develop a bonding film.

It is an object of the present invention to provide a pressure-sensitive adhesive composition that can be used in a dicing die bonding film that can reduce the cumbersomeness of a semiconductor manufacturing process in which the ultraviolet irradiation process must be further performed.

Another object of the present invention is to provide a pressure-sensitive adhesive composition that can be used in a dicing die bonding film that can solve the problem of having a high adhesion to the ring frame to further attach a film having a strong adhesion.

Still another object of the present invention is to provide a pressure-sensitive adhesive composition that can be used in a dicing die bonding film having high adhesion to a ring frame and no ring frame desorption and excellent pick-up success rate.

Still another object of the present invention is to provide a dicing die bonding film comprising a pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition.

The pressure-sensitive adhesive composition of the present invention is an acrylic copolymer having at least one alkyl group, at least one hydroxy group and at least one phosphate group; And a curing agent.

In one embodiment, the acrylic copolymer may be a copolymer obtained by polymerizing a (meth) acrylate having a hydroxy group, a (meth) acrylate having an alkyl group and a (meth) acrylate having a phosphate group.

In one embodiment, the (meth) acrylate having a phosphate group may have a structure of Formula 1 below.

≪ Formula 1 >

CH2 = CR-C (= O) O- (CH2) m-O-P (= O) (OR1) (OR2)

In which R is -H or-(CH2) n-CH3, n is an integer from 0 to 5,

R1 and R2 are independently of each other hydrogen, alkyl of 1-10 carbon atoms or aryl groups of 6-20 carbon atoms, m is an integer of 1-10)

In one embodiment, the (meth) acrylate having a phosphate group may be included in 0.1 to 10 parts by weight of 100 parts by weight of the acrylic copolymer.

In one embodiment, the acrylic copolymer may further have one or more selected from the group consisting of an epoxy group and a carboxyl group.

In one embodiment, the acrylic copolymer is a (meth) acrylate having a hydroxy group, a (meth) acrylate having an alkyl group, a (meth) acrylate having a phosphate group; And a copolymer obtained by polymerizing at least one member selected from the group consisting of an unsaturated epoxy compound having an epoxy group and a (meth) acrylate having a carboxyl group.

In one embodiment, the curing agent may be included in 3-10 parts by weight based on 100 parts by weight of the acrylic copolymer.

In one embodiment, the pressure-sensitive adhesive composition may not include a photo initiator.

The dicing die bonding film of this invention is a base film; An adhesive layer formed on the base film and formed of the adhesive composition; And it may include an adhesive layer formed on the adhesive layer.

The present invention provides a pressure-sensitive adhesive composition that can be used in a dicing die bonding film that can reduce the cumbersomeness of a semiconductor manufacturing process that should be further subjected to an ultraviolet irradiation process. The present invention provides a pressure-sensitive adhesive composition that can be used in a dicing die bonding film that can solve the problem of having to adhere to the ring frame is a high adhesive strength of the additional adhesion film. The present invention provides a pressure-sensitive adhesive composition that can be used in a dicing die bonding film having high adhesion to a ring frame and thus no ring frame detachment occurs and excellent pick-up success rate.

The pressure-sensitive adhesive composition of the present invention is an acrylic copolymer having an alkyl group, a hydroxyl group and a phosphate group; And a curing agent.

Acrylic copolymer

The acrylic copolymer may have one or more alkyl groups, one or more hydroxy groups and one or more phosphate groups.

The arrangement order of the alkyl group and the hydroxy group phosphate group in the acrylic copolymer is not particularly limited and can be appropriately changed. In addition, at least one alkyl group, at least one hydroxy group or at least one phosphate group in the acrylic copolymer may be arranged in series.

The acrylic copolymer may be a copolymer obtained by copolymerizing a (meth) acrylate having at least one hydroxy group, a (meth) acrylate having at least one alkyl group and a (meth) acrylate having at least one phosphate group.

The (meth) acrylate having a hydroxy group may mean a monomer including a hydroxy group and copolymerizable with a (meth) acrylate having the alkyl group or a (meth) acrylate having a phosphate group. For example, (meth) acrylate which has the said hydroxy group is 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy Hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 1-chloro-2-hydroxypropyl (meth) acrylate, di Ethylene glycol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, neopentyl glycol mono (meth) Acrylate, trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylic Latex, 2-hydroxy May include one or more selected from the group consisting of cy-3-phenyloxy (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, and cyclohexane dimethanol mono (meth) acrylate. However, the present invention is not limited thereto.

The (meth) acrylate having an alkyl group may include a (meth) acrylic acid ester having a linear or branched alkyl group of 1 to 20 carbon atoms in the ester moiety. For example, (meth) acrylate which has an alkyl group is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acryl Late, iso-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl It may include, but is not limited to, one or more selected from the group consisting of (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate and lauryl (meth) acrylate.

The (meth) acrylate having a phosphate group may mean a monomer having a phosphate group and copolymerizable with the (meth) acrylate having the hydroxy group and / or the (meth) acrylate having an alkyl group.

As used herein, a "phosphate group" is -OP (= O) (OH) 2 or -OP (= O) (OR1) (OR2) (wherein R1 and R2 are independently of each other hydrogen, alkyl having 1-10 carbon atoms or carbon number) 6-20 aryl group). Preferably, R1 and R2 may be independently of each other hydrogen, an alkyl group having 1 to 4 carbon atoms.

The (meth) acrylate having a phosphate group may have, for example, a structure of Formula 1 below.

≪ Formula 1 >

CH2 = CR-C (= O) O- (CH2) m-O-P (= O) (OR1) (OR2)

In which R is -H or-(CH2) n-CH3, n is an integer from 0-5,

R1 and R2 are independently of each other hydrogen, alkyl of 1-10 carbon atoms or aryl groups of 6-20 carbon atoms, m is an integer of 1-10)

For example, the (meth) acrylate having a phosphate group can be, but is not limited to, ethylene glycol (meth) acrylate phosphate.

The (meth) acrylate having a hydroxy group in the acrylic copolymer may be included in 10 to 50 parts by weight of 100 parts by weight of the acrylic copolymer. Within this range, it is possible to increase the adhesion with the polyolefin-based or polyvinyl chloride-based base film, it is possible to react smoothly when reacting with the isocyanate-based curing agent. Preferably it may be included in 20-30 parts by weight.

The (meth) acrylate having an alkyl group in the acrylic copolymer may be included in 50 to 85 parts by weight of 100 parts by weight of the acrylic copolymer. Within this range, the initial adhesive force can be maintained high, and the adhesion with the ring frame or the adhesive film can be made more smoothly. Preferably it may be included in 60-75 parts by weight.

The (meth) acrylate having a phosphate group in the acrylic copolymer may be included in an amount of 0.5-10 parts by weight in 100 parts by weight of the acrylic copolymer. Within this range, it is possible to increase the initial adhesive strength of the acrylic copolymer and to increase the success rate of pickup with the adhesion to the ring frame.

The acrylic copolymer may further have one or more selected from the group consisting of an epoxy group and a carboxy group, in addition to the alkyl group, the hydroxy group and the phosphate group.

In one embodiment, the acrylic copolymer may have one or more alkyl groups, one or more hydroxy groups, one or more phosphate groups and one or more epoxy groups.

The arrangement order of the alkyl group, hydroxy group, phosphate group and epoxy group in the acrylic copolymer is not particularly limited and may be appropriately changed. In addition, at least one alkyl group, at least one hydroxy group, at least one phosphate group or at least one epoxy group in the acrylic copolymer may be arranged in series.

Acrylic copolymers are copolymers of (meth) acrylates having at least one hydroxy group, (meth) acrylates having at least one alkyl group, (meth) acrylates having at least one phosphate group, and unsaturated epoxy compounds having at least one epoxy group. It may be coalescing.

The (meth) acrylate which has a hydroxyl group, the (meth) acrylate which has an alkyl group, and the (meth) acrylate which has a phosphate group are as above-mentioned.

An unsaturated epoxy compound having an epoxy group may have, for example, a structure of Formula 2 below.

(2)

Wherein R3, R4, R5, R8, R9 and R10 are each H, C1-C14 alkyl group or unsaturated alkyl group, C6-C14 aryl group, C1-12 saturated or unsaturated alkyl group An aryl group, Y is an ether group (-O-), a carboxy group (-O (C = O)-,-(C = O) O-), an alkylene group of C1-C12, an arylene group of C6-C14, or C1 A C6-C14 arylene group substituted with a saturated or unsaturated alkyl group of -12, wherein Y is an ether group (-O-) or a carboxy group (-O (C = O)-,-(C = O) O-) And R 6 and R 7 are each independently a single bond, C 1 -C 12 alkylene, C 6 -C 14 arylene, or C 6 -C 14 arylene group substituted with a C 1-12 saturated or unsaturated alkyl group, and Y is C 1- When an alkylene group of C12, an arylene group of C6-C14, or an arylene group of C6-C14 substituted with a saturated or unsaturated alkyl group of C1-12, Y represents (R6-Y-R7)).

In the above, the C1-12 alkyl group or the C1-C12 alkylene group may preferably be a C1-C6 alkyl group or an alkylene group, more preferably a C1-C4 alkyl group or an alkylene group.

In the above, the C6-C14 aryl group or the C6-C14 arylene group may preferably be a C6-C10 aryl group or an arylene group.

For example, unsaturated epoxy compounds with epoxy groups include glycidyl (meth) acrylates, epoxy alkyl acrylates, allyl glycidyl ethers, aryl glycidyl ethers, vinyl glycidyl ethers and glycidyl itaconates. It may be one or more selected from the group consisting of.

Based on 100 parts by weight of the acrylic copolymer, 20-30 parts by weight of a (meth) acrylate having a hydroxy group, 60-75 parts by weight of a (meth) acrylate having an alkyl group, and a (meth) acrylate having a phosphate group of 0.5- The unsaturated epoxy compound having 3 parts by weight and an epoxy group may be included at 4.5-7 parts by weight. Within this range, it is possible to prevent desorption with the ring frame that may occur in the sawing process, and to maintain a smooth pick-up performance in the pick-up process.

In other embodiments, the acrylic copolymer can have one or more alkyl groups, one or more hydroxy groups, one or more phosphate groups, and one or more carboxyl groups.

The arrangement order of the alkyl group, hydroxy group, phosphate group and carboxyl group in the acrylic copolymer is not particularly limited and can be appropriately changed. In addition, at least one alkyl group, at least one hydroxy group, at least one phosphate group or at least one carboxyl group in the acrylic copolymer may be arranged in series.

The acrylic copolymer is obtained by copolymerizing (meth) acrylate having at least one hydroxy group, (meth) acrylate having at least one alkyl group, (meth) acrylate having at least one phosphate group, and (meth) acrylate having at least one carboxyl group. It may be a copolymer.

The (meth) acrylate which has a hydroxyl group, the (meth) acrylate which has an alkyl group, and the (meth) acrylate which has a phosphate group are as above-mentioned.

The (meth) acrylate having a carboxyl group may have a structure of Formula 5 or 6.

≪ Formula 5 >

CH2 = CR-C (= O) O- (CH2) r-COOH

Wherein R is -H or-(CH2) n-CH3, n is an integer from 0 to 5,

r is an integer from 1-10)

(6)

CH2 = CR-C (= O) OH

(Wherein R is -H or-(CH2) n-CH3 and n is an integer from 0 to 5)

For example, the (meth) acrylate having a carboxyl group may be at least one selected from the group consisting of (meth) acrylic acid, itaconic acid, maleic acid and fumaric acid.

Based on 100 parts by weight of the acrylic copolymer, 20-30 parts by weight of a (meth) acrylate having a hydroxy group, 60-75 parts by weight of a (meth) acrylate having an alkyl group, and a (meth) acrylate having a phosphate group of 0.5- The (meth) acrylate having 3 parts by weight and carboxyl group may be included in 0.5-7 parts by weight. Within this range, it is possible to prevent desorption with the ring frame that may occur in the sawing process, and to maintain a smooth pick-up performance in the pick-up process.

In another embodiment, the acrylic copolymer may have one or more alkyl groups, one or more hydroxy groups, one or more phosphate groups, one or more epoxy groups, and one or more carboxyl groups.

The arrangement order of the alkyl group, hydroxy group, phosphate group, epoxy group and carboxyl group in the acrylic copolymer is not particularly limited and can be appropriately changed. In addition, at least one alkyl group, at least one hydroxy group, at least one phosphate group, at least one epoxy group or at least one carboxyl group in the acrylic copolymer may be arranged in series.

Acrylic copolymers include (meth) acrylates with one or more hydroxy groups, (meth) acrylates with one or more alkyl groups, (meth) acrylates with one or more phosphate groups, unsaturated epoxy compounds with one or more epoxy groups, and one or more carboxyl groups It may be a copolymer copolymerized with a (meth) acrylate having.

The (meth) acrylate which has a hydroxyl group, the (meth) acrylate which has an alkyl group, the (meth) acrylate which has a phosphate group, the unsaturated epoxy type compound with an epoxy group, and the (meth) acrylate which has a carboxyl group are as above-mentioned.

Based on 100 parts by weight of the acrylic copolymer, 20-30 parts by weight of a (meth) acrylate having a hydroxy group, 60-75 parts by weight of a (meth) acrylate having an alkyl group, and a (meth) acrylate having a phosphate group of 0.5- 3 parts by weight, 4-7 parts by weight of an unsaturated epoxy compound having an epoxy group, and (meth) acrylate having a carboxyl group may be included in an amount of 0.5-3 parts by weight. Within this range, it is possible to prevent desorption with the ring frame that may occur in the sawing process, and to maintain a smooth pick-up performance in the pick-up process. The carboxyl group and the epoxy group were simultaneously introduced to improve the adhesion.

In one embodiment, the acrylic copolymer of the present invention may be a copolymer obtained by copolymerizing one or more monomers of the following Chemical Formulas 1, 3, and 4.

≪ Formula 1 >

CH2 = CR-C (= O) O- (CH2) m-O-P (= O) (OR1) (OR2)

Wherein R is -H or-(CH2) n-CH3, n is an integer from 0-5,

R1 and R2 are independently of each other hydrogen, alkyl of 1-10 carbon atoms or aryl groups of 6-20 carbon atoms, m is an integer of 1-10)

<Formula 3>

CH2 = CR-C (= O) O- (CH2) p-CH3

Wherein R is -H or-(CH2) n-CH3, n is an integer from 0 to 5,

p is an integer from 0-10)

&Lt; Formula 4 >

CH2 = CR-C (= O) O- (CH2) q-OH

Wherein R is -H or-(CH2) n-CH3, n is an integer from 0 to 5,

q is an integer from 1-10)

The arrangement order of the monomers in the acrylic copolymer is not particularly limited, and the same monomers may be continuously arranged.

For example, the monomer of Formula 1, the monomer of Formula 3 and the monomer of Formula 4 in the acrylic copolymer may be copolymerized in a molar ratio of 0.5-2: 70-75: 24.5-28. Within this range, it is possible to prevent desorption with the ring frame that may occur in the sawing process, and to maintain a smooth pick-up performance in the pick-up process.

The acrylic copolymer may further copolymerize one or more monomers selected from the group consisting of the following Chemical Formulas 2, 5, and 6.

(2)

Wherein R3, R4, R5, R8, R9 and R10 are each H, C1-C14 alkyl group or unsaturated alkyl group, C6-C14 aryl group, C1-12 saturated or unsaturated alkyl group An aryl group, Y is an ether group (-O-), a carboxy group (-O (C = O)-,-(C = O) O-), an alkylene group of C1-C12, an arylene group of C6-C14, or C1 A C6-C14 arylene group substituted with a saturated or unsaturated alkyl group of -12, wherein Y is an ether group (-O-) or a carboxy group (-O (C = O)-,-(C = O) O-) And R6 and R7 are each independently of each other a single bond, C1-C12 alkylene, C6-C14 arylene, or C6-C14 arylene group substituted with C1-12 saturated or unsaturated alkyl group, and Y is C1 Y represents (R6-Y-R7) when an alkylene group of -C12, an arylene group of C6-C14 or a C6-C14 arylene group substituted with a saturated or unsaturated alkyl group of C1-12).

&Lt; Formula 5 >

CH2 = CHR-C (= O) O- (CH2) r-COOH

Wherein R is -H or-(CH2) n-CH3, n is an integer from 0 to 5,

r is an integer from 1-10)

(6)

CH2 = CR-C (= O) OH

(Wherein R is -H or-(CH2) n-CH3 and n is an integer from 0 to 5)

In this case, the arrangement order of the monomers in the acrylic copolymer is not particularly limited, and the same monomer may be continuously arranged.

For example, in the acrylic copolymer, the monomer of Formula 1, the monomer of Formula 2, the monomer of Formula 3 and the monomer of Formula 4 may be copolymerized in a molar ratio of 0.5-2: 4-7: 64-73.5: 22-27. Can be. Within this range, it is possible to prevent desorption with the ring frame that may occur in the sawing process, and to maintain a smooth pick-up performance in the pick-up process.

For example, in the acrylic copolymer, the monomer of Formula 1, the monomer of Formula 3, the monomer of Formula 4 and the monomer of Formula 5 or 6 may be present in a molar ratio of 0.5-2.5: 5-8.5: 82-93.5: 1-7 May be copolymerized. Within this range, it is possible to prevent desorption with the ring frame that may occur in the sawing process, and to maintain a smooth pick-up performance in the pick-up process.

For example, in the acrylic copolymer, monomers of formula (1), monomers of formula (2), monomers of formula (3), monomers of formula (4) and monomers of formula (5) are 0.5-2: 4-6.5: 59-73.5: 21-27: May be copolymerized in a molar ratio of 1-5.5. Within this range, it is possible to prevent desorption with the ring frame that may occur in the sawing process, and to maintain a smooth pick-up performance in the pick-up process.

The weight average molecular weight of the acrylic copolymer may be 500,000 to 800,000 g / mol. Within this range, pick-up performance and film forming performance are excellent.

The viscosity of the acrylic copolymer may be 4000 to 6000 cps at 25 ℃. Within this range, it exhibits a smooth coating processability in the adhesive film coating process.

The viscosity was measured in a 500 ml-nalgene bottle (73.8 mm outer diameter x 169.8 mm height) with a Brookfield viscometer DV-II +, and 100 rpm at 25 ° C. at 100 rpm. # 7.

The acrylic copolymer can be prepared by a conventional copolymerization method. For example, it can manufacture by well-known polymerization method including well-known emulsion polymerization, suspension polymerization, block polymerization, etc. A polymerization initiator including azobisisobutyronitrile or the like may be used for the polymerization.

Hardener

The curing agent is not particularly limited but may be a thermal curing agent. For example, it may be one or more selected from the group consisting of isocyanate, epoxy, aziridine, melamine, amine, imide, carbodiimide and amide, but is not limited thereto. Isocyanate curing agents are preferred.

Isocyanate-based curing agents can be used conventional ones known to those skilled in the art. For example, isocyanate-based curing agents are trimethylolpropane toluene diisocyanate (TMP-adduct), 2,4-trilene diisocyanate, 2,6-triylene diisocyanate, hydrogenated triylene diisocyanate, 1,3-xylene di Isocyanate, 1,4-xylene diisocyanate, diphenylmetal-4,4-diisocyanate, 1,3-bisisocyanatomethyl cyclohexane, tetramethylxylene diisocyanate, 1,5-naphthalene diisocyanate, 2,2, 4-trimethyl hexamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, triylene diisocyanate adduct of trimethylolpropane, xylene diosocyanate adduct of trimethylolpropane, toriphenylmethanetoriisocyanate and methylene bis It may be at least one selected from the group consisting of triisocyanates.

The curing agent may be included in 3-10 parts by weight based on 100 parts by weight of the acrylic copolymer in the pressure-sensitive adhesive composition. Within this range, the pick-up success rate can be increased by having an appropriate adhesive force, and the initial adhesive force is high, so that no scattering of chips or ring frame detachment of chips cut during the sawing process occurs. Preferably, it may be included in 5-7 parts by weight based on 100 parts by weight of the acrylic copolymer.

The pressure-sensitive adhesive composition of the present invention can be prepared by the following steps:

Copolymerizing a (meth) acrylate having a hydroxy group, a (meth) acrylate having an alkyl group and a (meth) acrylate having a phosphonate group to prepare an acrylic copolymer (first step); And

Adding a curing agent to the acrylic copolymer (second step).

Step 1

The first step is to prepare an acrylic copolymer, in which a copolymer is added by adding an initiator to a mixture containing a (meth) acrylate having a hydroxy group, a (meth) acrylate having an alkyl group and a (meth) acrylate having a phosphate group. Acrylic copolymers can be prepared.

Examples of the initiator include azobisisobutyronitrile, 2,2-azobis (2,4-dimethylvalenonitrile), benzoyl peroxide, dilauroyl peroxide, tertiary-butyl- (2-ethylhexyl) Monoperoxycarbonate, tertiary-amyl- (2-ethylhexyl) monoperoxycarbonate, 1,1-di (tertiary-butylperoxy) cyclohexane, 1,1-di (tertiary-amylperoxy) Cyclohexane, tert-butyl peroxy-3,5,5-trimethylhexanoate, 1,1-di (tert-butyl peroxy) -3,3,5-trimethylcyclohexane, potassium persulfate, sodium Although it may be 1 type, or 2 or more types selected from the group which consists of a persulfate, an amonium persulfate, and an azo water-soluble initiator, it is not limited to these. Preferably, azobisisobutyronitrile can be used.

The initiator may be included in an amount of 0.001-2 parts by weight based on 100 parts by weight of (meth) acrylate having a hydroxy group.

The first step may include a solvent capable of dissolving a (meth) acrylate having a hydroxy group, a (meth) acrylate having an alkyl group and a (meth) acrylate having a phosphate group. As the solvent, there can be used conventional ones known to those skilled in the art. For example, ethyl acetate and the like can be used.

In the first step, an acrylic copolymer may be prepared by further including at least one selected from the group consisting of an unsaturated epoxy compound having an epoxy group and a (meth) acrylate having a carboxyl group.

Polymerization temperature and polymerization time can be adjusted suitably. For example, the polymerization may be carried out at a polymerization temperature of 65 to 90 ° C. for 6 to 10 hours.

Step 2

The second step is to prepare a final pressure-sensitive adhesive composition by adding a curing agent to the acrylic copolymer. Preparation of the pressure-sensitive adhesive composition can be carried out by conventional methods. For example, it may be prepared by adding an acrylic copolymer and a curing agent to a solvent such as methyl ethyl ketone and stirring at 25-30 ° C. for 30 to 60 minutes.

The adhesive composition of this invention does not contain a photoinitiator. The pressure-sensitive adhesive composition of the present invention is used to form a pressure-sensitive adhesive layer in an ultraviolet non-irradiated dicing die bonding film. Conventionally, in the ultraviolet irradiation dicing die bonding film, the photoinitiator was included in the adhesion layer in order to cure the adhesion layer for separation of the adhesion layer and the adhesion layer. On the other hand, since the pressure-sensitive adhesive composition of the present invention is used as the pressure-sensitive adhesive layer of the ultraviolet non-irradiation dicing die bonding film does not require an ultraviolet irradiation step, it is not necessary to include a photo initiator.

The present invention provides a dicing die bonding film formed of the pressure-sensitive adhesive composition. The adhesive composition forms an adhesive layer in a dicing die bonding film.

The dicing die bonding film includes a base film; An adhesive layer formed on the base film; And an adhesive layer formed on the adhesive layer, wherein the adhesive layer may be formed of the adhesive composition of the present invention.

The base film supports an adhesive layer that holds the wafer to prevent shaking during dicing, and when the dicing is completed, an expansion process in which a gap between chips is increased to facilitate picking up individualized chips. It is preferable to use a film that can be stretched at room temperature so as to enable this.

Various polymer films may be used as the base film, but polyolefins such as polyethylene, polypropylene, ethylene / propylene copolymer, polybutene-1, ethylene / vinyl acetate copolymer, mixture of polyethylene / styrene butadiene rubber, polyvinyl chloride, etc. Films can be mainly used. Further, polymers such as polyethylene terephthalate, polycarbonate and poly (methyl methacrylate), thermoplastic elastomers such as polyurethane and polyamide-polyol copolymer, and mixtures thereof can be used. The thickness of the base film may be 30-300 μm, preferably 50-200 μm in view of strong elongation, workability, and the like.

The method for forming the pressure-sensitive adhesive layer on the base film may be directly coated with the pressure-sensitive adhesive composition, or after coating the pressure-sensitive adhesive layer on a release film or the like, and after completion of drying, may be transferred by a transfer method. In all cases, the coating method for forming the adhesive layer is not limited as long as it can form a uniform coating layer, but mainly bar coating, gravure coating, comma coating, reverse roll coating, applicator coating, spray coating, lip coating And the like are used. The thickness of the adhesion layer can be 3-40 micrometers, Preferably it is 5-30 micrometers.

The adhesive force to the adhesive layer-ring frame may be 1 to 3 N / 25 mm.

The adhesive layer is made into a film with a thermosetting composition and should have good adhesion to the grounded back side of the wafer. The adhesive layer is composed of a high molecular weight acrylic copolymer having a film forming ability, a thermosetting resin such as an epoxy resin, and a curing agent. Examples of the acrylic copolymer include acrylic rubbers such as acrylic acid esters, methacrylic acid esters and acrylonitrile. The epoxy resin is not particularly limited as long as it has an adhesive strength by curing, but since it needs to have two or more functional groups in order to perform a curing reaction, a bisphenol A type epoxy resin, a phenol novolak type epoxy resin and a cresol novolak type epoxy resin can be used have. The curing agent may be used a curing agent commonly used in the manufacture of the adhesive layer.

As the adhesive layer, a curing accelerator for curing the epoxy resin can be used, for example, an imidazole series, an amine series or the like can be used. In addition, in order to increase the adhesive force with a wafer, an adhesive layer can use 1 type, or 2 or more types of silane coupling agents.

The coating method of the adhesive layer is not particularly limited as long as it can form a uniform coating film thickness similarly to the adhesive layer. The coating thickness of the adhesive layer is preferably 5-100 μm, preferably 10-80 μm.

The adhesion to the adhesive layer-adhesive layer can be 0.05-0.5N / 25mm.

The adhesive layer may further include a release film in order to protect the adhesive layer from foreign matter and to facilitate winding in a roll.

The dicing die bonding film has a structure in which an adhesive layer is coated on a base film as described above, and an adhesive layer is laminated on the adhesive layer. Since the adhesive layer is adhered to a semiconductor chip and diced into a small size, when the chip is picked up, the adhesive layer is easily peeled off from the lower adhesive layer and die-bonded to the surface of a supporting member such as a PCB substrate or a lead frame while being attached to the back surface of the chip. .

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

Details that are not described herein will be omitted since those skilled in the art can sufficiently infer technically.

Preparation Example 1 Preparation of Acrylic Copolymer

245 g of ethyl acetate was added to a 2 L four-neck flask reaction vessel, a reflux cooler was installed on one side, a thermometer was installed on the other side, and a dropping funnel was installed on the other side. The flask solution was heated to reflux temperature 74 占 폚, 513 g of a mixture of 372.6 g of 2-ethylhexyl acrylate, 64.8 g of hydroxyethyl methacrylate, 64.8 g of hydroxyethyl acrylate, and 10.8 g of ethylene glycol phosphate methacrylate; 120 g of toluene and 0.18 g of azobisisobutyronitrile were prepared. The mixture was added dropwise at 74 ° C. for 3 hours using a dropping funnel. The stirring speed at the dropwise addition was 250rpm, the reaction was aged for 4 hours at 85 ℃ after the dropping. 120 g of ethyl acetate and 0.2 g of azobisisobutyronitrile were added for 20 minutes, and maintained at 85 ° C. for 4 hours. The viscosity and solids of the reactants were measured and the reaction was stopped to prepare an acrylic copolymer (viscosity: 4000 cps at 25 ° C.).

Preparation Example 2 Preparation of Acrylic Copolymer

In the flask of Preparation Example 1, 372.6 g of 2-ethylhexyl acrylate, 64.8 g of hydroxyethyl methacrylate, 64.8 g of hydroxyethyl acrylate, 27 g of glycidyl methacrylate, and 10.8 g of ethylene glycol phosphate methacrylate Mixed solution of 540 g of toluene and 120 g of toluene and 0.18 g of azobisisobutyronitrile Dropping was added using a dropping funnel. An acrylic copolymer (viscosity: 4500 cps at 25 ° C.) was prepared in the same manner as in Preparation Example 1.

Preparation Example 3 Preparation of Acrylic Copolymer

Into the flask of Preparation Example 1, a mixture of 383.4 g of 2-ethylhexyl acrylate, 64.8 g of hydroxyethyl methacrylate and 64.8 g of hydroxyethyl acrylate, 120 g of toluene, and 0.18 g of azobisisobutyronitrile were mixed. Dropping was added using a dropping funnel. An acrylic copolymer (viscosity: 3000 cps at 25 ° C.) was prepared in the same manner as in Preparation Example 1.

Preparation Example 4 Preparation of Acrylic Copolymer

Into the flask of Preparation Example 1, a mixture of 383.4 g of 2-ethylhexyl acrylate, 64.8 g of hydroxyethyl methacrylate, 64.8 g of hydroxyethyl acrylate, 27 g of glycidyl methacrylate, 120 g of toluene, and azobisiso Butyronitrile 0.18 g mixture Dropping was added using a dropping funnel. An acrylic copolymer (viscosity: 3500 cps at 25 ° C.) was prepared in the same manner as in Preparation Example 1.

Preparation Example 5 Preparation of Acrylic Copolymer

In the flask of Preparation Example 1, 383.4 g of 2-ethylhexyl acrylate, 64.8 g of hydroxyethyl methacrylate, 64.8 g of hydroxyethyl acrylate, 27 g of glycidyl methacrylate, and 10.8 g of ethylene glycol phosphate methacrylate 10.8 g of acrylic acid, 120 g of toluene and 0.18 g of azobisisobutyronitrile Dropping was added using a dropping funnel. An acrylic copolymer (viscosity: 4800 cps at 25 ° C.) was prepared in the same manner as in Preparation Example 1.

Specific specifications of each component used in the following examples and comparative examples are as follows.

1. Acrylic copolymer: The copolymer prepared in Production Example 1-5

2. Curing agent: trimethylolpropane toluene diisocyanate (TMP-adduct type, AK-75, Aekyung Chemical Co., Ltd.)

Example 1-3 and Comparative Example 1-2

To 25 parts by weight of methyl ethyl ketone, each component was added in the content (unit: parts by weight) shown in Table 1 below, and stirred at 25 ° C. for 1 hour to prepare a composition for dicing die bonding film.

Example Comparative Example One 2 3 One 2 Acrylic copolymer Production Example 1 100 - - - Production Example 2 - 100 - - Production Example 3 - - 100 - Production Example 4 - - - 100 Production Example 5 100 Hardener 7 7 7 7 7

Experimental Example : Dicing die Bonding  Measurement of physical properties of film composition

The film compositions prepared in Examples and Comparative Examples were coated on a release PET film with a thickness of 8 μm, and then transferred to a polyolefin film, which is a base film, and aged at 25 ° C. for 3 days. The aged sample was laminated with an adhesive film layer adhered to a chip to prepare a dicing die bonding film. A four-layer film composed of a release PET film, an adhesive film, an adhesive layer, and a polyolefin film was completed. The following physical properties were measured and the results are shown in Table 2 below.

Glue layer manufacturing:

69 parts by weight of an acrylic rubber binder (SG-P3, Nagase chemtex 17%) in an 1 L cylindrical flask, 13 parts by weight of an epoxy resin (EPPN-501H (Nippon Kayaku 81%)), a phenol hardener (HF-1M (Meiwa, 50%) ) 7 parts by weight, silane additive (KBM-403 (Shinetsu, 100%)) 1 part by weight, curing accelerator (TPP-K (HOKKO, 100%)) 0.5 part by weight, filler (R-972 (Degussa, 100%) ) 9.5 parts by weight was added, cyclohexanone was added and mixed, and the composition was prepared by dispersing at 5000 rpm for 30 minutes using a high-speed stirring rod, followed by filtration using a 200-mesh filter, and then, using an applicator, toyobo TS to a thickness of 20 μm. An adhesive film was prepared by coating on -002 (38um, 50um release PET), and dried at 100 ° C. for 20 minutes and then stored at room temperature for 1 day.

&Lt; Method for measuring physical properties &

1. Peeling force between the adhesive layer and the adhesive layer: The peeling force was measured in accordance with Clause 8 of Korean Industrial Standard KS-A-01107 (Test Method of Adhesive Tape and Adhesive Sheet). The dicing die bonding film prepared in the above Examples and Comparative Examples was compressed by reciprocating once at a speed of 300 mm / min using a compression roller having a load of 2 kg. After 30 minutes of squeezing, flip the folds of the specimens to 180 °, peel off 25 mm, place the specimen on the upper clip of the tensile strength tester (Instron Series 1X / s Automated materials Tester-3343), and fix the die-bonding film to the lower clip. The load at the time of pulling off at a tensile speed of 300 mm / min was measured.

2. Peel force between the adhesive layer and the ring frame (SUS): The peel force measurement was tested in accordance with Clause 8 of Korean Industrial Standard KS-A-01107 (Test Method of Adhesive Tape and Adhesive Sheet). After attaching a sample having a pressure-sensitive adhesive film of 25 mm and a length of 250 mm to the ring frame (SUS), it was pressed by reciprocating once at a speed of 300 mm / min using a 2 kg load roller. After 30 minutes after crimping, the folded part of the test piece is turned to 180 ° and peeled off about 25 mm, and then the test piece is fixed to the upper clip of the tensile strength tester by the lower clip of the ring frame (SUS) test plate and pulled at a tensile speed of 300 mm / min. The load at the time of peeling was measured. The tensile tester used Instron Series lX / s Automated materials Tester-3343.

3. Tackiness: Tackiness was measured using a probe tack tester (tacktoc-2000) using the prepared specimen. The measuring method is based on ASTM D2979-71, the maximum required when the tip of the clean probe is contacted with the adhesive layer of the specimen for 1.0 + 0.01 seconds at a rate of 10 + 0.1 mm / sec and a contact load of 9.79 + 1.01 kPa and then released. The force was measured.

4. Pick-up success rate: The PET film is removed from the prepared dicing die bonding film, the wafer is mounted and the dicing process is performed. Pickup success rate was measured using the die bonder apparatus (SDB-10M, Mechatronics Corporation) about 200 chips in the center of a wafer.

5. Ring frame detachment: Wafer Sawing is performed immediately after the Wafer mounting process. This is the process of cutting the wafer into pieces to assemble the IC package. The cutting method is using a physical saw or using a laser. During the dicing process, the silicon wafer is attached to the dicing tape, which has an adhesive on one side so that it is fixed to the wafer frame. When the wafer is cut into pieces, the remaining part of the tape is called a die and is attached to the lead-frame or pcb board. The part that is cut off during wafer cutting is called the die street and is generally about 75μm wide. After the wafer cutting process, the die remaining on the tape is processed again by die bonder and die sorter. At this time, the size of the die is generally about 0.5 ~ 35mm and processed into a straight line, so the shape of the die becomes a rectangular or square shape. Evaluation was carried out using a Disco dicing facility.

6. Desorption rate: 20 wafers were determined by the ratio of desorption after the sawing process.

Example Comparative Example One 2 3 One 2 Peel force between adhesive layer and adhesive layer (N / 25mm) 0.107 0.119 0.132 0.102 0.12 Peel force between adhesive layer and SUS (N / 25mm) 1.685 1.718 1.733 0.782 0.90 Adhesiveness (gf / mm ² ) 21 22 24 14 15 Pick-up Success Rate (%) 100 100 100 100 100 Ring frame tally Tally
Not Occurred Tally
Not Occurred Tally
Not Occurred Tally
Occur Tally
Occur Tally rate 0 0 0 65 45

As shown in Table 2, it can be seen that the pressure-sensitive adhesive composition of the present invention has a high adhesive strength to the ring frame, so that ring frame desorption does not occur and the pickup success rate is also high (Example 1-3). On the other hand, the pressure-sensitive adhesive composition comprising an acrylic copolymer prepared without a monomer containing a phosphonate group can be seen that ring frame desorption occurs and the pick-up success rate is also poor (see Example 1 and Comparative Example 1, Example 2 and Comparative Example 2).

Claims (24)

(Meth) acrylates having at least one hydroxy group, (meth) acrylates having at least one alkyl group, (meth) acrylates having at least one phosphate group, and unsaturated epoxy compounds having at least one epoxy group and at least one carboxylic acid group ( Acrylic copolymer which superposed | polymerized 1 or more types of the meta) acrylates; And
Adhesive composition containing a hardening | curing agent.
delete The pressure-sensitive adhesive composition of claim 1, wherein the (meth) acrylate having a phosphate group has a structure represented by the following Chemical Formula 1.
&Lt; Formula 1 >
CH2 = CR-C (= O) O- (CH2) mOP (= O) (OR1) (OR2)
In which R is -H or-(CH2) n-CH3, n is an integer from 0-5,
R1 and R2 are independently of each other hydrogen, alkyl of 1-10 carbon atoms or aryl groups of 6-20 carbon atoms, m is an integer of 1-10)
The pressure-sensitive adhesive composition according to claim 1, wherein the (meth) acrylate having a phosphate group is ethylene glycol (meth) acrylate phosphate.
The pressure-sensitive adhesive composition of claim 1, wherein the (meth) acrylate having the phosphate group is included in an amount of 0.1 to 10 parts by weight in 100 parts by weight of the acrylic copolymer.
The method of claim 1, wherein the (meth) acrylate having a hydroxy group is 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2 -Hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 1-chloro-2-hydroxypropyl (meth) acrylate , Diethylene glycol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, neopentyl glycol mono ( Meta) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 4-hydroxycyclohexyl (meth ) Acrylate, 2- At least one selected from the group consisting of hydroxy-3-phenyloxy (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, and cyclohexane dimethanol mono (meth) acrylate. Pressure-sensitive adhesive composition.
delete delete The pressure-sensitive adhesive composition of claim 1, wherein the unsaturated epoxy compound having an epoxy group has a structure of Formula 2 below.
(2)

Wherein R3, R4, R5, R8, R9 and R10 are each H, C1-C14 alkyl group or unsaturated alkyl group, C6-C14 aryl group, C1-12 saturated or unsaturated alkyl group An aryl group, Y is an ether group (-O-), a carboxy group (-O (C = O)-,-(C = O) O-), an alkylene group of C1-C12, an arylene group of C6-C14, or C1 A C6-C14 arylene group substituted with a saturated or unsaturated alkyl group of -12, wherein Y is an ether group (-O-) or a carboxy group (-O (C = O)-,-(C = O) O-) And R 6 and R 7 are each independently a single bond, C 1 -C 12 alkylene, C 6 -C 14 arylene, or C 6 -C 14 arylene group substituted with C 1-12 saturated or unsaturated alkyl group, and Y is C 1- When an alkylene group of C12, an arylene group of C6-C14, or an arylene group of C6-C14 substituted with a saturated or unsaturated alkyl group of C1-12, Y represents (R6-Y-R7)).
The method of claim 1, wherein the unsaturated epoxy compound having an epoxy group is glycidyl (meth) acrylate, epoxy alkyl acrylate, allyl glycidyl ether, aryl glycidyl ether, vinyl glycidyl ether and glycidyl Pressure-sensitive adhesive composition, characterized in that at least one member selected from the group consisting of itaconate.
The pressure-sensitive adhesive composition of claim 1, wherein the (meth) acrylate having a carboxylic acid group has a structure of Formula 5 or 6.
&Lt; Formula 5 >
CH2 = CR-C (= O) O- (CH2) r-COOH
Wherein R is -H or-(CH2) n-CH3, n is an integer from 0 to 5,
r is an integer from 1-10)
(6)
CH2 = CR-C (= O) OH
(Wherein R is -H or-(CH2) n-CH3 and n is an integer from 0 to 5)
The pressure-sensitive adhesive composition of claim 1, wherein the curing agent is an isocyanate curing agent.
The pressure-sensitive adhesive composition of claim 1, wherein the curing agent is included in an amount of 3-10 parts by weight based on 100 parts by weight of the acrylic copolymer.
The pressure-sensitive adhesive composition of claim 1, wherein the pressure-sensitive adhesive composition does not contain a photoinitiator.
The pressure-sensitive adhesive composition of claim 1, wherein the weight average molecular weight of the acrylic copolymer is 500,000 to 800,000 g / mol.
According to claim 1, wherein the viscosity of the acrylic copolymer is an adhesive composition, characterized in that 4000 to 6000cps at 25 ℃.
delete The method of claim 1, wherein the (meth) acrylate having the phosphate group in the acrylic copolymer: unsaturated epoxy compound having an epoxy group: (meth) acrylate having an alkyl group: (meth) acrylate having a hydroxy group is 0.5-2 : 4-7: 64-73.5: 22-27 It is contained in the molar ratio of the adhesive composition characterized by the above-mentioned.
The (meth) acrylate having the phosphate group in the acrylic copolymer, the (meth) acrylate having an alkyl group, the (meth) acrylate having a hydroxy group, and the (meth) acrylate having a carboxylic acid group. Pressure sensitive adhesive composition, characterized in that contained in a molar ratio of 2.5: 5-8.5: 82-93.5: 1-7.
2. The (meth) acrylate having the phosphate group in the acrylic copolymer: an unsaturated epoxy compound having an epoxy group: (meth) acrylate having an alkyl group: (meth) acrylate having a hydroxy group: having a carboxylic acid group (Meth) acrylate is an adhesive composition, characterized in that contained in a molar ratio of 0.5-2: 4-6.5: 59-73.5: 21-27: 1-5.5.
A base film;
A pressure-sensitive adhesive layer formed on the base film and formed of the pressure-sensitive adhesive composition of claim 1, 3 to 6, 9 to 16, and 18 to 20; And
Dicing die bonding film comprising an adhesive layer formed on the adhesive layer.
The dicing die bonding film of claim 21, wherein the dicing die bonding film has an adhesive force of 1 to 3 N / 25 mm between the adhesive layer and the ring frame.
22. The dicing die bonding film of claim 21, wherein the dicing die bonding film has an adhesive force of 0.05-0.5 N / 25 mm between the adhesive layer and the adhesive layer.
A base film;
An acrylic copolymer formed on the base film and having at least one alkyl group, at least one hydroxy group, and at least one phosphate group; And an adhesive layer formed of an adhesive composition comprising a curing agent. And
Including an adhesive layer formed on the adhesive layer,
Adhesive force between the adhesive layer and the ring frame is 1 to 3N / 25mm,
Dicing die bonding film, characterized in that the adhesion between the adhesive layer and the adhesive layer is 0.05-0.5N / 25mm.