JP2013122005A - Photosensitive adhesive film for semiconductor, and method of manufacturing semiconductor device using the film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive adhesive film of a single layer excellent in flexibility, and reduced in cutting waste.SOLUTION: The photosensitive adhesive film for semiconductor includes an adhesive layer containing (A) a copolymer shown by the following chemical formula (1), (B) a compound having an epoxy group, (C) a curing agent of an epoxy group, (D) a compound having an ethylenic unsaturated bond, and (E) a photoinitiator, and a coated substrate, wherein the A component is contained in 1-75 pts.mass in an adhesive.

Description

  The present invention relates to a photosensitive adhesive film and a method for manufacturing a semiconductor device using the film.

  Currently, semiconductor memory packages have been reduced in size and increased in capacity, and a package structure in which a plurality of chips are stacked in one package, as represented by MCP (multi-chip package), is common. . Among them is a TSV (through silicon via) package structure. In the TSV package, various adhesive films are used as a method for connecting the chip circuit surface and the wiring on the adherend, and one of them is a patternable photosensitive adhesive film (PAF).

  In conventional photosensitive adhesive films, the photoradical initiator is cleaved by high energy rays in the irradiation process, causing a polymerization reaction with a compound having an unsaturated bond, thereby curing the adhesion site, and then non-adhesion in the development process. A method of assembling the package after removing the site is common. At this time, as the reaction of the compound having an unsaturated bond contained in the photosensitive adhesive film proceeds, curing shrinkage of the adhesive film occurs. When the curing shrinkage is high, the flexibility of the obtained film is low. There is a problem that the adhesive film is apt to be crushed, the cutting waste is scattered during film processing, and workability is lowered. Examples of the manufacturing method for removing the generated cutting waste include the following Patent Documents 1 to 3.

  For example, Patent Document 1 discloses that a sheet-like object and an adhesive roll having adhesiveness are provided between the guide rolls so that the sheet-like object is curved, and the foreign substance attached to the sheet-like substance is blown with air and then sucked. A removal device is disclosed.

  Further, in Patent Document 2, since the combined force of the tension applied to the sheet material at the contact portion with the dust removal roller acts on the shaft side of the dust removal roller, the dust removal roller and the sheet can be used without passing the sheet material between the pair of rollers. There is disclosed a dust removing device for sheet material that can obtain sufficient adhesion to the material and removes dust and dirt from the sheet material.

  Furthermore, in Patent Document 3, the adhesive roll is brought into contact with the film without using the tension of the film by using the elasticity (reaction force) of the guide roll by pressing the adhesive roll from the opposite side of the guide roll. A dust removal mechanism for removing dust is disclosed.

  Although it can be seen from the inventions of Patent Documents 1 to 3 that the detrimental effects of the cutting scraps on the product are all, these are technologies related to the removal of the generated cutting scraps, and do not reduce the cutting scraps by improving the film itself. . For example, patent document 4 is mentioned as a film which reduces cutting waste itself.

  In Patent Document 4, a layer containing 30 to 80% by weight of a copolymer of a vinyl aromatic hydrocarbon and a conjugated diene hydrocarbon or a hydrogenated product thereof and 70 to 20% by weight of a polypropylene resin, polypropylene resin 0 to 20 %, And a layer containing 100 to 80% by weight of an olefinic thermoplastic elastomer, and 0 to 40% by weight of a copolymer of a vinyl aromatic hydrocarbon and a conjugated diene hydrocarbon or a hydrogenated product thereof, and a polypropylene resin 100 to 60% A three-layer film in which layers containing% by weight are sequentially laminated is disclosed. As a result, almost no cutting waste is generated in the dicing process of the semiconductor wafer.

JP 2010-2221076 A JP-A-8-173927 JP 2002-123933 A JP 2011-023632 A

  Patent Document 4 has a so-called sandwich structure in which a layer containing a resilient elastomer is sandwiched between layers containing a polypropylene-based or aromatic vinyl-based resin having relatively high crystallinity and excellent rigidity and impact resistance. The flexibility of the film itself is poor, and since it has a laminated structure, delamination inevitably occurs during dicing, which may cause cutting waste.

  Then, an object of this invention is to provide the single layer photosensitive adhesive film which is excellent in flexibility and in which cutting waste is reduced.

  The present inventors have intensively studied to solve the above problems. As a result, (A) a copolymer containing a unit represented by the following chemical formula (1) in the main chain, (B) a compound having an epoxy group, (C) a curing agent for the epoxy group, (D) an ethylenically unsaturated bond And (E) photopolymerization initiator

(In the above chemical formula 1, R ₁ , R ₂ and M ¹ are each independently, R ₁ and R ₂ are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
M ₁ is a —COOR ′ group,
R ′ is a group having a cyclic compound,
n is an integer of 1 to 1,000, and m is an integer of 1 to 1,000. )
An adhesive layer comprising:
A coated substrate for coating the adhesive layer, and a photosensitive semiconductor adhesive film comprising:
The copolymer containing the unit represented by the chemical formula (1) in the main chain contains 1 to 75 parts by mass with 100 parts by mass as the total content of the constituents in the adhesive layer. It aims at providing the invention of the adhesive film for semiconductors.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive adhesive film which reduces generation | occurrence | production of the cutting waste of a film can be provided.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive adhesive film which is excellent in the resolution and has favorable adhesiveness and storage stability can be provided.

It is a schematic diagram explaining the manufacturing method (process 2) of the semiconductor device by one Embodiment of this invention. It is a schematic diagram explaining the manufacturing method (process 3) of the semiconductor device by one Embodiment of this invention. It is a schematic diagram explaining the manufacturing method (process 4) of the semiconductor device by one Embodiment of this invention. It is a schematic diagram explaining the manufacturing method (process 5) of the semiconductor device by one Embodiment of this invention. It is a schematic diagram explaining the manufacturing method (process 6) of the semiconductor device by one Embodiment of this invention. It is a schematic diagram explaining the manufacturing method (process 7) of the semiconductor device by one Embodiment of this invention. It is a schematic diagram explaining the manufacturing method (process 8) of the semiconductor device by one Embodiment of this invention.

  The first of the present invention is (A) a copolymer containing a unit represented by the following chemical formula (1) in the main chain, (B) a compound having an epoxy group, (C) a curing agent for an epoxy group, (D) ethylenic. Compound having unsaturated bond, and (E) photopolymerization initiator

(In the above chemical formula 1, R ₁ , R ₂ and M ₁ are each independently, R ₁ and R ₂ are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
M ₁ is a —COOR ′ group,
R ′ is a group having a cyclic compound,
n is an integer of 1 to 1,000, and m is an integer of 1 to 1,000. )
An adhesive layer comprising:
A coated substrate for coating the adhesive layer, and a photosensitive semiconductor adhesive film comprising:
The copolymer containing the unit represented by Chemical Formula 1 in the main chain includes 1 to 75 parts by mass with respect to 100 parts by mass as the total content of the constituent components in the adhesive layer. It is an adhesive film.

  Since the adhesive film for photosensitive semiconductors of the present invention has a predetermined amount of a copolymer containing a unit represented by the chemical formula (1) in the main chain, the entanglement between the polymers is reduced by reducing the entanglement between the polymers. Flexibility is improved, and it is considered that generation of cutting scraps on the film can be reduced by suppressing an increase in the degree of cure shrinkage of the adhesive film.

  The copolymer containing the unit represented by the chemical formula (1) used in the adhesive film for photosensitive semiconductors of the present invention in the main chain has a very appropriate amount and type of carboxyl groups and other side chains. Since the structure is a conventional problem, “in order to improve the solubility of the adhesive layer, the increase in the amount of carboxyl groups and the dark reaction with the epoxy groups due to the increase in carboxyl groups promotes the photosensitive adhesive film. It is possible to eliminate or reduce the relationship of “tradeoff with characteristic degradation”.

  Furthermore, the photosensitive adhesive film of the present invention is excellent in resolution and has good adhesiveness and storage stability.

  The photosensitive adhesive film according to the present invention includes an adhesive layer and a covering base material that covers the adhesive layer as essential constituent requirements. Hereinafter, the photosensitive adhesive film according to the present invention is applied to the adhesive layer of the photosensitive adhesive film. After explaining each component contained in detail, the said coating | coated base material is demonstrated.

<Adhesive layer>
The adhesive layer according to the present invention comprises a copolymer containing a unit represented by the chemical formula (1) according to the present invention as a component (A) in the main chain, a compound having an epoxy group as a component (B), and a component (C ) As an epoxy group curing agent, as a component (D) a compound having an ethylenically unsaturated bond, and as a component (E) a photopolymerization initiator as essential components, and other known solvents, binder resins, Moreover, an additive etc. may be contained and this point is mentioned later.

  The thickness of the adhesive layer according to the present invention is not particularly limited, and is appropriately determined according to the use, but generally has a thickness in the range of 5 to 200 μm.

Hereinafter, each component (A)-(E) of the adhesive bond layer which concerns on this invention is explained in full detail.
“Component (A) Copolymer containing a unit represented by the following chemical formula (1) in the main chain”
The copolymer containing the unit represented by the chemical formula (1) according to the present invention in the main chain is represented by the following chemical formula 1

(In the above chemical formula 1, R ₁ , R ₂ and M ¹ are each independently, R ₁ and R ₂ are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
M ₁ is a —COOR ′ group,
R ′ is a group having a cyclic compound,
n is an integer of 1 to 1,000, and m is an integer of 1 to 1,000. )
Indicated by

  As a result, the amount and type of carboxyl groups and other side chains in the copolymer containing the unit represented by the chemical formula (1) according to the present invention in the main chain is a very appropriate structure. There is a relationship between the increase in the amount of carboxyl groups to improve the solubility of the adhesive layer and the trade-off between the dark reaction with the epoxy groups due to the increase in carboxyl groups and the deterioration in the characteristics of the photosensitive adhesive film. Can be eliminated or reduced.

  In addition, since a group having a cyclic compound is included in the copolymer, the cyclic compounds between the copolymer molecules or in the copolymer molecule are compatible with each other and take a microdomain form. It is considered that the flexibility of the entire photosensitive adhesive film is improved.

In a preferred copolymer according to the present invention containing a unit represented by the chemical formula (1) in the main chain, in the chemical formula 1, R ₁ , R ₂ and M ¹ are independent from each other, and the R ₁ and R ₂ are And each independently a hydrogen atom or an alkyl group having 1 to 16 carbon atoms, M ₁ is a —COOR ′ group (R ′ = a group having a cyclic compound), and n is 10 to 800. And m is an integer of 10 to 800.

In a more preferable copolymer according to the present invention containing a unit represented by the chemical formula (1) in the main chain, R ₁ , R ₂ and M ¹ in the chemical formula 1 are independent, and the R ₁ and R ₂ Are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, M ₁ is a —COOR ′ group (R ′ = a group having a cyclic compound), and n is 20 to 20 It is an integer of 700, and m is an integer of 20 to 700.

Moreover, the copolymer which contains the unit shown by Chemical formula 1 in a principal chain can be used individually or in combination of 2 or more types of resin. Further, in the copolymer containing the unit represented by the chemical formula 1 in the main chain, the blending amount of the acrylic acid unit substituted with the alkyl group R ₁ is the total amount of the copolymer containing the unit represented by the chemical formula 1 in the main chain. As 100 mass parts, it is desirable that it is 10-20 weight part, and it is especially desirable that it is 12-17 weight part. If the amount is less than 10 parts by weight, the solubility in the developer tends to decrease, and if it exceeds 20 parts by weight, the film adhesive force tends to decrease. Furthermore, the blending amount of the (meth) acrylic resin according to claim 1 is preferably 30 to 75 parts by weight, and particularly preferably 45 to 70 parts by weight. If the amount is less than 30 parts by weight, the cutting scrap reduction effect tends to decrease, and if the amount exceeds 75 parts by weight, the film adhesion tends to decrease.

  Since the copolymer containing the unit represented by Chemical Formula 1 in the main chain according to the present invention may be a copolymer literally containing the unit represented by Chemical Formula 1 in the main chain, other than the unit represented by Chemical Formula 1 above. It may further have a unit, preferably a copolymer obtained by copolymerizing 2 or more and 6 or less monomers, more preferably a copolymer obtained by copolymerizing 2 or more and 5 or less monomers. Although not preferred, preferred examples of the copolymer containing a unit represented by Chemical Formula 1 in the main chain according to the present invention include the following Chemical Formula 2a:

(In the above formula _2a, R 1 to R ₄ and _M 1 ~M ₃ is independently
R _{1 to} R ₄ are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
M ₁ is a —COOR ′ group,
M ₂ is a group having a cyclic compound or a —COOR group,
M ₃ is at least one group selected from the group consisting of a —COOR group, a group having a cyclic compound, and a cyano group;
R ′ is a group having a cyclic compound, and R is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a group consisting of a cyclic compound, — (CH ₂ —C (—OH) — ( _{CH 2) p -O-C (} = O) CR a = CH 2, and the following chemical formula 2c:

At least one group selected from the group consisting of:
R _a is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
n is 1 to 5,000, m is 1 to 1,000, l is 0 to 1,000, k is 0 to 1,000, and p is 1 to 16. It is an integer. )
And the following chemical formula 2b:

(In the chemical formula _2b, R 1 to R ₅ and _M 1 ~M ₄ is independently
R _{1 to} R ₅ are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
M ₁ is a —COOR ′ group,
M ₂ is a group having a cyclic compound or a —COOR group,
M ₃ is at least one group selected from the group consisting of a —COOR group, a group having a cyclic compound, and a cyano group;
M ₄ is at least one group selected from the group consisting of a —COOR group, a group having a cyclic compound, and a cyano group;
R ′ is a group having a cyclic compound, and R is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a group consisting of a cyclic compound, — (CH ₂ —C (—OH) — ( _{CH 2) p -O-C (} = O) CR a = CH 2, and the following chemical formula 2c:

At least one group selected from the group consisting of:
R _a is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
n is 1 to 5,000, m is 1 to 1,000, l is 0 to 1,000, k is 0 to 1,000, and h is 0 to 1. , And p is an integer of 1-16. ).

In the preferred copolymers represented by the chemical formulas 2a and 2b according to the present invention, in the chemical formulas 2a and 2b, R _{1 to} R ₅ and M _{1 to} M ₄ are independent of each other, and the R _{1 to} R ₅ is a hydrogen atom or an alkyl group having 1 to 16 carbon atoms, M ₁ is a —COOR ′ group (R ′ = group having a cyclic compound), and M ₂ is a cyclic compound. Or a group having —COOR group, M ₃ is a cyano group, M ₄ is a group having a cyclic compound or —COOR group, and R is a hydrogen atom, or a group having 1 to 16 carbon atoms. An alkyl group, a group having a cyclic compound, — (CH ₂ —C (—OH) — (CH ₂ ) _p —O—C (═O) CR _a ═CH ₂ , and the following chemical formula 2c:

At least one group selected from the group consisting of: R _a is a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, n is 10 to 800, and m is 10 to 800. Yes, 1 is 1 to 800, k is 1 to 800, h is 1 to 800, and p is an integer of 1 to 12. Since Chemical Formula 2a does not include R ₅ , M ₄ , and h, it is the same as Chemical Formula 2b except for the condition that h = 0 and the substituents R ₅ and M ₄ are not present. The same applies to the following preferable copolymers.

Further preferred copolymers according to the present invention represented by chemical formula 2a and chemical formula 2b are the above-mentioned chemical formulas 2a and 2b, wherein R _{1 to} R ₅ and M _{1 to} M ₄ are independent of each other, and R _{1 to} R ₅ Is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, M ₁ is a —COOR ′ group (R ′ = group having a cyclic compound), and M ₂ is a —COOR group. , M ₃ is a cyano group, M ₄ is a group having a cyclic compound or a —COOR group, and R is an alkyl group having 1 to 12 carbon atoms, a group having a cyclic compound, — ( CH ₂ —C (—OH) — (CH ₂ ) _p —O—C (═O) CR _a ═CH ₂ , and the following chemical formula 2c:

At least one group selected from the group consisting of: R _a is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, n is 20 to 700, and m is 70 to 700. Yes, l is 10 to 700, k is 10 to 700, h is 10 to 700, and p is an integer of 1 to 10.

In the more preferable copolymer according to the present invention represented by the chemical formulas 2a and 2b, in the chemical formulas 2a and 2b, R _{1 to} R ₅ and M _{1 to} M ₄ are independent of each other, and the R _{1 to} R ₅ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, M ₁ is a —COOR ′ group (R ′ = group having a cyclic compound), and M ₂ is a —COOR group ( The R group here is an alkyl group having 1 to 12 carbon atoms, M ₃ is a cyano group, M ₄ is a —COOR group (where the R group is a group represented by the above chemical formula 2c). Or — (CH ₂ —C (—OH) — (CH ₂ ) _p —O—C (═O) CR _a ═CH ₂ ), wherein R _a is a hydrogen atom having 1 to 12 carbon atoms. An alkyl group, n is 20 to 700, m is 70 to 700, and l is A 0-700, k is 20 to 700, h is 20 to 700, p is an integer from 1 to 8.

Further, in the copolymer represented by the above Formula 2a and 2b, the ratio of n, the degree of polymerization of acrylic acid units substituted with an alkyl group _{R 1 (n / (n +} m + l + k)) is 10 to 20 parts by weight Preferably, the amount is 12 to 17 parts by weight. Similarly, in the above chemical formulas 2a and 2b, the ratio of m (m / (n + m + l + k) of units (units having M ₁ ) that require a cyclic compound as an essential component. )) Is preferably 5 to 50 parts by weight, more preferably 10 to 45 parts by weight, and the total proportion of other units (l + k + h / (n + m + l + k + h)) is 40 to 85 parts by weight. It is preferable.

In the copolymer represented by the chemical formulas 2a and 2b, any one of M _{2 to} M ₄ may be represented by R as — (CH ₂ —C (—OH) — (CH ₂ ) _p —O—C (═O). CR _a = CH ₂ , or the following chemical formula 2c:

Is selected, the unit containing the substituent R preferably contains 1 to 10 parts by mass with the total amount of the copolymer containing the unit represented by the chemical formula 2b in the main chain as 100 parts by mass.

  The alkyl group having 1 to 20 carbon atoms in Chemical Formula 1 or Chemical Formula 2a and Chemical Formula 2b may be linear or branched. For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso-amyl group, tert-pentyl group, neopentyl group, n-hexyl group, 3-methylpentan-2-yl Group, 3-methylpentan-3-yl group, 4-methylpentyl group, 4-methylpentan-2-yl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 3,3-dimethylbutane 2-yl group, n-heptyl group, 1-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group 1- (n-propyl) butyl group, 1,1-dimethylpentyl group, 1,4-dimethylpentyl group, 1,1-diethylpropyl group, 1,3,3-trimethylbutyl group, 1-ethyl-2, 2-dimethylpropyl group, n-octyl group, 2-ethylhexyl group, 2-methylhexan-2-yl group, 2,4-dimethylpentan-3-yl group, 1,1-dimethylpentan-1-yl group, 2,2-dimethylhexane-3-yl group, 2,3-dimethylhexane-2-yl group, 2,5-dimethylhexane-2-yl group, 2,5-dimethylhexane-3-yl group, 3, 4-dimethylhexane-3-yl group, 3,5-dimethylhexane-3-yl group, 1-methylheptyl group, 2-methylheptyl group, 5-methylheptyl group, 2-methylheptan-2-yl group, 3-me Ruheptan-3-yl group, 4-methylheptan-3-yl group, 4-methylheptan-4-yl group, 1-ethylhexyl group, 2-ethylhexyl group, 1-propylpentyl group, 2-propylpentyl group, 1 , 1-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 1-ethyl-1-methylpentyl group, 1-ethyl-4-methylpentyl group, 1,1,4-trimethyl Pentyl group, 2,4,4-trimethylpentyl group, 1-isopropyl-1,2-dimethylpropyl group, 1,1,3,3-tetramethylbutyl group, n-nonyl group, 1-methyloctyl group, 6 -Methyloctyl group, 1-ethylheptyl group, 1- (n-butyl) pentyl group, 4-methyl-1- (n-propyl) pentyl group, 1,5,5-trimethylhexyl Group, 1,1,5-trimethylhexyl group, 2-methyloctane-3-yl group, n-decyl group, 1-methylnonyl group, 1-ethyloctyl group, 1- (n-butyl) hexyl group, 1 , 1-dimethyloctyl group, 3,7-dimethyloctyl group, n-undecyl group, n-dodecyl group, etc., from the viewpoint of easy adjustment of the glass transition temperature, ethyl group, n-butyl group, 2 -An ethylhexyl group etc. are preferable.

  The group having a cyclic compound in Chemical Formula 1 or Chemical Formulas 2a and 2b is not particularly limited as long as it has a cyclic compound in which atoms are bonded cyclically. Specifically, an alicyclic compound Any aromatic compound or heterocyclic compound may be used. For example, as the alicyclic compound, the aromatic compound, and the heterocyclic compound, an aryl group (preferably an aryl group having 5 to 15 carbon atoms, such as a phenyl group, a benzyl group, a toluyl group, a naphthyl group, 4-t-butylphenyl group, alkoxyphenyl group, phenoxyethyl group, biphenyl group, ethoxylated phenylphenol group, phenoxy (poly) ethylene glycol group, methacryloyloxyethyl group), heterocyclic group (preferably having 3 to 3 carbon atoms) 15 heterocyclic groups, for example, 2-thienyl group, 4-pyridyl group, 2-furyl group, tetrahydrofurfuryl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1 -Pyrazolyl group, benzotriazol-1-yl group), alicyclic cyclic hydrocarbon group (preferably C3-C15 saturated cyclic hydrocarbon group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, butylhexyl group, methylcyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, methylcycloheptyl group, Cyclooctyl group, cyclononyl group, cycloalkyl group such as cyclodecyl group, hydronaphthyl group, 1-adamantyl group, 2-adamantyl group, norbornyl group, methylnorbornyl group, isobornyl group, dicyclopentenyl group, dicyclopentanyl Group, dicyclopentenyloxyethyl group) and the like.

Further, the cyclic compound in Chemical Formula 1 or Chemical Formulas 2a and 2b is preferably any of the above-described alicyclic compounds, aromatic compounds, and heterocyclic compounds. Further, the group having a cyclic compound in the above chemical formula 1 or the above chemical formulas 2a and 2b is any of the listed alicyclic compounds, aromatic compounds and heterocyclic compounds, or these alicyclic compounds, aromatic compounds and heterocyclic rings. The compound is preferably bonded to the oxygen atom side of the carbonyloxy group (—C (═O) O—), and the group having a cyclic compound of M _{1 to} M _{4 in} the chemical formula 1 or the chemical formulas 2a and 2b Specific examples of the COOR group, COOR group, or COOR ′ group (when R and R ′ are groups having a cyclic compound) include a phenyl group, a phenoxydiethylene glycol carbonyloxy group (chemical formula 11), a phenoxy (poly) ethylene glycol group, and The following chemical formulas 3 to 16:

(In formula, d1 is an integer of 1-12, Preferably, it is an integer of 1-8.)

(Wherein d2 is an integer of 1 to 12, preferably an integer of 1 to 8.)

(In formula, d3 is an integer of 1-12, Preferably it is an integer of 1-8.)

(In formula, d4 is an integer of 1-12, Preferably it is an integer of 1-8.)

(In formula, d5 is an integer of 1-12, Preferably it is an integer of 1-8.)

(In formula, d6 is an integer of 1-12, Preferably it is an integer of 1-8.)

(In formula, d7 is an integer of 1-12, Preferably it is an integer of 1-8.)
It is more preferable that it is at least one kind represented by.

  The copolymer containing the unit represented by Chemical Formula 1 in the main chain according to the present invention (including the case represented by Chemical Formulas 2a and 2b) may be a block copolymer or a random copolymer.

  The weight average molecular weight of the copolymer containing the unit represented by Chemical Formula 1 in the main chain according to the present invention (including the case represented by Chemical Formulas 2a and 2b) is preferably 5000 to 50000, more preferably 7000 to 25000, and 8000 to 20000. Is more preferable. In this case, the weight average molecular weight in the present invention can be measured by a known method, for example, it can be measured by static light scattering, gel permeation chromatography (GPC), TOFMASS, etc. It is measured by a gel permeation chromatograph method (GPC method) which is a general known method.

  If the molecular weight is less than 5,000, the resistance to the developer tends to decrease, and a desired film may not be obtained. If the molecular weight exceeds 50,000, the solubility in the developer tends to decrease.

  Further, the copolymer containing the unit represented by Chemical Formula 1 in the main chain (including the case represented by Chemical Formulas 2a and 2b) may be used alone or in combination of two or more. The copolymer may be a synthetic product or a commercially available product.

  The synthesis method in the case of synthesis is not particularly limited, and conventionally known methods such as a solution polymerization method using a polymerization initiator, an emulsion polymerization method, a suspension polymerization method, a reverse phase suspension polymerization method, a thin film polymerization method, and a spray polymerization method. The method can be used. Examples of the polymerization control method include adiabatic polymerization, temperature controlled polymerization, and isothermal polymerization. In addition to the method of initiating polymerization with a polymerization initiator, a method of initiating polymerization by irradiating with radiation, electron beam, ultraviolet rays or the like can also be employed. Among these, the solution polymerization method using a polymerization initiator is preferable because the molecular weight can be easily adjusted and impurities can be reduced. For example, using ethyl acetate, toluene, methyl ethyl ketone or the like as a solvent, and preferably adding 0.01 to 0.50 parts by weight of a polymerization initiator with respect to 100 parts by weight of the total amount of monomers, It is obtained by reacting at a reaction temperature of 60 to 90 ° C. for 3 to 10 hours. Examples of the polymerization initiator include azo compounds such as azobisisobutyronitrile (AIBN), 2,2′-azobis (2-methylbutyronitrile), azobiscyanovaleric acid; tert-butyl peroxypivalate, organic peroxides such as tert-butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate, di-tert-butyl peroxide, cumene hydroperoxide, benzoyl peroxide, tert-butyl hydroperoxide; Examples thereof include inorganic peroxides such as hydrogen peroxide, ammonium persulfate, potassium persulfate, and sodium persulfate. These may be used alone or in combination of two or more.

  The glass transition temperature (Tg) of the copolymer (including the case represented by Chemical Formula 2) containing the unit represented by Chemical Formula 1 according to the present invention in the main chain is preferably −30 ° C. or more and 50 ° C. or less, It is more preferably −20 ° C. or higher and 30 ° C. or lower. If the glass transition temperature of the copolymer is less than −30 ° C., the viscosity of the film is too high, and operations such as cutting and processing of the film may be difficult. Since the effect tends to decrease, it is not preferable. As the glass transition temperature (Tg), a value measured by a DSC (differential scanning calorimetry) method is adopted.

  In addition, the acid value of the copolymer containing the unit represented by Chemical Formula 1 in the main chain (including the case represented by Chemical Formula 2) is preferably in the range of 80 to 120 KOHmg / g, and 85 to 110 KOHmg / g. More preferably, it is the range. If it is less than 80 KOHmg / g, the solubility in the developer tends to be reduced, and if it exceeds 120 KOHmg / g, a dark reaction with the epoxy resin in the adhesive layer occurs during storage, so film stability Tends to decrease. The acid value is a value measured by neutralization titration using a phenol-phthalein solution as an indicator.

  The compounding amount (mass) of the component (A) in the adhesive layer according to the present invention is 1 to 75 parts by mass with the total amount of the components (A) to (E) being 100 parts by mass. There exists a tendency for the reduction effect of cutting waste to fall that the compounding quantity of a component (A) is less than 1 mass part. On the other hand, when it exceeds 75 parts by mass, the film adhesive force tends to decrease. The blending amount is preferably 30 to 75 parts by mass, and more preferably 45 to 70 parts by mass.

(B) Epoxy resin The compound having an epoxy group used in the present invention is not particularly limited as long as it is cured and has an adhesive action, and an epoxy resin is preferable. Specific examples include, for example, bisphenol A type, bisphenol F type, bisphenol S type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol AF type, biphenyl type, naphthalene type, fluorene type, trishydroxyphenylmethane. Type, tetraphenylolethane type bifunctional epoxy resins; phenol novolac type epoxy resins and cresol novolac type epoxy resins, etc. novolak type epoxy resins; polyfunctional epoxy resins; glycidylamine type epoxy resins; heterocycle-containing epoxy resins; Examples thereof include cyclic epoxy resins. These epoxy resins may be used alone or in combination of two or more. The epoxy resin may be a synthetic product or a commercial product.

  More specific examples of preferable epoxy resins used in the present invention are listed below.

  Examples of the bisphenol A type epoxy resin include the Epicoat (registered trademark) series (Epicoat (registered trademark) 807, Epicoat (registered trademark) 815, Epicoat (registered trademark) 825, Epicoat (registered trademark) 827, Epicoat (registered trademark). 828, Epicoat (registered trademark) 834, Epicoat (registered trademark) 1001, Epicoat (registered trademark) 1004, Epicoat (registered trademark) 1007, Epicoat (registered trademark) 1009, or more manufactured by Japan Epoxy Resin Co., Ltd.), DER-330, DER-301, DER-361 (above, manufactured by Dow Chemical Co., Ltd.), YD8125, YDF8170 (above, manufactured by Tohto Kasei Co., Ltd.) and the like.

  Examples of the phenol novolac type epoxy resin include Epicoat (registered trademark) 152, Epicoat (registered trademark) 154 (manufactured by Japan Epoxy Resin Co., Ltd.), EPPN-501 (manufactured by Nippon Kayaku Co., Ltd.), DEN-438 ( Manufactured by Dow Chemical Co., Ltd.). Examples of the cresol novolac type epoxy resin include EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1025, EOCN-1027 (manufactured by Nippon Kayaku Co., Ltd.), YDCN700-10 (Tohto Kasei Co., Ltd.) Co., Ltd.), Araldite (registered trademark) ECN1280 (manufactured by Huntsman Japan Co., Ltd.) and the like.

  Examples of the polyfunctional epoxy resin include Epon 1031S (manufactured by Japan Epoxy Resin Co., Ltd.), Araldite (registered trademark) 0163 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Denacol (registered trademark) EX-611, EX-614, EX- 614B, EX-622, EX-512, EX-521, EX-421, EX-411, EX-321 (above, manufactured by Nagase ChemteX Corporation).

  Examples of the glycidylamine type epoxy resin include Epicoat (registered trademark) 604 (manufactured by Japan Epoxy Resin Co., Ltd.), YH-434 (manufactured by Toto Kasei Co., Ltd.), TETRAD (registered trademark) -X, and TETRAD (registered trademark)-. C (above, manufactured by Mitsubishi Gas Chemical Co., Ltd.), ELM-120 (manufactured by Sumitomo Chemical Co., Ltd.) and the like.

  Examples of the heterocyclic ring-containing epoxy resin include Araldite (registered trademark) PT810 (manufactured by Ciba Specialty Chemicals Co., Ltd.), ERL4234, ERL4299, ERL4221, and ERL4206 (manufactured by UCC).

  Examples of the alicyclic epoxy resin include Epolide (registered trademark) series, Celoxide (registered trademark) series (manufactured by Daicel Chemical Industries, Ltd.), and the like.

  100-1500 are preferable and, as for the weight average molecular weight of the compound containing the epoxy group which concerns on this invention, 200-800 are more preferable. Since the method for measuring the weight average molecular weight is the same as that of the copolymer, the description thereof is omitted here.

  The compounding quantity of the component (B) in the contact bonding layer which concerns on this invention is 10-30 mass parts by making the total amount of a component (A)-(E) into 100 mass parts. When the blending amount of the component (B) is less than 10 parts by mass, the reaction point between the epoxy resin and the epoxy resin curing agent in the adhesive film decreases, and the adhesive strength tends to decrease. On the other hand, when it exceeds 30 parts by mass, the solubility in the developer tends to be lowered. The amount is preferably 12 to 27 parts by mass, more preferably 15 to 25 parts by mass.

(C) Epoxy Group Curing Agent The epoxy group curing agent used in the present invention is not particularly limited, and a commonly used known curing agent can be used, and is a curing agent for an epoxy resin. Specifically, for example, bisphenols having two or more phenolic hydroxyl groups in one molecule such as amines, polyamides, acid anhydrides, polysulfides, boron trifluoride, dicyandiamide, bisphenol A, bisphenol F, and bisphenol S. Phenol phenolic resins such as phenol novolac resin, bisphenol A novolac resin, cresol novolac resin, and the like. In particular, a phenol novolac resin, or a phenol resin such as a bisphenol A novolac resin or a cresol novolac resin is preferable in terms of excellent electric corrosion resistance when absorbing moisture. In the present invention, the epoxy curing agent includes what is called a curing accelerator that acts catalytically on an epoxy group to promote crosslinking. These epoxy group curing agents may be used alone or in combination of two or more. The epoxy group curing agent may be a synthetic product or a commercially available product.

  More specific examples of a preferable epoxy group curing agent used in the present invention include Phenolite (registered trademark) LF4871, Phenolite (registered trademark) LF2822, Phenolite (registered trademark) TD-2090, Phenolite (registered trademark). TD-2149, Phenolite (registered trademark) VH-4150, Phenolite (registered trademark) VH4170 (above, Dainippon Ink & Chemicals, Inc.), HF-1M, HF-4, MEHC-7800 (above, Manufactured by Meiwa Kasei Co., Ltd., EpiCure (registered trademark) MP402FPY, EpiCure (registered trademark) YL6065, EpiCure (registered trademark) YLH129B65 (above, manufactured by Japan Epoxy Resin Co., Ltd.), Millex (registered trademark) XL, Millex (registered trademark) XLC, Millex (registered trademark) RN, Millet Scan (R) RS, Mirex (TM) VR (above, manufactured by Mitsui Chemicals Co., Ltd.) phenolic resin or the like.

  The weight average molecular weight of the epoxy group curing agent according to the present invention is preferably 100 to 2,000, and more preferably 150 to 800. Since the method for measuring the weight average molecular weight is the same as that of the copolymer, the description thereof is omitted here.

  The compounding quantity of the component (C) in the contact bonding layer which concerns on this invention is 5-25 mass parts by making the total amount of a component (A)-(E) into 100 mass parts. When the blending amount of the component (C) is less than 10 parts by mass, the reaction point between the epoxy resin in the adhesive film and the curing agent for the epoxy resin decreases, and the adhesive strength tends to decrease. On the other hand, when it exceeds 25 parts by mass, the solubility in the developer tends to be lowered. The amount is preferably 10 to 22 parts by mass, more preferably 12 to 20 parts by mass.

(D) Compound having an ethylenically unsaturated bond The adhesive layer provided in the photosensitive adhesive film of the present invention may further contain a compound having an ethylenically unsaturated bond.

  The compound having an ethylenically unsaturated bond is not particularly limited as long as it is a compound that is polymerized and cured by radiation such as ultraviolet rays and electron beams. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, pentenyl (meth) acrylate, tetrahydrofluor Furyl (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1 , 4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) Acrylate, dipentaerythritol hexa (meth) acrylate; styrene, divinylbenzene, 4-vinyltoluene; 4-vinylpyridine, N-vinylpyrrolidone, 1,3-acryloyloxy-2-hydroxypropane, 1,3-methacryloyloxy- Examples include 2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, tris (β-hydroxyethyl) isocyanurate triacrylate, and the like. These may be used alone or in combination of two or more.

The compounding quantity of the component (D) in the contact bonding layer which concerns on this invention is 3-50 mass parts by making the total amount of a component (A)-(E) into 100 mass parts. When the blending amount of the component (D) is less than 3 parts by mass, the radical photopolymerization reaction does not occur sufficiently even when irradiated with high energy rays, and the adhesive film dissolves in the developer during development, and the desired film is obtained. I can't get it. On the other hand, if it exceeds 50 parts by mass, the adhesiveness of the adhesive layer is too high and the workability tends to be lowered. The blending amount is preferably 5 to 40 parts by mass, more preferably 7 to 30 parts by mass. (E) Photopolymerization initiator The photopolymerization initiator used in the present invention is not particularly limited and is usually used. Known photopolymerization initiators can be used, and are mainly classified into photoradical polymerization initiators and photocationic polymerization initiators. In the present invention, the photopolymerization initiator may be a radical photopolymerization initiator or a cationic photopolymerization initiator alone, or a radical photopolymerization initiator and a cationic photopolymerization initiator may be used in combination. In this case, when the total amount (mass) of the photopolymerization initiator is 100, the mixing ratio of the photoradical polymerization initiator and the photocationic polymerization initiator is photoradical polymerization initiator: photocationic polymerization initiator = 90: 10. -30: 70 is preferable, and 80: 20-40: 60 is more preferable.

  Specific examples of the radical photopolymerization initiator according to the present invention include, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2 Acetophenone compounds such as -methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, Benzoin compounds such as benzoin ethyl ether, benzoin isopropyl ether, benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated Benzophenone compounds such as zophenone and 4-benzoyl-4'-methyldiphenyl sulfide, thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone and 2,4-diisopropylthioxatone, 2,4,6 -Trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (P-Tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-pienyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6 Styryl s-triazine, 2- (naphth-1-yl) -4,6-bis ( Lichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, Triazine compounds such as 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], O Oxime ester compounds such as-(acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxylamine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis ( Phosphine compounds such as 2,4,6-trimethylbenzoyl) phenylphosphine oxide, 9,10-phena Surenkinon, camphorquinone, quinone compounds such as ethyl anthraquinone, borate compounds, carbazole compounds, imidazole compounds, titanocene compounds, and the like. These radical photopolymerization initiators may be used alone or in combination of two or more. The radical photopolymerization initiator may be a synthetic product or a commercially available product.

  Examples of commercially available products include, for example, Irgacure (registered trademark) 651, Irgacure (registered trademark) 184, Irgacure (registered trademark) 2959, Irgacure (registered trademark) 127, Irgacure (registered trademark) 907, Irgacure (registered trademark) 369. , Irgacure (registered trademark) 379EG, Irgacure (registered trademark) 819, Irgacure (registered trademark) 784, Irgacure (registered trademark) 754, Irgacure (registered trademark) 500, Lucyrin (registered trademark) TPO, Darocur (registered trademark) 1173 ( Ciba Specialty Chemicals Co., Ltd.).

  Photocationic polymerization initiators according to the present invention include bis (alkylphenyl) iodonium hexafluorophosphate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis [4- (Diphenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate, bis [4- (diphenylsulfonio) phenyl] sulfide bistetrafluoroborate Bis [4- (diphenylsulfonio) phenyl] sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4- ( Enylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- (phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetrafluoroborate, diphenyl-4- (phenylthio) phenylsulfonium tetrakis (pentafluorophenyl) Borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, bis [4- (di (4- (2-hydroxyethoxy)) ) Phenylsulfonio) phenyl] sulfide Bishexafluorophosphate, Bi [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bishexafluoroantimonate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] Examples thereof include sulfide bistetrafluoroborate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide tetrakis (pentafluorophenyl) borate, triallylsulfonyl-hexafluoroantimony salt and the like. Of these, triallylsulfonyl-hexafluoroantimony salt is preferable. The above cationic photopolymerization initiators can be used alone or in combination of two or more. Further, a solvent may be included in consideration of dispersibility with other components.

The compounding quantity of the component (E) in the contact bonding layer which concerns on this invention is 0.1-15 mass parts by making the total amount of a component (A)-(E) into 100 mass parts. If the blending amount of component (B) is less than 0.1 parts by mass, the photoradical polymerization initiator will not undergo sufficient cleavage reaction even when irradiated with high energy rays, and the adhesive film will dissolve in the developer during development. The desired film cannot be obtained. On the other hand, when it exceeds 15 parts by mass, the reaction point between the epoxy resin in the adhesive film and the curing agent for the epoxy resin decreases, and the adhesive force tends to decrease. The blending amount is preferably 0.5 to 10 parts by mass, and more preferably 1 to 8 parts by mass. As described above, the adhesive layer provided in the photosensitive adhesive film of the present invention is the main component (A). A copolymer containing a unit represented by the chemical formula (1) according to the invention in the main chain, a compound having an epoxy group as the component (B), a curing agent of an epoxy group as the component (C), and ethylene as the component (D) A compound having a polymerizable unsaturated bond and a photopolymerization initiator as the component (E) are essential components, but within a range not impairing the effects of the present invention, a curing accelerator, an inorganic filler, a softener, and an antioxidant. Agent, anti-aging agent, stabilizer, tackifying resin, modifying resin (polyol resin, polyester resin, polyolefin resin, etc.), silane coupling agent, leveling agent, antifoaming agent, plasticizer, dye, pigment (color pigment, Extender pigments, etc. ), A processing agent, a viscosity modifier, a fluorescent brightening agent, a dispersant, a heat stabilizer, a light stabilizer, an antistatic agent, a lubricant, and a solvent. Although the usage-amount of an additive in the case of using these additives is not restrict | limited, For example, Preferably it is 0.1-20 mass% with respect to the total mass of an adhesive bond layer.

<Coating substrate>
As a covering base material used for the photosensitive adhesive film of the present invention, various resin films can be used, and there is no particular limitation as long as it is an easily peelable base material that easily peels the adhesive layer. Specific examples thereof include, for example, polyolefin films (polyethylene, polypropylene, etc.), polyester films (polyethylene terephthalate, polyethylene naphthalate, etc.), polyvinyl chloride, cellulose triacetate, polycarbonate, polyarylate, polystyrene (PS), aromatic polyamide. , Polyether ether ketone, polysulfone, polyether sulfone, polyimide, polyetherimide, and other resin films, as well as resin films formed by laminating two or more layers of the above resin films, among others, cutting scraps Polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide, and the like are preferably used from the viewpoint of preventing the scattering of water.

The thickness in particular of a covering base material is not restrict | limited, Usually, the thing of the range of 25-75 micrometers is used.
Various resin films can be used as the release substrate used in the photosensitive adhesive film of the present invention. Specific examples thereof include, for example, polyolefin films (polyethylene, polypropylene, etc.), polyester films (polyethylene terephthalate, polyethylene naphthalate, etc.), polyvinyl chloride, cellulose triacetate, polycarbonate, polyarylate, polystyrene (PS), aromatic polyamide. And resin films such as polyetheretherketone, polysulfone, polyethersulfone, polyimide, and polyetherimide, and a resin film obtained by laminating two or more layers of the above resin films. From the viewpoint of preventing scattering of cutting waste, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide, and the like are preferably used.

  The thickness in particular of a covering base material is not restrict | limited, Usually, the thing of the range of 25-75 micrometers is used.

<Method for producing photosensitive adhesive film>
Although the manufacturing method of the photosensitive adhesive film of the present invention is not particularly limited, the above components (A) to (E) and, if necessary, the component (F) and additives may be mixed together in a solvent, After each component is mixed sequentially, or after mixing a plurality of arbitrary components, the remaining components are mixed, and after preparing the coating solution for the adhesive layer by stirring to form a uniform mixture, The method of apply | coating this coating liquid for adhesive bond layers on a peeling base material, and drying is mentioned.

  Examples of the solvent used for the preparation of the adhesive layer coating solution include benzene, toluene, xylene, tetrahydrofuran, dioxane, methyl ethyl ketone, cyclohexanone, ethyl acetate, ethyl cellosolve, ethyl cellosolve acetate, dimethylformamide, and the like.

  For the preparation of the adhesive layer coating solution, for example, until it becomes uniform with a stirrer, for example, stir for 15 minutes or more in a normal environment without heating and pressurizing until uniform with a stirrer Can be performed. The method for applying the adhesive layer coating liquid onto the release substrate is not particularly limited. For example, natural coater, knife belt coater, floating knife, roll coat, air knife coat, knife over roll, knife on blanket, Various coating methods using apparatuses such as spray, dip, kiss roll, squeeze roll, reverse roll, air blade, curtain flow coater, doctor blade, wire bar, die coater, comma coater, baker applicator and gravure coater can be mentioned.

  The drying conditions after the application are not particularly limited, and examples thereof include a method of drying by drying in a temperature range of 50 to 150 ° C. for 3 to 60 minutes.

  The thickness of the adhesive layer after drying is preferably 5 to 200 μm.

<Method for Manufacturing Semiconductor Device>
The photosensitive adhesive film of this invention is used suitably for the manufacturing method of a semiconductor device. That is, the second of the present invention is a method for manufacturing a semiconductor device using the photosensitive adhesive film of the present invention.

Although the manufacturing method of the semiconductor device of the present invention is not particularly limited, the following steps 1 to 8;
(Step 1) (A) A copolymer containing a unit represented by the following chemical formula 1 in the main chain:

(In the above chemical formula 1, R ₁ , R ₂ and M ₁ are each independently, R ₁ and R ₂ are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
M ₁ is a —COOR ′ group,
R ′ is a group having a cyclic compound,
n is an integer of 1 to 1,000, and m is an integer of 1 to 1,000. ), (B) an epoxy group-containing compound, (C) an epoxy group curing agent, (D) a compound having an ethylenically unsaturated bond, (E) a photopolymerization initiator, and (F) an adhesive layer containing a solvent. Preparing a coating liquid for use,
(Step 2) After applying the adhesive coating liquid on the coating substrate to which the adhesive coating liquid is applied and drying it at a temperature range of 50 to 150 ° C. for 3 to 60 minutes to form an adhesive layer, A first attaching step of attaching the adhesive layer to the surface of the semiconductor wafer, and peeling the adhesive layer from the covering substrate to obtain a semiconductor wafer with an adhesive layer;
(Step 3) An irradiation step of curing the adhesive layer by irradiating the adhesive layer of the semiconductor wafer with high energy rays of 50 to 5000 mJ / Cm ² through a shielding mask;
(Step 4) A developing step of immersing the cured semiconductor wafer with an adhesive layer in an alkaline aqueous solution for 10 to 500 seconds to dissolve and remove the adhesive of the non-irradiated part;
(Step 5) a second attaching step for obtaining a semiconductor wafer with a laminate in which a base material with an adhesive layer is attached to the semiconductor wafer with an adhesive layer from the adhesive layer side;
(Step 6) A dicing step of obtaining a semiconductor element obtained by dicing the semiconductor wafer with a laminated body until at least an interface between the adhesive layer and the semiconductor wafer is reached, and cutting the semiconductor wafer;
(Step 7) Picking up the semiconductor element together with the adhesive layer from the pressure-sensitive adhesive layer to obtain a semiconductor element with the adhesive layer;
(Step 8) It is preferable to include an adhesion step of adhering the semiconductor element to the adherend through the adhesive layer in the semiconductor element with the adhesive layer.

  Hereafter, each said process 1-8 is explained in full detail, referring drawings.

(Process 1)
In this step, components (A) to (E) and, if necessary, components (F) and additives are mixed in a predetermined amount to prepare an adhesive layer coating solution. Since the solvent and preparation method used for the preparation are the same as described above, the description thereof is omitted here. The component (A) is a copolymer composed of at least two types of monomers. Preferably, an acrylic monomer in which R ₁ = alkyl group having 1 to 20 carbon atoms in Chemical Formula 1 is used. The other monomers are R ₁ = alkyl group having 1 to 20 carbon atoms and M ₁ = —COOR ′ group, and R ′ is a group having a cyclic compound (phenyl group, phenoxy) A diethylene glycol group and a group selected from the group consisting of phenoxy (poly) ethylene glycol groups) are mixed.

  More preferable component (A) is a copolymer represented by the above chemical formula 2b or a copolymer represented by the above chemical formula 2a, and since it has the same structure as the above preferred copolymer, it is omitted here.

(Process 2)
On the coating base material with which the coating liquid for adhesive layers obtained at the process 1 is coat | covered, the said coating liquid for adhesive layers is apply | coated, and the said coating liquid is 3 to 60 minutes in the temperature range of 50-150 degreeC. It is made to dry and an adhesive bond layer is formed, and a photosensitive adhesive film is obtained. Since the formation method of the covering base material and the adhesive layer used at this time is the same as described above, the description thereof is omitted here.

  Thereafter, using the photosensitive adhesive film, the adhesive layer is attached to the surface of the semiconductor wafer, and the covering base material is peeled off to obtain a semiconductor wafer with an adhesive layer (first attaching step, FIG. 1). reference).

  As described above, the coated substrate of the present invention is an easily peelable substrate, that is, the adhesive layer cured with the adhesive layer coating solution is easily peeled off. At this time, even if the adhesive layer is first peeled off from the coated substrate and then only the adhesive layer is attached to the surface of the semiconductor wafer, or the coated substrate itself with the adhesive layer formed as shown in the figure May be peeled off from the adhesive layer after bonding together so that the adhesive layer and the semiconductor wafer come into contact with each other.

  Examples of the method for attaching the adhesive layer to the surface of the semiconductor wafer include a method of thermocompression bonding using a laminator or the like.

(Process 3)
In this step, the adhesive layer is cured by irradiating the semiconductor wafer with the adhesive layer obtained in step 2 with a high energy ray from the adhesive layer side through a photomask (see FIG. 2).

  The type of high energy beam is not particularly limited, and examples include ultraviolet rays, electron beams, and radiation. Also, the light source for irradiating the high energy rays is not particularly limited. For example, the low pressure mercury lamp, the medium pressure mercury lamp, the high pressure mercury lamp, the ultra high pressure mercury lamp, the chemical lamp, the black light lamp, the microwave excitation mercury lamp, the metal halide lamp, the sodium lamp, the halogen lamp. A lamp, a xenon lamp, a fluorescent lamp, sunlight, an electron beam irradiation device, etc. are mentioned.

It is preferable that the irradiation amount of a high energy ray is 50-5000 mJ / cm < ² >.

(Process 4)
In this step, the adhesive layer cured in step 3 is developed with an alkaline aqueous solution to remove an unexposed portion (uncured portion) of the adhesive layer (see FIG. 3).

  The alkaline aqueous solution is not particularly limited, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, Inorganic alkaline compounds such as sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-, di- or triethanolamine, Mono, di or trimethylamine, mono, di or triethylamine, mono or diisopropylamine, n-butylamine, mono, di or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide ( MAH), include aqueous solutions containing an organic alkali compound choline. These alkaline compounds may be a mixture of two or more.

  The alkaline aqueous solution may contain a surfactant. Examples thereof include polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters. Nonionic surfactants such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinic acid ester salts, and other anionic surfactants, alkylbetaines, amino acids, etc. Surfactant is mentioned.

  Further, the alkaline aqueous solution may contain an organic solvent such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like.

  There are no particular limitations on the conditions of the development treatment, but the development temperature is usually 10 to 50 ° C. The development method is not particularly limited, and examples thereof include an immersion development method, a spray development method, a brush development method, and an ultrasonic development method.

(Process 5)
A base material with a pressure-sensitive adhesive layer (dicing tape) is attached to the adhesive layer side of the semiconductor wafer with an adhesive layer to obtain a semiconductor wafer with a laminated body (second attaching step, see FIG. 4).

  That is, when a base material with an adhesive layer and a semiconductor wafer with an adhesive layer are bonded together, as shown in the figure, the adhesive layer and the adhesive layer are bonded so that they are in direct contact with each other.

  A base material with a pressure-sensitive adhesive layer (dicing tape) is composed of a base material layer and a pressure-sensitive adhesive layer containing a high energy ray polymerizable component. As the base material layer, the same materials as those used as the release base material of the photosensitive adhesive film of the present invention can be used. Examples thereof include polyester films such as polyethylene terephthalate films, polytetrafluoroethylene films, polyethylene films, polypropylene films, polyolefin films such as polymethylpentene films and polyvinyl acetate films, plastic films such as polyvinyl chloride films and polyimide films. .

  By including a high energy ray polymerizable component in the adhesive layer, after adhering the adhesive layer to an adherend such as a semiconductor wafer, the high energy ray is irradiated before dicing, and adhesion during dicing Picking up can be facilitated by improving the force or conversely irradiating a high energy ray after dicing and reducing the adhesive force. As such a high energy ray polymerizable component, a compound conventionally used in a high energy ray polymerizable pressure-sensitive adhesive layer can be used without particular limitation.

  Examples of the high energy ray polymerizable component used in the pressure-sensitive adhesive layer include a radiation polymerizable component. Although it does not restrict | limit especially as a radiation polymerizable component, For example, methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, butoxy triethylene glycol acrylate, ECH (epichlorohydrin) modified butyl acrylate, dicyclopentanyl acrylate, EO (ethylene oxide) modified dicyclopentenyl acrylate, N, N-dimethylaminoethyl methacrylate, ethyl diethylene glycol acrylate, 2-ethylhexyl acrylate, glycerol methacrylate, heptadecafluorodecyl acrylate, 2-hydroxyethyl methacrylate, caprolactone modified-2-hydroxyethyl Acrylate, isobornyl acrylate, methoxydipropylene glycol acrylate, methoxylation Chlodecatriene acrylate, phenoxyhexaethylene glycol acrylate, EO-modified phosphoric acid acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, EO-modified bisphenol A diacrylate, ECH-modified bisphenol A diacrylate, bisphenol A dimethacrylate, 1,4-butanediol di Acrylate, 1,3-butylene glycol diacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol diacrylate, EO-modified phosphoric acid diacrylate, ECH-modified phthalic acid diacrylate, polyethylene glycol 400 diacrylate, polypropylene glycol 400 dimethacrylate , Tetraethylene glycol diacrylate, ECH 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, EO-modified phosphate triacrylate, EO-modified trimethylolpropane triacrylate, PO (propylene oxide) -modified trimethylolpropane triacrylate, tris ( Methacryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, acrylates such as dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and methacrylates corresponding to these. These high energy ray polymerizable components can be used singly or in combination of two or more.

  In addition, a radical photopolymerization initiator (for example, a compound that generates free radicals upon irradiation with high energy rays such as radiation) can be added to the pressure-sensitive adhesive layer. Examples of such photo radical polymerization initiators include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy. -4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy Aromatic ketones such as -cyclohexyl-phenyl-ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone-1,2,4-diethylthioxanthone, 2-ethylanthraquinone, phenanthrenequinone, Benzoin methyl ether, benzoin ethyl ether, benzoin Benzoin ether such as ether, benzoin such as methylbenzoin and ethylbenzoin, benzyl derivatives such as benzyldimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4 , 5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-phenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer 2-mer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxy) 2,4,5-triarylimidazole dimer such as phenyl) -4,5-diphenylimidazole dimer, Examples include acridine derivatives such as 9-phenylacridine and 1,7-bis (9,9′-acridinyl) heptane. These may be used alone or in combination of two or more.

  The thickness of the pressure-sensitive adhesive layer is preferably 10 to 500 μm, more preferably 25 to 200 μm, and still more preferably 50 to 150 μm. Furthermore, the pressure-sensitive adhesive layer may be a laminate of two or more layers.

  Adhesion of the semiconductor wafer with the adhesive layer and the base material with the adhesive layer (dicing tape) is performed while heating as necessary.

(Step 6)
In this step, the semiconductor wafer with a laminated body is diced until it reaches at least the interface between the adhesive layer and the semiconductor wafer, and the semiconductor wafer is cut into semiconductor elements of a predetermined size. Thereby, a plurality of semiconductor elements each having an adhesive layer and a semiconductor wafer are obtained (see FIG. 5). This dicing is performed using, for example, a dicing saw.

(Step 7)
In this step, the semiconductor element is picked up together with the adhesive layer from the pressure-sensitive adhesive layer to obtain a semiconductor element with an adhesive layer (see FIG. 6). The pickup method is not particularly limited, and various conventionally known methods can be employed. For example, a method of picking up a semiconductor element from the upper part of each semiconductor element by a pickup device can be mentioned.

(Process 8)
In this step, the semiconductor element on the semiconductor element with the adhesive layer is bonded to an adherend via the adhesive layer (see FIG. 7). Examples of the adherend include a transparent substrate such as an organic substrate, a semiconductor wafer, a flexible substrate or a rigid substrate called an interposer or a mother board, a lead frame, an insulating substrate made of an organic material or an inorganic material, an acrylic resin, or a glass substrate. Etc. Adhesion is performed while heating as necessary.

  The manufacturing method of the semiconductor device of the present invention is not limited to the above embodiment, and can be appropriately changed without departing from the gist of the present invention.

  The present invention will be described in further detail using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples.

Example 1
Araldite ECN1280 (trade name, manufactured by Huntsman Japan, cresol novolac type epoxy resin) 19 parts by weight as a compound having an epoxy group, MEHC-7800 4S (trade name, manufactured by Meiwa Kasei Co., Ltd.) 16 which is a phenol resin as a curing agent for the epoxy group Parts by weight, 0.5 parts by weight of triallylsulfonyl-hexafluoroantimony salt (manufactured by Aldrich) as a photocationic polymerization initiator, trimethylolpropane tetramethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) as a compound having an ethylenically unsaturated bond Methyl ethyl ketone was added to a composition comprising 10 parts by weight and 4.5 parts by weight of Irgacure 819 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) as a radical photopolymerization initiator, and the mixture was stirred and mixed for 90 minutes. As a copolymer, 45 parts by weight of vanaresin GH2851C1 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., weight average molecular weight 11,000, acid value 100), vanaresin GH2851C1-T15 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) 5 parts by weight of a weight average molecular weight of 11,000 and an acid value of 100) were mixed. The varnish was coated on a polyethylene terephthalate film with a thickness of 38 μm and heat-dried at 90 ° C. for 10 minutes to form a coating film with a thickness of 20 μm, and an adhesive layer provided with a coated substrate was produced. did.

  Vanaresin GH2851C1 is a quaternary copolymer of ethyl acrylate, styrene, acrylonitrile, and methacrylic acid, and Vanaresin GH2851C1-T15 is a quaternary copolymer of ethyl acrylate, acrylonitrile, methacrylic acid, and phenoxydiethylene glycol acrylate. is there.

(Example 2)
As an alternative to vanaresin GH2851C1-T15, a resin in which the carboxyl group of the methacrylic acid portion of the acrylic resin of vanaresin GH2851C1-T15 is modified with glycidyl methacrylate and the acid value is adjusted to 80 (Shin Nakamura Chemical Co., Ltd.) Except for mixing 5 parts by weight manufactured by company, weight average molecular weight 11,000, acid value 80), the same operation as in Example 1 was performed to prepare an adhesive layer.

(Example 3)
The adhesive layer was the same as in Example 1 except that 20 parts by weight of vanaresin GH2851C1-T15 (manufactured by Shin-Nakamura Chemical Co., Ltd., weight average molecular weight 11,000, acid value 100) was used as the acrylic resin. Was made.

Example 4
As a substitute for vanaresin GH2851C1-T15, a resin in which the carboxyl group of the methacrylic acid moiety of the acrylic resin is modified with 3 parts by weight of glycidyl methacrylate and the acid value is adjusted to 80 (manufactured by Shin-Nakamura Chemical Co., Ltd., weight average molecular weight 11,000, acid value 80) Except for mixing 20 parts by weight, the same operation as in Example 1 was performed to prepare an adhesive layer.

(Example 5)
The same procedure as in Example 1 was carried out except that 30 parts by weight of vanaresin GH2851C1-T15 (manufactured by Shin-Nakamura Chemical Co., Ltd., weight average molecular weight 11,000, acid value 100) was used as the acrylic resin, and the adhesive layer Was made.

(Example 6)
As a substitute for vanaresin GH2851C1-T15, a resin in which the carboxyl group of the methacrylic acid moiety of the acrylic resin is modified with 3 parts by weight of glycidyl methacrylate and the acid value is adjusted to 80 (manufactured by Shin-Nakamura Chemical Co., Ltd., weight average molecular weight 11,000, acid value 80) Except for mixing 30 parts by weight, the same operation as in Example 1 was performed to prepare an adhesive layer.

(Example 7)
The adhesive layer was the same as in Example 1 except that 45 parts by weight of vanaresin GH2851C1-T15 (manufactured by Shin-Nakamura Chemical Co., Ltd., weight average molecular weight 11,000, acid value 100) was used as the acrylic resin. Was made.

(Example 8)
As a substitute for vanaresin GH2851C1-T15, a resin in which the carboxyl group of the methacrylic acid moiety of the acrylic resin is modified with 3 parts by weight of glycidyl methacrylate and the acid value is adjusted to 80 (manufactured by Shin-Nakamura Chemical Co., Ltd., weight average molecular weight 11,000, acid value 80) Except for mixing 45 parts by weight, the same operation as in Example 1 was performed to prepare an adhesive layer.

Example 9
As an acrylic resin, vanaresin GH2851C1 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., weight average molecular weight 11,000, acid value 100) 30 parts by weight, vanaresin GH2851C1-T15 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., weight average) Except for using 20 parts by weight of a molecular weight of 11,000 and an acid value of 100), the same operation as in Example 1 was performed to prepare an adhesive layer.

(Example 10)
As an acrylic resin, Vanaresin GH2851C1 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., weight average molecular weight 11,000, acid value 100) 50 parts by weight, Vanaresin GH2851C1-T15 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., weight average) Except for using 20 parts by weight of a molecular weight of 11,000 and an acid value of 100), the same operation as in Example 1 was performed to prepare an adhesive layer.

(Example 11)
As an alternative to vanaresin GH2851C1-T15, the same operation as in Example 1 was performed except that 20 parts by weight of vanaresin 2851C1-T14 (manufactured by Shin-Nakamura Chemical Co., Ltd., weight average molecular weight 1 million, acid value 100) was mixed. An adhesive layer was prepared.

  GH2851C1-T14 is a quaternary copolymer of ethyl acrylate, acrylonitrile, methacrylic acid, and 2-phenoxyethyl acrylate.

(Example 12)
As an alternative to vanaresin GH2851C1-T15, 20 parts by weight of vanaresin GH2857 (Shin Nakamura Chemical Co., Ltd., weight average molecular weight 1 million, acid value 100) modified with 3,4-epoxycyclohexylmethyl acrylate were mixed. The same operation as in Example 1 was performed to prepare an adhesive layer. Vanaresin GH2857 is a quaternary copolymer of ethyl acrylate, acrylonitrile, methacrylic acid, and 2-phenoxyethyl acrylate, and the quaternary copolymer contains 3 parts by weight of a carboxyl group at the methacrylic acid moiety, 3, 4 -A resin modified with epoxycyclohexylmethyl acrylate and adjusted to an acid value of 80.

(Comparative Example 1)
Except not adding vanaresin GH2851C1-T15, the same operation as Example 1 was performed and the adhesive bond layer was produced.

(Comparative Example 2)
As an alternative to vanaresin GH2851C1, 20 parts by weight of vanaresin 2803 (manufactured by Shin-Nakamura Chemical Co., Ltd., weight average molecular weight 27,000, acid value 102) are mixed, and vanaresin GH2851C1-T15 is not added. The same operation was performed to produce an adhesive layer.

(Evaluation method)
(Cutting waste test)
The adhesive layer obtained by the above method was irradiated with 1000 mJ / cm ^{2 of} ultraviolet rays from the adhesive layer side through a photomask, and then immersed in a 2.38% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 60 seconds. An adhesive layer pattern was formed by washing with pure water. Thereafter, the adhesive layer pattern was cut with an NT cutter.

  At that time, the cut surface of the adhesive layer was observed with an optical microscope manufactured by Keyence Corporation at a magnification of 20 times to confirm the generation and scattering of the cutting waste, and the maximum length of the cutting waste was measured.

  As a result, as shown in Table 1, when the adhesive film according to the present invention is used, the maximum length of the cutting waste is 0.2 mm or less, and if it is within this range, the manufacturing yield of the semiconductor element is lowered. It is considered that there is no influence on the workability in the film manufacturing process.

(Opening width test)
1000 mJ / cm ^{2 of} ultraviolet rays from the adhesive layer side of the photosensitive adhesive film is passed through a photomask in which the opening size is 10.0 μmφ and the openings are dispersedly arranged so that the distance between the openings is 30 μm. After irradiation, the substrate was immersed in a 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution at 25 ° C. for 1 minute, and then washed with pure water to form an adhesive layer pattern.

  The formed pattern was visually observed with an optical microscope. With respect to the opening size of 10.0 μmφ, it was judged that the function as the photosensitive adhesive film was satisfied if the opening was 8.0 μm or more.

(Adhesion test)
After laminating a polyimide film on the adhesive layer of the photosensitive adhesive film using a nip roll heated to 60 ° C., the obtained laminated film was pulled in the direction of 180 ° C., and a tear test was performed. In addition, “adhesive strength OK” in the following Table 1 means that the peeling substrate is broken during the measurement, and no peeling of the bonded portion is observed, and “−” means that no measurement is performed. means.

  As a result, in any film other than Comparative Example 2, the base film was broken, and peeling of the bonded portion was not observed.

1 substrate to be coated,
2 adhesive layer,
3 Semiconductor wafer,
4 Photomask,
5 alkaline aqueous solution,
6 base material layer,
7 adhesive layer,
8 Ring frame,
9 Dicing saw,
10 Pickup device,
11 Adherent.

Claims (4)

(A) a copolymer containing a unit represented by the following chemical formula (1) in the main chain, (B) a compound having an epoxy group, (C) a curing agent for an epoxy group, (D) a compound having an ethylenically unsaturated bond, And (E) a photopolymerization initiator

(In the above chemical formula 1, R ₁ , R ₂ and M ¹ are each independently, R ₁ and R ₂ are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
M ₁ is a —COOR ′ group,
R ′ is a group having a cyclic compound,
n is an integer of 1 to 1,000, and m is an integer of 1 to 1,000. )
An adhesive layer comprising:
A coated substrate for coating the adhesive layer, and a photosensitive semiconductor adhesive film comprising:
The copolymer containing the unit represented by the chemical formula (1) in the main chain contains 1 to 75 parts by mass with 100 parts by mass as the total content of the constituents in the adhesive layer. Adhesive film for semiconductors. The copolymer containing the unit represented by the chemical formula (1) in the main chain is represented by the following chemical formula 2b:

(Wherein d7 is an integer from 1 to 12, preferably an integer of 1 to 8.) (In the chemical formula _2b, R 1 to R ₅ and _M 1 ~M ₄ is independently
R _{1 to} R ₅ are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
M ₁ is a —COOR ′ group,
M ₂ is a group having a cyclic compound or a —COOR group,
M ₃ is at least one group selected from the group consisting of a —COOR group, a group having a cyclic compound, and a cyano group;
M ₄ is at least one group selected from the group consisting of a —COOR group, a group having a cyclic compound, and a cyano group;
R ′ is a group having a cyclic compound, and R is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a group consisting of a cyclic compound, — (CH ₂ —C (—OH) — ( _{CH 2) p -O-C (} = O) CR a = CH 2, and the following chemical formula 2c:

At least one group selected from the group consisting of:
R _a is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
n is 1 to 5,000, m is 1 to 1,000, l is 0 to 1,000, k is 0 to 1,000, and h is 0 to 1. , And p is an integer of 1-16. )
The adhesive film for photosensitive semiconductors of Claim 1 shown by these. (A) 1 to 75 parts by mass of a copolymer containing a unit represented by the chemical formula (1) in the main chain;
(B) 10 to 30 parts by mass of the compound having the epoxy group;
(C) 5 to 15 parts by mass of the epoxy group curing agent;
(D) 3 to 50 parts by mass of the compound having an ethylenically unsaturated bond;
(E) The adhesive film for photosensitive semiconductors of Claim 1 or 2 containing the said photoinitiator 0.1-15 mass parts. (A) Copolymer containing a unit represented by the following chemical formula (1) in the main chain:
(In formula, d7 is an integer of 1-12, Preferably it is an integer of 1-8.)

(In the above chemical formula 1, R ₁ , R ₂ and M ₁ are each independently, R ₁ and R ₂ are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
M ₁ is a —COOR ′ group,
R ′ is a group having a cyclic compound,
n is an integer of 1 to 1,000, and m is an integer of 1 to 1,000. ),
(B) Adhesive coating liquid in which an epoxy group-containing compound, (C) an epoxy group curing agent, (D) a compound having an ethylenically unsaturated bond, (E) a photopolymerization initiator, and (F) a solvent are mixed. A step of preparing
The adhesive coating liquid is applied onto a coated substrate to be coated with the adhesive coating liquid, dried at a temperature range of 50 to 150 ° C. for 3 to 60 minutes to form an adhesive layer, and then the adhesive. A first attaching step of attaching a layer to the surface of the semiconductor wafer, and peeling off the adhesive layer from the coating substrate to obtain a semiconductor wafer with an adhesive layer;
An irradiation step of irradiating the adhesive layer of the semiconductor wafer through the shielding mask with high energy rays of 50 to 5000 mJ / Cm ² to cure the adhesive layer;
A developing step of immersing the cured semiconductor wafer with an adhesive layer in an alkaline aqueous solution for 10 to 500 seconds to dissolve and remove the adhesive of the non-irradiated part;
A second attaching step of obtaining a semiconductor wafer with a laminated body in which a base material with an adhesive layer is attached to the semiconductor wafer with an adhesive layer from the adhesive layer side;
Dicing the semiconductor wafer with a laminated body at least until reaching the interface between the adhesive layer and the semiconductor wafer, and a dicing step of obtaining a semiconductor element by cutting the semiconductor wafer;
Picking up the semiconductor element together with the adhesive layer from the pressure-sensitive adhesive layer, and obtaining a semiconductor element with the adhesive layer;
And a bonding step of bonding the semiconductor element to an adherend through the adhesive layer in the semiconductor element with the adhesive layer.

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