JP2012214585A - Anchor coating agent composition for energy ray-curing adhesive, coating film, and adhesive sheet for processing semiconductor wafer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anchor coating agent composition that has high adhesiveness to an energy ray-curing adhesive and base film in adhesive sheets for processing a semiconductor wafer using the energy ray-curing adhesive, such as a backgrind tape and a dicing tape, and that can form an anchor coating layer for preventing the occurrence of blocking.SOLUTION: The anchor coating agent composition has a configuration obtained by subjecting a predetermined polyester diol (a), a predetermined polyalkylene ether glycol (b) and a multivalent isocyanate compound (c) to polyesterification reaction. Moreover, the anchor coating agent composition further includes a copolyester urethane resin that contains 40 to 80 pts.mass of the (b) component and 20 to 50 pts.mass of the (c) component based on 100 pts.mass of the (a) component, and that has a number average molecular weight of 10,000 to 100,000.

Description

  The present invention relates to an anchor coating composition capable of improving the adhesion between an energy beam curable pressure-sensitive adhesive and a base film, and an energy beam curable pressure-sensitive adhesive having an anchor coating layer comprising the anchor coating composition. The present invention relates to a coated film and an adhesive sheet for processing semiconductor wafers.

  As an adhesive sheet for processing a semiconductor wafer, a back grind tape and a dicing tape are known. For example, as a back grind tape, an adhesive tape in which an energy ray curable adhesive layer is formed on the surface of an olefin-based film is attached to the circuit surface (surface) of a semiconductor wafer. However, since the olefin film has low thickness accuracy, the thickness of the wafer after grinding tends to vary.

  Although a polyester film is mentioned as a film with good thickness accuracy, the components constituting the energy ray-curable pressure-sensitive adhesive layer generally have low adhesion to the polyester film particularly after energy ray curing. Therefore, when the back grind tape with the energy ray curable pressure-sensitive adhesive layer directly laminated on the polyester film is peeled off from the semiconductor wafer, the energy ray curable pressure sensitive adhesive peels off from the polyester film, and the energy beam curable on the surface of the semiconductor wafer. The mold pressure-sensitive adhesive sometimes remained.

  Conventionally, it is known that an energy ray curable pressure-sensitive adhesive can be prevented from peeling from a polyester film by forming an anchor coat layer on the surface of the polyester film on which the energy beam curable pressure-sensitive adhesive layer is formed. For example, Patent Document 1 discloses an anchor having an anchor coat layer composed of an epoxy-modified block polymer composed of a vinyl aromatic compound block (A) and a partially epoxidized conjugated diene compound block (B). A polyester film with a coat layer is disclosed. However, due to the presence of the anchor coat layer, when the polyester film with the anchor coat layer is wound up and stored, the opposite surface of the polyester film on which the anchor coat layer is formed and the anchor coat layer adhere, and blocking occurs. was there. A composition using an aromatic-conjugated diene block copolymer as described in the above document is also used as a rubber-based pressure-sensitive adhesive, and it is difficult to eliminate tackiness. Such a polyester film with an anchor coat layer It was difficult to suppress blocking using.

  Patent Document 2 discloses a film for a semiconductor manufacturing process in which a seal layer containing a polyolefin resin containing a (meth) acrylic acid ester component is formed on the opposite surface of the anchor coat layer forming surface of the polyester film with an anchor coat layer. It is disclosed. According to Patent Document 2, blocking can be suppressed by the presence of the seal layer, but productivity is deteriorated.

JP-A-2005-231119 JP 2009-224375 A

  Therefore, there has been a demand for a film for semiconductor processing that can prevent blocking without providing an anti-blocking layer while providing an anchor coat layer and ensuring the adhesion of the energy ray-curable pressure-sensitive adhesive.

  In the adhesive sheet for semiconductor wafer processing (for example, a back grind tape or a dicing tape) using the energy beam curable adhesive as described above, the present invention has high adhesion between the energy beam curable adhesive and the base film. An object of the present invention is to provide an anchor coat agent composition capable of forming an anchor coat layer capable of preventing blocking.

The gist of the present invention is as follows.
[1] An acid component containing 80 mol% or more of an aromatic dicarboxylic acid component when the total acid component is 100 mol% and an aliphatic glycol component of 40 mol% or more when the total glycol component is 100 mol% A polyester diol (a) having a number average molecular weight of 1500 to 3000, comprising a glycol component;
A polyalkylene ether glycol (b) having a number average molecular weight of 1000 to 3000, and a polyvalent isocyanate compound (c),
It comprises a structure obtained by a polycondensation reaction of (a), and contains 100 parts by mass of the component (a), contains 40 to 80 parts by mass of the component (b), and 20 to 50 parts by mass of the component (c). An anchor coating composition for an energy ray-curable pressure-sensitive adhesive comprising a copolyester urethane resin having a molecular weight of 10,000 to 100,000.

[2] The anchor coating agent composition according to [1], which contains an amorphous polyester resin at a ratio of 100 parts by mass or less with respect to 100 parts by mass of the copolyester urethane resin.

[3] The anchor according to [2], further including a crosslinking agent in a proportion of 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the copolyester urethane resin and the amorphous polyester resin. Coating agent composition.

[4] A coating film for an energy ray-curable pressure-sensitive adhesive in which an anchor coat layer is provided on one side of a base film,
A coat film for an energy ray-curable pressure-sensitive adhesive, wherein the anchor coat layer is formed of the anchor coat agent composition according to [1] to [3].

[5] From the surface of the anchor coat layer, the hardness A measured by a nanoindentation test at a depth (depth (X)) ½ of the thickness of the anchor coat layer is measured in the same manner as described above. The coated film according to [4], which is lower than the hardness B at the depth (X) from the surface layer of the base film, and the difference between the hardness A and the hardness B is 0.35 GPa or less.

[6] The coat film according to [4] or [5], wherein the anchor coat layer has a thickness of 0.1 to 7 μm.

[7] A pressure-sensitive adhesive sheet for processing a semiconductor wafer, wherein an energy ray-curable pressure-sensitive adhesive layer is formed on the anchor coat layer of the coat film according to any one of [4] to [6].

  The anchor coating agent composition of the present invention has a high affinity with the energy beam curable pressure-sensitive adhesive, and improves the adhesion of the energy beam curable pressure-sensitive adhesive to the substrate film by coating on the substrate film. And has high blocking resistance.

The wafer back surface grinding process using the adhesive sheet for semiconductor wafer processing which concerns on this invention is shown. The top view of the circuit formation surface of a semiconductor wafer is shown. The dicing process using the adhesive sheet for semiconductor wafer processing which concerns on this invention is shown.

First, the copolymerized polyester urethane resin used for the anchor coating agent composition of the present invention will be described.
[Copolymer polyester urethane resin]
The copolymerized polyester urethane resin used in the present invention has a structure obtained by a polycondensation reaction of the polyester diol (a), polyalkylene ether glycol (b), and polyvalent isocyanate compound (c) shown below.

(Polyester diol (a))
The polyester diol (a) in the copolymerized polyester urethane resin used in the present invention comprises an acid component containing 80 mol% or more of an aromatic dicarboxylic acid component (aromatic dibasic acid component) when the total acid component is 100 mol%. When the total glycol component is 100 mol%, the glycol component contains 40 mol% or more of the aliphatic glycol component, and the number average molecular weight is 1500 to 3000.

  The polyester diol (a) has a moderate compatibility with the polyalkylene ether glycol (b) described later copolymerized by a urethane bond because 80 mol% or more of the total acid component is an aromatic dibasic acid component. The effects of the present invention are exhibited when the segments derived from both components (a) and (b) are aggregated to form a microphase separation structure. That is, by forming an anchor coat layer on the base film using the anchor coat agent composition of the present invention, (a) and (b) both components in the copolymerized polyester urethane resin in the anchor coat layer. Since the segment derived from is present in a moderately incompatible state, the anti-blocking property when the back surface of the base film and the anchor coat layer are overlapped, and the adhesion between the base film and the energy ray curable adhesive are At the same time, it is effectively improved. The reason is presumed as follows. First, the agglomerated structure of component (b) has flexibility at room temperature, so to speak, exhibits cushioning properties, absorbs stress at the time of shrinkage of the energy ray curable pressure sensitive adhesive, and has an affinity with the energy ray curable pressure sensitive adhesive. As a result, the adhesion is improved. Moreover, since the aggregate structure of the component (a) makes the viscoelasticity of the anchor coat layer elastic as a whole, adhesion to the back surface of the base film hardly occurs and blocking is suppressed.

  The copolymerization ratio of the aromatic dibasic acid component in the total acid component in the component (a) is 80 mol% or more. If it is less than 80 mol%, the compatibility with the segment derived from the component (b) is increased, and the segments derived from both the components (a) and (b) do not form a microphase separation structure, and thus the copolymer obtained. Affinity with the energy ray curable pressure sensitive adhesive, which is the effect of the aggregation structure of the segment derived from the component (b) in the polyester urethane resin, does not appear, and the adhesiveness of the energy ray curable pressure sensitive adhesive tends to be impaired. Furthermore, the blocking resistance which is the effect of the aggregate structure of the segment derived from the component (a) tends to be impaired.

  When the total glycol component in the component (a) is 100 mol%, the aliphatic glycol component is contained in an amount of 40 mol% or more, so that the solubility of the component (a) in a general-purpose solvent is improved, The copolymerized polyester urethane resin to be used is easily polymerized in a general-purpose organic solvent.

  Furthermore, the number average molecular weight of (a) component is 1500-3000. When the number average molecular weight is less than 1500, the compatibility with the segment derived from the component (b) increases, and the microphase separation of the segments derived from the components (a) and (b) does not occur, and thus the copolymer obtained The affinity with the energy ray curable pressure sensitive adhesive, which is the effect of the aggregate structure of the segments derived from the component (b) in the polyester urethane resin, is not expressed, and the adhesion with the energy ray curable pressure sensitive adhesive is impaired. In addition, the anti-blocking property, which is the effect of the aggregate structure of the segments derived from the component (a), tends to be impaired. On the other hand, when the number average molecular weight exceeds 3000, the incompatibility with the segment derived from the component (b) is excessively increased, and the reaction rate of the carboxyl group of the component (a) and the hydroxyl group of the component (b) is excessively decreased. However, the polymerization tends to be difficult. In addition, the said number average molecular weight is the value of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method.

  Examples of the aromatic dicarboxylic acid component constituting the component (a) include aromatic dibasic acids such as terephthalic acid, isophthalic acid and orthophthalic acid, and ester derivatives thereof. In order to develop compatibility, terephthalic acid, isophthalic acid, dimethyl terephthalate, dimethyl isophthalate, and dimethyl sodium 5-sulfoisophthalate are more preferable. In addition to these aromatic dicarboxylic acid components, the acid components (other dicarboxylic acid components) other than aromatic dicarboxylic acid components used in less than 20 mol% of the total acid components include fats such as adipic acid and sebacic acid. And alicyclic dibasic acids such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid. In addition, those having three or more carboxyl groups such as cyclohexane-1,2,4-tricarboxylic acid, hemimellitic acid, trimellitic acid, pyromellitic acid, citric acid and isocitric acid, and those having a hydroxyl group in the molecule Can also be used as appropriate.

  The aliphatic glycol component contained in the glycol component used in combination with the acid component in the component (a) includes an aliphatic glycol component represented by the following general formula (1) and / or general formula (2). Is preferred. Specific examples include 2-methyl-1,3-propanediol, neopentyl glycol, 1,2-propylene glycol, 2-ethyl-2-butyl-1,3-propanediol. Among these, neopentyl glycol is preferable from the viewpoint of more effectively increasing the solubility in a general-purpose solvent. Other glycol components copolymerized with these aliphatic glycols include straight chain fats such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. A group glycol component is preferably used. Among these, it is preferable to use ethylene glycol because the polymerization reaction is more likely to proceed.

（但し、Ｒ¹は炭素数１又は２のアルキル基である。） General formula (1):

(However, R ¹ is an alkyl group having 1 or 2 carbon atoms.)

（但し、Ｒ²は炭素数１又は２のアルキル基、Ｒ³は水素原子又は炭素数１〜４のアルキル基である。） General formula (2):

(However, R ² is an alkyl group having 1 or 2 carbon atoms, and R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

  Further, in combination with these aliphatic glycol components, glycol components other than the aliphatic glycol components used in less than 60 mol% of the total glycol components include those having an ether bond such as alkylene glycol ether, resorcinol, hydroquinone, Examples thereof include those having a phenolic hydroxyl group such as bisphenol A, bisphenol F and biphenol, and those having a carboxyl group in the molecule such as tartaric acid.

(Polyalkylene ether glycol (b))
The polyalkylene ether glycol (b) in the copolymerized polyester urethane resin used in the present invention has a number average molecular weight of 1000 to 3000. The polyalkylene ether glycol (b) preferably has a structure obtained by dehydration condensation of an aliphatic glycol having 2 to 4 carbon atoms. By using such a polyalkylene ether glycol (b) as a diol compound other than the polyester diol (a) used for the polycondensation of the copolymerized polyester urethane resin, for example, a continuous oxyalkylene group such as an aliphatic polyester diol. Microphase separation of segments due to a difference in compatibility with the polyester diol (a) is more likely to occur than when a diol compound having no structure is used. As a result, the predetermined effect of the present invention, in particular, the blocking resistance derived from the aggregate structure of the polyester diol (a) is easily obtained.

  Specific examples of the component (b) include polyether diols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Among these, polypropylene glycol is more preferable in order to develop moderate incompatibility with the segment derived from the component (a). Moreover, the number average molecular weight of (b) component is 1000-3000, and if this number average molecular weight is less than 1000, compatibility with the segment derived from (a) component will become low, (a), (b) both components Microphase separation of the segment derived from the resin does not occur, and therefore the affinity with the energy ray curable pressure sensitive adhesive, which is the effect of the aggregate structure of the segment derived from the component (b) in the copolymerized polyester urethane resin obtained, is expressed. Without adhering, the adhesiveness with the energy ray curable pressure-sensitive adhesive tends to be impaired, and further, the blocking resistance which is the effect of the aggregate structure of the segment derived from the component (a) tends not to be exhibited. On the other hand, when the number average molecular weight exceeds 3000, the incompatibility with the component (a) is too high, and the resin containing the component (a) at a high concentration and the component (b) are increased in the polymerization process of the copolymer polyester urethane resin. Phase separation occurs in the two phases of the resin contained at a concentration, and it tends to be difficult to obtain a uniform resin.

  The copolymerization ratio of the component (a) and the component (b) is 40 to 80 parts by mass of the component (b) with respect to 100 parts by mass of the component (a). When the component (b) is less than 40 parts by mass, the affinity with the energy beam curable adhesive, which is the effect of the aggregate structure of the segments derived from the component (b), is not sufficiently expressed. The adhesion of is impaired. Moreover, although the anti-blocking property of the anchor coating agent composition of the present invention is presumed to be due to the rigid structure in the aggregated structure of the segment of the component (a), the component (b) is less than 40 parts by mass. And, since the aggregate structure of the segment of the component (a) becomes difficult to form, blocking resistance may be impaired. On the other hand, when the component (b) exceeds 80 parts by mass, the glass transition temperature of the entire copolymer polyester urethane resin is lowered, and the blocking resistance is impaired.

(Polyvalent isocyanate compound (c))
The polyvalent isocyanate compound (c) used in the copolymerized polyester urethane resin may be any aromatic, aliphatic or alicyclic polyvalent isocyanate compound, such as diphenylmethane diisocyanate, tolylene diisocyanate, 1 , 3-xylylene diisocyanate, isophorone diisocyanate, 1,6-hexane diisocyanate, and the like, and diphenylmethane diisocyanate is preferred because of its good reactivity. The copolymerization amount of these polyvalent isocyanate compounds is 20 to 50 parts by mass with respect to 100 parts by mass of the component (a) in the copolymerized polyester urethane resin used in the present invention. If it is less than 20 parts by mass, the toughness will not be exhibited when the copolymerized polyester urethane resin is used as a coating layer, and if it exceeds 50 parts by mass, the solubility of the produced copolymerized polyester urethane resin in a general-purpose solvent will decrease.

  Moreover, the copolymerization polyester urethane resin used for this invention may contain aliphatic polyhydric alcohol (d) as a copolymerization monomer as arbitrary components other than said (a)-(c) component.

(Aliphatic polyhydric alcohol (d))
The aliphatic polyhydric alcohol (d) in the copolymerized polyester urethane resin preferably has 4 to 6 carbon atoms, and acts as a chain extender when used in the copolymerized polyester urethane resin. Specific examples of the component (d) include linear aliphatic glycols such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 2-methyl-1,3-propane. Examples thereof include branched glycols such as diol, neopentyl glycol, and 1,2-propylene glycol. Further, for the purpose of improving the reactivity with the crosslinking agent, a trifunctional or higher polyhydric alcohol may be used, and examples thereof include triols such as trimethylolpropane and glycerin, and tetraols such as pentaerythritol. Of these polyhydric alcohols, branched glycols are preferable from the viewpoint of improving the solubility of the copolymer polyester urethane resin obtained, and neopentyl glycol is most preferable.

  By copolymerizing these aliphatic polyhydric alcohols (d), the concentration of urethane bonding groups in the copolymerized polyester urethane resin can be adjusted, and the physical properties such as the glass transition temperature of the copolymerized polyester urethane resin can be controlled. it can. (D) A component can be copolymerized in 0-8 mass parts with respect to 100 mass parts of said (a) component, and it is still more preferable that it is 6 mass parts or less. When the amount exceeds 8 parts by mass, the above-mentioned component (c) and a crosslinked product having a large number of branched structures are formed and precipitated in the polyester urethane resin solution, or (c) component, (a) component and (b) component. Reaction may be hindered, which is not preferable. (D) Although a component is not an essential component, when using, since an effect will not be exhibited if the usage-amount is too small, it may be 0.2 mass part or more with respect to 100 mass parts of (a) component. Preferably, 0.6 parts by mass or more is more preferable, and 1.6 parts by mass or more is more preferable.

(Properties of copolymer polyester urethane resin)
The number average molecular weight of the copolymerized polyester urethane resin used in the present invention is 10,000 to 100,000. If the number average molecular weight is lower than this, the adhesiveness with the energy ray curable pressure-sensitive adhesive becomes insufficient, and if the number average molecular weight is higher than this, the viscosity of the polyester urethane resin solution becomes high and handling workability is deteriorated.

  The glass transition temperature in the dynamic viscoelasticity measurement of the copolyester urethane resin used in the present invention is preferably 40 ° C. or higher, more preferably 50 to 75 ° C. The glass transition temperature refers to a temperature at which the loss tangent tan δ is maximized in the dynamic viscoelasticity measurement. When the glass transition temperature is in such a range, there is a tendency that an anchor coat layer having sufficient blocking resistance and adhesion between the base film and the energy ray curable pressure-sensitive adhesive tends to be obtained.

(Polymerization of copolymerized polyester urethane resin)
The copolymerized polyester urethane resin used in the present invention is, for example, in a ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, or in a mixed solvent of an aromatic hydrocarbon solvent such as toluene and xylene and the above ketone solvent. Polymerization is preferably performed by a polycondensation reaction between the component (a), the component (b), the component (c), and the component (d) that is an optional component. As the polymerization catalyst, for example, an organic tin complex such as dibutyltin laurate or an amine catalyst such as triethylenediamine can be used.

Next, the anchor coating agent composition for energy beam curable pressure sensitive adhesive according to the present invention will be described.
[Anchor coating composition]
The anchor coating agent composition for energy beam curable pressure sensitive adhesive according to the present invention (hereinafter sometimes simply referred to as “anchor coating agent composition”) includes the above-described copolymer polyester urethane resin. The anchor coating agent composition preferably contains an amorphous polyester resin and a crosslinking agent in addition to the copolymerized polyester urethane resin.

(Amorphous polyester resin)
Examples of the amorphous polyester resin include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neo At least one selected from alcohol components such as pentyl glycol, cyclohexane-1,4-dimethanol, hydrogenated bisphenol A, ethylene oxide or propylene oxide adduct of bisphenol A, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, Obtained by polycondensation with at least one selected from carboxylic acid components such as cyclohexane-1,4-dicarboxylic acid, adipic acid, azelaic acid, maleic acid, fumaric acid, itaconic acid and acid anhydrides thereof Heavy Or the like can be mentioned the body.

  An amorphous polyester resin is a polyester resin that does not exhibit crystallinity in the solid state. The term “amorphous” as used herein includes those in which local crystal parts such as a folded structure and parts where molecular chains are isotropically coexist. By using an amorphous polyester resin, the surface hardness of the anchor coating layer formed from the anchor coating agent composition of the present invention is kept low, and the coating layer and an energy ray curable pressure-sensitive adhesive provided on the coating layer High adhesion to the layer is likely to be obtained. Moreover, blocking can be prevented more efficiently. In particular, since the shrinkage at the time of curing of the energy ray curable pressure-sensitive adhesive is large, blocking occurs when the thickness of the anchor coat layer is increased when the thickness of the anchor coat layer is set to, for example, 0.1 to 7 μm as described later. Although it becomes easy, it is easy to suppress blocking by including an amorphous polyester resin in the anchor coating agent composition even when the anchor coating layer is thick.

  The blending amount of the amorphous polyester resin is preferably 100 parts by mass or less, more preferably 1 to 50 parts by mass, and 5 to 25 parts by mass with respect to 100 parts by mass of the copolyester urethane resin. More preferably, it is 5-15 mass parts especially preferable. By setting the blending amount of the amorphous polyester resin in such a range, the adhesion to the base film described later can be sufficiently obtained, and the anchor coat layer formed from the anchor coating agent composition of the present invention. The surface hardness of the coating layer is kept low, and high adhesion between the coating layer and the energy ray-curable pressure-sensitive adhesive layer provided on the coating layer is easily obtained. Moreover, blocking can be suppressed efficiently. Furthermore, since the compatibility with the copolymerized polyester urethane resin in the anchor coating agent composition is hardly lowered, the haze value is kept low and the transparency is easily increased.

(Crosslinking agent)
The anchor coating agent of the present invention may further contain a crosslinking agent. As this crosslinking agent, an isocyanate-based crosslinking agent is preferable. The cross-linking agent has reactivity with active hydrogen groups such as hydroxyl groups possessed by the copolymerized polyester urethane resin and active hydrogen groups such as hydroxyl groups possessed by the amorphous polyester resin. In this case, the polymer chain of the copolymer polyester urethane resin, the polymer chains of the amorphous polyester resin, or the polymer chain of the copolymer polyester resin and the polymer chain of the amorphous polyester resin are bonded to each other to form an anchor coating agent composition. This improves the cohesive force and improves the adhesion to the substrate film.

  Examples of the isocyanate compound include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; dicyclohexylmethane-4,4′-diisocyanate, bicycloheptane triisocyanate, cyclopentylene diene Alicyclic isocyanate compounds such as isocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, hydrogenated xylylene diisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, etc. Aliphatic isocyanate; and the like. In addition, biuret bodies and isocyanurate bodies of these compounds; and adduct bodies that are reaction products of these compounds with non-aromatic low-molecular active hydrogen-containing compounds such as ethylene glycol, trimethylolpropane, castor oil, etc. Modified products such as; can also be used.

  It is preferable that the compounding quantity of a crosslinking agent is 0.1-30 mass parts with respect to 100 mass parts (solid content) of the total amount of copolyester urethane resin and an amorphous polyester resin, especially 0.25-0.5. It is preferable that it is 30 mass parts. When the blending amount of the crosslinking agent is in the above range, the anchor coat layer is maintained at an appropriate hardness, and good adhesion to the base film is easily obtained.

(Preparation of anchor coating composition)
The anchor coating agent composition of the present invention is prepared by a known method of mixing and stirring the above-described copolymerized polyester urethane resin, the amorphous polyester resin used as required, the crosslinking agent and other additives, and a solvent. Can be prepared. Examples of other additives include an ultraviolet absorber, a plasticizer, a filler, an antioxidant, a tackifier, a pigment, a dye, and a coupling agent.

  Examples of the solvent include ethers such as diethyl ether, diisopropyl ether, dibutyl ether, 1,2-dimethoxyethane, tetrahydrofuran, and 1,4-dioxane; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, and methyl lactate Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, and cyclohexanone: amides such as N, N-dimethylformamide, N, N-dimethylacetamide, hexamethylphosphate phosphoramide, and N-methylpyrrolidone; -Lactams such as caprolactam; Lactones such as γ-lactone and δ-lactone; Sulfoxides such as dimethyl sulfoxide and diethyl sulfoxide; Aliphatic hydrocarbons such as pentane, hexane, heptane, octane, nonane and decane Cyclopentane, cyclohexane, cyclooctane and other alicyclic hydrocarbons; benzene, toluene, xylene and other aromatic hydrocarbons; dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene and other halogenated hydrocarbons And a mixed solvent comprising two or more of these; and the like.

  Although the usage-amount of a solvent is not specifically limited, The quantity from which the solid content concentration of the anchor coating agent composition for energy-beam curable adhesives is 10-50 mass% is preferable.

Next, the coating film for energy beam curable adhesives according to the present invention will be described.
[Coated film]
The coated film for energy beam curable pressure-sensitive adhesive according to the present invention (hereinafter sometimes simply referred to as “coated film”) is provided with an anchor coat layer on one side of the base film, and the anchor The coat layer is formed by the anchor coat agent composition described above. The coated film of the present invention may be any of a long roll-like material in addition to a sheet-like material.

(Base film)
As a base film used for the coated film of the present invention, a polyester film is preferable because of high thickness accuracy. The polyester constituting the polyester film is a linear saturated polyester obtained by polycondensation from an aromatic dibasic acid or an ester derivative thereof and a diol or an ester derivative thereof. Specific examples of the polyester include polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, polyethylene-2,6 naphthalene dicarboxylate, and the like. These copolymers or blends thereof with a small proportion of other resins. Things are also included.

  The polyester film can be produced by a conventionally known method. For example, the biaxially stretched polyester film is obtained by drying the polyester, melting it with an extruder at a temperature of Tm to (Tm + 70) ° C. (Tm: melting point of the polyester), and from a die (eg, T-die, I-die, etc.). Extruded onto a rotating cooling drum at 40 to 90 ° C., rapidly cooled to produce an unstretched film, and then the unstretched film was heated at a temperature of (Tg-10) to (Tg + 70) ° C. (Tg: glass transition temperature of polyester). Stretch in the longitudinal direction at a magnification of 2.5 to 8.0 times, stretch in the transverse direction at a magnification of 2.5 to 8.0 times, and heat for 1 to 60 seconds at a temperature of 180 to 250 ° C. as necessary. It can be manufactured by fixing.

  The thickness of the base film is preferably in the range of 5 to 250 μm. When the thickness of the substrate film is less than 5 μm, there is a problem that the deformation resistance (dimensional stability) at a high temperature range is inferior, and when it exceeds 250 μm, the rigidity is too high.

  Moreover, a suitable filler can be contained in a base film as needed. Examples of the filler include those conventionally known as slipperiness imparting agents for base film, and specific examples thereof include calcium carbonate, calcium oxide, aluminum oxide, silica, kaolin, silicon oxide, zinc oxide, and carbon. Examples thereof include black, silicon carbide, tin oxide, crosslinked acrylic resin particles, crosslinked polystyrene resin particles, melamine resin particles, and crosslinked silicone resin particles. Furthermore, a coloring agent, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and the like can be appropriately added to the base film.

  The base film may be transparent, may be colored or vapor-deposited as desired, and may contain an ultraviolet absorber, a light stabilizer, an antioxidant, and the like. Moreover, as a base film, said single layer film may be sufficient and a laminated film may be sufficient.

(Manufacture of coated film)
In order to produce a coating film for an energy ray-curable pressure-sensitive adhesive according to the present invention, an anchor coat containing the above-described anchor coating composition, preferably an amorphous polyester resin or a crosslinking agent, with respect to the base film. After applying the agent composition, it may be dried with hot air or the like.

  The anchor coating agent composition may be applied by a conventional method, for example, a bar coating method, a knife coating method, a Mayer bar method, a roll coating method, a blade coating method, a die coating method, or a gravure coating method. After applying the anchor coating agent composition and forming a coating film on one side of the substrate film, it is preferable to dry the coating film at about 50 to 120 ° C. to form an anchor coating layer.

  Although the thickness of an anchor coat layer is not specifically limited, For example, it is preferable that it is 0.1-7 micrometers, and it is more preferable that it is 1-5 micrometers. By setting it to such a thickness, the anchor coat layer can efficiently absorb the shrinkage at the time of energy ray curing of the energy ray curable pressure-sensitive adhesive layer, and can suppress the peeling of the anchor coat layer and the substrate film, Moreover, blocking is difficult to occur.

(Properties of coated film)
In the thus-obtained coating film for energy beam-curable pressure-sensitive adhesive according to the present invention, from the surface layer of the anchor coat layer, a depth half the depth of the anchor coat layer (depth (X)) The hardness A measured by the nanoindentation test is lower than the hardness B at the depth (X) from the surface layer of the base film measured in the same manner as described above, and the difference between the hardness A and the hardness B is 0 .35 GPa or less is preferable.

  When the difference between the hardness A and the hardness B is larger than 0.35 GPa, the blocking resistance may be lowered. From the viewpoint of semiconductor use, the lower limit of the difference between hardness A and hardness B is preferably about 0.01 GPa. A more preferable range of the difference between the hardness A and the hardness B is 0.02 to 0.3 GPa, and particularly preferably 0.1 to 0.3 GPa. The hardness measurement test by the nanoindentation test is performed by the following method.

<Hardness measurement test>
The coated film is conditioned at 23 ° C. and 50% RH for 1 week, and then cut into a size of 10 mm × 10 mm to obtain sample A. In addition, the base film is conditioned at 23 ° C. and 50% RH for one week, and then cut into a size of 10 mm × 10 mm to obtain a sample B. Next, the base film surface (the surface opposite to the surface having the anchor coat layer) of sample A and sample B are fixed on a glass plate adhered to an aluminum base with a two-component epoxy adhesive. The hardness A at a depth (depth (X)) ½ of the thickness of the anchor coat layer is measured for the sample A using a nanoindenter [manufactured by MTS, model name “Nano Indenter SA2”]. Next, for sample B, the hardness B at the depth (X) (depth of 1/2 of the thickness of the anchor coat layer of sample A) is measured from the surface layer of the base film.

  The haze value of the coated film of the present invention is preferably 5 or less. By being in such a range, for example, when a pressure-sensitive adhesive sheet for processing a semiconductor wafer is produced using the coated film of the present invention and is attached to a circuit surface or the like of a semiconductor wafer, the visibility of the application surface such as a circuit surface is visible. Will increase.

Next, the adhesive sheet for processing a semiconductor wafer of the present invention will be described.
[Semiconductor wafer processing adhesive sheet]
In the pressure-sensitive adhesive sheet for processing a semiconductor wafer of the present invention, an energy ray-curable pressure-sensitive adhesive layer is formed on the anchor coat layer of the above-described coat film.

(Energy ray curable adhesive layer)
The energy ray-curable pressure-sensitive adhesive layer can be formed of various energy ray-curable pressure-sensitive adhesives that are cured by irradiation of energy rays such as gamma rays, electron beams, UV, and visible light that are conventionally known. It is preferable to use an agent.

  Examples of the UV curable adhesive include an adhesive obtained by mixing an acrylic copolymer with a polyfunctional ultraviolet curable resin. Examples of the polyfunctional ultraviolet curable resin include low molecular compounds having a plurality of (meth) acryloyl groups. Moreover, the adhesive containing the acrylic copolymer which has a photopolymerizable functional group in a side chain can also be used. (Meth) acryloyl group is mentioned as a photopolymerizable functional group. In addition, even if it is a thing except here, if a deformation | transformation arises at the time of hardening with UV curable adhesive, a predetermined effect will be expressed by using the coat film of this invention.

  The energy beam curable pressure-sensitive adhesive layer (hereinafter, sometimes simply referred to as “pressure-sensitive adhesive layer”) is used to form an energy beam curable pressure-sensitive adhesive layer on the anchor coat layer of the above-described coat film. You may provide by apply | coating the coating liquid for adhesive layers, or form an adhesive layer in the surface by which the peeling process of the peeling sheet was given, and this adhesive layer is formed on the anchor coat layer of the coat film mentioned above. You may form an adhesive layer with a peeling sheet by laminating | stacking. The method for forming the energy ray-curable pressure-sensitive adhesive layer is not particularly limited, and a normal method can be used. For example, the energy ray-curable pressure-sensitive adhesive layer can be formed by a gravure roll method, a roll knife method, or the like.

  In the present invention, the thickness of the energy ray-curable pressure-sensitive adhesive layer is not particularly limited, but is usually in the range of 3 to 200 μm, and particularly preferably in the range of 5 to 150 μm.

  The release sheet is not particularly limited. For example, a film made of a resin such as polyethylene terephthalate, polypropylene, or polyethylene or a foamed film thereof, paper such as glassine paper, coated paper, laminated paper, silicone-based, fluorine A system and a release agent such as a long chain alkyl group-containing carbamate can be used.

  Next, the back surface grinding method of the semiconductor wafer using the adhesive sheet for semiconductor wafer processing of this invention is demonstrated.

  In the backside grinding of the wafer, as shown in FIG. 1, the energy ray curable pressure-sensitive adhesive layer 1 of the adhesive sheet 10 for semiconductor wafer processing is temporarily attached to the circuit surface of the semiconductor wafer 11 having a circuit formed on the surface, The back surface of the wafer is ground by the grinder 20 while protecting the circuit surface to obtain a wafer having a predetermined thickness.

  The semiconductor wafer 11 may be a silicon wafer or a compound semiconductor wafer such as gallium / arsenic. Formation of the circuit 12 on the wafer surface can be performed by various methods including conventionally used methods such as an etching method and a lift-off method. In the circuit forming process of the semiconductor wafer, a predetermined circuit 12 is formed. As shown in FIG. 2, the circuit 12 is formed in a lattice pattern on the surface of the inner peripheral portion 13 of the wafer 11, and a surplus portion 14 that does not have a circuit remains in a range of several mm from the outer peripheral end. The thickness of the wafer 11 before grinding is not particularly limited, but is usually about 500 to 1000 μm.

  At the time of back surface grinding, as shown in FIG. 1, in order to protect the circuit on the wafer surface, the adhesive sheet 10 for processing a semiconductor wafer of the present invention is temporarily attached to the circuit surface. Here, temporarily attaching the sheet means fixing the sheet to the adherend so as to be removable again. The temporary attachment of the semiconductor wafer processing adhesive sheet 10 to the wafer surface is performed by a general-purpose method using a tape mounter or the like. Further, the semiconductor wafer processing adhesive sheet 10 may be previously cut in substantially the same shape as the semiconductor wafer 11, and after the sheet is temporarily attached to the wafer, the excess sheet may be cut and removed along the outer periphery of the wafer. Good.

  The back surface of the wafer 11 is ground by a known method using a grinder 20 and a suction table (not shown) for fixing the wafer, with the semiconductor wafer processing adhesive sheet 10 temporarily attached to the entire surface of the circuit. . In the present invention, the semiconductor wafer 11 is temporarily attached by the energy ray curable pressure-sensitive adhesive layer 1, and the wafer can be stably held against the shearing force at the time of grinding the back surface of the wafer. In addition, the back surface of the wafer can be ground uniformly.

  In the present invention, the adhesive sheet 10 for processing a semiconductor wafer is temporarily attached to the wafer circuit surface at room temperature (for example, 23 ° C.). In order to securely seal the outer periphery of the wafer and prevent the intrusion of grinding water, even when the adhesive sheet 10 for processing a semiconductor wafer is temporarily attached to the wafer circuit surface, the sheet 10 may be heated and pasted on the outer periphery of the wafer. Good. The surplus portion 14 described above is formed on the outer periphery of the wafer (see FIG. 2). Therefore, when the sheet 10 is bonded by heating, it is preferable to bond the sheet 10 and the wafer 11 at the surplus portion 14.

  The thickness of the semiconductor wafer after back grinding is not particularly limited, but is preferably 10 to 300 μm, and particularly preferably about 25 to 200 μm.

  After the back surface grinding is completed, the energy ray curable pressure-sensitive adhesive layer is irradiated with energy rays, and the semiconductor wafer processing pressure-sensitive adhesive sheet 10 is peeled off from the wafer surface. According to the pressure-sensitive adhesive sheet 10 for processing a semiconductor wafer of the present invention, when the pressure-sensitive adhesive sheet 10 is peeled from the wafer surface after completion of the back surface grinding, the contamination of the wafer surface by the residue derived from the pressure-sensitive adhesive sheet is extremely small, and generation of defective products The quality of the obtained semiconductor chip can be stabilized.

  Next, a semiconductor device is obtained through processes such as wafer dicing, chip mounting, and resin sealing.

  The pressure-sensitive adhesive sheet for processing a semiconductor wafer of the present invention can also be used in a semiconductor wafer dicing process.

  After the back surface grinding step, as shown in FIG. 3, the semiconductor wafer processing pressure-sensitive adhesive sheet 10 of the present invention is attached to the ground surface side of the wafer 11, and the wafer 11 is diced. The pressure-sensitive adhesive sheet (surface protective sheet) for protecting the wafer surface that is affixed to the wafer surface may be peeled off before the semiconductor wafer processing pressure-sensitive adhesive sheet 10 is affixed. You may peel off after sticking. Moreover, you may peel a surface protection sheet from the chip | tip surface separated into pieces after completion | finish of a dicing process.

  The adhesion of the semiconductor wafer processing adhesive sheet 10 to the back surface of the wafer is generally performed by an apparatus called a mounter, but is not particularly limited.

  The method for dicing the semiconductor wafer 11 is not particularly limited. For example, when the wafer 11 is diced, the peripheral portion of the semiconductor wafer processing adhesive sheet 10 is fixed by the ring frame 5 and then the wafer 11 is chipped by a known technique such as using a rotating round blade such as the dicing blade 30. Etc. According to the pressure-sensitive adhesive sheet for processing a semiconductor wafer 10 of the present invention, the wafer and the chips can be securely held during dicing, the yield of the chips can be improved, and the dicing apparatus can be prevented from being damaged by the scattering of the chips.

  Next, the semiconductor wafer (semiconductor chip) separated from the pressure-sensitive adhesive sheet 10 for semiconductor wafer processing is picked up. Prior to picking up, the chip is picked up after the pressure-sensitive adhesive layer 1 is irradiated with ultraviolet rays to reduce the adhesive strength. According to the pressure-sensitive adhesive sheet 10 for processing a semiconductor wafer of the present invention, since the chip back surface is hardly contaminated by a residue derived from the pressure-sensitive adhesive sheet at the time of pickup, the reliability of the obtained semiconductor chip is improved.

  Further, if the adhesive sheet 10 for processing a semiconductor wafer is expanded prior to picking up, the chip interval is expanded, and chip pick-up can be performed more easily.

  In addition, after the dicing is completed, the chip group aligned on the semiconductor wafer processing adhesive sheet 10 may be transferred to another adhesive sheet for pickup, and then the expansion and chip pickup may be performed.

  The picked-up chip is then die-bonded and resin-sealed by a conventional method to manufacture a semiconductor device.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. The measurement and evaluation methods employed in the present invention are as follows.

(1) Number average molecular weight Using a “gel permeation chromatograph (GPC) 150C” manufactured by Waters, the number average molecular weight was measured at a flow rate of 1 ml / min using tetrahydrofuran as a carrier solvent. Three columns, “Shodex KF-802”, “KF-804”, and “KF-806” manufactured by Showa Denko KK were connected as columns, and the column temperature was set to 30 ° C. An RI detector was used as the detector. A polystyrene standard was used as the molecular weight standard sample.

(2) Acid value After 0.2 g of resin was dissolved in 20 ml of chloroform, phenolphthalein was measured with a 0.1 N NaOH ethanol solution as an indicator, and the measured value was shown as an equivalent in 1000 kg of resin solid content.

(3) Glass transition temperature Using a dynamic viscoelasticity measuring apparatus [“DVA-220” manufactured by IT-Measurement Control Co., Ltd.], the peak temperature of the obtained temperature dependence curve of tan δ was defined as the glass transition temperature. A measurement sample was prepared as follows and measured under the following measurement conditions.
The copolymerized polyester polyurethane resin solution was applied to a release film (OPP) so that the dry thickness was 20 μm, dried for 1 hour with a 120 ° C. hot air dryer, and a 4 mm × 40 mm strip-shaped measurement sample piece was cut out. It was. Using the dynamic viscoelasticity measuring apparatus, the obtained sample piece for measurement was measured for temperature dependency data of tan δ value at a frequency of 10 Hz, a temperature increase rate of 4 ° C./min, and a frequency of 10 Hz.

(4) Resin composition The resin was dissolved in chloroform-d, and the resin composition ratio was determined by ¹ H-NMR using a nuclear magnetic resonance analyzer (NMR) “Gemini-200” manufactured by Varian.

(5) Hardness measurement The hardness of the anchor coat layer of the base film and the coat film was measured by the hardness measurement test described in the specification text.

(6) Adhesiveness of energy ray curable pressure-sensitive adhesive and anchor coat layer According to JIS K 5600-5-6: 1999, the semiconductor wafer processing pressure-sensitive adhesive sheet produced in Examples or Comparative Examples was irradiated with ultraviolet rays (230 mW / cm ² and 190 mJ / cm ² ), a 20 mm × 20 mm square grid was formed on the energy ray curable pressure-sensitive adhesive layer, and cellophane tape [“CT24” manufactured by Nichiban Co., Ltd.] was attached. When the tape was peeled, the number of squares in which the energy ray-curable pressure-sensitive adhesive layer was peeled from the coat film was examined out of 400 squares. It shows that it is excellent in the adhesiveness of an energy-beam curable adhesive and an anchor coat layer, so that there are few peeled squares. Moreover, the quality of adhesion was evaluated according to the following criteria.
A: 0 cell B: 0 cell or more and less than 10 cell peeling C: 10 cell or more and less than 40 cell peeling D: 40 cell or more peeling

Moreover, it was confirmed by Fourier transform type near infrared spectroscopy measurement whether or not the anchor coat layer remained on the grid where the energy ray curable pressure-sensitive adhesive layer was peeled off from the coat film. As the measuring device, Spectrum One manufactured by PerkinElmer Co., Ltd. was used. The presence or absence of the anchor coat layer was confirmed by the presence or absence of a peak at 1530 cm ⁻¹ derived from the polyvalent isocyanate compound (diphenylmethane diisocyanate) contained in the anchor coat layer. The number of squares in which no anchor coat layer remained was examined. It shows that it is excellent in the adhesiveness of a base film and an anchor coat layer, so that there are few squares without an anchor coat layer remaining.

(7) Blocking resistance After the coated film was allowed to stand at 23 ° C. and 50% RH for 1 week, the anchor coating layer surface and the non-coated surface (base film surface) of the coated film were each overlapped, Sandwiched between glass plates. Next, a load of 20 g / cm ² was applied under a 40 ° C., 80% RH environment or a 50 ° C., 30% RH environment and left for 7 days. Then, after being allowed to stand in an environment of 23 ° C. and 50% RH for 24 hours, the overlaid coated film was peeled off, and the blocking resistance against the uncoated surface was evaluated according to the following criteria.
A: There is no adhesion with the non-coated surface.
B: Although there is some adhesion between the non-coated surface and the anchor coat layer surface, it can be peeled off by hand, and no change is observed on the surface of the anchor coat layer after peeling.
C: The non-coated surface and the anchor coat layer surface are bonded, and it is impossible to peel both by hand, or both can be peeled by hand, but the anchor coat layer surface after peeling is broken. Or deformation is seen.

(8) Haze value measurement The haze value of the coat film was measured based on JIS K 7105: 1981 using the Nippon Denshoku Industries Co., Ltd. haze meter.

The synthesis example and comparative synthesis example of the copolyester urethane resin used for the Example of this invention and the comparative example are shown below.
<Synthesis Example-1>
(Synthesis of polyester diol A1)
In a 2 L four-necked flask equipped with a thermometer, a stirring blade, and a Liebig condenser, 194 parts by mass of dimethyl terephthalate, 194 parts by mass of dimethyl isophthalate, 161 parts by mass of ethylene glycol, 146 parts by mass of neopentyl glycol, and a catalyst 0.2 parts by mass of tetrabutyl titanate (TBT) was charged, and the transesterification reaction was allowed to proceed at 190 to 230 ° C. for 3 hours. Subsequently, after heating up to 250 degreeC, it superposed | polymerized for 20 minutes under reduced pressure, and polyester diol A1 which is (a) component was obtained. The composition, number average molecular weight, and acid value of the obtained polyester diol A1 are shown in Table 1.

(Polymerization of copolymer polyester urethane resin U-1)
In a 1 L four-necked flask equipped with a thermometer, a stirring blade, and a condenser, 100 parts by mass of polyester diol A1 obtained in Synthesis Example-1 as a component (a), 45 parts by mass of methyl ethyl ketone, and 55 parts of toluene. A mass part was charged and dissolved uniformly at 70 ° C. Next, as a component (c), 32 parts by mass of diphenylmethane diisocyanate was added, reacted at 70 ° C. for 1 hour, and diluted with 50 parts by mass of methyl ethyl ketone and toluene, respectively. As component (b), 67 parts by mass of “New Pole PP-1200” (polypropylene glycol, number average molecular weight: 1200) manufactured by Sanyo Chemical Industries, Ltd. was added, and after 30 minutes at 70 ° C., 0.02 parts by mass of dibutyltin laurate Was added and reacted at 70 ° C. for an additional 2 hours. Next, dilute each with 76 parts by mass of methyl ethyl ketone and toluene, and after adding 3 parts by mass of neopentyl glycol as component (d) and react for another 2 hours, dilute with 60 parts by mass of methyl ethyl ketone and toluene to complete the reaction. (Solid content concentration 30% by mass). Table 2 summarizes the resin composition, number average molecular weight, and glass transition temperature of the obtained copolymer polyester urethane resin (U-1).

<Synthesis Example-2>
(Synthesis of polyester diol A2)
In a 2 L four-necked flask equipped with a thermometer, a stirring blade, and a Liebig condenser, 380 parts by mass of dimethyl terephthalate, 11.8 parts by mass of dimethyl sodium 5-sulfoisophthalate, 274 parts by mass of 1,2-propylene glycol, 42 parts by mass of neopentyl glycol and 0.2 parts by mass of tetrabutyl titanate (TBT) as a catalyst were charged, and the transesterification reaction was allowed to proceed at 190 to 230 ° C. for 3 hours. Next, after raising the temperature to 250 ° C., polymerization was carried out for 20 minutes under reduced pressure to obtain polyester diol A2 as component (a). Table 1 shows the composition, number average molecular weight, and acid value of the resulting polyester diol A2.

(Polymerization of copolymer polyester urethane resin U-2)
In a 1 L four-necked flask equipped with a thermometer, a stirring blade, and a condenser, as component (a), 100 parts by mass of polyester diol A2 obtained in Synthesis Example-2, 45 parts by mass of methyl ethyl ketone, and 55 parts of toluene as component (a). A mass part was charged and dissolved uniformly at 70 ° C. Next, as a component (c), 32 parts by mass of diphenylmethane diisocyanate was added, reacted at 70 ° C. for 1 hour, and diluted with 50 parts by mass of methyl ethyl ketone and toluene, respectively. As a component (b), 67 parts by mass of “New Pole PP-1200” (polypropylene glycol, number average molecular weight: 1200) manufactured by Sanyo Chemical Industries, Ltd. was added, and after 30 minutes at 70 ° C., 0.02 parts by mass of dibutyltin laurate Was added and reacted at 70 ° C. for an additional 2 hours. Next, dilute each with 76 parts by mass of methyl ethyl ketone and toluene, and after adding 3 parts by mass of neopentyl glycol as component (d) and react for another 2 hours, dilute with 60 parts by mass of methyl ethyl ketone and toluene to complete the reaction. (Solid content concentration 30% by mass). Table 2 shows the resin composition, number average molecular weight, and glass transition temperature of the obtained copolymerized polyester urethane resin (U-2).

<Synthesis Example-3>
(Polymerization of copolymer polyester urethane resin U-3)
In a 1 L four-necked flask equipped with a thermometer, a stirring blade, and a condenser, 100 parts by mass of polyester diol A1 obtained in Synthesis Example-1 as a component (a), 50 parts by mass of methyl ethyl ketone, and 50 parts of toluene. A mass part was charged and dissolved uniformly at 70 ° C. Next, as component (c), 29 parts by mass of diphenylmethane diisocyanate was added, reacted at 70 ° C. for 1 hour, and diluted with 50 parts by mass of methyl ethyl ketone and toluene, respectively. As component (b), 45 parts by mass of “New Pole PP-1200” (polypropylene glycol, number average molecular weight: 1200) manufactured by Sanyo Chemical Industries, Ltd. was added, and after 30 minutes at 70 ° C., 0.02 parts by mass of dibutyltin laurate Was added and reacted at 70 ° C. for an additional 2 hours. Next, after diluting each with 33 parts by mass of methyl ethyl ketone and toluene, and adding 3 parts by mass of neopentyl glycol as component (d) and reacting for another 2 hours, diluting with 74 parts by mass of methyl ethyl ketone and toluene respectively to complete the reaction (Solid content concentration 30% by mass). Table 2 summarizes the resin composition, number average molecular weight, and glass transition temperature of the obtained copolymer polyester urethane resin (U-3).

<Synthesis Example-4>
(Polymerization of copolymer polyester urethane resin U-4)
In a 1 L four-necked flask equipped with a thermometer, a stirring blade, and a condenser, 100 parts by mass of polyester diol A1 obtained in Synthesis Example-1 as a component (a), 50 parts by mass of methyl ethyl ketone, and 50 parts of toluene. A mass part was charged and dissolved uniformly at 70 ° C. Next, as a component (c), 38 parts by mass of diphenylmethane diisocyanate was added, reacted at 70 ° C. for 1 hour, and diluted with 50 parts by mass of methyl ethyl ketone and toluene, respectively. (B) As a component, 75 parts by mass of “PTMG1000” (polytetramethylene glycol, number average molecular weight: 1000) manufactured by Mitsubishi Chemical is added, and after 30 minutes at 70 ° C., 0.03 parts by mass of dibutyltin laurate is added. The mixture was further reacted at 70 ° C. for 2 hours. Next, dilute each with 62 parts by mass of methyl ethyl ketone and toluene, and after adding 3 parts by mass of neopentyl glycol as component (d) and further react for 2 hours, dilute with 90 parts by mass of methyl ethyl ketone and toluene to complete the reaction. (Solid content concentration 30% by mass). Table 2 shows the resin composition, number average molecular weight, and glass transition temperature of the obtained copolymerized polyester urethane resin (U-4).

<Synthesis Example-5>
(Polymerization of copolymerized polyester urethane resin U-5)
In a 1 L four-necked flask equipped with a thermometer, a stirring blade, and a condenser, 100 parts by mass of polyester diol A1 obtained in Synthesis Example-1 as a component (a), 50 parts by mass of methyl ethyl ketone, and 50 parts of toluene. A mass part was charged and dissolved uniformly at 70 ° C. Next, as component (c), 35 parts by mass of diphenylmethane diisocyanate was added and reacted for 1 hour at 70 ° C., and diluted with 50 parts by mass of methyl ethyl ketone and toluene, respectively. As component (b), 60 parts by mass of “New Pole PP-1200” (polypropylene glycol, number average molecular weight: 1200) manufactured by Sanyo Chemical Industries, Ltd. was added, and after 30 minutes at 70 ° C., 0.01 parts by mass of dibutyltin laurate Was added and reacted at 70 ° C. for an additional 2 hours. As component (d), 0.3 part by weight of neopentyl glycol was added and reacted for another 30 minutes, and then diluted with 50 parts by weight of methyl ethyl ketone and toluene, respectively, and further 5 parts of trimethylolpropane as component (d). Part was added. After 30 minutes at 70 ° C, 0.02 part by weight of dibutyltin laurate was added, and the reaction was further continued at 70 ° C for 2 hours. Subsequently, it diluted with 83 mass parts of methyl ethyl ketone and toluene, respectively, and reaction was complete | finished (solid content concentration 30 mass%). Table 2 summarizes the resin composition, number average molecular weight, and glass transition temperature of the obtained copolymer polyester urethane resin (U-5).

<Synthesis Example-6>
(Polymerization of copolymer polyester urethane resin U-6)
In a 2 L four-necked flask equipped with a thermometer, a stirring blade, and a condenser, as a component (a), 100 parts by mass of the polyester diol A1 obtained in Synthesis Example 1 as a component, “Polylite OD-X-688” manufactured by DIC. (Aliphatic polyester diol, number average molecular weight: 2000) 150 parts by mass, (d) 10 parts by mass of neopentyl glycol, 200 parts by mass of methyl ethyl ketone, and 200 parts by mass of toluene are charged and dissolved uniformly at 70 ° C. It was. Next, as component (c), 55 parts by mass of diphenylmethane diisocyanate was added and reacted for 1 hour at 70 ° C., 0.05 part by mass of butyltin laurate was added, and the mixture was further reacted at 70 ° C. for 3 hours. Subsequently, it diluted with 168 mass parts of methyl ethyl ketone and toluene, respectively, and reaction was complete | finished (solid content concentration 30 mass%). Table 2 shows the resin composition, number average molecular weight, and glass transition temperature of the obtained copolymer polyester urethane resin (U-6).

<Synthesis Example-7>
(Polymerization of copolymer polyester urethane resin U-7)
In a 1 L four-necked flask equipped with a thermometer, a stirring blade, and a condenser, 100 parts by mass of polyester diol A2 obtained in Synthesis Example-2, 50 parts by mass of methyl ethyl ketone, and 50 parts of toluene as component (a). A mass part was charged and dissolved uniformly at 70 ° C. Next, as a component (c), 27 parts by mass of diphenylmethane diisocyanate was added, reacted at 70 ° C. for 1 hour, and diluted with 50 parts by mass of methyl ethyl ketone and toluene, respectively. (B) As a component, 30 parts by mass of “New Pole PP-1200” (polypropylene glycol, number average molecular weight: 1200) manufactured by Sanyo Chemical Industries, Ltd. was added, and after 30 minutes at 70 ° C., 0.01 parts by mass of dibutyltin laurate Was added and reacted at 70 ° C. for an additional 2 hours. Next, the mixture was diluted with 20 parts by mass of methyl ethyl ketone and toluene, respectively, and 3 parts by mass of neopentyl glycol was added as component (d), followed by further reaction for 2 hours, and then diluted with 67 parts by mass of methyl ethyl ketone and toluene to complete the reaction. (Solid content concentration 30% by mass). Table 2 summarizes the resin composition, number average molecular weight, and glass transition temperature of the obtained copolymer polyester urethane resin (U-7).

<Synthesis Example-8>
(Polymerization of copolymerized polyester urethane resin U-8)
In a 1 L four-necked flask equipped with a thermometer, a stirring blade, and a condenser, 100 parts by mass of polyester diol A1 obtained in Synthesis Example-1 as a component (a), 50 parts by mass of methyl ethyl ketone, and 50 parts of toluene. A mass part was charged and dissolved uniformly at 70 ° C. Next, as component (c), 42 parts by mass of diphenylmethane diisocyanate was added, reacted at 70 ° C. for 1 hour, and diluted with 50 parts by mass of methyl ethyl ketone and toluene, respectively. (B) As a component, 90 parts by mass of “PTMG1000” (polytetramethylene glycol, number average molecular weight: 1000) manufactured by Mitsubishi Chemical is added, and after 30 minutes at 70 ° C., 0.01 parts by mass of dibutyltin laurate is added. And further reacted at 70 ° C. for 2 hours. Next, after diluting each with 76 parts by mass of methyl ethyl ketone and toluene, adding 3 parts by mass of neopentyl glycol as component (d) and further reacting for 2 hours, diluting with 98 parts by mass of methyl ethyl ketone and toluene respectively to complete the reaction (Solid content concentration 30% by mass). Table 2 shows the resin composition, number average molecular weight, and glass transition temperature of the obtained copolymer polyester urethane resin (U-8).

<Synthesis Example-9>
(Synthesis of polyester diol A3)
In a 2 L four-necked flask equipped with a thermometer, a stirring blade, and a Liebig condenser, 262 parts by mass of dimethyl terephthalate, 262 parts by mass of dimethyl isophthalate, 187 parts by mass of neopentyl glycol, 261 parts by mass of ethylene glycol, and a catalyst 0.3 parts by mass of tetrabutyl titanate (TBT) was charged, and the transesterification reaction was allowed to proceed at 190 to 230 ° C. for 3 hours. Next, the reaction system was cooled to 180 ° C., and 60.6 parts by mass of sebacic acid was added. After raising the reaction temperature to 250 ° C. in about 1 hour, polymerization was carried out for 20 minutes under reduced pressure to obtain polyester diol A3 as component (a). Table 1 shows the composition, number average molecular weight, and acid value of the resulting polyester diol A3.

(Polymerization of copolymer polyester urethane resin U-9)
A 1 L four-necked flask equipped with a thermometer, stirring blade and condenser was charged with 100 parts by mass of polyester diol A3, 50 parts by mass of methyl ethyl ketone, and 50 parts by mass of toluene as component (a), and uniformly at 70 ° C. Dissolved in. Next, as component (c), 20 parts by mass of diphenylmethane diisocyanate and 0.01 parts by mass of dibutyltin laurate were added, reacted at 70 ° C. for 2 hours, and diluted with 50 parts by mass of methyl ethyl ketone and toluene, respectively. Next, 4 parts by mass of neopentyl glycol was added as a component (d), and the mixture was further reacted for 2 hours, and then diluted with 45 parts by mass of methyl ethyl ketone and toluene, respectively, to complete the reaction (solid content concentration 30% by mass). Table 2 shows the resin composition, number average molecular weight, and glass transition temperature of the obtained copolymer polyester urethane resin (U-9).

Example 1
Copolymerized polyester urethane resin U-1 obtained in Synthesis Example-1 100 parts by mass, isocyanate compound [trade name “Coronate L, solid content concentration 75% by mass” manufactured by Nippon Polyurethane Co., Ltd.] as a crosslinking agent 3 parts by mass 145 parts by weight of toluene and 15 parts by weight of cyclohexane as a solvent were mixed and stirred to obtain an anchor coating composition for an energy ray curable pressure-sensitive adhesive.

  The thickness after drying the anchor coating agent composition obtained above on a PET film having a thickness of 50 μm as a base film [trade name “Lumirror PET50 T-60” manufactured by Toray Industries, Inc.] by a gravure roll method. It was applied so as to have a thickness of 2 μm, and dried at 80 ° C. for 1 minute to form an energy ray-curable pressure-sensitive adhesive anchor coat layer, thereby producing an energy ray-curable pressure-sensitive adhesive coat film. Table 4 shows the performance evaluation of the coated film.

  Further, acrylic pressure-sensitive adhesive (copolymer of n-butyl acrylate and acrylic acid (n-butyl acrylate / acrylic acid = 90/10 (mass ratio), weight average molecular weight = 600,000, glass transition temperature = −44 ° C)) 100 parts by mass, 200 parts by mass of a urethane acrylate oligomer having a molecular weight of 7000, 10 parts by mass of a crosslinking agent (isocyanate type), and 10 parts by mass of an energy ray curing reaction initiator (benzophenone type). A wire curable pressure-sensitive adhesive composition was prepared.

  Next, the energy beam curable pressure-sensitive adhesive composition is applied to the anchor coat layer surface of the coat film and dried (90 ° C., 1 minute) to form an energy beam curable pressure-sensitive adhesive layer. Obtained. Table 4 shows the performance evaluation of the pressure-sensitive adhesive sheet.

(Examples 2 to 13 and Comparative Examples 1 to 4)
Copolymerized polyester urethane resin, amorphous polyester resin [manufactured by Toyobo Co., Ltd., trade name “Byron 200”, solid content concentration 100% by mass] and the composition and composition of the crosslinking agent were changed according to Table 3, A coated film and a pressure-sensitive adhesive sheet for processing a semiconductor wafer were prepared in the same manner as in Example 1 except that the thickness of the coat layer was changed according to Table 4, and performance evaluation was performed. In addition, about what added the amorphous polyester resin, when mixing and stirring an amorphous polyester resin, polyester urethane resin, a crosslinking agent, and a solvent in Example 1, the mass part of Table 3 is mentioned for a solvent. Was dissolved and added. The results are shown in Table 4.

(Comparative Example 5)
A 50 μm-thick PET film [trade name “Lumirror PET50 T-60” manufactured by Toray Industries, Inc.] was used as the base film, and no anchor coat layer was formed. Table 4 shows the performance evaluation of the base film. The hardness at a depth of 1.0 μm from the surface layer of the base film is 0.289 GPa, the hardness at a depth of 0.05 μm from the surface layer of the base film is 0.253 GPa, and the hardness from the surface layer of the base film is 3.5 μm. The hardness was 0.283 GPa. Table 4 does not describe these hardnesses. Moreover, since the anchor coat layer is not provided, the evaluation of the remaining anchor coat layer is not described.

  As can be seen from Table 4, all of the coated films of Examples 1 to 13 have good anti-blocking properties and evaluation of the adhesion between the energy ray-curable pressure-sensitive adhesive and the anchor coat layer. On the other hand, in the coated films of Comparative Examples 1 to 5, any one of blocking resistance, haze, energy beam curable pressure-sensitive adhesive and anchor coat layer adhesion is poor.

DESCRIPTION OF SYMBOLS 1 ... Energy-beam curable adhesive layer 2 ... Anchor coat layer 3 ... Base film 5 ... Ring frame 10 ... Adhesive sheet 11 for semiconductor wafer processing ... Semiconductor wafer 12 ... Circuit 20 ... Grinder 30 ... Dicing blade

Claims (7)

An acid component containing 80 mol% or more of an aromatic dicarboxylic acid component when the total acid component is 100 mol%, and a glycol component containing 40 mol% or more of an aliphatic glycol component when the total glycol component is 100 mol% A polyester diol (a) having a number average molecular weight of 1500 to 3000,
A polyalkylene ether glycol (b) having a number average molecular weight of 1000 to 3000, and a polyvalent isocyanate compound (c),
It comprises a structure obtained by a polycondensation reaction of (a), and contains 100 parts by mass of the component (a), contains 40 to 80 parts by mass of the component (b), and 20 to 50 parts by mass of the component (c). An anchor coating composition for an energy ray-curable pressure-sensitive adhesive comprising a copolyester urethane resin having a molecular weight of 10,000 to 100,000.   The anchor coating agent composition according to claim 1, comprising an amorphous polyester resin in a proportion of 100 parts by mass or less with respect to 100 parts by mass of the copolymerized polyester urethane resin.   Furthermore, the anchor coating agent composition of Claim 2 which contains a crosslinking agent in the ratio of 0.1-30 mass parts with respect to 100 mass parts of total amounts of the said copolyester urethane resin and the said amorphous polyester resin. object. A coating film for an energy ray curable pressure-sensitive adhesive in which an anchor coat layer is provided on one side of a base film,
A coat film for an energy ray-curable pressure-sensitive adhesive, wherein the anchor coat layer is formed of the anchor coat agent composition according to claim 1.   A base film in which the hardness A measured by a nanoindentation test at a depth (depth (X)) ½ of the anchor coat layer thickness from the surface layer of the anchor coat layer is measured in the same manner as described above. The coated film according to claim 4, which is lower than the hardness B at the depth (X) from the surface layer of the film and the difference between the hardness A and the hardness B is 0.35 GPa or less.   The coated film according to claim 4 or 5, wherein the anchor coat layer has a thickness of 0.1 to 7 µm.   A pressure-sensitive adhesive sheet for processing a semiconductor wafer, wherein an energy ray-curable pressure-sensitive adhesive layer is formed on the anchor coat layer of the coat film according to claim 4.

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