JP2022056985A - Resin composition for semiconductor manufacturing process and film - Google Patents

Abstract

To provide a resin composition for a semiconductor manufacturing process which enables formation of a film that has low water absorption, has a small coefficient of linear expansion, and is excellent in dimension stability.SOLUTION: A resin composition for a semiconductor manufacturing process contains a resin and a filler, in which a water absorption rate of a film composed of the resin composition is 2.2% or less, and a coefficient of linear expansion of the film is 42×10-6/°C or less.SELECTED DRAWING: None

Description

The present invention relates to a resin composition that can be used in a process of manufacturing a semiconductor and a film comprising the resin composition.

A method for manufacturing a semiconductor device generally includes a grinding step for adjusting the thickness of the wafer and a cutting step for cutting the wafer along a dividing line in order to obtain individual dies.
The grinding step is performed from the front surface of the wafer on which the device region is formed, that is, the back surface of the wafer opposite the element forming surface.
At this time, a protective film may be attached to the wafer surface before processing to protect the device formed on the wafer from contamination by, for example, cracking, deformation and / or debris, wafer grinding water or wafer cutting water. It is done.

Further, in order to prevent the encapsulant from wrapping around to the back surface of the lead frame opposite to the semiconductor element during the encapsulation molding for forming the encapsulation layer for manufacturing the semiconductor package, a protective film is formed on the back surface of the lead frame. It may be temporarily protected by pasting.

As described above, in the semiconductor manufacturing process, tapes and films are used to protect wafers, devices and the like. In the present invention, such tapes and films are collectively referred to as "films for semiconductor manufacturing processes".

Regarding this type of film for a semiconductor manufacturing process, for example, in Patent Document 1, it is a flip-chip type semiconductor back surface film disposed on the back surface of a semiconductor element connected to a flip-chip on an adherend, and is an adhesive layer. And a protective layer laminated on the adhesive layer, the protective layer being at least one selected from the group consisting of polyimide, polyphenylene sulfide, polysulfone, polyetherimide, polyetherketone and polyetheretherketone. Those formed from a heat-resistant resin, which is a seed, are disclosed.

Patent Document 2 discloses an adhesive tape having a base material made of special polyester, polyetheretherketone, polyamide or polyimide and an adhesive layer with respect to the adhesive tape which is attached to a semiconductor wafer to form a laminate.

Paragraph 0014 of Patent Document 3 describes two layers of a base material composed of a main component such as polyester or polyolefin having a thickness of about 0.1 to 0.3 mm and an adhesive material containing an acrylic polymer as a main component and a cross-linking material added. A protective tape consisting of a structure is disclosed.

Patent Document 4 includes a support film and a pressure-sensitive adhesive layer provided on one or both sides of the support film. The support film is a polyimide film, and the thickness of the pressure-sensitive adhesive layer is less than 8 μm. A temporary protective film has been disclosed.

Japanese Unexamined Patent Publication No. 2012-33626 Japanese Unexamined Patent Publication No. 2018-27011 Japanese Unexamined Patent Publication No. 2020-136383 Japanese Patent No. 6744004

When the film for the semiconductor manufacturing process is made of thermosetting polyimide, it has a high water absorption rate and may cause dimensional change due to moisture absorption during heating, so it is necessary to insert a dehydration process.
On the other hand, when the film for the semiconductor manufacturing process is made of a thermoplastic resin such as polyetheretherketone (PEEK) or polyethylene naphthalate, the linear expansion coefficient is large, so that when the temperature is repeatedly raised and lowered, for example, a semiconductor wafer. In the case of polishing the wafer by laminating the glass substrate with the glass substrate via the film, problems such as peeling of the film from the glass and poor dimensional stability may occur.

Therefore, the present invention relates to a resin composition for a semiconductor manufacturing process, and is a new resin composition capable of forming a film for a semiconductor manufacturing process having low water absorption, a small linear expansion coefficient, and excellent dimensional stability. Is intended to be provided.

The present invention is a resin composition for a semiconductor manufacturing process containing a resin and a filler, wherein the water absorption rate and the linear expansion coefficient of the film made of the resin composition are within a specific range. We found that we could solve the problem and came up with the present invention. That is, the present invention provides the following [1] to [13].

[1] A resin composition for a semiconductor manufacturing process containing a resin and a filler, the water absorption rate of the film made of the resin composition is 2.2% or less, and the linear expansion coefficient of the film is 42 × 10. A resin composition for a semiconductor manufacturing process, characterized by having a temperature of ^-6 / ° C. or lower.
[2] The semiconductor manufacturing process according to [1], wherein the filler contains a scaly filler, a plate-like filler, a flaky filler, or a mixture of two or more of these as a main component filler. Resin composition for.
[3] The resin composition for a semiconductor manufacturing process according to [1] or [2], wherein the filler has an average aspect ratio of 10 or more.
[4] The resin composition for a semiconductor manufacturing process according to any one of [1] to [3], wherein the filler has an average maximum diameter of 30 μm or less.
[5] The resin composition for a semiconductor manufacturing process according to any one of [1] to [4], wherein the filler has an average thickness of 1 μm or less.
[6] The resin composition for a semiconductor manufacturing process according to any one of [1] to [5], wherein the filler contains mica as a main component filler.
[7] The resin for a semiconductor manufacturing process according to any one of [1] to [6], wherein the resin contains a crystalline resin having a crystal melting temperature (Tm) of 250 ° C. or higher as a main component resin. Composition.
[8] The resin for the semiconductor manufacturing process according to any one of [1] to [6], wherein the resin contains an amorphous resin having a glass transition temperature (Tg) of 200 ° C. or higher as a main component resin. Resin composition.
[9] The resin composition for a semiconductor manufacturing process according to any one of [1] to [8], wherein the resin contains a polyaryletherketone as a main component resin.
[10] The resin for a semiconductor manufacturing process according to any one of [1] to [9], wherein the content of the filler is 5 parts by mass or more with respect to 100 parts by mass of the total content of the resin and the filler. Composition.
[11] The resin composition for a semiconductor manufacturing process according to any one of [1] to [10], which is used for wafer polishing.
[12] A film comprising the resin composition for a semiconductor manufacturing process according to any one of [1] to [11].
[13] The film according to [12], wherein the relative crystallinity of the film is 60% or more.

According to the resin composition for a semiconductor manufacturing process proposed by the present invention, since a film or the like having a sufficiently low water absorption rate can be formed, dimensional changes due to moisture absorption are unlikely to occur during heating, for example, and the dehydration step can be omitted. .. Further, since the coefficient of linear expansion of the film or the like can be sufficiently reduced, peeling or deformation can be suppressed even if high and low temperatures are repeated in a state of being bonded to glass, for example.

Next, an example of the embodiment of the present invention will be described. However, the present invention is not limited to the embodiments described below.

<This resin composition>
The resin composition according to an example of the present invention (referred to as "the present resin composition") is a resin composition containing at least a resin and a filler.

(resin)
The main component resin of the present resin composition may be a crystalline resin or an amorphous resin. Above all, the crystalline resin is preferable from the viewpoint of easily maintaining the elastic modulus from the glass transition temperature (Tg) to the melting point, that is, the crystal melting temperature (Tm) and maintaining the dimensional stability.

The "main component resin" means the resin having the largest mass content among the resins constituting the present resin composition, and is preferably 50% by mass or more of the resin constituting the present resin composition. It is a resin that accounts for 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, and 95% by mass or more (including 100% by mass).

From the viewpoint of enhancing heat resistance, the main component resin of the present resin composition is preferably a crystalline resin having a crystal melting temperature (Tm) of 250 ° C. or higher, and above all, a crystal melting temperature (Tm) of 270 ° C. or higher. Among them, a crystalline resin having a temperature of 290 ° C. or higher, particularly 300 ° C. or higher is particularly preferable.
However, from the viewpoint of film forming property and processability, the crystal melting temperature (Tm) is preferably 400 ° C. or lower, more preferably 380 ° C. or lower, and further preferably 370 ° C. or lower, 360 ° C. or lower. It is particularly preferable to have it.

The crystalline resin is preferably a thermoplastic resin. For example, polyetheretherketone, polyaryletherketone such as polyetherketoneketone, polyphenylene sulfide, polyimide, liquid crystal polymer, fluororesin, polymethylpentene, aliphatic polyamide, polyamide such as semi-aromatic polyamide, polyethylene terephthalate, polybutylene terephthalate. , Polyester naphthalate, polycyclohexanedimethylene terephthalate and other polyesters, polypropylene, polyacetal, crystalline polystyrene and the like can be mentioned. These may be used alone or in combination of two or more. Among them, polyaryletherketone is preferable because it is excellent in heat resistance, mechanical properties, chemical resistance and the like.

A polyaryl etherketone is a homopolymer or copolymer containing a monomer unit containing one or more aryl groups, one or more ether groups, and one or more ketone groups. For example, polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyetherketone (PEK), polyetherketone etherketoneketone (PEKEKK), polyetheretherketoneketone (PEEKK), polyetherdiphenyletherketone (PEDEK). ) And the like, and these copolymers (for example, PEEK-PEDEK copolymer) can be mentioned. Among them, polyetheretherketone (PEEK) is particularly preferable because it is excellent in heat resistance, mechanical properties, chemical resistance and the like.

When polyetheretherketone is contained as the main component resin of the present resin composition, the content ratio of the polyetheretherketone in the resin constituting the present resin composition is preferably 50% by mass or more, preferably 60% by mass or more. It is more preferably 70% by mass or more, particularly preferably 80% by mass or more, and most preferably 90% by mass or more. As long as the content ratio of the polyetheretherketone is within such a range, even when a resin other than the polyetheretherketone is contained, it becomes easy to appropriately impart a necessary effect while maintaining the effect of the present invention.

Further, when the other resin is blended for the purpose of modifying the polyetheretherketone, the type thereof is not particularly limited. Among them, from the viewpoint that the molding temperature is close to that of polyetheretherketone and it is easy to suppress decomposition and cross-linking during melt molding, the other resins include, for example, polyphenylene sulfide, polyarylate, polyetherimide, polyetherketone, and poly. Etherketone ketone, polyetherketone etherketoneketone, polyetheretherketoneketone, polyamideimide, polysalphon, polyethersalphon, liquid crystal polymer and the like can be preferably used. These may be used alone or in combination of two or more. Among these, polyetherimide can be particularly preferably used. Since polyetheretherketone and polyetherimide are highly compatible and easy to mix at the molecular level, the polyetherimide can be used to improve the glass transition temperature of polyetheretherketone while maintaining the crystallinity of the resin composition. It becomes easy to impart the property.

[Polyetheretherketone (PEEK)]
The polyether ether ketone may be a resin having at least two ether groups and a ketone group as structural units. Above all, since it is excellent in thermal stability, melt moldability, rigidity, chemical resistance, impact resistance, and durability, it preferably has a repeating unit represented by the following general formula (1).

(General formula (1))

In the general formula (1), the arylene groups of Ar ¹ to Ar ³ may be different from each other, but are preferably the same. Examples of the arylene group of Ar ¹ to Ar ³ include a phenylene group and a biphenylene group. Of these, a phenylene group is preferable, and a p-phenylene group is more preferable.

Examples of the substituent that the arylene group of Ar ¹ to Ar ³ may have include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and a carbon atom number such as a methoxy group and an ethoxy group. Examples thereof include 1 to 20 alkoxy groups. When Ar ¹ to Ar ³ have substituents, the number of the substituents is not particularly limited.

Among them, polyetheretherketone having a repeating unit represented by the following structural formula (2) is preferable from the viewpoint of thermal stability, melt moldability, rigidity, chemical resistance, impact resistance, and durability.

(Structural formula (2))

The molecular weight distribution of the polyetheretherketone is preferably 3.3 or more, more preferably 3.5 or more, further preferably 3.6 or more, and particularly preferably 3.8 or more. It is preferably 4 or more, and most preferably 4 or more. When the molecular weight distribution is equal to or higher than the above value, a sufficient amount of low molecular weight components are contained, so that the crystallinity and crystallization rate can be increased, which in turn tends to lead to improvement in heat resistance, rigidity, and productivity. ..
On the other hand, the molecular weight distribution of the polyetheretherketone is preferably 8 or less, more preferably 7 or less, further preferably 6.5 or less, and particularly preferably 6 or less. Most preferably: When the upper limit of the molecular weight distribution of the polyetheretherketone is not more than the above-mentioned numerical value, the ratio of the high molecular weight component and the low molecular weight component is not too large, so that the balance between the crystallinity, the fluidity and the mechanical properties tends to be excellent. The molecular weight distribution is obtained by dividing the mass average molecular weight by the number average molecular weight.

The mass average molecular weight of the polyetheretherketone is preferably 87,000 or less, more preferably 83,000 or less, further preferably 80,000 or less, and particularly preferably 75,000 or less. When the mass average molecular weight of the polyetheretherketone is not more than the above-mentioned numerical value, the crystallinity, the crystallization rate, and the fluidity at the time of melt molding tend to be excellent.
On the other hand, the mass average molecular weight is preferably 10,000 or more, more preferably 30,000 or more, further preferably 40,000 or more, particularly preferably 50,000 or more, and most preferably 55,000 or more. preferable. When the mass average molecular weight is equal to or higher than the above value, the mechanical properties such as durability and impact resistance tend to be excellent.

The mass average molecular weight and the number average molecular weight in the present invention can be obtained by measuring using gel permeation chromatography.

The crystal melting temperature (Tm) of the polyetheretherketone is preferably 320 ° C. or higher, more preferably 330 ° C. or higher, further preferably 335 ° C. or higher, and more preferably 340 ° C. or higher. Especially preferable. When the crystal solution temperature of the polyetheretherketone is equal to or higher than the above temperature, the heat resistance tends to be excellent.
On the other hand, the crystal melting temperature is preferably 370 ° C. or lower, more preferably 365 ° C. or lower, further preferably 360 ° C. or lower, particularly preferably 355 ° C. or lower, and 350 ° C. or lower. Is most preferable. When the crystal melting temperature of the polyetheretherketone is equal to or lower than the above temperature, the fluidity tends to be excellent at the time of melt molding such as at the time of film production.

The crystal melting temperature in the present invention is raised to a temperature range of 23 to 400 ° C. at a rate of 10 ° C./min using a differential scanning calorimeter (for example, Pyris1 DSC manufactured by PerkinElmer) according to JIS K7121: 2012. It can be obtained from the peak top temperature of the melting peak of the DSC curve detected when the temperature is lowered to 23 ° C. at a rate of 10 ° C./min and then raised again to 400 ° C. at a rate of 10 ° C./min.

The calorific value for crystal melting of the polyetheretherketone is preferably 42 J / g or more, more preferably 44 J / g or more, further preferably 46 J / g or more, and more preferably 48 J / g or more. It is particularly preferable, and most preferably 50 J / g or more. When the amount of heat of crystal melting of the polyetheretherketone is equal to or higher than the above value, the molded product such as a film obtained from the present resin composition has a sufficient crystallinity, and thus tends to be excellent in heat resistance and rigidity.
On the other hand, the heat of crystal melting of the polyetheretherketone is preferably 60 J / g or less, more preferably 58 J / g or less, further preferably 56 J / g or less, and 54 J / g or less. Is particularly preferable. If the amount of heat of crystal melting of the polyetheretherketone is equal to or less than the above value, the crystallinity is not too high, and therefore the melt moldability when molding the present resin composition tends to be excellent. It tends to have excellent durability and impact resistance.

The amount of heat of crystal melting in the present invention is increased to a temperature range of 23 to 400 ° C. at a rate of 10 ° C./min using a differential scanning calorimeter (for example, Pyris1 DSC manufactured by PerkinElmer) according to JIS K7122: 2012. It can be obtained from the area of the melting peak of the DSC curve detected when the temperature is lowered to 23 ° C. at a rate of 10 ° C./min and then raised again to 400 ° C. at a rate of 10 ° C./min.

The crystallization temperature (Tc) in the temperature lowering process of the polyetheretherketone is preferably 296 ° C. or higher, more preferably 300 ° C. or higher, further preferably 302 ° C. or higher, and more preferably 303 ° C. or higher. Is particularly preferable, and the temperature is most preferably 304 ° C. or higher. When the crystallization temperature in the temperature lowering process of the polyetheretherketone is higher than the above temperature, the crystallization rate is high, and the productivity when molding the present resin composition into a molded product such as a film tends to be excellent. Specifically, for example, in the case of producing a film, the resin is in contact with the cast roll by setting the temperature (cooling temperature) of the cast roll to a temperature equal to or higher than the glass transition temperature and lower than the crystal melting temperature. During that time, crystallization is promoted and a crystallized film is obtained. When the crystallization temperature in the temperature lowering process is higher than the above temperature, the crystallization rate is high and the crystallization can be completed with the cast roll, so that the elastic modulus is high, and as a result, sticking to the roll is suppressed. The appearance of the film tends to improve.

On the other hand, the crystallization temperature in the temperature lowering process is preferably 320 ° C. or lower, more preferably 315 ° C. or lower, further preferably 312 ° C. or lower, and particularly preferably 310 ° C. or lower. If the crystallization temperature in the temperature lowering process of the polyether ether ketone is lower than the above temperature, the crystallization is not too fast, so that the cooling unevenness when producing a molded product such as a film is reduced, and the crystallization is uniformly crystallized. It becomes easy to obtain high-quality molded products with excellent dimensional stability.

The crystallization temperature in the temperature lowering process in the present invention is a speed of 10 ° C./ Obtained from the peak top temperature of the crystallization peak of the DSC curve detected when the temperature is raised in minutes, the temperature is lowered to 23 ° C at a rate of 10 ° C / min, and the temperature is raised again to 400 ° C at a rate of 10 ° C / min. Can be done.

On the other hand, the main component resin of the present resin composition may be an amorphous resin.
Examples of the amorphous resin include cyclic olefin resins, amorphous polystyrenes such as atactic polystyrene, polycarbonates, acrylic resins, amorphous polyesters, polysulfones, polyethersulfones, polyetherimide sulfones, polyetherimides, and heat. Examples include plastic polyimide.

When the main component resin of this resin composition is an amorphous resin, the elastic modulus may drop and a dimensional change may occur when the temperature becomes higher than the glass transition temperature. Therefore, the glass transition temperature (Tg) is heat resistant. From the viewpoint of enhancing the properties, the temperature is preferably 200 ° C. or higher, particularly preferably 220 ° C. or higher, particularly 230 ° C. or higher, and particularly preferably 240 ° C. or higher.
However, from the viewpoint of film forming property and processability, the glass transition temperature (Tg) is preferably 300 ° C. or lower, particularly preferably 280 ° C. or lower, and more preferably 270 ° C. or lower, 260 ° C. or lower. Is particularly preferable.

The glass transition temperature in the present invention is raised to a temperature range of 23 to 400 ° C. at a speed of 10 ° C./min using a differential scanning calorimeter (for example, Pyris1 DSC manufactured by PerkinElmer) according to JIS K7121: 2012. It can be obtained from the DSC curve detected when the temperature is lowered to 23 ° C. at a rate of 10 ° C./min and then raised again to 400 ° C. at a rate of 10 ° C./min.

(Filler)
The filler is not particularly limited and may be an organic filler or an inorganic filler.
Examples of the filler include inorganic fillers such as clay, glass, alumina, silica, aluminum nitride and silicon nitride, fibers such as glass fiber, aramid fiber, carbon fiber and potassium titanate fiber, scaly, plate-like or Filamentous, preferably inorganic scaly, plate or flaky powders such as (synthetic) mica, natural mica, boehmite, talc, sericite, illite, kaolinite, montmorillonite, vermiculite, smectite, plate. Alumina, scaly titanate (for example, scaly magnesium potassium titanate, scaly lithium potassium titanate, etc.) and the like can be mentioned.

Among them, mica is preferable as the main component filler because of its excellent mechanical strength, heat resistance, film forming property, and low coefficient of linear expansion.
At this time, the main component filler means the type of filler having the largest content mass among the types constituting the filler, preferably 50% by mass or more, particularly 60% by mass or more of the filler. Among them, it accounts for 70% by mass or more, 80% by mass or more, 90% by mass or more, and 95% by mass or more (including 100% by mass). The same applies to other main component fillers.

The filler has less anisotropy, can further suppress dimensional changes in molded products such as films, and is excellent in film-forming properties of films, particularly thin film films. A plate-shaped filler, a flaky filler, or a mixture of two or more of these is preferably used as the main component filler.

Therefore, as the main component filler, for example, scaly or flaky mica, plate-shaped or flaky titanium dioxide, potassium titanate, lithium titanate, boehmite, γ-alumina, α-alumina and the like are preferably used. Of these, scaly or flaky mica is particularly preferred.

From the same viewpoint, that is, from the viewpoint of further suppressing the dimensional change of the molded product such as a film, the average aspect ratio (maximum diameter / thickness average value) of the filler is preferably 10 or more, particularly 20 Above, among them, 25 or more is more preferable, and 30 or more is particularly preferable. On the other hand, from the viewpoint of anisotropy, it is preferably 100 or less, more preferably 80 or less, still more preferably 60 or less, and particularly preferably 50 or less.
The average aspect ratio of the filler means the average aspect ratio of the plurality of filler particles, and specifically, it can be calculated from the measurement results of the maximum diameter and the thickness of each filler particle described later. can.

The average maximum diameter of the filler is preferably 30 μm or less, more preferably 20 μm or less, still more preferably 15 μm or less, and particularly preferably 10 μm or less, from the viewpoint of film forming property and mechanical properties. On the other hand, from the viewpoint of dimensional stability such as the coefficient of linear expansion, it is preferably 1 μm or more, more preferably 1.5 μm or more, particularly preferably 2 μm or more, and particularly preferably 3 μm or more. It is particularly preferable that the thickness is 5.5 μm or more.
The average maximum diameter of the filler means the average length of the portion observed with the longest length when each filler particle is observed using an electron microscope such as a scanning electron microscope. Specifically, observation was performed on a cross section perpendicular to the flow direction of the resin composition of the molded product made of the present resin composition, and 30 filler particles were selected from the longest ones, and the length was the longest. It can be obtained by measuring and averaging the lengths of the parts that are observed for a long time.

From the viewpoint of film-forming property, the average thickness of the filler is preferably 1 μm or less, more preferably 0.8 μm or less, still more preferably 0.6 μm or less, and more preferably 0.4 μm or less. Especially preferable. On the other hand, from the viewpoint of the strength of the filler, it is preferably 0.01 μm or more, more preferably 0.03 μm or more, still more preferably 0.06 μm or more, and particularly preferably 0.08 μm or more. , 0.1 μm or more is particularly preferable.
The average thickness of the filler means the average length of the portion observed with the shortest length when each filler particle is observed using an electron microscope such as a scanning electron microscope. Specifically, observation is performed on a cross section perpendicular to the flow direction of the resin composition of the molded product made of the present resin composition, 30 filler particles are arbitrarily selected, and the shortest length is observed. It can be obtained by measuring the length of the portion and averaging it.

The filler may be surface-treated with a surface-treating agent such as a coupling agent.
By surface-treating with a surface-treating agent such as a coupling agent, mechanical strength and heat resistance can be further increased, deterioration of the resin can be reduced, and moldability can be improved.
The surface treatment agent such as a coupling agent is not particularly limited, and general coupling agents such as silane-based, titanate-based, and aluminate-based can be used.
As the surface treatment method, a dry type or a wet surface treatment method can be used, and a wet surface treatment method is particularly desirable.

(composition)
In the present resin composition, the content of the filler is preferably 5 parts by mass or more with respect to 100 parts by mass in total of the contents of the resin and the filler from the viewpoint of reducing the linear expansion coefficient. Among them, 8 parts by mass or more, particularly preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and particularly preferably 17 parts by mass or more.
On the other hand, from the viewpoint of toughness and film-forming property, the content of the filler is preferably 40 parts by mass or less, more preferably 35 parts by mass or less, and more preferably 30 parts by mass or less, and 25 parts by mass. It is more preferably parts or less, and particularly preferably 23 parts by mass or less.

The present resin composition may also contain the resin and other materials other than the filler.
Examples of the other materials include general resin additives such as heat stabilizers, lubricants, mold release agents, pigments, dyes, ultraviolet absorbers, flame retardants, lubricants, fillers, and reinforcing agents. can. One of them or two or more of them can be contained.

(Production method)
The present resin composition can be produced by a known production method.
As a specific example of the method for producing the present resin composition, a method of dry-blending the resin, the filler and other components added as needed in a batch and then melt-kneading with a twin-screw kneader or the like is exemplified. can do.
In melt kneading, the filler can be supplied from the side feeder in the middle of the extruder without dry blending.
In addition, a masterbatch containing a resin and a filler is manufactured in advance, and the masterbatch, the remaining resin, and other components added as necessary are dry-blended and melt-kneaded by a twin-screw extruder or the like. The method is also preferred. However, the present invention is not limited to such a manufacturing method.
A single-screw extruder, a conider, a multi-screw screw extruder, or the like can also be used for kneading. Thereby, for example, a pellet-shaped resin composition can be obtained.

<Characteristics of this resin composition>
The present resin composition can have the following characteristics.

(Linear expansion coefficient)
A film made of the present resin composition, specifically, an unstretched film having a thickness of 10 to 500 μm, which is obtained by melt-kneading the resin composition at a temperature 100 to 250 ° C. higher than the glass transition temperature and extruding the resin composition. The linear expansion coefficient can be 42 or less, preferably 40 or less, more preferably 37 or less, still more preferably 34 or less, particularly preferably 31 or less, and particularly preferably 28 or less.
The linear expansion coefficient is an average value of the linear expansion coefficients measured in each of the resin flow direction (MD) of the film and the direction orthogonal to the resin flow direction (MD), and can be measured by the method in Examples described later.
The coefficient of linear expansion can be adjusted to a desired range by, for example, considering the type of resin and filler used as a raw material and appropriately selecting the content ratio of the filler in the composition.

(Water absorption rate)
A film made of the present resin composition, specifically, an unstretched film having a thickness of 10 to 500 μm, which is obtained by melt-kneading the resin composition at a temperature 100 to 250 ° C. higher than the glass transition temperature and extruding the resin composition. The water absorption rate can be 2.2% or less, preferably 1.5% or less, more preferably 1.2% or less, still more preferably 1% or less, particularly preferably 0.7% or less, and particularly preferably. Can be 0.5% or less.
The water absorption rate of the film can be measured by the method in the examples described later.

(Glass-transition temperature)
From the viewpoint of heat resistance, the glass transition temperature of the present resin composition is preferably 200 ° C. or higher, more preferably 220 ° C. or higher, more preferably 230 ° C. or higher, and more preferably 240 ° C. or higher. Especially preferable. On the other hand, from the viewpoint of film forming property and processability, the temperature is preferably 300 ° C. or lower, more preferably 280 ° C. or lower, particularly preferably 270 ° C. or lower, and particularly preferably 260 ° C. or lower.

(Crystal melting temperature)
From the viewpoint of heat resistance, the crystal melting temperature of the present resin composition is preferably 250 ° C. or higher, more preferably 270 ° C. or higher, still more preferably 300 ° C. or higher, and particularly preferably 320 ° C. or higher. preferable. On the other hand, from the viewpoint of film forming property and processability, the temperature is preferably 400 ° C. or lower, more preferably 380 ° C. or lower, particularly preferably 370 ° C. or lower, and particularly preferably 360 ° C. or lower.

(Tension breaking elongation)
A film made of the present resin composition, specifically, an unstretched film having a thickness of 10 to 500 μm, which is obtained by melt-kneading the resin composition at a temperature 100 to 250 ° C. higher than the glass transition temperature and extruding the resin composition. The tensile elongation at break can be 1% or more, preferably 3% or more, more preferably 5% or more, still more preferably 7% or more, and particularly preferably 10% or more. On the other hand, from the viewpoint of film processability, it can be preferably 300% or less, more preferably 280% or less, still more preferably 250% or less. Since a molded product such as a film made of this resin composition has excellent toughness, it tends to be soft and easy to peel off when used in a semiconductor manufacturing process, and also has excellent handleability.
The tensile elongation at break of the film is a value measured in a direction (TD) orthogonal to the resin flow direction (MD) of the film, and can be measured by the method in Examples described later.

(Use of this resin composition)
This resin composition can be suitably used for forming a molded product such as a film that can be used in a process of manufacturing a semiconductor, that is, a molded product such as a film for a semiconductor manufacturing process. In particular, it can be more preferably used when a protective film for polishing a wafer, more specifically, for example, a glass substrate used for polishing and a wafer to be polished are bonded together via the film.

<This film>
The film according to an example of the present invention is a film (referred to as "the present film") formed from the present resin composition.

(thickness)
From the viewpoint of handleability, the thickness of this film is preferably 5 μm or more, more preferably 10 μm or more, particularly preferably 30 μm or more, particularly preferably 50 μm or more, and particularly preferably 70 μm or more. On the other hand, from the viewpoint of productivity, it is preferably 500 μm or less, of which 400 μm or less, of which 300 μm or less, of which 200 μm or less, and of which 150 μm or less is more preferable.

(Relative crystallinity)
The relative crystallinity of this film can be 60% or more, particularly 70% or more, 80% or more, 85% or more, and 90% or more. The upper limit is usually 100%. When the relative crystallinity of this film is within the above numerical range, dimensional changes such as shrinkage due to heat can be suppressed, and heat resistance and rigidity can be improved.
The relative crystallinity of the film can be measured by the method in the examples described later.

In order to keep the relative crystallinity of this film within the above range, for example, the selection of the resin used as a raw material, the conditions for extruding the film, and the like may be appropriately adjusted. Above all, it is preferable to adopt the following methods (1) to (4). These methods may be used in combination. Above all, the method (1) with low productivity and low energy consumption is preferable.

(1) Method of adjusting the cooling conditions when the molten resin is cooled into a film shape As described above, cooling is performed by, for example, using a cast roll as a cooler and bringing the extruded molten resin into contact with the cast roll. Although it can be performed, specifically, it is preferable to adopt the following method.

Examples thereof include a method in which the cooling temperature is set to a temperature 30 to 150 ° C. higher than the glass transition temperature of the raw material resin. The cooling temperature is more preferably 35 to 140 ° C. higher than the glass transition temperature of the resin, and particularly preferably 40 to 135 ° C. higher. By setting the cooling temperature within the above range, the cooling rate of the film can be slowed down, and the relative crystallinity tends to be increased.
In particular, when the resin contains polyetheretherketone as a main component, the cooling temperature is preferably 180 ° C. or higher, more preferably 190 ° C. or higher, further preferably 200 ° C. or higher, and 210 ° C. or higher. Is particularly preferable. On the other hand, the cooling temperature is preferably 300 ° C. or lower, more preferably 280 ° C. or lower, further preferably 260 ° C. or lower, particularly preferably 250 ° C. or lower, and 240 ° C. or lower. Is the most preferable.

(2) Method of reheating the film using a heating roll Specifically, a method of heating with a roll different from the cast roll such as a longitudinal stretching machine can be mentioned. The temperature at the time of heating is preferably in the same range as the cooling temperature of (1) above.

(3) Method of reheating the film in an oven Specific examples thereof include a method of passing the film through a drying device such as a floating dryer, a tenter, and a band dryer and heating the film with hot air.
The temperature at the time of heating is preferably in the same range as the cooling temperature of (1) above.

(4) Method of reheating the film with infrared rays Specifically, a far-infrared heater such as a ceramic heater may be installed between rolls to heat the film by roll-to-roll, or the film may be passed through a far-infrared dryer. It may be heated. The temperature at the time of heating is preferably in the same range as the cooling temperature of (1) above.

The processes (2) to (4) may be performed at the same time as the film production by providing equipment for that purpose in the film production line, or once the film is wound into a roll, the film roll may be performed. May be carried out by these facilities outside the production line.

(Production method)
This film can be molded by a general molding method, for example, extrusion molding, calendar molding, casting molding such as solution casting, inflation molding, or the like. Of these, the extrusion molding method, particularly the T-die method, is preferable.

This film may be either a non-stretched film or a stretched film.
The non-stretched film means a film that is not actively stretched for the purpose of controlling the orientation of the film, and is an oriented film when the molten resin is withdrawn or taken up by a cast roll in extrusion molding such as the T-die method. Also included is a film having a draw ratio of less than 2 times on a stretch roll.

The present film can be produced by melting, preferably melt-kneading the present resin composition, extrusion-molding, and cooling.
Examples of the extruder include a single-screw extruder, a twin-screw extruder, and the like, and the machine functions to melt and knead the charged resin composition.

It is preferable to appropriately adjust the melting temperature according to the type and mixing ratio of the resin, the presence or absence of additives, and the type. From the viewpoint of productivity and the like, the temperature is preferably 320 ° C. or higher, more preferably 340 ° C. or higher, further preferably 350 ° C. or higher, and particularly preferably 360 ° C. or higher.
When the melting temperature is set to the above temperature or higher, the crystals of the raw material such as pellets are sufficiently melted and are less likely to remain on the film, so that the durability such as the number of folding times and the puncture impact strength can be easily improved. On the other hand, the melting temperature is preferably 450 ° C. or lower, more preferably 430 ° C. or lower, further preferably 410 ° C. or lower, and particularly preferably 390 ° C. or lower. By setting the melting temperature to the above temperature or lower, the resin is less likely to decompose during melt molding and the molecular weight is easily maintained, so that the heat resistance and tensile elastic modulus of the film tend to be improved.

Then, the present resin composition melt-kneaded is extruded by a T-die to form a film.
The T-die functions to continuously push the strip-shaped film downward.
The temperature at the time of extrusion of the T-die is usually in the range of the melting point of the resin or higher and lower than the thermal decomposition temperature, specifically, preferably 280 ° C. or higher, more preferably 300 ° C. or higher, 320. The temperature is more preferably 340 ° C. or higher, particularly preferably 340 ° C. or higher, and most preferably 350 ° C. or higher.
On the other hand, the temperature at the time of extrusion of the T-die is preferably 450 ° C. or lower, more preferably 430 ° C. or lower, further preferably 410 ° C. or lower, and particularly preferably 390 ° C. or lower.

The present resin composition extruded as a film by the T-die is cooled by being brought into contact with a cooler such as a crimping roll or a roll such as a cast roll.
The crimping roll is rotatably pivotally supported below the T-die and holds the cast roll in a slidable manner. Further, the cast roll is made of, for example, a metal roll having a larger diameter than the crimping roll, and the film rotatably supported and extruded below the T-die is sandwiched between the crimping roll and the crimping roll. It functions to control the thickness of the film within a predetermined range while cooling the film.

The cooling temperature (for example, the temperature of the cast roll) may be appropriately selected so as to obtain a desired relative crystallization degree, but is preferably a temperature 30 to 150 ° C. higher than the glass transition temperature of the resin. A temperature as high as 35 to 140 ° C. is more preferable, and a temperature as high as 40 to 135 ° C. is particularly preferable. By setting the cooling temperature within the above range, the cooling rate of the film can be slowed down, and the relative crystallinity tends to be increased. For example, when polyetheretherketone is contained as a resin component, the cooling temperature is preferably 180 ° C. or higher, more preferably 190 ° C. or higher, further preferably 200 ° C. or higher, and 210 ° C. or higher. Is particularly preferred. On the other hand, the cooling temperature is preferably 300 ° C. or lower, more preferably 280 ° C. or lower, further preferably 260 ° C. or lower, particularly preferably 250 ° C. or lower, and 240 ° C. or lower. Is the most preferable.

In general, the crystallization rate of a polymer material is considered to be maximized in the temperature range between the glass transition temperature and the crystal melting temperature from the balance between the crystal nucleation rate and the growth rate. When producing a film with a high degree of relative crystallization, if the lower and upper limits of the cooling temperature (temperature of cast rolls, etc.) are within the range, the crystallization rate is maximized and a crystallized film with excellent productivity can be obtained. Easy to get rid of.

When the resin to be used is a mixture of a plurality of types of crystalline resins and a plurality of glass transition temperatures are present, the highest temperature may be regarded as the glass transition temperature of the resin and the cooling temperature may be adjusted.

Downstream of the cast roll, a heating roll for reheating the film, an oven such as a floating dryer, an infrared heater, and the like may be provided in order to adjust the relative crystallinity.

When the film is a stretched film, a stretching device such as a uniaxial stretching device, a sequential biaxial stretching device, and a simultaneous biaxial stretching device is usually provided downstream of the cast roll.

(Use of this film)
This film can be used in various semiconductor manufacturing processes such as a polishing process, a dicing process, and a heat resistant process. It can be used as a protective film for a film for a semiconductor manufacturing process used in each process of semiconductor manufacturing.
Above all, this film can be suitably used as a protective film for a wafer surface (circuit forming surface), for example, in a back grinding step.

When this film is used in a semiconductor manufacturing process, it is preferable to use an adhesive layer laminated on one side or both sides of the film.

At this time, examples of the pressure-sensitive adhesive or adhesive (referred to as “sticking agent or the like”) constituting the adhesive layer include acrylic, epoxy-based, allyl-based, silicone-based, and fluorine-based pressure-sensitive adhesives. .. Of these, acrylic pressure-sensitive adhesives and the like are preferable from the viewpoints of heat resistance and ease of adjusting the adhesive strength.

The pressure-sensitive adhesive or the like may be a curable pressure-sensitive adhesive or the like, or a non-curable pressure-sensitive adhesive or the like. However, a curable pressure-sensitive adhesive or the like is preferable because it is possible to suppress adhesion promotion due to a high temperature during the heat treatment by curing the semiconductor chip before the heat treatment, and it is easy to pick up the semiconductor chip without adhesive residue.

Examples of the curable pressure-sensitive adhesive include a photo-curable pressure-sensitive adhesive that is crosslinked and cured by light irradiation, a thermosetting pressure-sensitive adhesive that is cross-linked and cured by heating, and the like.
Examples of the photocurable pressure-sensitive adhesive include a photo-curable pressure-sensitive adhesive containing a photopolymerization initiator as a main component of a polymerizable polymer.
Examples of the thermosetting pressure-sensitive adhesive include a thermosetting pressure-sensitive adhesive containing a polymerizable polymer as a main component and a thermosetting initiator.

The thickness of the adhesive layer is not particularly limited, but the preferred lower limit is 5 μm and the preferred upper limit is 100 μm. When the thickness of the adhesive layer is within this range, it can be attached to the semiconductor wafer with sufficient adhesive force, and the semiconductor wafer being processed can be protected. In addition, the deformation stress can be easily adjusted within the above range. A more preferable lower limit of the thickness of the adhesive layer is 10 μm, a more preferable upper limit is 70 μm, a further preferable lower limit is 20 μm, and a further preferable upper limit is 50 μm.

The means for forming the adhesive layer is arbitrary. For example, a film-like adhesive layer and a spot-like adhesive layer can be formed by a method of applying a composition such as an adhesive on the present film, a method of transferring (transferring) the adhesive layer formed on the separator, or the like.

<Explanation of words and phrases>
In the present invention, the term "film" shall include a "sheet", and the term "sheet" shall include a "film".

In the present invention, when "X to Y" (X and Y are arbitrary numbers) is described, it means "X or more and Y or less" and "preferably larger than X" or "preferably Y". It also includes the meaning of "smaller".
Further, when described as "X or more" (X is an arbitrary number), it includes the meaning of "preferably larger than X" and is described as "Y or less" (Y is an arbitrary number). In this case, unless otherwise specified, it also includes the meaning of "preferably smaller than Y".

Next, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the examples described below.

<Evaluation method>
In the following, various physical properties were measured and evaluated as follows.

(Average maximum diameter, average thickness, average aspect ratio of filler)
Arbitrarily select 30 filler particles, observe each filler particle with a field emission scanning electron microscope (NOVANanoSEM manufactured by Thermo Fisher Scientific Co., Ltd., magnification 5000 to 500,000 times), and determine the maximum diameter of each filler particle. The thickness was measured and the aspect ratio was calculated from the following formula. In addition, the average maximum diameter, the average thickness, and the average aspect ratio as the average value of these 30 pieces were obtained.
Aspect ratio = maximum diameter / thickness

(Linear expansion coefficient)
For the films (samples) obtained in Examples and Comparative Examples, a thermomechanical analyzer (TMA / SDAT841 manufactured by METTLER TOLEDO) was used, and the test piece width was 6 mm, and the measurement chuck was measured in accordance with JIS K7197: 2012. Under the conditions of a distance of 10 mm and a tension mode, the temperature was raised to 40 to 240 ° C. at a speed of 5 ° C./min, held at 240 ° C. for 1 hour, then lowered to 40 ° C. at a speed of 5 ° C./min, and then to 240 ° C. again. The coefficient of linear expansion was calculated by measuring the sample length at every 20 ° C. when the temperature was raised at a rate of 5 ° C./min, and the average value of the obtained measurement results was taken as the coefficient of linear expansion (1 / ° C.).
The measurement was performed in each of the resin flow direction (MD) of the film and the direction orthogonal to it (TD), and the average value of MD and TD was obtained and shown in Table 1.

(Water absorption rate)
A test piece (thickness 50 μm) having a diameter of 10 cm was cut out from the films (samples) obtained in Examples and Comparative Examples, and obtained as a measurement sample.
According to JIS K7209: 2000, the obtained measurement sample was immersed in water at 23 ° C. for 24 hours, and the water absorption rate was measured from the mass change before and after immersion.
Water absorption rate (%) = ((mass after immersion-mass before immersion) / mass before immersion) x 100

(Tension breaking elongation)
For the films (samples) obtained in Examples and Comparative Examples, the tensile elongation at break (%) of the film at an atmospheric temperature of 23 ° C. was measured at a tensile speed of 200 mm / min in accordance with JIS K7127: 1999. The average value of the five measured values is shown in Table 1.
The measurement was performed in a direction orthogonal to the resin flow direction of the film (TD direction).

(Relative crystallinity)
The films (samples) obtained in Examples and Comparative Examples were detected when the temperature was raised to a temperature range of 23 to 400 ° C. at a rate of 10 ° C./min using a differential scanning calorimeter Pyris1 DSC (manufactured by PerkinElmer). From the DSC curve, the calorific value of the crystal melting peak (J / g) and the calorific value of the recrystallization peak (J / g) were obtained, and the relative crystallization degree was calculated using the following formula.
Relative crystallinity (%) = {1- (ΔHc / ΔHm)} × 100
ΔHc: calorific value of the recrystallization peak of the film under the heating condition of 10 ° C./min (J / g) ΔHm: calorific value of the crystal melting peak of the film under the heating condition of 10 ° C./min (J / g) )

(Glass transition temperature / crystal melting temperature)
In accordance with JIS K7121: 2012, a differential scanning calorimeter Pyris1 DSC (manufactured by PerkinElmer) was used to raise the temperature to a temperature range of 23 to 400 ° C. at a rate of 10 ° C./min, and then 23 at a rate of 10 ° C./min. The glass transition temperature (Tg) and the crystal melting temperature (Tm) were obtained from the DSC curve detected when the temperature was lowered to ° C. and the temperature was raised to 400 ° C. again at a rate of 10 ° C./min.
The crystal melting temperature (Tm) was defined as the temperature at the top of the detected endothermic peak.

[material]
The following raw materials were used in Examples and Comparative Examples.

a-1-1: Polyetheretherketone (PEEK, molecular weight distribution 5.1, mass average molecular weight 87000, crystal melting temperature 340 ° C, crystal melting heat 41 J / g, crystallization temperature 295 ° C)
a-1-2: Polyetheretherketone (PEEK, molecular weight distribution 4.0, mass average molecular weight 100,000, crystal melting temperature 339 ° C, crystal melting heat 40 J / g, crystallization temperature 295 ° C) is 70% by mass, as described below. Master batch containing 30% by mass of mica a-2: Polyetherimide (PEI, "Ultem CRS5001" manufactured by Sabic Innovative Plastics, amorphous resin with a glass transition temperature of 225 ° C)
a-3: Polyetherimide sulphon (PEIS, "EXTEM VH1003" manufactured by Sabic Innovative Plastics, amorphous resin with a glass transition temperature of 242 ° C)
a-4: Polyimide (PI, Toray DuPont polyimide film "Kapton H")

Mica: Average maximum diameter 4.0 μm, average thickness 0.13 μm, average aspect ratio 33

[Examples 1 to 6]
After the raw materials are dry-blended so as to have the ratio shown in Table 1, they are kneaded at 380 ° C. using a Φ40 mm single-screw extruder, extruded from a T-die, and then cooled by a casting roll at 210 ° C. to a thickness of 50 μm. A crystallized film (sample) of the above was produced.
Using the obtained film (sample), the linear expansion coefficient, water absorption rate, tensile elongation at break, relative crystallinity, crystal melting temperature, and glass transition temperature were measured.

[Comparative Examples 1 to 3]
The above raw materials were kneaded at 380 ° C. using a Φ40 mm single-screw extruder, extruded from a T-die, and then cooled with a casting roll at 210 ° C. to produce a film (sample) having a thickness of 50 μm.
Using the obtained film (sample), the linear expansion coefficient, water absorption rate, tensile elongation at break, relative crystallinity, crystal melting temperature, and glass transition temperature were measured.

[Comparative Example 4]
Using the purchased polyimide film, the linear expansion coefficient, water absorption rate, tensile elongation at break, relative crystallinity, crystal melting temperature, and glass transition temperature were measured.

<Discussion>
With respect to the resin composition containing the resin and the filler from the results of the above Examples and Comparative Examples and the test results conducted by the present inventor so far, the resin and the filler are selected and mixed in an appropriate ratio. By doing so, it was found that the water absorption rate of the film made of the resin composition can be 2.2% or less, and the linear expansion coefficient of the film can be 42 × 10 ^-6 / ° C. or less. rice field. Since such a film has a sufficiently low water absorption rate and a sufficiently small coefficient of linear expansion, it can be usefully used as a film for a semiconductor manufacturing process, particularly a protective film for wafer polishing.

Claims (13)

A resin composition for a semiconductor manufacturing process containing a resin and a filler.
A resin composition for a semiconductor manufacturing process, characterized in that the water absorption rate of the film made of the resin composition is 2.2% or less, and the linear expansion coefficient of the film is 42 × 10 ^-6 / ° C. or less. The resin composition for a semiconductor manufacturing process according to claim 1, wherein the filler contains a scaly filler, a plate-like filler, a flaky filler, or a mixture of two or more of these as a main component filler. thing. The resin composition for a semiconductor manufacturing process according to claim 1 or 2, wherein the filler has an average aspect ratio of 10 or more. The resin composition for a semiconductor manufacturing process according to any one of claims 1 to 3, wherein the filler has an average maximum diameter of 30 μm or less. The resin composition for a semiconductor manufacturing process according to any one of claims 1 to 4, wherein the filler has an average thickness of 1 μm or less. The resin composition for a semiconductor manufacturing process according to any one of claims 1 to 5, wherein the filler contains mica as a main component filler. The resin composition for a semiconductor manufacturing process according to any one of claims 1 to 6, wherein the resin contains a crystalline resin having a crystal melting temperature (Tm) of 250 ° C. or higher as a main component resin. The resin composition for a semiconductor manufacturing process according to any one of claims 1 to 6, wherein the resin contains an amorphous resin having a glass transition temperature (Tg) of 200 ° C. or higher as a main component resin. The resin composition for a semiconductor manufacturing process according to any one of claims 1 to 8, wherein the resin contains a polyaryletherketone as a main component resin. The resin composition for a semiconductor manufacturing process according to any one of claims 1 to 9, wherein the content of the filler is 5 parts by mass or more with respect to 100 parts by mass of the total content of the resin and the filler. The resin composition for a semiconductor manufacturing process according to any one of claims 1 to 10, which is used for wafer polishing. A film comprising the resin composition for a semiconductor manufacturing process according to any one of claims 1 to 11. The film according to claim 12, wherein the relative crystallinity of the film is 60% or more.