KR102087022B1 - Film-like plastic material and film-like plastic material which has a support sheet - Google Patents

Abstract

The film-like baking material of this invention is a film-like baking material 1 containing the sinterable metal particle 10 and the binder component 20, and is 40 degreeC-600 degreeC by the temperature increase rate of 10 degree-C / min in air | atmosphere. From the thermogravimetric curve (TG curve) measured up to 40 ° C. to 600 ° C. at an elevated temperature rate of 10 ° C./min under an atmospheric atmosphere as the reference sample using the alumina particles and the time (A1) after the start of the temperature rising with the largest negative slope. In the measured differential thermal analysis curve (DTA curve), the maximum peak time B1 in the time range from 0 second to 2160 seconds after the start of temperature rise satisfies the relationship of A1 <B1 <A1 + 200 seconds, and is A1 <2000 seconds.

Description

Film-like plastic material and film-like plastic material which has a support sheet

The present invention relates to a film-like fired material having a film-like fired material and a support sheet.

This application is filed in Japanese Patent Application No. 2017-090714, filed in Japan on April 28, 2017, Patent Application 2017-179797, filed in Japan on September 20, 2017, and in Japan on October 2, 2017. Priority is claimed based on patent application No. 2017-192821, which is incorporated herein by reference.

In recent years, with the rise of high voltages and high currents in automobiles, air conditioners, and personal computers, the demand for power semiconductor devices (also called power devices) mounted thereon is increasing. In the power semiconductor device, the heat generation from the semiconductor device tends to be a problem because of the characteristics used under high voltage and high current.

Conventionally, heat sinks are sometimes mounted around semiconductor devices for heat dissipation of heat generated from semiconductor devices. However, if the thermal conductivity is not good at the junction between the heat sink and the semiconductor element, efficient heat dissipation is hindered.

As a joining material excellent in thermal conductivity, for example, Patent Document 1 discloses a paste-like metal particulate composition in which specific heat-sinterable metal particles, specific polymer dispersants, and specific volatile dispersion media are mixed. When the composition is sintered, it is considered to be a solid metal having excellent thermal conductivity.

Patent Document 1: Japanese Patent Application Publication No. 2014-111800

However, when the baking material is paste-like like patent document 1, it is difficult to equalize the thickness of the paste apply | coated, and there exists a tendency for thickness stability to run short.

The present invention has been made in view of the above-described fact, and an object thereof is to provide a film-like plastic material which is excellent in thickness stability and thermal conductivity and exhibits excellent shear adhesion after firing. Moreover, it aims at providing the film-like baking material which has a support sheet provided with the said film-like baking material.

Conventionally, it is thought that the lower the thermal decomposition temperature is, the better the materials other than the metal particles contained in the firing material are. However, the inventors of the present invention have studied the sintering mechanism from the viewpoint of thermal properties, so that a film-like plastic material having a specific relationship between a thermogravimetric curve (TG curve) and a differential thermal analysis curve (DTA curve) has a thickness stability and a thermoelectricity. At the same time, it was found that excellent shear adhesion could be expressed after firing, and the invention was completed.

That is, this invention includes the following forms.

[1] as a film-like baking material containing sinterable metal particles and a binder component,

In the thermogravimetric curve (TG curve) measured from 40 degreeC to 600 degreeC at the temperature increase rate of 10 degree-C / min in air | atmosphere, time (A1) after the start of temperature rising with the largest negative slope,

In a differential thermal analysis curve (DTA curve) measured from 40 ° C. to 600 ° C. at an elevated temperature rate of 10 ° C./min under an atmospheric atmosphere as an a reference sample with alumina particles, the maximum peak in the time range from 0 to 2160 seconds after the start of the temperature rise. Time (B1)

The film-like baking material which satisfy | fills the relationship of A1 <B1 <A1 + 200 second, and is A1 <2000 second.

[2] The negative slope of the thermogravimetric curve (TG curve) measured from 40 ° C to 600 ° C at an elevated temperature rate of 10 ° C / min in an air atmosphere with respect to the component excluding the sinterable metal particles from the film-like baking material. Is the time after the start of the largest temperature rise (A1 °),

For the above sinterable metal particles, in a differential thermal analysis curve (DTA curve) measured from 40 ° C. to 600 ° C. at an elevated temperature rate of 10 ° C./min in an atmospheric atmosphere using alumina particles as a reference sample, from 960 seconds to 2160. The peak time (B1 ms) observed at the shortest time within the peak observed in the second time range,

The film-like baking material as described in said [1] which satisfy | fills the relationship of B1 '<A1'.

[3] 후 After the start of temperature rise, a differential thermal analysis curve (DTA curve) measured from 40 ° C. to 600 ° C. at an elevated temperature rate of 10 ° C./min was used as a reference sample of the alumina particles as the reference sample. The film-like baking material as described in said [1] or [2] which does not have an endothermic peak in the time range from 0 second to 2160 second.

[4] as a film-like baking material containing sinterable metal particles and a binder component,

In the thermogravimetric curve (TG curve) measured at the temperature increase rate of 10 degree-C / min in nitrogen atmosphere, the temperature (A2) with the largest negative slope,

In a differential thermal analysis curve (DTA curve) measured at an elevated temperature rate of 10 ° C./min under a nitrogen atmosphere as a reference sample, the maximum peak temperature (B2) in the temperature range of 25 ° C. to 400 ° C.,

The film-like baking material which satisfy | fills the relationship of A2 <B2 <A2 + 60 degreeC.

[5] 온도 The temperature at which the negative slope is the greatest (A2) in the thermogravimetric curve (TG curve) measured at a temperature increase rate of 10 ° C / min under a nitrogen atmosphere with respect to the component excluding the sinterable metal particles from the film-like plastic material. ')Wow,

Within the peak observed in the temperature range of 200 ° C. to 400 ° C. in a differential thermal analysis curve (DTA curve) measured at a temperature increase rate of 10 ° C./min under a nitrogen atmosphere for the sinterable metal particles as a reference sample. The peak temperature (B2 저온) observed at the lowest temperature is

The film-like baking material as described in said [4] which satisfy | fills the relationship of B2 '<A2'.

[6] In the temperature range of 25 ° C. to 400 ° C., in the differential thermal analysis curve (DTA curve) measured at a temperature increase rate of 10 ° C./min under a nitrogen atmosphere, the alumina particles were used as reference samples for the film-like fired material. The film-like baking material as described in said [4] or [5] which does not have the endothermic peak of.

[7] The film-like firing material according to any one of the above [1] to [6], wherein the sinterable metal particles are silver nanoparticles.

[8] 필름 Film-like plastic material which has a support sheet provided with the film-like baking material in any one of said [1]-[7], and the support sheet provided in at least one side of the said film-like baking material.

[9] The pressure sensitive adhesive layer is provided on the base film in the 지지 support sheet.

The film-like baking material which has the support sheet as described in said [8] in which the said film-like baking material is provided on the said adhesive layer.

According to the present invention, it is possible to provide a film-like plastic material which is excellent in thickness stability and thermal conductivity and exhibits excellent shear adhesion after firing. Furthermore, the film-like baking material provided with the said film-like baking material and having a support sheet used for sintering joining of a semiconductor element can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically a film-like baking material which concerns on one Embodiment of this invention.
It is sectional drawing which shows typically the form estimated before and after baking of the film-form baking material which concerns on one Embodiment of this invention.
3 is a cross-sectional view schematically showing a form estimated before and after firing other plastic materials.
It is sectional drawing which shows typically the state in which the film-form plastic material which has a support sheet which stuck to one Embodiment of this invention was affixed on the ring frame.
It is sectional drawing which shows typically the state which the film-form plastic material which has a support sheet which affixed on one Embodiment of this invention affixed on the ring frame.
It is a perspective view which shows typically the state in which the film-form plastic material which has a support sheet which concerns on one Embodiment of this invention affixed on the ring frame.
7 is a graph of the TG curve and the DTA curve obtained by measurement under an atmospheric atmosphere.
8 is a graph of the TG curve and the DTA curve obtained by the measurement under the atmospheric atmosphere.
9 is a graph of the TG curve and the DTA curve obtained by measurement under an atmospheric atmosphere.
10 is a graph of the TG curve and the DTA curve obtained by the measurement under the atmospheric atmosphere.
11 is a graph of the TG curve and the DTA curve obtained by the measurement under nitrogen atmosphere.
12 is a graph of TG curve and DTA curve obtained by measurement under nitrogen atmosphere.
It is a graph of the TG curve and DTA curve obtained by the measurement in nitrogen atmosphere.
14 is a graph of TG curve and DTA curve obtained by measurement under nitrogen atmosphere.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described suitably with reference to drawings.

In addition, the drawing used for the following description may expand and show the part used as a main part for convenience, in order to make the characteristics of this invention easy to understand, and it is not limited that the dimension ratio etc. of each component are actual.

≪Film-like plastic materials≫

The film-like baking material of 1st Embodiment is a film-like baking material containing a sinterable metal particle and a binder component, The thermogravimetry curve measured from 40 degreeC to 600 degreeC at the temperature increase rate of 10 degree-C / min in air | atmosphere ( TG curve), the differential thermal analysis curve (A1) measured from 40 ° C. to 600 ° C. at a temperature increase rate of 10 ° C./min under an atmospheric atmosphere as a reference sample using the alumina particles and the time (A1) after the start of the temperature increase with the highest negative slope. In the DTA curve), the maximum peak time B1 in the time range from 0 second to 2160 seconds after the start of the temperature rise satisfies the relationship A1 <B1 <A1 + 200 seconds, and is A1 <2000 seconds.

The film-like baking material of 2nd Embodiment is a film-like baking material containing a sinterable metal particle and a binder component, and is negative in the thermogravimetry curve (TG curve) measured at the temperature increase rate of 10 degree-C / min in nitrogen atmosphere. In the differential thermal analysis curve (DTA curve) measured at a temperature increase rate of 10 ° C./min under a nitrogen atmosphere as a reference sample, the temperature (A2) of which the slope of which is the largest is in the temperature range of 25 ° C. to 400 ° C. The maximum peak temperature B2 satisfies the relationship of A2 <B2 <A2 + 60 ° C.

1: is sectional drawing which shows typically the film-like baking material of 1st Embodiment and 2nd Embodiment. The film-like baking material 1 contains the sinterable metal particle 10 and the binder component 20. As shown in FIG.

A film-like baking material may consist of one layer (single layer), and may consist of two or more layers. When a film-form baking material consists of multiple layers, these multiple layers may mutually be same or different, and the combination of such multiple layers is not specifically limited unless the effect of this invention is impaired.

In addition, in this specification, it is not limited to the case of a film-like baking material, "The multiple layers may mutually be same or different" and "All layers may be the same, all layers may differ, and only some layers may be the same." It means that "a plurality of layers differ from each other" also means "the constituent material of each layer, the compounding ratio of a constituent material, and at least one thickness differ from each other".

Although the thickness before baking of a film-form baking material is not specifically limited, 10-200 micrometers is preferable, 20-150 micrometers is preferable, and 30-90 micrometers is more preferable.

Here, "thickness of a film-like baking material" means the thickness of the whole film-like baking material, For example, the thickness of the film-like baking material which consists of multiple layers is the sum total of all the layers which comprise a film-like baking material. Means the thickness.

In this specification, "thickness" is a value represented by the average which measured thickness in arbitrary 5 places, and can acquire it using a static pressure thickness meter according to JISKK7130.

(Peel film)

The film-like baking material can be provided in the state laminated | stacked on the peeling film. When using, what is necessary is just to remove a peeling film and to arrange | position a film-form baking material on the object to be sintered and joined. The release film also has a function as a protective film for preventing damage to the film-like plastic material and adhesion of contaminants. The release film should just be provided in at least one side of a film-like baking material, and may be provided in both sides of a film-like baking material.

Examples of the release film include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, and poly Butylene terephthalate film, polyurethane film, ethylene vinyl acetate copolymer film, ionomer resin film, ethylene- (meth) acrylic acid copolymer film, ethylene- (meth) acrylic acid ester copolymer film, polystyrene film, polycarbonate Transparent films, such as a film, a polyimide film, and a fluororesin film, are used. Moreover, these crosslinked films are also used. Moreover, these laminated | multilayer film may be sufficient. Moreover, the film, opaque film, etc. which colored these can be used. As a peeling agent, peeling agents, such as a silicone type, a fluorine type, an alkyd type, an olefin type, long chain alkyl group containing carbamate, are mentioned, for example.

The thickness of a peeling film is 10-500 micrometers normally, Preferably it is 15-300 micrometers, Especially preferably, it is about 20-250 micrometers.

<Sinterable Metal Particles>

Sinterable metal particles are metal particles which can be melted and bonded to each other to form a sintered body by being heat treated as calcination of a film-like plastic material. By forming a sintered compact, the film-form baking material and the article baked in contact with it can be sintered and joined.

Examples of the metal species of the sinterable metal particles include silver, gold, copper, iron, nickel, aluminum, silicon, palladium, platinum, titanium, barium titanate, oxides or alloys thereof, and silver and silver oxide are preferred. Only one type may be mix | blended with the sinterable metal particle, and it may be mix | blended in two or more types of combinations.

It is preferable that a sinterable metal particle is silver nanoparticle which is a silver particle of nanosize.

The particle diameter of the sinterable metal particles contained in the film-like firing material is not particularly limited as long as the sinterability can be exhibited, but may be 100 nm or less, 50 nm or less, or 30 nm or less. In addition, the particle diameter of the metal particle contained in a film-like baking material is made into the circle equivalent diameter of the projection area of the particle diameter of the metal particle observed with the electron microscope.

Metal particles belonging to the range of the above particle diameters are preferable because of their excellent sintering properties.

The particle diameter of the sinterable metal particles contained in the film-like baking material may be 0.1-95 nm in the number average of the particle diameters calculated | required about the particle | grains whose projected area circle equivalent diameter of the particle diameter of the metal particle observed with the electron microscope was 100 nm or less, 0.3-50 nm may be sufficient and 0.5-30 nm may be sufficient. In addition, the metal particle of a measurement object shall be 100 or more randomly selected per one film-like baking material.

Since a sinterable metal particle is made into the state without agglomerate before mixing with a binder component and other additive components, you may disperse | distribute previously in high boiling point solvents, such as isoboroyl hexanol and decyl alcohol. As a boiling point of a high boiling point solvent, you may be 200-350 degreeC, for example. At this time, when a high boiling point solvent is used, since it hardly volatilizes at room temperature, the concentration of the sinterable metal particles is prevented from increasing, and workability is improved, and re-agglomeration of the sinterable metal particles is also prevented, and the quality is also improved. It may become favorable.

As a dispersion method, a kneader, three rolls, a bead mill, an ultrasonic wave, etc. are mentioned.

In addition, in this specification, "normal temperature" means the temperature which does not specifically cool or heat, ie, normal temperature, For example, the temperature of 15-25 degreeC, etc. are mentioned.

In addition to the metal particles (sinterable metal particles) having a particle size of 100 nm or less, non-sinterable metal particles having a particle size exceeding 100 nm may be further blended into the film-like baking material of the above embodiment. Particle diameters of non-sintered metal particles having a particle diameter of more than 100 nm have a number average of the particle diameters obtained for particles whose projected area circle equivalent diameter of the particle diameter of the metal particles observed with an electron microscope exceeding 100 nm is greater than 150 nm and 50000 nm. The following may be sufficient, 150-10000 nm may be sufficient, and 180-5000 nm may be sufficient.

Examples of the metal species of the non-sinterable metal particles having a particle diameter of more than 100 nm include those exemplified above, and silver, copper, and oxides thereof are preferable.

The metal particles having a particle diameter of 100 nm or less and the non-sinterable metal particles having a particle diameter of more than 100 nm may be the same metal species or may be different metal species. For example, the metal particles having a particle size of 100 nm or less may be silver particles, and the non-sinterable metal particles having a particle size of more than 100 nm may be silver or silver oxide particles. For example, the metal particles having a particle size of 100 nm or less may be silver or silver oxide particles, and the non-sinterable metal particles having a particle size of more than 100 nm may be copper or copper oxide particles.

In the film-like baking material of the said embodiment, 20-100 mass parts may be sufficient as content of the metal particle of 100 nm or less of particle diameters with respect to 100 mass parts of all the metal particles, 30-99 mass parts may be sufficient, and 50 95 mass parts may be sufficient.

At least one surface of the sinterable metal particles and the non-sinterable metal particles may be covered with an organic substance. By having an organic coating film, compatibility with a binder component improves. In addition, the particles can be prevented from agglomeration and can be uniformly dispersed.

When the organic substance is coated on at least one surface of the sinterable metal particle and the non-sinterable metal particle, the mass of the sinterable metal particle and the non-sinterable metal particle is taken as the value including a coating material.

<Binder component>

By mix | blending a binder component, a baking material can be shape | molded in a film form and adhesiveness can be provided to the film-like baking material before baking. The binder component may have a thermal decomposition property that is thermally decomposed by heat treatment as calcination of the film-like plastic material.

Although a binder component is not specifically limited, Resin is mentioned as a suitable example of a binder component. Examples of the resin include acrylic resins, polycarbonate resins, polylactic acid, and polymers of cellulose derivatives. Acrylic resins are preferred. Acrylic resin contains the homopolymer of a (meth) acrylate compound, the 2 or more types of copolymers of a (meth) acrylate compound, and the copolymer of a (meth) acrylate compound and another copolymerizable monomer.

In resin which comprises a binder component, it is preferable that content of the structural unit derived from a (meth) acrylate compound is 50-100 mass% with respect to whole quantity of a structural unit, It is more preferable that it is 80-100 mass%, It is more preferable that it is 90-100 mass%.

"Derived" here means having received the change of the structure which the said monomer requires for superposition | polymerization.

Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth ) Acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (Meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth Alkyl, such as acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth) acrylate Methacrylate;

Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) Hydroxyalkyl (meth) acrylates such as acrylate and 3-hydroxybutyl (meth) acrylate; Phenoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate and 2-hydroxy-3-phenoxy propyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxy ethyl (meth) acrylate, 2-butoxy ethyl (meth) acrylate, 2--methoxybutyl Alkoxy alkyl (meth) acrylates, such as (meth) acrylate; Polyethylene glycol mono (meth) acrylate, ethoxy diethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, nonyl phenoxy polyethylene glycol (meth) acrylate Polyalkylene glycols such as polypropylene glycol mono (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, ethoxy polypropylene glycol (meth) acrylate, and nonyl phenoxy polypropylene glycol (meth) acrylate (Meth) acrylates; Cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, bonyl Cycloalkyl (meth) acrylates such as (meth) acrylate, isobonyl (meth) acrylate, and tricyclodecanyl (meth) acrylate;

Benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and the like. Alkyl (meth) acrylate or alkoxyalkyl (meth) acrylate is preferred, and as a particularly preferred (meth) acrylate compound, butyl (meth) acrylate, ethylhexyl (meth) acrylate, lauryl (meth) acrylate, Isodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and 2-ethoxyethyl (meth) acrylate.

In this specification, "(meth) acrylic acid" is a concept including both "acrylic acid" and "methacrylic acid", and "(meth) acrylate" is a thing of "acrylate" and "methacrylate". The concept includes both.

As an acrylic resin, methacrylate is preferable. When a binder component contains the structural unit derived from methacrylate, the said film (A1) and the said time (B1) have a relationship of A1 <B1 <A1 + 200 second, and it is easy to obtain the film-like baking material which becomes A1 <2000 second. Moreover, when a binder component contains the structural unit derived from methacrylate, the film-form baking material which has the relationship of said temperature (A2) and said temperature (B2) A2 <B2 <A2 + 60 degreeC is easy to be obtained.

In resin which comprises a binder component, it is preferable that content of the structural unit derived from methacrylate is 50-100 mass% with respect to whole quantity of a structural unit, It is more preferable that it is 80-100 mass%, 90-100 It is more preferable that it is mass%.

As another copolymerizable monomer, if it is a compound which can be copolymerized with the said (meth) acrylate compound, there will be no restriction | limiting in particular, For example, unsaturated carboxylic acids, such as (meth) acrylic acid, vinyl benzoic acid, maleic acid, vinyl phthalic acid; And vinyl group-containing radically polymerizable compounds such as vinyl benzyl methyl ether, vinyl glycidyl ether, styrene, α-methyl styrene, butadiene and isoprene.

It is preferable that it is 1,000-1,000,000, and, as for the weight average molecular weight (Mw) of resin which comprises a binder component, it is more preferable that it is 10,000-800,000. When the weight average molecular weight of resin is in the said range, it becomes easy to express sufficient film strength as a film and to give flexibility.

In addition, in this specification, "weight average molecular weight" is a polystyrene conversion value measured by the gel permeation chromatography (GPC) method unless there is particular notice.

The glass transition temperature (Tg) of resin which comprises a binder component can be calculated | required by calculation using the following Fox formula, It is preferable that it is -60-50 degreeC, It is more preferable that it is -30-10 degreeC It is more preferable that they are -20 or more and less than 0 degreeC. Since Tg calculated | required from the Fox formula of resin is below the said upper limit, the adhesive force before baking of a film-form baking material and a to-be-adhered body (for example, a semiconductor element, a chip, a board | substrate, etc.) improves. On the other hand, the Tg determined from the Fox formula of the resin is more than the lower limit, so that the film shape can be maintained and separation of the film-like plastic material from the support sheet or the like becomes easier.

Tg of the acrylic polymer, according to Fox formula from the weight ratio of the monomer of each polymer portion,

1 / Tg = (W1 / Tg1) + (W2 / Tg2) +... + (Wm / Tgm)

W1 + W2 +... + Wm = 1

Indicates a relationship. In the formula, Tg represents the glass transition temperature of the polymer portion, and Tg1, Tg2, ... , Tgm represents the glass transition temperature of each polymerization monomer. In addition, W1, W2,... And Wm represent the weight ratio of each polymerization monomer.

As the glass transition temperature of each polymerization monomer in the Fox formula, values described in the polymer data handbook and the adhesion handbook can be used.

The binder component may have a thermal decomposition property that is thermally decomposed by heat treatment as calcination of the film-like plastic material. The thermal decomposition of the binder component can be confirmed by mass reduction of the binder component by firing. In addition, although the component mix | blended as a binder component may be thermally decomposed substantially by baking, the total mass of the component mix | blended as a binder component does not need to be thermally decomposed by baking.

As for the binder component, the mass after baking may be 10 mass% or less with respect to 100 mass% of the mass of the binder component before baking, may be 5 mass% or less, and may be 3 mass% or less.

In addition to the sinterable metal particles, the non-sinterable metal particles, and the binder component described above, the film-like fired material of the embodiment does not correspond to the sinterable metal particles, the non-sinterable metal particles, and the binder component within a range that does not impair the effects of the present invention. May contain other additives.

As another additive which may be contained in the film-like baking material of the said embodiment, a solvent, a dispersing agent, a plasticizer, a tackifier, a storage stabilizer, an antifoamer, a thermal decomposition promoter, antioxidant, etc. are mentioned. 1 type of additives may be contained and may be contained 2 or more types. Such additives are not particularly limited and may be appropriately selected from those commonly used in this field.

<Composition>

The film-like baking material of the said embodiment may consist of sinterable metal particle, a binder component, and other additives, and the sum total of these content (mass%) may be 100 mass%.

When the film-like baking material of the said embodiment contains a non-sinterable metal particle, a film-like baking material may consist of sinterable metal particle, a non-sinterable metal particle, a binder component, and other additives, and these content The total of (mass%) may be 100 mass%.

In a film-like baking material, 10-98 mass% is preferable, and, as for content of the sinterable metal particle with respect to 100 mass% of total content of all components other than a solvent (it calls it "solid content" hereafter), 15-90 mass % Is more preferable, and 20-80 mass% is more preferable.

When the film-like baking material contains non-sinterable metal particles, the total content of the sinterable metal particles and the non-sinterable metal particles with respect to 100% by mass of the total content of solids in the film-like baking material is preferably from 50 to 98% by mass. 70-95 mass% is more preferable, and 80-90 mass% is more preferable.

2-50 mass% is preferable, as for content of the binder component with respect to 100 mass% of total content of solid content in a film-like baking material, 5-30 mass% is more preferable, 10-20 mass% is more preferable.

In a film-like baking material, 50: 1-1: 5 are preferable, as for the mass ratio (sinterable metal particle: binder component) of a sinterable metal particle and a binder component, 20: 1-1: 2 are more preferable, 10: 1 to 1: 1 are more preferable. When the film-like baking material contains non-sinterable metal particles, the mass ratio ((sinterable metal particles + non-sinterable metal particles): binder component) between the sinterable metal particles, the non-sinterable metal particles, and the binder component is 50: 1 to 1. 1: 1 is preferable, 20: 1 ~ 2: 1 are more preferable, and 9: 1-4: 1 are more preferable.

[Film-shaped baking material of 1st Embodiment]

The film-like baking material of 1st Embodiment has the composition shown above, The said film (A1) and the said time (B1) have a relationship of A1 <B1 <A1 + 200 second, and A1 <2000 second is obtained the film-like baking material Easy to lose

The film-like baking material of 1st Embodiment may contain the high boiling point solvent used when mixing a sinterable metal particle, a non-sinterable metal particle, a binder component, and other additive components. 20 mass% or less is preferable, as for content of a high boiling point solvent with respect to 100 mass% of total masses of the film-like baking material of 1st embodiment, 15 mass% or less is more preferable, 10 mass% or less is more preferable. . When content of a high boiling point solvent is below the said upper limit, the said time A1 and the said time B1 have a relationship of A1 <B1 <A1 + 200 second, and it is easy to obtain the film-like baking material which becomes A1 <2000 second. Moreover, in the said differential thermal analysis curve (DTA curve) by measurement in air | atmosphere, a film-like baking material which does not have an endothermic peak in the time range from 0 second to 2160 second after a temperature rise start is easy to be obtained.

<Time (A1), time (B1)>

The film-like baking material of 1st Embodiment is the time after the temperature rising start with the largest negative slope in the thermogravimetry curve (TG curve) measured from 40 degreeC to 600 degreeC at the temperature increase rate of 10 degree-C / min in air | atmosphere. In the differential thermal analysis curve (DTA curve) measured from 40 ° C. to 600 ° C. at an elevated temperature rate of 10 ° C./min under an atmospheric atmosphere using (A1) and alumina particles as reference samples, a time range of 0 to 2160 seconds after the start of the temperature rise. The maximum peak time B1 at satisfies the relationship of A1 <B1 <A1 + 200 seconds, and is A1 <2000 seconds.

The TG curve shows the weight change of the film-like calcined material in the process of heat-processing the film-like calcined material in the air atmosphere.

The DTA curve shows the differential thermal change of the film-like calcined material in the process of heat-processing the film-like calcined material in the air atmosphere.

Hereinafter, the form of the film-like baking material in the baking process estimated from the TG curve and DTA curve by measurement in air | atmosphere is demonstrated suitably with reference to drawings.

Fig. 2 satisfies the relationship of A1 <B1 <A1 + 200 seconds and before baking (Fig. 2 (a)), during baking (Fig. 2 (b)), after baking of the film-like baking material 1 having A1 <2000 seconds. It is sectional drawing which shows typically the form estimated about FIG.2 (c).

The weight of the binder component 20 contained in the film-like plastic material (FIG. 2 (a)) before baking reduces by heating (FIG. 2 (b)-(c)), and this phenomenon is a TG curve Appears as the negative slope of.

The binder component 20 contained in the film-like baking material (FIG. 2 (a)) before baking is thermally decomposed by endotherm at the time of heating, and is sinterable metal contained in the film-like baking material (FIG. 2 (A)) before baking. The particles 10 are melted by endotherming at the time of heating (FIG. 2B), and then sintered (FIG. 2C) while generating heat. Although this endothermic heat process is observed as a DTA curve, when the sintering process is sufficiently progressed, the calorific value is large and the thermal decomposition and sinterable metal particles 10 of the binder component 20 contained in the film-like plastic material (FIG. 2 (a)) It greatly exceeds the endothermic amount due to melting. That is, in the DTA curve obtained by the measurement, only the positive parallax train due to the exotherm is observed and appears as a peak.

The time A1 and the time B1 satisfy the relationship of A1 <B1 <A1 + 200 seconds, and A1 <2000 seconds means that melting and sintering of the sinterable metal particles are completed at the heating time immediately following the reduction of the binder component. I think it means to be. It is generally known that the combustion temperature is related to the size of the metal particles, and that the smaller the metal particles tend to be, the lower the combustion temperature is. Therefore, the film-like baking material 1 which satisfy | fills the relationship of A1 <B1 <A1 + 200 second and whose A1 <2000 second is not confirmed cohesion and fusion of sinterable metal particles in the starting stage of sintering, and melt | dissolved as a particulate form is sinterable metal It is estimated that the particles 10m are sintered.

Fig. 3 does not satisfy the relationship of A1 <B1 <A1 + 200 seconds and before firing (Fig. 3 (a)) and during firing (Fig. 3 (b)) of the firing material 1c in which the time of B1 is larger than A1 + 200 seconds. It is sectional drawing which shows typically the form estimated after baking (FIG. 3 (c)). The binder component 21 contained in the film-like plastic material (FIG. 3 (a)) before baking also reduces weight by heating (FIG. 3 (b)-(c)), and this phenomenon also shows a TG curve Appears as the negative slope of.

The binder component 21 contained in the film-like baking material (FIG. 3 (a)) before baking is also thermally decomposed by endotherm at the time of heating, and is included in the film-like baking material (FIG. 3 (a)) before baking. The sinterable metal particles 11 cause melting by endotherm and sintering by heat generation (FIG. 3C). The adsorption and heat generation process of the sinterable metal particles 11 occurs almost simultaneously because the binder component 21 does not already exist or is present. However, since the calorific value by sintering is large, the DTA curve generates an exothermic process. Only positive peaks appear.

The fact that the time A1 and the time B1 do not satisfy the relationship of A1 <B1 <A1 + 200 seconds means that the firing of the sinterable metal particles is not completed in the heating time immediately following the reduction of the binder component. do. The combustion temperature is related to the size of the metal particles, and the larger the metal particles tend to be, the higher the combustion temperature is. Therefore, for example, in the baking material 1c which does not satisfy the relationship of A1 <B1 <A1 + 200 seconds and the time of B1 is larger than A1 + 200 seconds, it is estimated that the size of the sinterable metal particles is large in the sintering step. This is probably because the decrease in the binder component by heating proceeds before the peak of melting and sintering of the sinterable metal particles, so that the sinterable metal particles 11 form agglomerates of a certain size at the start of sintering, It is thought that time B1 is increasing by sintering the obtained metal particle.

Moreover, the inventors found that the film-like baking material whose time A1 and time B1 satisfy | fills the relationship of A1 <B1 <A1 + 200 second, and A1 <2000 second, was excellent in the shear adhesive force after baking.

In a sintering material that does not satisfy the relationship of A1 <B1 <A1 + 200 seconds and the time of B1 is larger than A1 + 200 seconds, the sintered metal particles which become agglomerate are sintered, so that there are many cases where sintering is not sufficient or there are not sintered places It is considered that the material after sintering is insufficient in adhesive strength (strength of shear adhesive force). Or a space | gap tends to generate | occur | produce in the adhesive interface with a to-be-adhered body, and it is thought that adhesive strength falls because the adhesive area becomes small.

Moreover, even if the relationship of A1 <B1 <A1 + 200 second is satisfied, the film-like baking material of A1≥2000 second is considered to have a bad influence on the device member by the productivity fall by tact time extension, and the temperature required for baking increases.

On the other hand, in the film-like baking material which satisfies the relationship of A1 <B1 <A1 + 200 seconds and A1 <2000 seconds, the sinterable metal particles melted in the form of fine particles in the state in which the binder component is present are sintered, whereby the sinterable metals are uniform and dense. It is thought that the metal bond is caused to improve the adhesive strength of the material after sintering.

The shear adhesive force after baking of a film-like baking material can be measured in accordance with the method as described in an Example.

In the film-like baking material of the first embodiment, the time A1 and the time B1 satisfy the relationship of A1 <B1 <A1 + 200 seconds, and for example, satisfy the relationship of A1 <B1 <A1 + 100 seconds. It may be sufficient, and may satisfy | fill the relationship of A1 <B1 <A1 + 60 second, and may satisfy | fill the relationship of A1 <B1 <A1 + 30 second.

The maximum peak time (B1) in the time range of 0 second to 2160 seconds after the start of the temperature rise is a differential thermal analysis curve measured from 40 ° C. to 600 ° C. at a temperature rising rate of 10 ° C./min under an atmospheric atmosphere using alumina particles as a reference sample. In the (DTA curve), it is preferable to have a maximum peak time at 960 seconds to 2160 seconds after the start of the temperature rise, more preferably to have a maximum peak time at 1080 to 2100 seconds after the start of the temperature rise, and 1260 to 2040 seconds after the start of the temperature rise. More preferably, there is a maximum peak time.

<Time (A1 '), time (B1')>

The film-like baking material of 1st Embodiment is the thermogravimetry curve measured from 40 degreeC to 600 degreeC at the temperature increase rate of 10 degree-C / min with respect to the component except the said sinterable metal particle from the film-like baking material ( TG curve), from 40 ° C to 600 ° C at a temperature increase rate of 10 ° C / min under an atmospheric atmosphere with reference to the alumina particles as the reference sample for the time after the start of the temperature increase (A1 °) with the largest negative slope. In the differential thermal analysis curve (DTA curve) measured up to, the peak time (B1 ') observed at the shortest time within the peak observed in the time range of 960 seconds to 2160 seconds after the start of the temperature rise satisfies the relationship of B1' <A1 '. It is desirable to.

The TG curve shows the change in weight of the components excluding the sinterable metal particles from the film-like baking material in the process of being heat treated as firing in an air atmosphere.

The DTA curve shows the differential thermal change of the sinterable metal particles during the heat treatment as firing in an atmospheric atmosphere.

When the film-like baking material of 1st Embodiment contains a non-sinterable metal particle, about the component except the said sinterable metal particle and non-sinterable metal particle from the film-like baking material, In the thermogravimetric curve (TG curve) measured from 40 degreeC to 600 degreeC at the temperature increase rate of 10 degree-C / min in air | atmosphere, time (A1 ') after the start of temperature rising with the largest negative slope, and said sinterable metal particle and arsenic For the formed metal particles, in the differential thermal analysis curve (DTA curve) measured from 40 ° C. to 600 ° C. at an elevated temperature rate of 10 ° C./min under an atmospheric atmosphere using the alumina particles as a reference sample, the temperature increased from 960 seconds to 2160 seconds. It is preferable that the peak time B1 'observed at the shortest time in the peak observed in the time range satisfies the relationship of B1' <A1 '.

From the film-like plastic material containing the binder component contained in the film-like plastic material before baking, the component except the said sinterable metal particle and the non-sinterable metal particle is reduced in weight by heating in an air atmosphere, and this phenomenon is Appear as negative slope in TG curve.

In the sinterable metal particles contained in the film-like plastic material before firing, melting and sintering occur in heating under an atmospheric atmosphere. appear.

The time A1 'and time B1' satisfying the relationship of B1 '<A1' are the timings at which the components distributed around the sinterable metal particles of the film-like plastic material lose weight in the course of heat treatment. Compared with that, it is thought that the melting and sintering of the sinterable metal particles are started early. Therefore, the film-like baking material which satisfy | fills the relationship of B1 '<A1' becomes in the state isolate | separated by the component distributed around the sinterable metal particle, and it is easy to melt as a particulate form, and in time (A1 ') At the point of arrival, the collision frequency is sharply increased, and the sintered metal particles melted in the form of fine particles tend to be sintered. As a result, in the film-like baking material which satisfy | fills the relationship of B1 '<A1', sinterable metals are metal-bonded uniformly and densely, and it is thought that the strength of the material after sintering improves.

The time (A1 ') and time (B1') separate the sinterable metal particles and the components except the sinterable metal particles from the film-like plastic material before firing, and from the TG curve and the DTA curve for each separated sample. You can get it.

Separation of the remaining components except the sinterable metal particles and the sinterable metal particles from the film-like plastic material before firing can be carried out according to the following method, for example.

First, the film-like baking material before baking and a sufficient amount of an organic solvent are mixed and then left to stand for a sufficient time until the sinterable metal particles settle. By removing the supernatant with a syringe or the like and recovering the residue after drying at 120 ° C for 10 minutes, the component except for the sinterable metal particles can be separated from the film-like baking material. After removing the supernatant with the syringe or the like, the liquid containing the sinterable metal particles is again mixed with a sufficient amount of an organic solvent, and then left to stand for a sufficient time until the sinterable metal particles are settled. Pull out.

After repeating mixing of the organic solvent, standing still and removing the supernatant five times or more, the residue after drying the remaining liquid at 120 ° C. for 10 minutes can be collected by separating the sinterable metal particles.

This is the same also when the film-like baking material of 1st Embodiment contains a non-sinterable metal particle, The said time (A1 ') and time (B1') are sinterable metal particle and the film-like baking material before baking, Non-sinterable metal particles and components other than the sinterable metal particles and non-sinterable metal particles can be separated and obtained from the TG curve and the DTA curve for each separated sample.

Separation of the remaining components other than the sinterable metal particles and the non-sinterable metal particles and the sinterable metal particles and the non-sinterable metal particles from the film-like plastic material before firing can be performed according to the following method, for example.

First, the film-like baking material before baking and a sufficient amount of an organic solvent are mixed and then left to stand for a sufficient time until the sinterable metal particles and the non-sinterable metal particles settle. By removing the supernatant with a syringe or the like and recovering the residue after drying at 120 ° C. for 10 minutes, the component except for the sinterable metal particles and non-sinterable metal particles can be separated from the film-like baking material. In addition, after removing the supernatant with the syringe or the like, a sufficient time until the sinterable metal particles and the non-sinterable metal particles are settled after mixing a sufficient amount of an organic solvent with respect to the liquid containing the sinterable metal particles and the non-sinterable metal particles. Allow to stand, and remove the supernatant with a syringe or the like. After repeating the mixing of the organic solvent and the standing and removing the supernatant five times or more, the residue after drying the remaining liquid at 120 ° C. for 10 minutes can be collected by separating the sinterable metal particles and the non-sinterable metal particles.

It is preferable that the solvent used here can melt | dissolve a binder component and can volatilize on the drying conditions for 10 minutes at said 120-250 degreeC, and a suitable thing can be used suitably according to the kind of binder component, etc. For example, Hydrocarbons, such as toluene and xylene; Alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol) and 1-butanol; Esters such as ethyl acetate; Ketones such as acetone and methyl ethyl ketone; Ethers such as tetrahydrofuran; Amides (compounds having amide bonds) such as dimethylformamide and N-methylpyrrolidone.

<Endothermic peak>

The film-like baking material of the first embodiment has a differential thermal analysis curve measured from 40 ° C. to 600 ° C. at an elevated temperature rate of 10 ° C./min in an atmospheric atmosphere with reference to alumina particles as the film-like baking material. DTA curve), preferably does not have an endothermic peak in the time range from 0 seconds to 2160 seconds after the start of the temperature rise.

The DTA curve shows the differential thermal change of the film-like calcined material in the process of heating the film-like calcined material as calcined.

When the endothermic peak is recognized in the DTA curve, it is thought that the film-like plastic material contains a component having a property of absorbing and changing (for example, evaporating) heat from the film-like plastic material after 0 to 2160 seconds after the start of the temperature rise. do. That is, it can be considered that evaporation of the components occurs and the heat of vaporization accompanying them is necessary. Or it shows that many components which endotherm and thermally decompose are exceeding the amount of heat generate | occur | produced by sintering.

Therefore, it is preferable that the film-like baking material of 1st Embodiment has little or no content of the component which has the property to evaporate from a film-like baking material from 0 second to 2160 second after the start of temperature rising. In addition, it is preferable that the amount of components absorbing a large amount of heat for pyrolysis and hindering the exothermic process by sintering is low or not included.

Here, before measuring the DTA curve with respect to a film-form baking material, it is recommended to pretreat a film-like baking material, such as drying, and to prevent the moisture absorbed as an impurity from being measured. As dry processing conditions, 4 minutes is mentioned at 110 degreeC.

The DTA curve does not have an endothermic peak in the time range of 0 second to 2160 seconds after the start of the temperature increase, and there is no fear that the components distributed around the sinterable metal particles will not decrease, and the components distributed around the sinterable metal particles Each particle tends to be in an isolated state. As a result, in the film-like plastic material which does not have an endothermic peak in the time range from 0 second to 2160 seconds after the start of the temperature rise, the sinterable metals form metal bonds uniformly and densely, and the strength of the material after sintering is increased. Easy to improve In addition, the loss of energy required for firing is reduced, and firing in a favorable environment is realized. In addition, it is thought that the shear adhesive force after baking of a film-form baking material improves by this.

According to the film-like baking material of said 1st Embodiment, since it is a film form, it is excellent in thickness stability. Moreover, since the film-like baking material of 1st Embodiment contains a sinterable metal particle, it is excellent in thermal conductivity. Moreover, the film-like baking material of 1st Embodiment satisfy | fills the relationship of said A1 <B1 <A1 + 200 second, and is A1 <2000 second, and shows the outstanding shear adhesive force after baking.

[Film-shaped baking material of 2nd Embodiment]

Since the film-like baking material of 2nd Embodiment has the composition shown above, the film-like baking material which has the relationship of said temperature (A2) and said temperature (B2) A2 <B2 <A2 + 60 degreeC is easy to be obtained.

The film-like baking material of 2nd Embodiment may contain the high boiling point solvent used when mixing a sinterable metal particle, a non-sinterable metal particle, a binder component, and other additive components. 20 mass% or less is preferable, as for content of a high boiling point solvent with respect to 100 mass% of total masses of the film-like baking material of 2nd Embodiment, 15 mass% or less is more preferable, 10 mass% or less is more preferable. . When content of a high boiling point solvent is below the said upper limit, the film-like baking material which the said temperature (A2) and the said temperature (B2) has A2 <B2 <A2 + 60 degreeC relationship is easy to be obtained. Moreover, in the said differential thermal analysis curve (DTA curve) by measurement in nitrogen atmosphere, the film-like baking material which does not have an endothermic peak in the temperature range of 25 degreeC-400 degreeC is easy to be obtained.

<Temperature (A2), temperature (B2)>

In the film-like baking material of the second embodiment, the thermogravimetric curve (TG curve) measured at a temperature increase rate of 10 ° C / min in a nitrogen atmosphere refers to the temperature (A2) having the largest negative slope and the alumina particles. In the differential thermal analysis curve (DTA curve) measured at a temperature increase rate of 10 ° C./min under a nitrogen atmosphere, the maximum peak temperature (B 2) in the temperature range of 25 ° C. to 400 ° C. is A2 <B2 <A2 + 60 ° C. To satisfy the relationship.

The TG curve shows the weight change of the film-like calcined material in the process of heat-processing the film-like calcined material under nitrogen atmosphere.

The DTA curve shows the differential thermal change of the film-like calcined material in the process of heating the film-like calcined material under nitrogen atmosphere.

Hereinafter, the form of the film-like baking material in the baking process estimated from the TG curve and the DTA curve by measurement in nitrogen atmosphere is demonstrated suitably with reference to drawings.

Fig. 2 shows the film-like baking material 1 satisfying the relationship of A2 <B2 <A2 + 60 ° C before firing (Fig. 2 (a)), during firing (Fig. 2 (b)), after firing (Fig. 2 ( It is sectional drawing which shows typically the form estimated about c)).

The weight of the binder component 20 contained in the film-like plastic material (FIG. 2 (a)) before baking reduces by heating (FIG. 2 (b)-(c)), and this phenomenon is a TG curve Appears as the negative slope of.

The binder component 20 contained in the film-like baking material (FIG. 2 (a)) before baking is thermally decomposed by endotherm at the time of heating, and is sinterable metal contained in the film-like baking material (FIG. 2 (A)) before baking. The particles 10 are melted by endotherming at the time of heating (FIG. 2B), and then sintered (FIG. 2C) while generating heat. Although this endothermic heat process is observed as a DTA curve, when the sintering process is sufficiently progressed, the calorific value is large and the thermal decomposition and sinterable metal particles 10 of the binder component 20 contained in the film-like plastic material (FIG. 2 (a)) It greatly exceeds the endothermic amount due to melting. That is, in the DTA curve obtained by the measurement, only the positive parallax train due to the exotherm is observed and appears as a peak.

When temperature A2 and temperature B2 satisfy | fill the relationship of A2 <B2 <A2 + 60 degreeC, it means that melting and sintering of sinterable metal particle are completed at the heating temperature immediately following a decrease of a binder component. I think. It is generally known that the combustion temperature is related to the size of the metal particles, and that the smaller the metal particles tend to be, the lower the combustion temperature is. Therefore, the film-like baking material 1 which satisfy | fills the relationship of A2 <B2 <A2 + 60 degreeC is sinterable metal particle (10m) which melt | dissolved as a particulate form, without agglomeration and fusion of the sinterable metal particles confirmed at the start stage of sintering. ) Sintered together.

Fig. 3 does not satisfy the relationship of A2 <B2 <A2 + 60 ° C, and before firing (Fig. 3 (a)) and during baking (Fig. 3 (b)) of the firing material 1c having a temperature of B2 greater than A2 + 60 ° C. ) Is a cross-sectional view schematically showing a form estimated after firing (FIG. 3 (c)). The binder component 21 contained in the film-like plastic material (FIG. 3 (a)) before baking also reduces weight by heating (FIG. 3 (b)-(c)), and this phenomenon also shows a TG curve Appears as the negative slope of.

The binder component 21 contained in the film-like baking material (FIG. 3 (a)) before baking is also thermally decomposed by endotherm at the time of heating, and is included in the film-like baking material (FIG. 3 (a)) before baking. The sinterable metal particles 11 cause melting by endotherm and sintering by heat generation (FIG. 3C). The endothermic heat process of the sinterable metal particles 11 occurs almost simultaneously because the binder component 21 does not already exist or is present even though it is present. However, since the calorific value due to sintering is large, the exothermic process is performed in the DTA curve. Only positive peaks appear.

When temperature A2 and temperature B2 do not satisfy the relationship of A2 <B2 <A2 + 60 degreeC, it means that baking of a sinterable metal particle is not completed at the heating temperature immediately following a decrease of a binder component. I think. The combustion temperature is related to the size of the metal particles, and the larger the metal particles tend to be, the higher the combustion temperature is. Therefore, for example, in the baking material 1c which does not satisfy the relationship of A2 <B2 <A2 + 60 degreeC, and whose temperature of B2 is larger than A2 + 60 degreeC, it is estimated that the size of sinterable metal particle is large at the stage of sintering. This is probably because the reduction of the binder component due to heating proceeds before the peak of melting and sintering of the sinterable metal particles, so that the sinterable metal particles 11 form agglomerates of a certain size at the start of sintering, and become bulky. It is thought that temperature B2 rises because this metal particle sintered.

Moreover, the inventors found that the film-like baking material which temperature (A2) and temperature (B2) satisfy | fill the relationship of A2 <B2 <A2 + 60 degreeC is excellent in the shear adhesive force after baking.

In a sintered material that does not satisfy the relationship of A2 <B2 <A2 + 60 ° C and the temperature of B2 is larger than A2 + 60 ° C, sintered sintered metal particles are sintered, whereby sintering is not sufficient and many places where sintering is not performed. It is thought that the material after sintering will be insufficient in adhesive strength (strength of shear adhesive force). Or a space | gap tends to generate | occur | produce in the adhesive interface with a to-be-adhered body, and it is thought that adhesive strength falls because the adhesive area becomes small.

On the other hand, in the film-like plastic material which satisfies the relationship of A2 <B2 <A2 + 60 ° C, the sinterable metal particles melted as fine particles are sintered, so that the sinterable metals are uniformly and densely metal-bonded, and the adhesive strength of the material after sintering is increased. I think it improves.

The shear adhesive force after baking of a film-like baking material can be measured in accordance with the method as described in an Example.

In the film-like baking material of 2nd Embodiment, the said temperature (A2) and the said temperature (B2) satisfy | fill the relationship of A2 <B2 <A2 + 60 degreeC, for example, satisfy | fill the relationship of A2 <B2 <A2 + 50 degreeC. It may be sufficient, the relationship of A2 <B2 <A2 + 40 degreeC may be sufficient, and the relationship of A2 <B2 <A2 + 30 degreeC may be sufficient.

The maximum peak temperature (B2) in the temperature range of 25 ° C. to 400 ° C. is 200 to 200 on a differential thermal analysis curve (DTA curve) measured at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere with alumina particles as a reference sample. It is preferable to have a maximum peak temperature at 400 degreeC, it is more preferable to have a maximum peak temperature at 220-390 degreeC, and it is still more preferable to have a maximum peak temperature at 250-380 degreeC.

<Temperature (A2 °), temperature (B2 °)>

The film-like baking material of 2nd Embodiment is negative in the thermogravimetry curve (TG curve) measured at the temperature increase rate of 10 degree-C / min in nitrogen atmosphere with respect to the component except the said sinterable metal particle from the film-like baking material. 200 ° C. on the differential thermal analysis curve (DTA curve) measured at a temperature rising rate of 10 ° C./min under nitrogen atmosphere as the reference sample for the sinterable metal particles and the temperature at which the slope of A2 was greatest. It is preferable that the peak temperature (B2 ′) observed at the lowest temperature in the peak observed in the temperature range of from 400 ° C. satisfies the relationship of B2 ′ <A2 ′.

The TG curve shows a change in weight of the component excluding the sinterable metal particles from the film-like plastic material in the process of heat treatment as calcination in a nitrogen atmosphere.

The said DTA curve shows the temperature change of the differential heat of a sinterable metal particle in the process of heat-processing as baking in nitrogen atmosphere.

When the film-like baking material of 2nd Embodiment contains a non-sinterable metal particle, about the component except the said sinterable metal particle and non-sinterable metal particle from the film-like baking material, In the thermogravimetric curve (TG curve) measured at the temperature increase rate of 10 degree-C / min in nitrogen atmosphere, alumina particle | grains were made with respect to the temperature (A2 ') with the largest negative slope, and the said sinterable metal particle and non-sinterable metal particle. In the differential thermal analysis curve (DTA curve) measured at a temperature rising rate of 10 ° C./min under a nitrogen atmosphere as a reference sample, the peak temperature observed at the lowest temperature in the peak observed in the temperature range of 200 ° C. to 400 ° C. ) Satisfies the relationship of B2 '<A2'.

From the film-like baking material containing the binder component contained in the film-like baking material before baking, the component except the said sinterable metal particle and the non-sinterable metal particle is reduced in weight by heating in nitrogen atmosphere, and this phenomenon is Appear as negative slope in TG curve.

In the sinterable metal particles contained in the film-like plastic material before firing, melting and sintering occur under heating in a nitrogen atmosphere, and the melting phenomenon appears as a negative peak in the DTA curve, and the sintering phenomenon as a positive peak in the DTA curve. .

The temperature A2 'and the temperature B2' satisfying the relationship of B2 '<A2' include the timing at which the components distributed around the sinterable metal particles of the film-like plastic material lose weight in the course of heat treatment. In comparison, it is thought that the melting and sintering of the sinterable metal particles are started early. Therefore, the film-like baking material which satisfy | fills the relationship of B2 '<A2' becomes in the state isolate | separated by the component distribute | circulated around sinterable metal particle, and it is easy to melt as a particulate form, and it is easy to At the point of arrival, the collision frequency is sharply increased, and the sintered metal particles melted in the form of fine particles tend to be sintered. As a result, in the film-like baking material which satisfy | fills the relationship of B2 '<A2', it is thought that sinterable metals are metal-bonded uniformly and densely, and the strength of the material after sintering improves.

The said temperature (A2 ') and temperature (B2') isolate | separate the sinterable metal particle and the component except the said sinterable metal particle from the film-form plastic material before baking, and from the TG curve and DTA curve for each separated sample. You can get it.

Separation of the remaining components except the sinterable metal particles and the sinterable metal particles from the film-like plastic material before firing can be carried out according to the following method, for example.

First, the film-like baking material before baking and a sufficient amount of an organic solvent are mixed and then left to stand for a sufficient time until the sinterable metal particles settle. By removing the supernatant with a syringe or the like and recovering the residue after drying at 120 ° C for 10 minutes, the component except for the sinterable metal particles can be separated from the film-like baking material. After removing the supernatant with the syringe or the like, the liquid containing the sinterable metal particles is again mixed with a sufficient amount of an organic solvent, and then left to stand for a sufficient time until the sinterable metal particles are settled. Pull out.

After repeating mixing of the organic solvent, standing still and removing the supernatant five times or more, the residue after drying the remaining liquid at 120 ° C. for 10 minutes can be collected by separating the sinterable metal particles.

This is the same also when the film-like baking material of 2nd Embodiment contains a non-sinterable metal particle, The said temperature (A2 ') and temperature (B2') are sinterable metal particle and the film-like baking material before baking. Non-sinterable metal particles and components other than the sinterable metal particles and non-sinterable metal particles can be separated and obtained from the TG curve and the DTA curve for each separated sample.

Separation of the sinterable metal particles and the non-sinterable metal particles from the film-like plastic material before firing and the remaining components except for the sinterable metal particles and the non-sinterable metal particles can be performed according to the following method, for example.

First, the film-like baking material before baking and a sufficient amount of an organic solvent are mixed and then left to stand for a sufficient time until the sinterable metal particles and the non-sinterable metal particles settle. By removing the supernatant with a syringe or the like and recovering the residue after drying at 120 ° C. for 10 minutes, the component except for the sinterable metal particles and the non-sinterable metal particles can be separated from the film-like baking material. In addition, after removing the supernatant with the syringe or the like, a sufficient time until the sinterable metal particles and the non-sinterable metal particles are settled after mixing a sufficient amount of an organic solvent with respect to the liquid containing the sinterable metal particles and the non-sinterable metal particles. Allow to stand, and remove the supernatant with a syringe or the like. After repeating the mixing of the organic solvent and the standing and removing the supernatant five times or more, the residue after drying the remaining liquid at 120 ° C. for 10 minutes can be collected by separating the sinterable metal particles and the non-sinterable metal particles.

It is preferable that the solvent used here can melt | dissolve a binder component and can volatilize on the drying conditions of said 120-250 degreeC / min, and a suitable thing can be suitably used according to the kind of binder component, etc. For example, Hydrocarbons, such as toluene and xylene; Alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol) and 1-butanol; Esters such as ethyl acetate; Ketones such as acetone and methyl ethyl ketone; Ethers such as tetrahydrofuran; Amides (compounds having amide bonds) such as dimethylformamide and N-methylpyrrolidone.

<Endothermic peak>

The film-like calcined material of the second embodiment is 25 in the differential thermal analysis curve (DTA curve) measured at an elevated temperature rate of 10 ° C./min in a nitrogen atmosphere as the reference sample with respect to the film-like calcined material. It is preferable not to have an endothermic peak in the temperature range of 400 degreeC.

The said DTA curve shows the temperature change of the parallax heat of a film-like baking material in the process of heat-processing a film-like baking material as baking.

When the endothermic peak is recognized in the DTA curve, it is considered that the film-like calcined material contains a component having a property of absorbing and changing (for example, evaporating) heat from the film-like calcined material at 25 ° C to 400 ° C. That is, it can be considered that evaporation of the components occurs and the heat of vaporization accompanying them is necessary. Or it shows that many components which endotherm and thermally decompose and exceed the amount of heat generate | occur | produced by sintering.

Therefore, it is preferable that the film-like baking material of 2nd Embodiment has little or no content of the component which has the property to evaporate from a film-like baking material from 25 degreeC to 400 degreeC. In addition, it is preferable that the amount of components absorbing a large amount of heat for pyrolysis and preventing the exothermic process by sintering is small or not included.

Here, before measuring the DTA curve with respect to a film-form baking material, it is recommended to pretreat a film-like baking material, such as drying, and to prevent the moisture absorbed as an impurity from being measured. As dry processing conditions, 4 minutes is mentioned at 110 degreeC.

In the DTA curve, the particles do not have an endothermic peak in the temperature range of 25 ° C. to 400 ° C., and there is no fear that the components distributed around the sinterable metal particles are not reduced, and the particles are distributed by the components distributed around the sinterable metal particles. This is likely to be isolated. As a result, in the film-like fired material having no endothermic peak in the temperature range of 25 ° C to 400 ° C in the DTA curve, the sinterable metals form metal bonds uniformly and densely, and the strength of the material after sintering is improved. easy. In addition, the loss of energy required for firing is reduced, and firing in a favorable environment is realized. In addition, it is thought that the shear adhesive force after baking of a film-form baking material improves by this.

According to the film-like baking material of said 2nd Embodiment, since it is a film form, it is excellent in thickness stability. Moreover, since the film-like baking material of 2nd Embodiment contains sinterable metal particle, it is excellent in thermal conductivity. Moreover, the film-like baking material of 2nd Embodiment satisfies the said relationship of A2 <B2 <A2 + 60 degreeC, and exhibits the outstanding shear adhesive force after baking.

`` Method for producing film-like plastic material ''

A film-like baking material can be formed using the baking material composition containing the structural material.

For example, the target site | part is formed by coating the baking material composition containing each component and solvent which comprise a film-like baking material on the surface to be formed of a film-like baking material, drying as needed, and volatilizing a solvent. A film adhesive can be formed in.

It is preferable that boiling point is less than 250 degreeC as a solvent, It is more preferable that boiling point is less than 200 degreeC, For example, n-hexane (boiling point: 68 degreeC), ethyl acetate (boiling point: 77 degreeC), 2-butanone (boiling point) : 80 ° C), n-heptane (boiling point: 98 ° C), methylcyclohexane (boiling point: 101 ° C), toluene (boiling point: 111 ° C), acetylacetone (boiling point: 138 ° C), n-xylene (boiling point: 139 ° C ), Dimethylformamide (boiling point: 153 ° C), butyl carbitol (boiling point: 230 ° C), and the like. These may be used independently and may be used in combination.

The surface of a peeling film is mentioned as a formation object surface of a film-like baking material.

Coating of a baking material composition may be performed by a well-known method, For example, an air knife coater, a blade coater, a bar coater, a gravure coater, a comma (trademark) coater, a roll coater, a roll knife coater, a curtain coater And a coater such as a die coater, a knife coater, a screen coater, a Mayer bar coater, a kiss coater, and the like.

Although the drying conditions of a baking material composition are not specifically limited, When a baking material composition contains a solvent, it is preferable to heat-dry, In this case, for example, 70-250 degreeC, for example, 80-180 degreeC It is preferable to dry on the conditions of 10 second-10 minutes.

≪Film-shaped plastic material having a support sheet≫

The film-like baking material which has the support sheet of embodiment is provided with the support sheet provided in at least one side of the said film-like baking material and the said film-like baking material. It is preferable that an adhesive layer is provided in the front surface or outer peripheral part on a base film on the said support sheet, and the said film-like baking material is provided on the said adhesive layer. The said film-like baking material may be provided in direct contact with an adhesive layer, and may be provided in direct contact with a base film. By taking this form, it can be used as a dicing sheet used when individualizing a semiconductor wafer into an element. In addition, by separating the wafer together using a blade or the like, it can be processed as a film-like plastic material of the same type as the device, and a semiconductor device having a film-like plastic material can be manufactured.

Hereinafter, embodiment of the film-form baking material which has a support sheet is described. In FIG.4 and FIG.5, schematic sectional drawing of the film-form baking material which has the support sheet of this embodiment is shown. As shown to FIG. 4, FIG. 5, the film-like baking material 100a, 100b which has the support sheet of this embodiment is a film-like baking material 1 in the inner peripheral part of the support sheet 2 which has an adhesion part in the outer peripheral part. ) Is attached to be peeled off. As shown in FIG. 4, the support sheet 2 is an adhesive sheet which has the adhesive layer 4 in the upper surface of the base film 3, and the inner peripheral surface of the adhesive layer 4 is covered with a film-like baking material And the adhesive part was exposed in the outer peripheral part. In addition, as shown in FIG. 5, the structure which has the ring-shaped adhesive layer 4 may be sufficient as the support sheet 2 in the outer peripheral part of the base film 3. As shown in FIG.

The film-like baking material 1 is formed in the substantially same shape as the workpiece | work (semiconductor wafer etc.) affixed on the inner peripheral part of the support sheet 2, and is formed. The outer peripheral part of the support sheet 2 has an adhesion part. In a preferable embodiment, the film-like plastic material 1 having a smaller diameter than the support sheet 2 is laminated on the circular support sheet 2 in a concentric manner. The adhesive part of an outer peripheral part is used for fixing the ring frame 5 as shown.

(Substrate film)

The base film 3 is not particularly limited, and for example, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene / propylene copolymer, polypropylene, polybutene, polybutadiene, polymethylpentene, ethylene / acetic acid Vinyl copolymer, ethylene (meth) acrylic acid copolymer, ethylene methyl (meth) acrylate copolymer, ethyl ethylene (meth) acrylate copolymer, polyvinyl chloride vinyl, vinyl chloride vinyl acetate copolymer, polyurethane film, The film etc. which consist of ionomer etc. are used. In addition, in this specification, "(meth) acryl" is used by the meaning containing both an acryl and methacryl.

Moreover, when higher heat resistance is calculated | required with respect to a support sheet, as the base film 3, polyester films, such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyolefin films, such as polypropylene and polymethyl pentene, Etc. can be mentioned. Moreover, the modified film by these crosslinked films, radiation, discharge, etc. can also be used. The base film may be a laminate of the above films.

In addition, these films may be used in combination of two or more kinds. Moreover, what colored such film, or performed printing can also be used. In addition, the film may be formed by sheeting thermoplastic resin by extrusion molding, may be stretched, or may be used by thinning and curing curable resin by predetermined means.

The thickness of a base film is not specifically limited, Preferably it is 30-300 micrometers, More preferably, it is 50-200 micrometers. By making the thickness of a base film into the said range, even if the notch by dicing is performed, heat insulation hardly arises in a base film. Moreover, since sufficient flexibility is provided to the film-like baking material which has a support sheet, it shows favorable adhesiveness with respect to a workpiece | work (for example, a semiconductor wafer etc.).

A base film can also be obtained by apply | coating a peeling agent to a surface, and performing peeling process. Alkyd-based, silicone-based, fluorine-based, unsaturated polyester-based, polyolefin-based, wax-based, etc. are used as the release agent used in the peeling treatment, but the alkyd-based, silicone-based, and fluorine-based release agents are particularly preferable because they have heat resistance.

In order to peel-process the surface of a base film using said peeling agent, a peeling agent is applied as it is without a solvent, or solvent dilution or emulsification is carried out, and it is apply | coated by a gravure coater, a Meyer bar coater, an air knife coater, a roll coater, etc. The coated base film may be provided at room temperature or under heating, or may be cured by an electron beam, or a laminate may be formed by wet lamination, dry lamination, hot melt lamination, melt extrusion lamination, coextrusion, or the like.

(Adhesive layer)

The support sheet 2 has an adhesion part at least in the outer peripheral part. It is preferable that an adhesion part has a function which temporarily fixes the ring frame 5 to the outer peripheral parts of the film-shaped baking material 100a, 100b which has a support sheet, and the ring frame 5 can peel after a necessary process. . Therefore, a weakly adhesive thing may be used for the adhesive layer 4, and an energy ray curable thing in which adhesive force falls by energy ray irradiation may be used. The re-peelable pressure-sensitive adhesive layer contains a variety of conventionally known pressure-sensitive adhesives (for example, general-purpose pressure-sensitive adhesives such as rubber, acrylic, silicone, urethane, and vinyl ether), pressure-sensitive adhesives with surface irregularities, energy ray-curable pressure-sensitive adhesives, and thermal expansion components. Pressure sensitive adhesive and the like).

As shown in FIG. 4, the support sheet 2 is an adhesive sheet of the usual structure which has the adhesive layer 4 in the upper whole surface of the base film 3, and the inner peripheral surface of the adhesive layer 4 has a film form. The structure may be covered with a baking material and the adhesive part was exposed to the outer peripheral part. In this case, the outer peripheral part of the adhesive layer 4 is used for fixing the above-mentioned ring frame 5, and the inner peripheral part is laminated so that a film-like plastic material can peel. As the adhesive layer 4, a weakly adhesive thing may be used similarly to the above, or an energy ray curable adhesive may be used.

In addition, in the structure shown in FIG. 5, the ring-shaped adhesive layer 4 is formed in the outer peripheral part of the base film 3, and it is set as an adhesion part. At this time, the pressure-sensitive adhesive layer 4 may be a single-layer pressure-sensitive adhesive layer made of the pressure-sensitive adhesive, or may be an annular cut of the double-sided adhesive tape including the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive.

As a weak adhesive, acrylic type and silicone type are used preferably. In addition, considering the peelability of the film-like plastic material, it is preferable that the adhesive force to the SUS plate at 23 ° C. of the pressure-sensitive adhesive layer 4 is 30 to 120 mN / 25 mm, and is 50 to 100 mN / 25 mm. It is more preferable, and it is more preferable that it is 60-90 mN / 25 mm. If this adhesive force is too low, the adhesiveness of the film-like baking material 1 and the adhesive layer 4 may become inadequate, and a film-like baking material and an adhesive layer may peel off or a ring frame may fall off in a dicing process. . If the adhesive force is too high, the film-like plastic material and the pressure-sensitive adhesive layer are excessively in contact with each other, which causes a pickup failure.

In the support sheet of the structure of FIG. 4, when an energy ray curable re-peelable adhesive layer is used, energy ray irradiation may be previously performed to the area | region where a film-form baking material is laminated | stacked, and adhesiveness may be reduced. At this time, other areas may not be irradiated with energy rays, and for example, the adhesive force may be kept high for the purpose of adhesion to the ring frame 5. In order not to perform energy ray irradiation only in another area | region, what is necessary is to provide an energy ray shielding layer by printing etc. in the area | region corresponding to another area | region of a base film, for example, and to perform an energy ray irradiation from the base film side. Moreover, in the support sheet of the structure of FIG. 4, in the surface in which the adhesive layer 4 of the base film 3 is provided in order to strengthen adhesion | attachment of the base film 3 and the adhesive layer 4 as needed, Uneven treatment by sand blast or solvent treatment, or oxidation treatment such as corona discharge treatment, electron beam irradiation, plasma treatment, ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment and the like can be performed. It is also possible to add a primer treatment.

Although the thickness of the adhesive layer 4 is not specifically limited, Preferably it is 1-100 micrometers, More preferably, it is 2-80 micrometers, Especially preferably, it is 3-50 micrometers.

(Film-like Plastic Material Having a Support Sheet)

The film-like plastic material which has a support sheet is temporarily attached so that a film-like plastic material may peel on the inner peripheral part of the support sheet which has an adhesion part in an outer peripheral part. In the structural example shown in FIG. 4, the film-like baking material 100a which has a support sheet is a film-like baking material 1 in the inner peripheral part of the support sheet 2 which consists of the base film 3 and the adhesive layer 4. Laminated | stacked so that peeling may be possible, and the adhesive layer 4 is exposed in the outer peripheral part of the support sheet 2. In this structural example, it is preferable that the film-form baking material 1 of a smaller diameter than the support sheet 2 is laminated | stacked so that peeling may be carried out concentrically on the adhesive layer 4 of the support sheet 2.

The film-like baking material 100a which has the support sheet of the said structure is affixed on the ring frame 5 in the adhesive layer 4 exposed to the outer peripheral part of the support sheet 2.

Moreover, you may provide an annular double-sided tape or an adhesive layer separately on the margin (the adhesive layer exposed by the outer peripheral part of an adhesive sheet) with respect to a ring frame. The double-sided tape has a constitution of a pressure-sensitive adhesive layer / core material / adhesive layer, and the pressure-sensitive adhesive layer is not particularly limited in the double-sided tape. For example, pressure-sensitive adhesives such as rubber, acrylic, silicone, and polyvinyl ether are used. When manufacturing an element mentioned later, an adhesive layer is affixed on the ring frame in the outer peripheral part. As a core material of a double-sided tape, a polyester film, a polypropylene film, a polycarbonate film, a polyimide film, a fluororesin film, a liquid crystal polymer film, etc. are used preferably, for example.

In the structural example shown in FIG. 5, the ring-shaped adhesive layer 4 is formed in the outer peripheral part of the base film 3, and it is set as an adhesion part. 6, the perspective view of the film-like baking material 100b which has a support sheet shown in FIG. 5 is shown. At this time, the pressure-sensitive adhesive layer 4 may be a single-layer pressure-sensitive adhesive layer made of the pressure-sensitive adhesive, or may be an annular cut of the double-sided adhesive tape including the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive. The film-like baking material 1 is laminated | stacked so that peeling may be carried out in the inner peripheral part of the base film 3 surrounded by an adhesion part. In this structural example, it is preferable that the film-form baking material 1 of a smaller diameter than the support sheet 2 is laminated | stacked so that peeling may be carried out concentrically on the base film 3 of the support sheet 2.

The film-like plastic material which has a support sheet is provided with a peeling film for the purpose of surface protection in order to avoid contact with the outside of the surface of either or both of a film-like plastic material and an adhesion part until it uses for use, Also good.

As a surface protection film (peel film), it can also be obtained by apply | coating a peeling agent to the surface of base film, such as polyethylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polypropylene mentioned above, and performing a peeling process. Alkyd-based, silicone-based, fluorine-based, unsaturated polyester-based, polyolefin-based, wax-based, etc. are used as the release agent used in the peeling treatment, but the alkyd-based, silicone-based, and fluorine-based release agents are particularly preferable because they have heat resistance.

In order to peel-process the surface of a base film using said peeling agent, a peeling agent is just unsolvent-free or solvent dilution or emulsification, apply | coats with a gravure coater, a Meyer bar coater, an air knife coater, a roll coater, etc. The coated base film may be provided at room temperature or under heating, or may be cured by an electron beam, or a laminate may be formed by wet lamination, dry lamination, hot melt lamination, melt extrusion lamination, coextrusion, or the like.

1-500 micrometers is preferable, as for the thickness of the film-like baking material which has a support sheet, 5-300 micrometers is more preferable, and its 10-150 micrometers are more preferable.

`` Method for producing film-like plastic material having a support sheet ''

The film-like plastic material which has the said support sheet can be manufactured by laminating | stacking each layer mentioned above so that it may become a corresponding positional relationship.

For example, when laminating an adhesive layer or a film-like baking material on a base film, the adhesive composition or baking material composition containing the component and solvent which comprise this on a peeling film is coated, and it dried as needed. By evaporating the solvent to form a film, the pressure-sensitive adhesive layer or film-like plastic material is formed in advance on the release film, and the exposure on the side opposite to the side in contact with the release film of the formed pressure-sensitive adhesive layer or film-like plastic material The surface may be bonded to the surface of the base film. At this time, it is preferable to coat an adhesive composition or a baking material composition to the peeling process surface of a peeling film. What is necessary is just to remove a peeling film as needed after formation of a laminated structure.

For example, the film-like plastic material which has a support sheet by which an adhesive layer is laminated | stacked on a base film and the film-like plastic material is laminated | stacked on the said adhesive layer (support sheet which is a laminated body of a base film and an adhesive layer is used. In the case of manufacturing a film-like baking material), a pressure-sensitive adhesive layer is laminated on a base film by the above-described method, and a baking material composition containing a component and a solvent for constituting this on a release film is coated separately. By drying, if necessary, by evaporating the solvent to form a film, a film-like plastic material is formed on the release film, and the exposed surface of the film-like plastic material is bonded to the exposed surface of the pressure-sensitive adhesive layer laminated on the substrate. By laminating a film-like baking material on an adhesive layer, the film-like baking material which has a support sheet is obtained. Also when forming a film-form baking material on a peeling film, it is preferable to coat a baking material composition on the peeling process surface of a peeling film, and a peeling film may be removed as needed after formation of a laminated structure.

Thus, since all layers other than the base material which comprises the film-form plastic material which has a support sheet are previously formed on the peeling film, and can be laminated | stacked by the method of bonding to the surface of the layer made into the objective, it is such a necessity. What is necessary is just to select suitably the layer which employ | adopts a process, and to manufacture the film-form baking material which has a support sheet.

Moreover, after providing all the necessary layers, the film-like baking material which has a support sheet may be stored in the state which bonded the peeling film to the surface of the outermost layer on the opposite side to the support sheet.

`` Method of manufacturing element ''

Next, the case where the said baking material is applied to manufacture of an element (for example, a semiconductor element) is demonstrated about the usage method of the film-form baking material which has a support sheet concerning this invention as an example.

In one embodiment of the present invention, a method for manufacturing a semiconductor device using a film-like firing material having a support sheet is obtained by peeling a release film of the film-like firing material having a support sheet and forming a circuit on the surface of the semiconductor wafer (work). The film-like plastic material which has a support sheet is affixed on the back surface, and you may perform the following process (1)-(2) in order of (1), (2), and the following process (1)-(4 ) May be performed in the order of (1), (2), (3), and (4).

Process (1): The process of dicing a semiconductor wafer (work) and a film-like baking material of the laminated body by which the support sheet, the film-like baking material, and the semiconductor wafer (work) were laminated | stacked in this order,

Process (2): The process of peeling a film plastic material and a support sheet, and obtaining an element which has a film plastic material,

Process (3): The process of affixing the element which has a film-form baking material on the surface of a to-be-adhered body,

Process (4): The process of baking a film-like baking material and joining a semiconductor element and a to-be-adhered body.

Hereinafter, the case where the said process (1)-(4) is performed is demonstrated.

The semiconductor wafer may be a silicon wafer, a silicon carbide wafer, or a compound semiconductor wafer such as gallium arsenide. Formation of the circuit on the wafer surface can be performed according to various methods including conventionally used methods such as an etching method and a lift-off method. Next, the opposite surface (rear surface) of the circuit surface of a semiconductor wafer is ground. The grinding method is not particularly limited and may be ground by a known means using a grinder or the like. In the case of back grinding, in order to protect the circuit of a surface, the adhesive sheet called a surface protection sheet is affixed on a circuit surface. Back surface grinding fixes the circuit surface side (namely, the surface protection sheet side) of a wafer with a chuck table etc., and grinds the back surface side in which the circuit is not formed with a grinder. Although the thickness after grinding of a wafer is not specifically limited, Usually, it is about 20-500 micrometers. Then, the crushing layer which arose at the time of back surface grinding as needed is removed. The fracture layer is removed by chemical etching, plasma etching, or the like.

Next, the film-like baking material of the film-like baking material which has the said support sheet is stuck on the back surface of a semiconductor wafer. After that, steps (1) to (4) are performed in the order of (1), (2), (3), and (4).

The laminated body of a semiconductor wafer / film plastic material / support sheet is diced for every circuit formed in the wafer surface, and the laminated body of a semiconductor element / film plastic material / support sheet is obtained.

Dicing is performed so that a wafer and a film-shaped baking material may be cut | disconnected together. According to the film-like plastic material which has the support sheet of this embodiment, since adhesive force is exhibited between a film-like plastic material and a support sheet at the time of dicing, chipping and element flutter can be prevented and it is excellent in dicing aptitude. . Dicing is not specifically limited, For example, when dicing a wafer, after fixing the periphery part (outer peripheral part of a support body) of a support sheet with a ring frame, it is well-known, such as using rotating ring printing, such as a dicing blade. The method of individualizing a wafer according to a method, etc. are mentioned. The notch depth of the support sheet by dicing may be cut | disconnected completely, and it is preferable to set it as 0-30 micrometers from the interface of a film-like plastic material and a support sheet. By making the notch amount to a support sheet small, melting | fusing of the adhesive layer and base film which comprise the support sheet by the friction of a dicing blade, generation | occurrence | production of a burr etc. can be suppressed.

Thereafter, the supporting sheet may be expanded. When selecting the thing excellent in extensibility as a base film of a support sheet, a support sheet has the outstanding expandability. The film-like plastic material and the support sheet are peeled off by picking up a semiconductor element having the diced film-like plastic material by a general means such as a collet. As a result, a semiconductor device (semiconductor device having a film-like baking material) having a film-like baking material on the back side is obtained.

Subsequently, the element which has a film-like baking material is affixed on the surface of to-be-adhered bodies, such as a board | substrate, a lead frame, and a heat sink.

Subsequently, the film-like baking material is fired, and the substrate and the adherend such as the lead frame and the heat sink and the element are sintered and joined. At this time, when the exposed surface of the film-like firing material of the semiconductor element having the film-like firing material is affixed to a substrate, a lead frame, an adherend such as a heat sink, and the like, the semiconductor wafer (work) and the The adherend can be sintered and joined.

The heating temperature for firing the film-like firing material may be appropriately determined in consideration of the kind of the film-like firing material and the like, but is preferably from 100 to 600 ° C, more preferably from 150 to 550 ° C, and even more preferably from 250 to 500 ° C. The heating time may be appropriately determined in consideration of the kind of film-like baking material and the like, but is preferably 10 seconds to 60 minutes, more preferably 10 seconds to 30 minutes, and even more preferably 10 seconds to 10 minutes.

The firing of the film-like baking material may be performed by pressing and firing by applying pressure to the film-like baking material. Pressurization conditions can be made into about 1-50 Mpa as an example.

According to the manufacturing method of the element of this embodiment, the film-form baking material with high uniformity of thickness can be easily formed in the back surface of an element, and it becomes difficult to produce the dicing process and the crack after packaging. In addition, according to the device manufacturing method of the present embodiment, a semiconductor device having a film-like plastic material can be obtained without separately attaching a film-like plastic material to the back surface of the individualized semiconductor device, thereby simplifying the manufacturing process. have. Then, by arranging and firing a semiconductor element having a film-like firing material on a desired adherend such as an apparatus substrate, it is possible to manufacture a semiconductor device in which the semiconductor element and the adherend are sintered and joined through a film-like firing material.

As one embodiment, a semiconductor device having a film-like baking material comprising a semiconductor device and the film-like baking material is obtained. The semiconductor element which has a film-like baking material can be manufactured by the manufacturing method of the said element as an example.

In addition, in the said embodiment, although the sintering joining of the semiconductor element of a film-form baking material and its to-be-adhered body was illustrated, the object of sintering joining of a film-like baking material is not limited to what was illustrated above, but contact | connects with a film-like baking material Sintering and joining can be carried out about various articles sintered.

Example

Hereinafter, although an Example etc. demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples.

<Production of Plastic Material Composition>

The component used for manufacture of a baking material composition is shown below. Here, the metal particles having a particle size of 100 nm or less are referred to as "sinterable metal particles", and the metal particles having a particle size of 100 nm or more are referred to as "non-sinterable metal particles".

(Sinterable Metal Particle Inclusion Paste Material)

Alconano silver paste ANP-1 (organic coated composite silver nano paste, APPLIED NANOPARTICLE LABORATORY CORPORATION: silver derivative coated silver particles, metal content of 70 wt% or more, silver particles of average particle size of 100 nm or less, 60 wt% or more)

Alconano silver paste ANP-4

(Binder component)

Acrylic polymer 1 (2-ethylhexyl methacrylate polymer, weight average molecular weight 280,000, L-0818, manufactured by The Nippon Synthetic Chemical Industry Co., Ltd., MEK dilution product, 54.5 mass% of solid content, Tg: -10 degreeC ( Calculation using Fox's formula)

Acrylic polymer 2 (methyl acrylate / 2-hydroxyethyl acrylate copolymer, copolymer weight ratio 85/15, weight average molecular weight 370,000, N-4617, manufactured by The Nippon Synthetic Chemical Industry Co., Ltd., ethyl acetate / Toluene = 1/1 mixed solvent dilution product, solid content 35.7 mass%, Tg: 4 degreeC (calculated value using the theoretical formula of Fox)

Each component was mixed by the formulation shown in following Table 1, and the baking material composition corresponding to Examples 1-2 and Comparative Examples 1-2 was obtained. The value of each component of Table 1 shows a mass part. Since the sinterable metal particle-containing paste material is sold with a high boiling point solvent and remains in the film-like baking material after coating or after drying, the components of the sinterable metal particle-containing paste material are described including these. . The solvent in the binder component is considered to volatilize at the time of drying, and represents the solid content mass part except the solvent component.

<Production of Film-like Plastic Material>

On one side of a release film (38 micrometers in thickness, SP-PET381031, the product made by LINTEC Corporation), the baking material composition obtained above was coated, and it dried at 110 degreeC for 4 minutes, and obtained the film-like baking material which has the thickness shown in Table 1 .

<Method for Separating Sinterable Metal Particles and Non-Sinterable Metal Particles and Components Excluding These from Film-like Plastic Materials>

After mixing about 10 times of organic solvent by weight with the film-form baking material before baking, it left still for about 30 minutes until the sinterable metal particle and the non-sinterable metal particle settled. The supernatant was removed with a syringe, and the residue after drying at 120 ° C. for 10 minutes was collected, and the components except for the sinterable metal particles and the non-sinterable metal particles were separated from the film-like baking material. In addition, after removing the supernatant with the syringe, the liquid containing the sinterable metal particles and the non-sinterable metal particles is again mixed with about 10 times the amount of the organic solvent of the film-like plastic material, and then the sinterable metal particles and the non-sinterable metal particles It was left to stand for about 30 minutes until it settled, and the supernatant liquid was removed by the syringe. After repeating the mixing of the organic solvent and the standing and removing the supernatant five times, the remaining liquid was dried at 120 ° C. for 10 minutes, and then the residue was recovered to fractionate the sinterable metal particles and the non-sinterable metal particles.

<Evaluation of film-like baking material>

The following items were evaluated about the film-like baking material obtained above.

(Measurement of TG / DTA in Atmosphere)

For the film-like fired material obtained above, using a thermal analysis measuring device (thermal analysis system TG / DTA simultaneous measuring device # DTG-60, manufactured by Shimadzu Corporation), alumina particles almost equal to the measurement sample were used as a reference sample under an atmospheric atmosphere. It measured from 40 degreeC to 600 degreeC by the temperature increase rate of 10 degree-C / min, and calculated | required the TG curve and the DTA curve. The result of Example 1 is shown in FIG. 7, the result of Example 2 is shown in FIG. 8, the result of the comparative example 1 is shown in FIG. 9, and the result of the comparative example 2 is shown in FIG. In addition, Table 1 shows the time (A1) after the start of the temperature increase with the highest negative slope in the TG curve and the maximum peak time (B1) in the time range from 0 second to 2160 second after the start of the temperature increase in the DTA curve.

In addition, according to the separation method, the temperature after the start of the temperature increase (A1 °) and the DTA curve in which the negative slope is the greatest in the TG curve for the components excluding the sinterable metal particles and the non-sinterable metal particles from the film-like plastic material is raised. Table 1 shows the peak time (B1 ms) observed at the shortest time within the peak observed in the time range of 960 seconds to 2160 seconds after the start.

(Measurement of TG / DTA in Nitrogen Atmosphere)

For the film-like fired material obtained above, using a thermal analysis measuring device (thermal analysis system TG / DTA simultaneous measuring device # DTG-60, manufactured by Shimadzu Corporation), alumina particles almost equal to the measurement sample were used as a reference sample under nitrogen atmosphere, It measured at the temperature increase rate of 10 degree-C / min, and calculated | required the TG curve and the DTA curve. The result of Example 1 is shown in FIG. 11, the result of Example 2 is shown in FIG. 12, the result of the comparative example 1 is shown in FIG. 13, and the result of the comparative example 2 is shown in FIG. In addition, Table 1 shows the temperature (A2) with the highest negative slope in the TG curve and the maximum peak temperature (B2) in the temperature range of 25 ° C to 400 ° C in the DTA curve.

In addition, according to the separation method, for the components except for the sinterable metal particles and the non-sinterable metal particles from the film-like plastic material, the temperature at which the negative slope is the largest in the TG curve (A2 °) and from 200 ° C in the DTA curve Table 1 shows the peak temperatures observed at the lowest temperatures in the peaks observed in the 400 ° C. temperature range (B 2 kPa).

(Measurement of Shear Adhesion)

The shear adhesive force after baking of a film-like baking material was measured in accordance with the following method.

The film-like plastic material obtained above was cut into 10 mm x 10 mm, and this was affixed to the upper surface of the cylindrical copper adherend of 5 mm in height having a cross section of 10 mm in diameter, and a cross section of 5 mm in diameter thereon. A columnar copper adherend having a height of 2 mm having a diameter was disposed, and calcined under the conditions of the following (1) to (3) in an air atmosphere or a nitrogen atmosphere to obtain a test piece for bonding adhesion measurement. At room temperature, the strength at the time of breaking the adhesive state by applying a force from the shear direction to the adhesive surface of this test piece at a rate of 6 mm / min was measured, and the highest bonding in the measurement results of the test piece obtained under the following pressure firing conditions It was set as the shear adhesive force with the average value of the value of the conditions which showed adhesive strength. The results are shown in Table 1.

(1) 300 ° C./min, 30 MPa,

(2) 350 ° C./min, 10 MPa,

(3) 400 ° C / min, 10 MPa

(Measurement of thickness)

According to JIS 정 K7130, it measured using the static pressure thickness meter (the product name "PG-02" by TECLOCK company).

The film-like baking materials of Examples 1 and 2 were higher in shear adhesion than the baking materials of Comparative Examples 1 and 2.

Each structure in each embodiment, its combination, etc. are an example, and addition, omission, substitution, and other change of a structure can be made in the range which does not deviate from the meaning of this invention. In addition, this invention is not limited by each embodiment, Only by the range of a claim (claim).

According to the present invention, it is possible to provide a film-like plastic material which is excellent in thickness stability and thermal conductivity and exhibits excellent shear adhesion after firing. Furthermore, the film-like baking material provided with the said film-like baking material and having a support sheet used for sintering joining of a semiconductor element can be provided.

1: film-like plastic material,
1c: plastic material,
10, 11: sinterable metal particles,
20, 21: binder component,
100: film-like plastic material having a support sheet,
2: support sheet,
3: base film,
4: adhesive layer,
5: ring frame

Claims (9)

As a film-like baking material containing a sinterable metal particle and a binder component,
In the thermogravimetric curve (TG curve) measured from 40 degreeC to 600 degreeC at the temperature increase rate of 10 degree-C / min in air | atmosphere, time (A1) after the start of temperature rising with the largest negative slope,
In the differential thermal analysis curve (DTA curve) measured from 40 ° C. to 600 ° C. at an elevated temperature rate of 10 ° C./min under an atmospheric atmosphere as an a reference sample with alumina particles, the maximum peak time in the time range from 0 to 2160 seconds after the start of the temperature rise. (B1)
The film-like baking material which satisfy | fills the relationship of A1 <B1 <A1 + 200 second, and is A1 <2000 second. The method of claim 1,
In the thermogravimetric curve (TG curve) measured from 40 degreeC to 600 degreeC at the temperature increase rate of 10 degree-C / min in air atmosphere about the component except the said sinterable metal particle from a film-like baking material, the negative slope has the largest Time (A1 °) after the start of the temperature rise,
For the above sinterable metal particles, in a differential thermal analysis curve (DTA curve) measured from 40 ° C. to 600 ° C. at an elevated temperature rate of 10 ° C./min in an atmospheric atmosphere using alumina particles as a reference sample, from 960 seconds to 2160. The peak time (B1 ms) observed at the shortest time within the peak observed in the second time range,
The film-like baking material which satisfy | fills the relationship of B1 '<A1'. The method according to claim 1 or 2,
For the film-like calcined material, in the differential thermal analysis curve (DTA curve) measured from 40 ° C. to 600 ° C. at an elevated temperature rate of 10 ° C./min in an atmospheric atmosphere with alumina particles as a reference sample, from 0 second after the start of temperature increase. The film-like baking material which does not have an endothermic peak in the time range of 2160 second. As a film-like baking material containing a sinterable metal particle and a binder component,
In the thermogravimetric curve (TG curve) measured at the temperature increase rate of 10 degree-C / min in nitrogen atmosphere, temperature (A2) with the largest negative slope,
In a differential thermal analysis curve (DTA curve) measured at an elevated temperature rate of 10 ° C./min under a nitrogen atmosphere as a reference sample, the maximum peak temperature (B2) in the temperature range of 25 ° C. to 400 ° C.,
The film-like baking material which satisfy | fills the relationship of A2 <B2 <A2 + 60 degreeC. The method of claim 4, wherein
In the thermogravimetric curve (TG curve) measured with the temperature increase rate of 10 degree-C / min in nitrogen atmosphere with respect to the component except the said sinterable metal particle from the film-like baking material, the temperature with the largest negative slope (A2Pa) and ,
Within the peak observed in the temperature range of 200 ° C. to 400 ° C. in a differential thermal analysis curve (DTA curve) measured at a temperature increase rate of 10 ° C./min under a nitrogen atmosphere for the sinterable metal particles as a reference sample. The peak temperature (B2 저온) observed at the lowest temperature is
The film-like baking material which satisfy | fills the relationship of B2 '<A2'. The method according to claim 4 or 5,
The endothermic peak in the temperature range of 25 ° C. to 400 ° C. in a differential thermal analysis curve (DTA curve) measured at a temperature increase rate of 10 ° C./min under a nitrogen atmosphere for the film-like fired material as a reference sample. Film-like plastic material having no. The method according to any one of claims 1, 2, 4 and 5,
The film-like baking material whose said sinterable metal particle is silver nanoparticle. The film which has a support sheet provided with the film-like baking material of any one of Claims 1, 2, 4, and 5, and the support sheet provided in at least one side of the said film-like baking material. Phase firing materials. The method of claim 8,
The said support sheet is an adhesive layer provided on the base film,
The film-like baking material which has a support sheet in which the said film-like baking material is provided on the said adhesive layer.

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