JP2012240348A - Composite sheet, method for manufacturing the composite sheet, electronic component, and electronic instrument - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite sheet excellent in handling property and strength which can be manufactured without requiring a large-scale equipment.SOLUTION: The composite sheet 1 has a resin layer 2 composed of thermosetting resin composition, and a fiber base material layer 3 having fiber base material formed to be in close contact with at least one main surface of the resin layer 2.

Description

  The present invention relates to a composite sheet that is excellent in handling properties and strength and can be manufactured without requiring large-scale equipment, a manufacturing method thereof, and an electronic component and an electronic apparatus using the composite sheet.

  Conventionally, what consists of thermosetting resin compositions, such as an epoxy resin composition, is known as an adhesive sheet used for the electronic component field (for example, refer patent document 1). However, the conventional adhesive sheet is not necessarily excellent in handling property and strength, and the embedding property of the adhesive sheet in the adhesive region is not excellent. Further, when processing an electronic component to which a conventional adhesive sheet is bonded, the adhesive sheet may be peeled off, and an adhesive sheet having a high adhesive force is required.

  On the other hand, a prepreg composed of a fiber base material and a thermosetting resin composition, such as a glass epoxy prepreg, is also used as an adhesive sheet (see, for example, Patent Document 2). Although the prepreg has relatively good handling properties and strength, it is not necessarily excellent in embedding property in an adhesive region, and the usable electronic parts are limited. In addition, the manufacture of a prepreg generally requires a dedicated large-sized coating machine, and also requires an organic solvent and the like.

JP 2002-60720 A JP-A-2-102281

  The present invention has been made to solve the above-described problems, and is an adhesive sheet that is suitably used for insulation or the like by being bonded to an electronic component element body in order to manufacture an electronic component. An object of the present invention is to provide a composite sheet that is excellent in properties and strength and can be manufactured without requiring extensive facilities. Moreover, this invention aims at providing the manufacturing method of an above described composite sheet. Furthermore, an object of the present invention is to provide an electronic component that includes the above-described composite sheet and that suppresses the occurrence of peeling and cracking of the composite sheet during processing, particularly during cutting.

  The composite sheet of the present invention is characterized by having a resin layer made of a thermosetting resin composition and a fiber substrate layer having a fiber substrate formed in close contact with at least one main surface of the resin layer. .

  The method for producing a composite sheet of the present invention includes a step of kneading the components of the thermosetting resin composition at a temperature of 50 to 110 ° C. to obtain a kneaded product, and supplying the kneaded product to one side of the fiber substrate. Or after supplying the kneaded material between a pair of fiber base materials, pressing the kneaded material against the fiber base material so as to be integrally formed into a sheet to obtain a composite sheet, To do.

  The electronic component of the present invention includes an electronic component element body and the above-described composite sheet of the present invention which is disposed on at least a part of the surface of the electronic component element body and insulates the surface. The electronic device of the present invention includes an electronic component and the above-described composite sheet of the present invention that seals the electronic component.

  According to the composite sheet of the present invention, since the fiber base material layer is formed in close contact with at least one main surface of the resin layer, it is excellent in handling properties and strength, and can be manufactured without requiring large-scale equipment. it can. Moreover, when it applies to an electronic component or an electronic device, it is possible to suppress the occurrence of peeling or cracking during processing, particularly during cutting. Thereby, it can contribute to the improvement of the yield in manufacture of an electronic component or an electronic device.

  According to the method for producing a composite sheet of the present invention, the above-described composite sheet of the present invention can be efficiently produced. Moreover, according to the electronic component and electronic device of this invention, the yield at the time of manufacture of an electronic component or an electronic device can be improved by using the composite sheet of this invention mentioned above.

Sectional drawing which shows schematic structure of 1st Embodiment of a composite sheet. Sectional drawing which shows schematic structure of 2nd Embodiment of a composite sheet. Sectional drawing which shows schematic structure of the conventional prepreg. Explanatory drawing explaining 1st Embodiment of the manufacturing method of a composite sheet. Explanatory drawing explaining 2nd Embodiment of the manufacturing method of a composite sheet. Explanatory drawing explaining 3rd Embodiment of the manufacturing method of a composite sheet. Explanatory drawing explaining 4th Embodiment of the manufacturing method of a composite sheet. Sectional drawing which shows an example of the electronic component element body to which a composite sheet is applied. Sectional drawing which shows an example of the electronic component to which the composite sheet was applied. Sectional drawing which shows the other example of the electronic component to which the composite sheet was applied.

Hereinafter, the present invention will be described in detail.
The composite sheet of the present invention has a resin layer made of a thermosetting resin composition, and a fiber base layer having a fiber base formed in close contact with at least one main surface of the resin layer. . Hereinafter, the thermosetting resin composition may be simply referred to as a resin.

  FIG. 1 is a cross-sectional view showing a schematic configuration of the first embodiment of the composite sheet, and FIG. 2 is a cross-sectional view showing a schematic configuration of the second embodiment of the composite sheet. In addition, FIG. 3 is sectional drawing which shows schematic structure of the conventional prepreg.

  For example, as shown in FIG. 1 (a) or FIG. 2 (a), the composite sheet 1 is a fiber base layer having a fiber base on one or both main surfaces of a resin layer 2 made of a thermosetting resin composition. 3 is formed in close contact. A release film 4 made of, for example, polyethylene terephthalate is provided on both main surfaces of the composite sheet 1. The release film 4 is peeled off at the time of use, and the composite sheet 1 is used by adhering to an electronic component element body in order to manufacture an electronic component in the state shown in FIG. 1B or FIG. 2B, for example.

  In the composite sheet 1 of the present invention, the fiber base layer 3 is formed in close contact with at least one main surface of the resin layer 2. According to such a composite sheet 1, since the fiber base layer 3 is formed in close contact with the main surface of the resin layer 2, it is excellent in handling properties and strength, and does not require extensive equipment, and is complicated. It can be manufactured without going through a complicated process. Moreover, when it adheres to an electronic component element | base_body and is used for manufacture of an electronic component, generation | occurrence | production of peeling and a crack at the time of a process to an electronic component, especially a cutting | disconnection can be suppressed, and the yield of an electronic component can be improved.

  FIG. 3 is a cross-sectional view showing a conventional prepreg 50. The conventional prepreg 50 has a fiber base material 51, and the fiber base material 51 is impregnated with a thermosetting resin composition 52. The conventional prepreg 50 requires a large facility such as an impregnation tank in order to impregnate the fiber base material 51 with the thermosetting resin composition 52, and also requires an organic solvent and the like. According to the composite sheet 1 of the present invention, the thermosetting resin composition is molded into a sheet shape as described later by adopting a structure in which the fiber base layer 3 is formed in close contact with the main surface of the resin layer 2. Large-scale equipment that can be manufactured by supplying and pressing a fiber substrate to the surface of the sheet-shaped resin composition, or by supplying and pressing a melt of the thermosetting resin composition to the surface of the fiber substrate Can be produced without requiring a complicated process.

  The ratio of the resin component in the composite sheet 1 is preferably 65 to 93% by volume. By setting the ratio of the resin component to 65 to 93% by volume, the adhesive force of the composite sheet 1 can be sufficient, and the resin bleeding from the composite sheet 1 and the warp at the time of curing of the composite sheet 1 can be suppressed. Peelability and crack resistance can also be improved.

  That is, when the resin content is less than 65% by volume, the resin content is small, so that the embeddability of the composite sheet 1 in an adhesive region where sealing or insulation is performed, for example, a recess between electrodes, is insufficient. There is a risk that peeling or cracking at the time of cutting, particularly during cutting, cannot be sufficiently suppressed. On the other hand, when the proportion of the resin exceeds 93% by volume, there are many thermosetting resin compositions attached to the surface of the fiber base material, and the outflow of the resin increases, so that the spread to areas other than the adhesion region increases. Further, cracks are likely to occur in the composite sheet 1.

In addition, the ratio of a resin part means the ratio in the volume of the thermosetting resin composition in the whole composite sheet 1. The ratio [volume%] of the resin can be obtained from the following formula.
Resin content [volume%]
= {(Thickness of composite sheet [μm] −mass of fiber substrate [g / m ² ] / specific gravity of fiber [g / cm ³ ])
/ Composite sheet thickness [μm]} × 100
For example, the composite sheet 1 has one glass cloth as a fiber substrate, the thickness of the composite sheet 1 is 160 [μm], the mass of the glass cloth is 48 [g / m ² ], and the specific gravity of the glass Is 2.54 [g / cm ³ ], it is determined as follows.
Resin content [volume%]
= {(160 [μm] −48 [g / m ² ] /2.54 [g / cm ³ ]) / 160 [μm]} × 100
= 88

  The thickness of the resin layer 2 is preferably 30 to 500 μm. When the thickness is less than 30 μm, for example, the handling property of the sheet-shaped resin composition used for forming the resin layer 2 alone is not excellent. Further, when an electronic component is manufactured by adhering the composite sheet 1 to the electronic component element body, the composite sheet 1 may be peeled from the electronic component when the electronic component is processed, particularly when it is cut. On the other hand, if it exceeds 500 μm, cracks are likely to occur in the resin layer 2 and it is difficult to make the electronic component thinner.

  As for the thickness of the fiber base material layer 3, 30-180 micrometers is preferable. When the thickness is less than 30 μm, the handleability of a single fiber substrate used for forming the fiber substrate layer 3 is not excellent. On the other hand, when it exceeds 180 μm, it is difficult to impregnate the entire fiber base material with resin.

  Although the thickness of the composite sheet 1 can be suitably selected according to the thickness of the resin layer 2 and the fiber base layer 3 and the use of the composite sheet 1, it is usually preferably 100 to 500 μm.

  The plasticity at normal temperature (25 ° C.) of the thermosetting resin composition constituting the resin layer 2 is preferably 60 to 90. When the plasticity is less than 60, the flow of the thermosetting resin composition cannot be suppressed, the bleeding to the outside of the adhesion region increases, leading to poor appearance and contamination around the adhesion region. In addition, when the plasticity exceeds 90, voids in the adhesion region increase, which may cause poor adhesion or poor filling. In addition, the plasticity in this specification is measured with a parallel plate plasticity meter based on a method based on JIS K6249.

  The fiber base layer 3 is formed in close contact with at least one main surface of the resin layer 2. The fiber base material constituting the fiber base layer 3 is preferably impregnated with the thermosetting resin composition constituting the resin layer 2 in at least a part of the voids. It is preferable that the thermosetting resin composition which comprises is impregnated. That is, the fiber base material constituting the fiber base layer 3 is preferably arranged so as to be embedded in the surface portion of the resin layer 2.

  The fiber substrate may be a woven fabric or a non-woven fabric, and can be any fiber substrate. Moreover, it does not specifically limit about the constituent material, It can be set as glass fiber, aromatic polyamide fiber, a cellulose fiber, a polyester fiber, etc., These can be used individually or in mixture of 2 or more types.

  The fiber base material is preferably glass cloth or glass paper, particularly glass cloth. The type of glass cloth is not particularly limited, but plain weave E glass cloth defined in IPC-EG-140 is preferable, and 30-180 μm such as 1078 type, 1080 type, 1037 type, 1084 type, 2110 type, 7628 type. Thickness is particularly preferred.

  The resin layer 2 is made of a thermosetting resin composition. Examples of the thermosetting resin include an epoxy resin, an acrylic resin, a urethane resin, a melamine resin, and a phenol resin.

  Especially as a thermosetting resin composition, an epoxy resin composition is preferable, (A) Liquid bisphenol type epoxy resin, (B) Solid polyfunctional epoxy resin whose softening point is 70 degrees C or less, (C) Curing for epoxy resins An agent and (D) an inorganic filler as essential components are preferred. Here, the mass ratio (A) / (B) is preferably 10/90 to 25/75, and the proportion of the component (D) in the whole thermosetting resin composition is preferably 10 to 50 mass%.

  The liquid bisphenol type epoxy resin as the component (A) is not particularly limited as long as it is a liquid bisphenol type compound having two or more epoxy groups in one molecule, and examples thereof include bisphenol A type and bisphenol F type. Is preferred. Among these, bisphenol A type epoxy resin is preferably used. Specific examples thereof include “DER383J” manufactured by Dow Chemical Company, “Epicoat 828” (epoxy equivalent 190) manufactured by Mitsubishi Chemical Corporation, and “R140P” manufactured by Mitsui Chemicals. (Epoxy equivalent 188). In the present invention, the liquid bisphenol type epoxy resin refers to a bisphenol type epoxy resin that exhibits a liquid state at 25 ° C.

  (B) As a solid polyfunctional epoxy resin whose softening point of a component is 70 degrees C or less, the mixture of the biphenyl frame | skeleton containing aralkyl type epoxy resin represented, for example by following formula (1) is mentioned. In following formula (1), m shows the integer of 1-4.

  Furthermore, the mixture etc. of the dicyclopentadiene type epoxy resin represented by following formula (2) are mentioned. In following formula (2), n shows the integer of 1-10.

In addition, the softening point of these solid polyfunctional epoxy resins is a value measured by the following method.
<Measurement of softening point>
Based on JISK2207, a sample is filled in a specified ring, supported horizontally in a water bath or a glycerin bath, a specified sphere is placed in the center of the sample, and the bath temperature is increased at a rate of 5 ° C. per minute. It is the temperature read when the encased sample contacts the bottom plate of the platform.

  As a commercial product of a solid polyfunctional epoxy resin having a softening point of 70 ° C. or lower, “NC3000 (softening point 57 ° C.)”, “NC3000H (softening point 70 ° C.)” manufactured by Nippon Kayaku Co., Ltd. is preferably used. The

  By combining (A) liquid bisphenol type epoxy resin and (B) solid polyfunctional epoxy resin having a softening point of 70 ° C. or lower, that is, by blending two types of epoxy resins having different melting points, A thermosetting resin composition having a shape and a liquid behavior at high temperatures can be obtained.

  The mass ratio (A) / (B) is preferably in the range of 10/90 to 25/75. When the component (A) liquid bisphenol-type epoxy resin is less than the above range, or when the softening point of the component (B) solid polyfunctional epoxy resin exceeds 70 ° C., the resistance during processing of electronic parts, particularly during cutting There is a possibility that the cracking property is not sufficient. Moreover, when there are more liquid bisphenol-type epoxy resins of (A) component than the said range, or when the softening point of the solid polyfunctional epoxy resin of (B) component is too low, peeling resistance and crack resistance will become favorable. However, workability may not be sufficient. From such a viewpoint, the (A) / (B) mass ratio is more preferably in the range of 15/85 to 20/80, and the lower limit of the softening point of the solid polyfunctional epoxy resin of the component (B) is Usually about 40 ° C is preferred.

  There is no restriction | limiting in particular as a hardening | curing agent for epoxy resins used as (C) component, Arbitrary things can be suitably selected and used from what was conventionally used as a hardening | curing agent of an epoxy resin, for example, an amine type | system | group. , Phenol-based, acid anhydride-based and the like. Preferred examples of the amine curing agent include dicyandiamide and aromatic diamines such as m-phenylenediamine.

  The above-described thermosetting resin composition can contain an epoxy resin curing accelerator as necessary, within a range where the effects of the present invention are not impaired. There is no restriction | limiting in particular as this hardening accelerator for epoxy resins, Arbitrary things can be suitably selected and used from what was conventionally used as a hardening accelerator of an epoxy resin. For example, ureas such as aromatic dimethylurea and aliphatic dimethylurea can be exemplified.

  There is no restriction | limiting in particular as an inorganic filler of (D) component, For example, normally used things, such as metal hydrates, such as silicas, such as a fused silica and spherical silica, an alumina, aluminum hydroxide, and magnesium hydroxide, are used. can do. The mass average particle diameter of the inorganic filler is preferably in the range of 1 to 30 μm from the viewpoint of workability during production and filling efficiency. In addition, this mass average particle diameter is a value measured by a laser diffraction scattering method (for example, Shimadzu Corporation, apparatus name: SALD-3100).

  The inorganic filler is preferably aluminum hydroxide or spherical silica. For example, in the former case, “H42M” manufactured by Showa Denko KK and in the latter case, “FB-959 (mass average particle diameter: 25 μm) manufactured by Denki Kagaku Kogyo Co., Ltd. And the like are preferred. In particular, the former case is preferred because it can also be used as a flame retardant.

  As for content of the said inorganic filler, 10-50 mass% is preferable in the thermosetting resin composition whole quantity. If the content of the inorganic filler is less than 10% by mass, the fluidity at the time of melting is high, and the composite sheet 1 tends to be warped or twisted when it is hardened. On the other hand, when it exceeds 50 mass%, the fluidity | liquidity at the time of a fusion | melting will fall, and there exists a possibility that an unfilled location may generate | occur | produce in an adhesion | attachment area | region.

  From the viewpoint of filling properties, the thermosetting resin composition may contain a coupling agent as necessary. Examples of the coupling agent include silane-based, titanate-based, and aluminum-based, among which silane-based coupling agents are preferable. Content of a silane coupling agent is about 0.03-5.0 mass% based on the thermosetting resin composition whole quantity, Preferably it is 0.1-2.5 mass%.

  Moreover, a flame retardant can be contained in a thermosetting resin composition as needed. There is no restriction | limiting in particular as a flame retardant, For example, a phosphorus compound, a metal hydrate, etc. can be used. Examples of phosphorus compounds include (a) phosphazene compounds, (b) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, derivatives thereof, (c) phosphate ester compounds, (d) Examples include phosphoric ester amides.

  As the phosphazene compound of the above (a), a phosphazene compound which is substantially free of halogen and has a melting point of 80 ° C. or higher from the viewpoint of heat resistance, moisture resistance, flame retardancy, chemical resistance and the like. Preferably used. Specific examples include cyclophosphazene oligomers represented by the following general formula (3).

In the general formula (3), R ¹ and R ² each independently represent an organic group containing no hydrogen atom or a halogen, k is an integer of 3-10. In the general formula (3), examples of the organic group containing no halogen of R ^1, R ^2, for example, an alkoxyl group having 1 to 10 carbon atoms, a phenoxy group, an amino group, an allyl group and the like. Examples of such phosphazene compounds include “SPB-100” manufactured by Otsuka Chemical Co., Ltd.

  The (b) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide has a structure represented by the formula (4).

  Examples of the derivative include (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide represented by the formula (5).

  The compound represented by the above formula (4) is “SANKO-HCA” (trade name, manufactured by Sanko Co., Ltd.), and the compound represented by the above formula (5) is “SANKO HCA-HQ”. "[Product name, manufactured by Sanko Co., Ltd.]. Furthermore, as a derivative, SANKO M-Acid-AH [manufactured by Sanko Co., Ltd., trade name] is commercially available.

  Examples of the phosphoric acid ester compound of (c) above include esters using trivalent phosphates such as triphenyl phosphate and cresyl diphenyl phosphate, or polyhydric phenols such as resorcin, and monohydric phenols such as phenol and cresol. And a reactive phosphate ester “RDP” [trade name, manufactured by Ajinomoto Fine-Techno Co., Ltd.] in which at least one hydroxyl group of the polyhydric phenol is left as a reactive free radical. Examples thereof include condensed phosphate ester “PX-200” [trade name, manufactured by Daihachi Chemical Industry Co., Ltd.] obtained by esterifying a free hydroxyl group in a phosphate ester.

  Furthermore, the phosphoric ester amide of (d) includes a binding mode of phosphoric ester and phosphoric amide, and JP-A-2001-139823, JP-A-2000-154277, JP-A-10-175985. The phosphoric acid ester amides described in JP-A-8-59888 and JP-A-63-235363 can be used. Preferred phosphoric ester amides include condensed phosphoric ester amides.

  On the other hand, as the kind of metal hydrate, aluminum hydroxide and magnesium hydroxide are used. As the aluminum hydroxide compound, for example, “H42M” manufactured by Showa Denko KK is preferably used.

  A flame retardant may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, although the content depends on the type of the flame retardant, it is preferably 5 to 50% by mass, more preferably based on the total amount of the resin composition, from the viewpoint of the balance between flame retardancy and other physical properties. 10 to 40% by mass, more preferably 10 to 35% by mass.

  The thermosetting resin composition has a heat resistance such as a powder of silicone rubber or silicone gel, a silicone-modified epoxy resin or a phenol resin, or a methyl methacrylate-butadiene-styrene copolymer as long as the effects of the present invention are not impaired. Low stress agent such as plastic resin; Diluent for reducing viscosity such as n-butyl glycidyl ether, phenyl glycidyl ether, styrene oxide, t-butylphenyl glycidyl ether, dicyclopentadiene diepoxide, phenol, cresol, t-butylphenol; Nonionic surfactants, fluorine surfactants, wetting improvers such as silicone oil, antifoaming agents, and the like can be appropriately contained.

  Although there is no restriction | limiting in particular in the preparation method of a thermosetting resin composition, For example, it can prepare as follows. First, (A) liquid bisphenol type epoxy resin, (B) a solid polyfunctional epoxy resin having a softening point of 70 ° C. or less, (C) a curing agent for epoxy resin, and (D) an essential component comprising an inorganic filler, In addition, various optional components added as necessary are uniformly mixed by a high-speed mixer or the like, and then sufficiently kneaded by a kneader, a two-roller, a continuous kneader or the like. The kneading temperature is preferably about 50 to 110 ° C.

  The kneaded product thus obtained is cooled and then pulverized to obtain a bulk resin. In addition, when using a sheet-like resin composition for formation of the resin layer 2, it presses on the conditions of a temperature of about 50-100 degreeC and a pressure of 0.5-1.5 MPa with a molding machine, and shape | molds a kneaded material in a sheet form To do.

  The composite sheet 1 includes, for example, a step of kneading the components of the thermosetting resin composition at a temperature of 50 to 110 ° C. to obtain a kneaded product, supplying the kneaded product to one side of the fiber base material, or After supplying between a pair of fiber base materials, the kneaded material can be manufactured through a step of integrally forming into a sheet shape by pressing the kneaded material against the fiber base material.

  According to such a manufacturing method, the composite sheet 1 in which the fiber base layer 3 is formed in close contact with the main surface of the resin layer 2 can be easily manufactured. In addition, in such a manufacturing method, the composite sheet 1 which has the release film 4 can be manufactured by supplying the release film 4 to these one side or both sides with a kneaded material and a fiber base material.

  The supply form in particular of a kneaded material is not restrict | limited, It can be set as a lump shape, a sheet form, and a molten form. In addition, the kneaded product and the fiber base material may be molded by a batch method, or continuously by using a hot press or a pressure roll.

  In particular, the composite sheet 1 is manufactured by supplying the kneaded material to one side of a fiber base material, or supplying the kneaded material between a pair of fiber base materials and then passing them between a pair of pressure rolls. A method in which the sheet is integrally formed is preferable. The pair of pressure rolls is preferably one that can adjust the gap size, and for example, one having a diameter of about 20 to 60 mm and a gap size of about 5 to 500 μm is preferable. Moreover, it is preferable that the shaping | molding for integration is a temperature range of 30-180 degreeC, and lets a pressure roll pass at the speed | rate of 0.1-5 m / min. By setting such a temperature and a passing speed, a good composite sheet 1 can be obtained.

  FIG. 4 is a schematic configuration diagram showing a first embodiment showing a manufacturing apparatus and a manufacturing method of the composite sheet 1. The manufacturing apparatus 10 includes, for example, a supply device 11 for supplying a thermosetting resin composition 5 to be the resin layer 2 in a molten form from a lump, a fiber base 6 is wound, and the fiber base 6 is A pair of rolls for substrate 12 to be supplied, a pair of release film rolls 13 for supplying the release film 4 while the release film 4 is wound, and a pair for guiding the fiber substrate 6 and the release film 4 Guide roll 14, fiber substrate 6, release film 4, and a pair of pressure rolls 15.

  The supply device 11, the base material roll 12, and the release film roll 13 are arranged corresponding to the laminated structure of the composite sheet 1. For example, as shown in FIG. 4, the fiber base 6 and the one release film 4 are wound around a part of the outer periphery of one guide roll 14 (the right guide roll 14) of the pair of guide rolls 14. The other release film 4 is disposed around a part of the outer periphery of the other guide roll 14. By setting it as such arrangement | positioning, the slight clearance gap for supplying the thermosetting resin composition 5 between the fiber base material 6 and the other mold release film 4 can be formed.

  In this manufacturing apparatus 10, a pair of release films 4 is continuously supplied from a pair of release film rolls 13 between a pair of guide rolls 14, and a substrate roll 12 is provided therebetween. The fiber base 6 is continuously supplied from Further, a thermosetting resin composition 5 in which a lump is melted is supplied from a supply device 11 between the fiber base 6 and one release film 4. Further, these supplies are passed between a pair of pressure rolls 15.

  By doing in this way, the fiber base material 6 is embed | buried under the main surface of the thermosetting resin composition 5, or while the fiber base material 6 is impregnated with the thermosetting resin composition 5, a mold release is carried out to the outermost layer. The composite sheet 1 provided with the film 4 can be manufactured. In particular, the gap dimension can be adjusted by a pair of pressure rolls 15, and the constituent material of the composite sheet 1 is allowed to pass through these gaps, so that the fiber substrate 6 can be applied to the thermosetting resin composition 5. The degree of embedding or the degree of impregnation of the thermosetting resin composition 5 into the fiber base 6 can be adjusted, and the overall thickness of the composite sheet 1 can also be adjusted.

  FIG. 5 is a schematic configuration diagram showing a second embodiment showing a manufacturing apparatus and a manufacturing method of the composite sheet 1. In this manufacturing apparatus 10, a base material roll 12 is further added to the manufacturing apparatus 10 shown in FIG. 4, and a pair of base material rolls 12 is provided. The pair of base material rolls 12 are arranged so that the respective fiber base materials 6 are wound around a part of the outer periphery of the pair of guide rolls 14.

  In this manufacturing apparatus 10, a pair of release films 4 is continuously supplied from a pair of release film rolls 13 between a pair of guide rolls 14, and a pair of base materials is interposed therebetween. A pair of fiber base materials 6 are continuously supplied from the roll 12 for use. By doing in this way, the composite sheet 1 which has a pair of fiber base material 6 in both the main surfaces of the resin layer 2 can be manufactured.

  FIG. 6 is a schematic configuration diagram showing a third embodiment showing a manufacturing apparatus and a manufacturing method of the composite sheet 1. The basic structure of the manufacturing apparatus 10 is the same as that of the manufacturing apparatus 10 shown in FIG. 4, but instead of the supply apparatus 11, a single sheet-shaped resin composition 7 obtained by molding a thermosetting resin composition into a sheet shape is used. The point which has the roll 16 for sheets which winds and supplies this sheet-like resin composition 7 differs. Thus, the composite sheet 1 may be manufactured by supplying the sheet-shaped resin composition 7 obtained by previously molding the thermosetting resin composition into a sheet shape.

  FIG. 7 is a schematic configuration diagram showing a fourth embodiment showing a manufacturing apparatus and a manufacturing method of the composite sheet 1. In this manufacturing apparatus 10, a base material roll 12 is further added to the manufacturing apparatus 10 shown in FIG. 6, and a pair of base material rolls 12 is provided. By doing in this way, the composite sheet 1 which has a pair of fiber base material 6 in both the main surfaces of the resin layer 2 can be manufactured.

  As mentioned above, although the method of manufacturing the composite sheet 1 continuously using the pressure roll 15 was demonstrated, the composite sheet 1 is laminated | stacked the constituent material in a predetermined order, and is about 50-100 degreeC with a molding machine. You may manufacture by pressing on the conditions of temperature and pressure 0.5-1.5MPa.

Next, electronic parts and electronic devices using the composite sheet 1 will be described with reference to the drawings.
For example, the composite sheet 1 is used for manufacturing an electronic component by adhering to the surface of an electronic component element body and insulating the surface. Moreover, the composite sheet 1 is used for manufacturing an electronic device by covering the electronic component and sealing the electronic component, for example. Although it does not restrict | limit especially as an electronic component, For example, a semiconductor element, a resistor, a diode, a capacitor | condenser is mentioned. Examples of the electronic component include a hollow device such as a surface acoustic wave device (SAW device), a crystal device, a high-frequency device, and an acceleration sensor. The composite sheet 1 can be suitably used for, for example, fixing electronic components in addition to the above-described insulation and sealing.

  FIG. 8 shows an example of an electronic component element body used for manufacturing an electronic component. The electronic component element body 21 includes, for example, an element body main body 22 and two external connection electrodes 23 provided separately on the surface of the element body main body 22. For example, the distance between the electrodes of the two external connection electrodes 23 is 2.0 mm, and the electrode height is 0.3 mm. The composite sheet 1 is used for insulation between two external connection electrodes 23, for example. Insulation by the composite sheet 1 can be performed, for example, as follows.

  That is, the composite sheet 1 is placed between the two external connection electrodes 23. Then, it heats to the temperature of about 80-200 degreeC, Preferably it is 100-150 degreeC, and the resin part of the composite sheet 1 is fluidized. Furthermore, the fluidized resin component is cured by heating at a temperature of 100 to 180 ° C. for about 0.5 to 2 hours. By doing so, as shown in FIGS. 9 and 10, the electronic component 24 can be obtained by appropriately covering the space between the external connection electrodes 23 with the cured product of the composite sheet 1. Since the composite sheet 1 has the fiber base layer 3, it is particularly easy to obtain a flat surface as shown in FIG.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples. In addition, the various characteristics in each example were calculated | required according to the method shown below.

(1) Handling property The composite sheet of the example, the prepreg of the comparative example, and the like were evaluated according to the following criteria.
○: When handling at room temperature, no cracks are generated and no stickiness occurs.
Δ: When handling at room temperature, cracking or chipping occurs, or there is no waist and it is difficult to handle.
X: It becomes a liquid or highly viscous liquid and does not form a sheet.

(2) Plasticity A parallel plate plasticity meter based on a method in accordance with JIS K6249 with respect to a resin used for producing a thermosetting resin composition used for producing the composite sheet of the example and a prepreg of the comparative example. It was measured by. The sample shape is 10 mm in diameter and 1.0 mm in thickness, and the measurement conditions are room temperature 25 ° C., load 400 g, and pressurization time 1 hour.

(3) Cross-sectional shape The cross-sectional shape (for example, shown in FIGS. 9 and 10) of an adhesive (cured product made of the composite sheet of the example, a prepreg of the comparative example) formed in the adhesive region of the electronic component body. Such cross-sectional shape) was evaluated according to the following criteria.
○: The adhesive completely covers the adhesion area and is below the electrode height.
Δ: An uncoated portion is present in the adhesion region or is coated but exceeds the electrode height.
X: Adhesive material seeps into the electrode part or the peripheral part is contaminated.

(4) Crack resistance during cutting Adhesives (cured products made of composite sheets of examples, cured products of comparative examples, etc.) formed in the adhesion region of the electronic component body are cut by a cutting machine (manufactured by Shibakawa Seisakusho). , MS1206), and the value obtained by dividing the area of the crack generation region by the area of the entire adhesion region was defined as the crack area ratio, and was evaluated according to the following criteria.
○: Crack area ratio 0%
Δ: Crack area ratio More than 0% and less than 5% ×: Crack area ratio 5% or more

(5) Peeling resistance at the time of cutting An adhesive (cured product made of a composite sheet of an example, a cured product of a prepreg of a comparative example) formed in an adhesive region of an electronic component body is cut by a cutting machine (manufactured by Shibakawa Seisakusho) , MS1206), and a value obtained by dividing the area of the peeled area on the cut surface by the area of the entire adhesion area was defined as a peeled area ratio, and evaluated according to the following criteria.
○: peeling area ratio 0%
Δ: peeling area ratio greater than 0% and less than 5% ×: peeling area ratio of 5% or more

(Examples 1-7)
Each raw material was charged into a kneader with the composition shown in Table 1, and stirred and mixed at 75 ° C. for 1 hour to prepare a thermosetting resin composition. Next, the thermosetting resin composition was cooled to 30 ° C. to obtain a lump. Supplying to one side of glass cloth (manufactured by Nitto Boseki Co., Ltd., trade name: WTX1078, thickness 50 μm) or aramid cloth (trade name: 350, thickness 50 μm) manufactured by Hexel as a fiber base material in a molten state after the bulk resin is melted However, it was integrally formed by passing between a pair of pressure rolls. The diameter of the pressure roll was 60 mm, and the roll gap (gap size) was 50 to 320 μm. Further, the molding was carried out at a temperature of 70 ° C. and passed through a pressure roll at a speed of 2 m / min. Thereby, the fiber base material layer which has a fiber base material was closely formed in the single side | surface of the resin layer which consists of a thermosetting resin composition, Comprising: 50-320 micrometers in thickness, 61-94 volume% of resin components are composites A sheet was obtained.

  As an electronic component element body, one having two external connection electrodes separated from each other on the surface of an element body body as shown in FIG. 8 was prepared. Here, the distance between the electrodes of the two external connection electrodes is 2.0 mm, and the electrode height is 0.3 mm. An adhesive region is between the two external connection electrodes. After covering a composite sheet with a sheet width of 1.95 mm so as to cover the adhesion region, the composite sheet resin was fluidized by heating at 120 ° C. for 20 minutes and then cured. As a result, an electronic component having an adhesive region covered with an adhesive made of a cured product of the composite sheet was obtained.

(Comparative Example 1)
Instead of the composite sheet, an electronic component was obtained by the same operation as in Example using a prepreg (Kyocera Chemical Co., Ltd., trade name: TLP-551, thickness 100 μm) in which glass fiber was impregnated with epoxy resin. .

(Comparative Example 2)
Instead of the composite sheet, an adhesive sheet (manufactured by Kyocera Chemical Co., Ltd., trade name: TBS-702, thickness 50 μm) was used to obtain an electronic component by the same operation as in the example.

(Comparative Example 3)
Instead of placing the composite sheet in the bonding area of the electronic component body, a liquid resin (trade name: TCG-1730, manufactured by Kyocera Chemical Co., Ltd.) is applied to a thickness of 50 μm, and an electronic component is obtained by the same operation as in the example. It was.

In addition, each component used in the Example is as follows.
1. Liquid bisphenol type epoxy resin Shrimp Coat 828: bisphenol A type epoxy resin manufactured by Mitsubishi Chemical Corporation (epoxy equivalent: 190)
2. Solid epoxy resin having a softening point of 70 ° C. or less NC3000: polyfunctional epoxy resin containing biphenyl skeleton manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent: 285, softening point: 57 ° C.)
3. 3. Curing agent for epoxy resin DICY: Dicyandiamide manufactured by Nippon Carbide Corporation Catalyst U-CAT3512T: aromatic dimethylurea manufactured by San Apro Inorganic filler (flame retardant)
H42M: Aluminum hydroxide manufactured by Showa Denko (particle size: 1.5 μm)
6). Fiber substrate WTX1078: Glass cloth made by Nittobo 350: Aramid cloth made by Hexel

  As is apparent from Table 1, the composite sheets of Examples 1 to 7 generally have good handling properties, and the cross-sectional shape of the adhesive, which is a cured product, as well as good crack resistance and peeling resistance when cut. I know that there is. On the other hand, it can be seen that the prepreg of Comparative Example 1 is not excellent in peel resistance. Moreover, about the adhesive sheet of the comparative example 2, it turns out that the cross-sectional shape of the adhesive substance which is a hardened | cured material, the crack resistance at the time of cutting | disconnection, and peeling resistance are not excellent. About the liquid resin of Comparative Example 3, since it is difficult to form a sheet, the handling property is not excellent, and since the adhesive which is a cured product adheres to the electrode part, the cross-sectional shape is not excellent, and the crack resistance at the time of cutting Is also not good.

  DESCRIPTION OF SYMBOLS 1 ... Composite sheet, 2 ... Resin layer, 3 ... Fiber base material layer, 4 ... Release film, 5 ... Thermosetting resin composition, 6 ... Fiber base material, 7 ... Sheet-like resin composition, 10 ... Manufacturing apparatus DESCRIPTION OF SYMBOLS 11 ... Supply apparatus, 12 ... Roll for base materials, 13 ... Roll for release films, 14 ... Guide roll, 15 ... Pressure roll, 16 ... Roll for thermosetting resin sheet, 21 ... Element body for electronic components, 24 ... Electronic components

Claims (10)

A resin layer comprising a thermosetting resin composition;
And a fiber base layer having a fiber base formed in close contact with at least one main surface of the resin layer.   2. The composite sheet according to claim 1, wherein a ratio of a resin component in the composite sheet is 65 to 93% by volume, and a plasticity of the thermosetting resin composition is 60 to 90 at 25 ° C. 3.   The composite sheet according to claim 1 or 2, wherein the fiber substrate is at least one selected from an inorganic fiber substrate and an organic fiber substrate.   The thermosetting resin composition includes (A) a liquid bisphenol type epoxy resin, (B) a solid polyfunctional epoxy resin having a softening point of 70 ° C. or less, (C) a curing agent for epoxy resin, and (D) an inorganic filler. Is an essential component, the mass ratio (A) / (B) is 10/90 to 25/75, and the proportion of the component (D) in the entire thermosetting resin composition is 10 to 50 mass%. The composite sheet according to claim 1, wherein the composite sheet is provided. Kneading the components of the thermosetting resin composition at a temperature of 50 to 110 ° C. to obtain a kneaded product;
After the kneaded product is supplied to one side of the fiber base material, or the kneaded product is supplied between a pair of fiber base materials, the kneaded product is pressed into the fiber base material to be integrally formed into a sheet shape. And a step of obtaining a composite sheet.   6. The method for producing a composite sheet according to claim 5, wherein the kneaded material is supplied in a lump shape, a sheet shape, or a molten state between one side of the fiber base material or the pair of fiber base materials. .   The method for producing a composite sheet according to claim 5 or 6, wherein the pressing is performed by a pressure roll or a press. An electronic component body,
An electronic component comprising: the composite sheet according to any one of claims 1 to 4 disposed on at least a part of a surface of the electronic component element body and insulating the surface. Electronic components,
An electronic apparatus comprising: the composite sheet according to claim 1 that seals the electronic component.   The electronic component is at least one selected from a semiconductor element, a resistor, a diode, and a capacitor, or at least one hollow device selected from a surface acoustic wave device (SAW device), a crystal device, a high-frequency device, and an acceleration sensor. The electronic device according to claim 9, wherein the electronic device is an electronic device.

Images