JP2017031340A - Sheet-like adhesive and component package - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sheet-like adhesive excellent in workability and shape stability, good in adhesiveness to various components and capable of enhancing adhesive strength, durability or the like and further flexible with efficiently following even when sealed on not only flat face, but also three dimensional curve or uneven surface or the like.SOLUTION: There is provided a sheet-like adhesive 1 by laminating (A) a substrate layer 2, (B) a thermosetting resin layer 3 and (C) an adhesive layer 4 in this order, where the (A) substrate layer 2 consists of a nonwoven fabric with basis weight of 5 to 200 g/mand porosity of 70 to 95%.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a sheet-like adhesive having a structure in which a thermosetting resin layer and an adhesive material layer are laminated, and a component package using the sheet-like adhesive. This sheet-like adhesive is suitable for use in protecting the surfaces and end faces of various components.

  Conventionally, what consists of thermosetting resin compositions, such as an epoxy resin composition, is known as a sheet-like adhesive material used for the electronic component field (for example, refer patent documents 1 and 2). However, conventional sheet-like adhesives do not always have sufficient performance with respect to handling properties and shape stability.

  Moreover, the prepreg which consists of fiber base materials, such as a glass epoxy prepreg, and a thermosetting resin composition is known as a sheet-like adhesive material (for example, refer patent document 3). The prepreg is relatively good in terms of handling properties, strength, and shape stability. However, conventional prepregs are not necessarily excellent in surface adhesiveness of electronic components, and there are cases where the adherends that can be used are limited because they contain a fiber base material.

  Further, as a sheet-like adhesive material, it is known to heat and pressurize from the sheet side to soften the epoxy resin so as to have viscosity and adhesive force (for example, Patent Document 4). reference). However, such an epoxy resin sheet is difficult to bond at room temperature by bringing about an adhesive force by heating and pressing.

  Furthermore, in sheet-like adhesives using thermosetting resins, after the bonded parts are cured, no seepage of the resin from the edge of the base material is observed, the base material does not peel off, and the shape is stable. There was nothing that fulfilled the property of superiority.

JP 2002-60720 A JP-A-2-102281 JP 2011-108733 A JP 2003-249509 A

  The present invention has been made in view of the current situation as described above. After the bonded parts are cured, the resin does not exude from the end of the base material, the base material does not peel off, the shape, etc. The object is to provide a sheet-like adhesive having excellent stability.

  The present invention has been made by finding that the above-described problems can be solved by using a nonwoven fabric as a base material layer and laminating a thermosetting resin layer and an adhesive layer in a predetermined order to form a sheet. is there.

That is, the sheet-like adhesive of the present invention is a sheet-like adhesive formed by laminating (A) a base material layer, (B) a thermosetting resin layer, and (C) an adhesive layer in this order. And the said (A) base material layer consists of a nonwoven fabric with a basis weight of 5-200 g / m < ² >, and a porosity of 70-95%, It is characterized by the above-mentioned.

  The component package of the present invention is characterized in that the component is sealed with the sheet-like adhesive of the present invention.

  The sheet-like adhesive of the present invention has no exudation of resin from the edge of the base material after curing of the bonded parts, no peeling of the base material, excellent shape stability, and the packaging of parts. Is preferred. In addition, a component package obtained using this sheet-like adhesive has a good appearance and a stable shape.

It is sectional drawing which shows the structure of the sheet-like adhesive material of this invention.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. can do.

<Sheet adhesive>
As shown in FIG. 1, the sheet-like adhesive of the present invention comprises (A) a base material layer 2, (B) a thermosetting resin layer 3, and (C) an adhesive layer 4 in this order. It is a sheet-like adhesive 1 formed by laminating. Hereinafter, each of these layers will be described.

(A) Base material layer The base material layer 2 used for this invention is a member which suppresses that a thermosetting resin spreads in a plane direction at the time of the heat melting of the thermosetting resin of the thermosetting resin layer 3 mentioned later. . This base material layer is soaked with a thermosetting resin into the base material, thereby suppressing the spread to a flat surface and making it possible to cure while maintaining the shape. It consists of the nonwoven fabric which has.

As this nonwoven fabric, those having a basis weight of 5 to 200 g / m ² and a porosity of 70 to 95% are used. If the basis weight is 5 g / m ² or less, the base fiber is too few to suppress the seepage of the thermosetting resin, and the shape may not be sufficiently maintained. In addition, when the basis weight is 200 g / m ² or more, the amount that can be infiltrated into the base material is reduced, so that the thermosetting resin oozes out and there is a possibility that the shape cannot be maintained.

  When the non-woven fabric has a porosity of 70% or less, since the void is small when the thermosetting resin is softened, the amount that can be infiltrated into the base material is reduced, and exudation occurs, resulting in poor appearance. There is a risk of becoming. Further, when the porosity is 95% or more, the voids are too large, so that the seepage cannot be suppressed when the thermosetting resin is softened, and the shape may not be maintained.

  Here, the “nonwoven fabric” refers to a sheet-like material in which fibers are entangled without weaving (according to JIS L 0222. Paper, felt and knitted fabric are not included). Specific examples of the non-woven fabric include aramid fibers, glass fibers, cellulose fibers, nylon fibers, vinylon fibers, polyester fibers, polyolefin fibers, rayon fibers, etc., from the viewpoint of flexibility, penetration, and porosity. Cellulose fibers are preferred. The fiber diameter of the nonwoven fabric fiber used here is preferably 5 to 60 μm, and more preferably 5 to 20 μm, in order to provide porosity and flexibility.

In addition, the “porosity” of the nonwoven fabric in this specification is obtained by the following formula.
Porosity (%) = (1−total volume of fibers constituting nonwoven fabric / nonwoven fabric volume) × 100

  Moreover, 5-1000 micrometers is preferable and, as for the thickness of this (A) base material layer, 20-500 micrometers is more preferable. If the thickness is less than 5 μm, handling properties and shape stability may be insufficient, and if it exceeds 1000 μm, flexibility may be insufficient and adhesion may be insufficient.

(B) Thermosetting resin layer The thermosetting resin layer 3 used in the present invention is an adhesive layer containing an epoxy resin as an essential component as a thermosetting resin. For example, the thermosetting resin layer 3 is a sheet-like epoxy resin composition containing (B-1) an epoxy resin, (B-2) a curing agent, and (B-3) an inorganic filler as essential components. To be obtained. The type of the epoxy resin used here is not particularly limited, and may be any epoxy resin that is generally used for bonding applications. By using the epoxy resin composition, a cured product having high adhesive strength can be obtained.

  Here, as (B-1) epoxy resin, a solid polyfunctional epoxy resin having a softening point of 100 ° C. or less, and (B-2) a curing agent for liquid epoxy resin as a curing agent, It is preferable that a sheet-like resin composition exhibiting a liquid behavior can be obtained. Hereinafter, this preferable combination will be described in more detail.

  Examples of the solid polyfunctional epoxy resin having a softening point of 100 ° C. or lower used as the component (B-1) include bisphenol A type epoxy resins, CTBN-modified bisphenol A type epoxy resins, and biphenyl skeleton-containing aralkyl type epoxy resins. A mixture, a mixture of cresol novolac type epoxy resin, and the like are used. In addition, solid form means here what is solid at normal temperature (25 degreeC).

  As the solid polyfunctional epoxy resin having a softening point of 100 ° C. or lower, “NC3000” (softening point 57 ° C.), “NC3000H” (softening point 70 ° C.) (above, Nippon Kayaku Co., Ltd., trade name), “EPICLON N-660” (manufactured by DIC Corporation, trade name: softening point 67 ° C.), “jER1001” (manufactured by Japan Epoxy Resin Co., Ltd., trade name: softening point 64 ° C.), bisphenol A type epoxy resin “1004” (JER Co., Ltd., trade name: softening point 97 ° C.), CTBN-modified bisphenol A type epoxy resin “SR35K” (Printech Co., Ltd., trade name: softening point 98 ° C.), o-cresol novolac type epoxy Resin “YDCN703J (manufactured by Toto Kasei Co., Ltd., trade name; softening point 80 ° C.)” is preferably used, but not limited thereto.

  Moreover, these solid polyfunctional epoxy resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  (B-2) As a hardening agent for liquid epoxy resins used as a component, various things including a well-known thing can be used. For example, alicyclic acid anhydride type curing agent, 3 or 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, 3 or 4-methyl-hexahydrophthalic anhydride, methyl-3,6 endomethylene -1,2,3,6-tetrahydrophthalic anhydride, aliphatic polyamines such as triethylenetetramine and tetraethylenepentamine, cyclic aliphatic amines such as N-aminoethylpiperazine, and aromatic amines such as m-xylylenediamine , Polyaminoamide compounds (polyamide resins), heterocyclic amines, polymercaptan curing agents, and the like. A particularly preferred liquid epoxy curing agent is a polymercaptan curing agent. In addition, liquid state means here what is a liquid at normal temperature (25 degreeC).

  A mercapto group reacts with an epoxy group in the presence of a basic catalyst such as a tertiary amine, and the relative nucleophilic substitution reaction rate is extremely large as compared with a phenol, a carboxyl group, an amine and the like. Furthermore, compounds having two or more mercapto groups in the molecule are used for rapid curing or low temperature curing.

  Commercially available products include “Karenz PE-1,” “Karenz BD1,” “Karenz NR2” (above, Showa Denko Co., Ltd., trade name), “TEMPIC”, “TMMP”, “PEMP”, “DPMP” ( As mentioned above, there is SC Organic Chemical Co., Ltd., trade name), but not limited thereto.

  A liquid epoxy hardening | curing agent may use 1 type and can also use 2 or more types together.

  (B-3) As an inorganic filler used as a component, if it is a well-known inorganic filler mix | blended in a resin composition, it can be used without being specifically limited. Examples thereof include inorganic fillers such as calcium carbonate, talc, silica, alumina and aluminum hydroxide, inorganic hollow bodies such as glass balloons, alumina balloons and ceramic balloons, and single fibers made of glass.

  In addition, the thermosetting resin composition can contain other components as necessary within a range not impairing the object of the present invention.

  Other components include, for example, curing accelerators, storage stability improvers, adhesion improvers such as coupling agents, leveling agents, colorants such as pigments and dyes, conductive particles such as silver, flame retardants, acrylic rubber, Examples include organic filler plasticizers such as silicone rubber, organic solvents, antioxidants, antifoaming agents, rheology control agents, and the like. These additives may be blended in appropriate amounts. By these additions, it is possible to obtain a thermosetting resin composition having excellent resin strength, adhesive strength, flame retardancy, thermal conductivity, storage stability, workability, and the like, and a cured product thereof.

  As a hardening accelerator, Preferably, the imidazole compound containing the compound which has one imidazole ring per molecule is mentioned. Examples of such imidazole compounds include imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4- Examples include methylimidazole, 1-benzyl-2-methylimidazole, 2-ethylimidazole 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine.

  Examples of the storage stability improver include boric acid esters, phosphoric acid esters, inorganic acids, and organic acids. By the addition of the storage stability improver, a resin composition and a cured product having better storage stability can be obtained. As the preservability improver, a borate ester is more preferable.

  By adding a preservability improver, the inside of the system is made neutral or weakly acidic, and the room temperature stability of the compound is increased. Examples of commercially available preservability improvers include “JP-3CP”, “JPP-31”, “JPA-541” (trade name, manufactured by Johoku Chemical Industry Co., Ltd.), L-07N (Shikoku Chemical Industries ( Co., Ltd., product name), etc.

  In addition, by using together with a silane coupling agent having a functional group capable of reacting with an epoxy group such as an amino group, an epoxy group, a mercapto group, a phenolic hydroxyl group, or a carboxyl group, the strength of the cured product and adhesion to an adherend The property can be further improved. Further, a tackifier resin may be used in combination to increase the adhesive strength, and a filler may be used in combination to improve the shear adhesive strength.

  In addition, an epoxy resin is indispensable as the thermosetting resin of this embodiment, but other resins such as polyimide resin, polyamide resin, liquid bisphenol A type phenoxy resin, bisphenol F type phenoxy resin, bisphenol A / bisphenol F General purpose phenoxy resins such as copolymerized phenoxy resins, polymethacrylate resins, polyacrylate resins, polyvinyl butyral resins, SBS resins (styrene-butadiene / styrene block copolymers) and their modified epoxy resins and thermoplastic elastomers You may use together.

  The thickness of the thermosetting resin layer 3 is not particularly limited and can be selected as appropriate. In order to ensure a certain hardness without impairing the infiltration effect of the nonwoven fabric, the sheet It is preferable that it is 50 to 90% of the whole adhesive material, and it is more preferable that it is 60 to 70%.

  Moreover, if this thickness is expressed concretely, it is preferably 0.1 to 2000 μm, more preferably 1 to 1500 μm. If it is the said range, adhesive physical property will be stabilized. In addition, when the thickness is less than 0.1 μm, the adhesiveness of the sheet-like adhesive may be affected by the surface unevenness of the joining member, and when it exceeds 2000 μm, the curing does not proceed sufficiently or the curing time is long. There is a case.

  In addition, the thickness of the thermosetting resin layer 3 of the present invention is preferably 1 to 1000 μm, more preferably 10 to 500 μm, considering ease of handling. If it is the said range, it will have favorable softness | flexibility, while having moderate softness | flexibility.

(C) Adhesive layer The adhesive layer 4 used by this invention should just be formed with well-known adhesive resin. Here, the adhesive resin is preferably an adhesive that not only has excellent adhesiveness but also has excellent cohesive strength and excellent holding power after adhesion. Examples of such adhesive resins include acrylic, rubber-based, and silicone-based adhesive resins. Among them, acrylic resins that are thermoplastic resins, that is, adhesive acrylic resins are preferable.

  Note that the pressure-sensitive adhesive layer in the present specification is necessary for stably bonding parts together. With only the adhesive layer, the bonding is not stable in summer and winter, and the part and the sheet-like adhesive are partially peeled off. Here, the pressure-sensitive adhesive layer is composed of a high molecular weight body by cross-linking or (co) polymerization, and before heating (curing), a thermosetting resin layer that has not become a high molecular weight body by cross-linking or (co) polymerization And the structure is different.

  The tacky acrylic resin includes a main monomer component having a low glass transition point (low Tg) that imparts tackiness, a comonomer component having a high glass transition point (high Tg) that imparts adhesion and cohesion, and crosslinking and adhesion improvement. For example, a polymer or a copolymer mainly composed of a functional group-containing monomer component is typically used.

  As the main monomer component, for example, ethyl acrylate, butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, cyclohexyl acrylate, benzyl acrylate, alkyl acrylate, butyl methacrylate, Examples include methacrylic acid alkyl esters such as 2-ethylhexyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate.

  Examples of the comonomer component include methyl acrylate, methyl methacrylate, ethyl methacrylate, vinyl acetate, vinyl propionate, vinyl ether, styrene, acrylonitrile, methacrylonitrile and the like.

  Examples of the functional group-containing monomer component include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth). Acrylate, 4-hydroxybutyl (meth) acrylate, N-methylolacrylamide, hydroxyl group-containing monomers such as allyl alcohol, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, etc. Secondary amino group-containing monomers, amide group-containing monomers such as acrylamide and methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methoxymethyl (meth) acrylami , N- ethoxymethyl (meth) acrylamide, N-t-butyl acrylamide, N- substituted amide group-containing monomers such as N- octyl acrylamide, an epoxy group-containing monomers such as glycidyl Clute.

  The reason why such a material is preferable is that it has excellent adhesive strength and cohesive strength, and can obtain arbitrary quality and characteristics according to the application by selecting the type and molecular weight of the monomer.

  Examples of rubber-based adhesives include natural rubber-based, isoprene rubber-based, styrene-butadiene-based, recycled rubber-based, polyisobutylene-based, and blocks containing rubber such as styrene-isoprene-styrene and styrene-butadiene-styrene. The thing mainly having a copolymer is mentioned.

  Examples of the silicone pressure-sensitive adhesive include dimethylsiloxane-based and diphenylsiloxane-based known silicone pressure-sensitive adhesives.

  Further, the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer 4 may be any of a solvent system, an emulsion system, and an aqueous system.

  The thickness of the pressure-sensitive adhesive layer 4 is not particularly limited and can be appropriately selected. However, if the pressure-sensitive adhesive layer is thick, it affects the hardness after curing of the thermosetting resin layer and is thin. Since the bonding to the parts is unstable, the thickness is preferably 5 to 50 μm, more preferably 10 to 30 μm.

  The above-described materials (A) to (C) are laminated in this order to obtain the sheet-like adhesive of this embodiment. At this time, the thickness of the sheet-like adhesive is preferably 6 to 1500 μm, and more preferably 24 to 1000 μm, in order to achieve good handling properties and excellent shape stability. Furthermore, even if the surface shape of the component to be applied is a three-dimensional curved surface, an uneven surface, or the like, 30 to 500 μm is preferable, and 50 to 300 μm is more preferable when sufficient adhesion can be achieved.

  The sheet-like adhesive thus obtained can be cured while maintaining its shape because the thermosetting resin soaks into the nonwoven fabric when it is thermally melted and suppresses spread to a flat surface. By curing in this way, the shape stability is improved. In addition, by making the surface an adhesive layer, handling can be performed without depending on tackiness, and bonding can be performed stably.

<Method for producing sheet-like adhesive>
The sheet-like adhesive of the present invention is not particularly limited with respect to the production method as long as the base material 2, the thermosetting resin layer 3, and the pressure-sensitive adhesive layer 4 can be laminated in this order, and can be produced by a known method. The following manufacturing method can be illustrated.

<Formation of adhesive sheet>
First, the adhesive sheet used as the material of the adhesive layer 4 is formed. The pressure-sensitive adhesive sheet is provided with a pressure-sensitive adhesive sheet with a release film by applying and drying a coating liquid serving as a pressure-sensitive adhesive material on the surface of the release film on the release agent layer side according to a conventional method. Next, the pressure-sensitive adhesive layer side is finished with a release film.

  The method for applying the coating solution for forming the pressure-sensitive adhesive layer on the release film is not particularly limited, and a conventionally known method can be used. Examples of the forming method by printing include a gravure printing method, a flexographic printing method, and an offset printing method. Examples of the coating method include roll coating, reverse coating, comma coating, knife coating, die coating, and gravure coating.

In this case, as the release film, high-density base paper such as glassine paper, clay-coated paper, craft paper, polylamination paper laminated with polyethylene etc. on high-quality paper, or film such as polypropylene, water-based, solvent-type or solvent-free type After applying a fluororesin or silicone resin of about 0.05 to 8 g / m ² by dry weight, a release layer is formed by heat curing, ionizing radiation curing or the like. The thickness used is 0.01 to 0.5 mm, preferably 0.003 to 0.1 mm.

<Formation of thermosetting resin sheet>
(B-1) A solid polyfunctional epoxy resin having a softening point of 100 ° C. or lower, (B-2) a curing agent for liquid epoxy resin, and (B-3) an inorganic filler, and further if necessary. Various optional components to be used 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 100 ° C, more preferably 60 to 80 ° C.

  After cooling the thermosetting resin composition thus obtained, the thermosetting resin material is pressed with a molding machine at a temperature of about 60 to 80 ° C. and a pressure of 0.5 to 1.5 MPa. Make it.

  The manufacturing method of the thermosetting resin sheet of this invention is not specifically limited, A conventionally well-known method can be used. For example, it passes between a pair of pressure rolls while supplying a resin or a resin sheet to various carrier films. The pair of rolls are rolls whose gap sizes can be adjusted. Examples of the roll used here include those having a diameter of 2 to 5 cm and a roll gap of about 5 to 500 μm.

  As a bonding condition, a satisfactory thermosetting resin sheet can be obtained by passing it at a temperature range of 30 to 100 ° C. and a heating and pressing roll at a speed of 0.1 to 5 m / min.

  The carrier film used here is a film formed of a material such as PET (polyethylene terephthalate), PBT (polybutylene terephthalate), PC (polycarbonate), PE (polyethylene), PPS (polyphenylene sulfide), PES (polyethersulfone). Is mentioned.

<Manufacture of sheet adhesives>
The carrier film provided on both sides of the obtained thermosetting resin sheet is peeled off, the non-woven fabric is laminated on one side of the thermosetting resin layer, and the pressure-sensitive adhesive sheet obtained above is laminated on the opposite side and laminated by thermal lamination. And a sheet-like adhesive material is manufactured. At this time, thermal lamination can be performed at 40 to 70 ° C., a pressure of 1 to 5 kg / cm ² , and a speed of 0.1 to 1.0 m / min, for example.

<Use of sheet adhesive>
The sheet-like adhesive obtained as described above is heat-cured for 10 minutes so that the pressure-sensitive adhesive layer is bonded to the base material or component to be bonded, and the temperature of the sheet-like adhesive becomes about 80 ° C. Then, it can adhere | attach without pressure by taking out and allowing to cool. In addition, at the time of this adhesion, pressure may be applied to ensure adhesion.

<Parts package>
The component package of the present invention is formed by sealing various components with the above sheet-like adhesive. Here, examples of the component include a semiconductor product, a high-frequency component, a sensor component, and the like.

  For example, in a semiconductor device, the sheet-like adhesive can be used as a coverlay that protects the surface of the semiconductor substrate. Moreover, it can use as reinforcement of the edge part of the components which have a rectangular parallelepiped shape and an uneven surface.

  Next, the present invention will be described in more detail with reference to examples. Tables 1 and 2 show the evaluation results of the structures and various properties of the sheet-like adhesives obtained in Examples and Comparative Examples.

(Production Example 1) Production of thermosetting resin layer (B-2) Tetrafunctional thiol-based curing agent (manufactured by Showa Denko KK, trade name: Karenz MT PE-1) 25 parts as component (B-1) 100 parts of bisphenol A type epoxy resin (epoxy equivalent: 450-500, manufactured by Mitsubishi Chemical Co., Ltd., trade name: jER1001, softening point 64 ° C.) as a component, boric acid compound (Shikoku Kasei Kogyo Co., Ltd.) as a preservative Manufactured, trade name: L-07N) 1.5 parts, (B-3) 74 parts of spherical silica (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name “FB-959”) is blended for 1 hour at 80 ° C. Mix and knead. Next, the kneading temperature is lowered to 65 ° C., 3 parts of an amine compound (manufactured by T & K TOKA, trade name: Fuji Cure FXR-1081) is added as a curing accelerator, and the mixture is kneaded for 10 minutes for thermosetting resin composition. I got a thing. Here, “part” means “part by mass”.

  While supplying the thermosetting resin composition obtained above on the release film, it passes between the hot rolls under the conditions of 65 ° C. and 0.5 mm / min, and the release film layer / thermosetting resin layer / release film. A sheet-like thermosetting resin layer was prepared so as to form a layer. The thermosetting resin layer was adjusted to 150 μm, and the release film was PET (polyethylene terephthalate).

Example 1
The release film on one side of the sheet-like thermosetting resin layer obtained in Preparation Example 1 was peeled off, and a non-carrier adhesive sheet (manufactured by Lintec Corporation, trade name) on the exposed surface of the thermosetting resin layer. : Non-carrier 8ECPATI8EB (general strong adhesion type); thickness 0.025 mm) was fed and passed between heated laminating rolls under the conditions of 40 ° C., 0.8 m / min, and pressure 3 kgf / cm ² .

Next, the other release film is peeled off, and a cellulose non-woven fabric (Asahi Kasei Fibers Co., Ltd., trade name: Benrize SN-140; thickness 0) serving as a base material layer on the surface of the exposed thermosetting resin layer. .07 mm, basis weight 13 g / m ² , porosity 88%), and superposed and passed between heated laminate rolls under conditions of 60 ° C., 0.8 m / min, pressure 3 kgf / cm ² , and base material layer A sheet-like adhesive 1 laminated in the order of / thermosetting resin layer / adhesive layer was produced. The obtained sheet-like adhesive 1 had a thickness of 160 μm.

(Examples 2 to 5)
Sheet-like adhesives 2 to 5 were produced in the same manner as in Example 1 except that a base material layer having the characteristics shown in Table 1 was used as the base material layer. The base material layer used here is as follows, and the lamination conditions were adjusted so that the thickness of the obtained sheet-like adhesive was 160 μm.

Example 2: Benlyse ST-18G (manufactured by Asahi Kasei Fibers Co., Ltd., trade name; material cellulose, thickness 0.13 mm, basis weight 27.5 g / m ² , porosity 86%)
Example 3: SR601 (manufactured by Asahi Kasei Fibers Co., Ltd., trade name; material cellulose, thickness 0.47 mm, basis weight 60 g / m ² , porosity 90%)
Example 4: UCOO 40 (manufactured by Kuraray Flex Co., Ltd., trade name; material polyurethane, thickness 0.18 mm, basis weight 40 g / m ² , porosity 81%)
Example 5: MBBK14FZSO (manufactured by Kuraray Flex Co., Ltd., trade name; material, liquid crystal polymer (LCP), thickness 0.07 mm, basis weight 14 g / m ² , porosity 86%)

(Comparative Examples 1-3)
As a base material layer, a sheet-like adhesive obtained by the same operation as in Example 1 (Comparative Example 1) except that a base material without voids was used, and the same as in Example 1 except that no adhesive layer was provided. The sheet-like adhesive obtained by the operation (Comparative Example 2) and the sheet-like adhesive obtained by the same operation as in Example 1 (Comparative Example 3) were obtained except that the thermosetting resin layer was not provided.

(Characteristics of sheet adhesive)
In addition, the various characteristics of each layer and sheet-like adhesive material obtained by each Example and the comparative example were calculated | required according to the method shown below.

(1) Adhesive strength measurement Before curing, a sheet-like adhesive having a thickness of 160 μm is bonded to an aluminum sheet (Mitsubishi Chemical Co., Ltd., trade name: AB180250P; aluminum sheet of surface nylon bonded to a SUS plate) Two 500 g rollers were reciprocated and bonded together. Ten minutes later, the 90 ° C. peel adhesive strength (N / 10 mm) between the sheet-like adhesive and the aluminum sheet was measured under the conditions of 20 ° C. and 28 ° C. at a tensile rate of 50 mm / min.

(2) Adhesive strength measurement A sheet adhesive having a thickness of 160 μm is bonded to an aluminum sheet (Mitsubishi Chemical Co., Ltd., trade name: AB180250P; aluminum sheet of surface nylon bonded to a SUS plate) with a 500 g roller. Was pasted twice. 10 minutes later, heated at 80 ° C. for 10 minutes, taken out, allowed to cool, and returned to room temperature (25 ° C.), at a tensile rate of 50 mm / min, 90 ° C. peel adhesive strength between the sheet-like adhesive and the aluminum sheet (N / 10 mm) was measured.

(3) Exudation (appearance after curing)
The obtained sheet-like adhesive was adjusted to a size of width 10 mm × length 50 mm, and a 500 g roller was reciprocated twice on a surface nylon aluminum sheet (product name: AB180250P). . After heating at 80 ° C. for 10 minutes, the sample was taken out, allowed to cool, returned to room temperature, and observed.

The exudation of the appearance after curing was visually evaluated according to the following criteria.
◯: The shape of the base material is maintained, and no resin oozes out from the end.
X: The shape of the base material is not maintained, and the resin oozes out from the end.

(4) Peel (state after curing)
(3) About the peeling after hardening of the hardened | cured material obtained by the oozing-out test, it evaluated visually by the following criteria.
○: The sheet is not peeled off from the adherend.
X: Part of the sheet is peeled off from the adherend.

(5) Hardness (3) About the hardened | cured material obtained by the oozing-out test, hardness was measured with the Shore A hardness meter, and the following reference | standard evaluated.
◯: Shore A hardness is 80 or more ×: Shore A hardness is less than 80

(6) Evaluation with electronic parts (models) Create a model case made of aluminum that has 10 rectangular projections with a depth of 100mm x 60mm x 80mm and a depth of 1mm on the end face. The sheet-like adhesive was bonded to the end face by hand. After heat curing at 80 ° C. for 10 minutes, the temperature was returned to room temperature to obtain an electronic component (model).

The following judgment criteria were used to visually evaluate the seepage and appearance.
・ Leaking out
○: No resin seepage from the edge of the substrate after the bonded parts are cured.
X: The resin exuded from the end of the base material after the bonded parts are cured.
・ Appearance (shape stability)
○: No peeling or shape change of the substrate is observed after the bonded parts are cured.
X: Peeling or shape change of the substrate is observed after the bonded parts are cured.

  As shown in Table 2, it was found that Examples 1 to 5 exuded and had good appearance and were excellent. On the other hand, in Comparative Example 1 in which the porosity was 0%, bleeding was confirmed. In Comparative Example 2 having no adhesive layer, peeling occurred. In Comparative Example 3 having no thermosetting resin layer, a change in shape was observed.

  DESCRIPTION OF SYMBOLS 1 ... Sheet-like adhesive material, 2 ... Base material layer, 3 ... Thermosetting resin layer, 4 ... Adhesive layer

Claims (5)

(A) A base material layer, (B) a thermosetting resin layer, and (C) a pressure-sensitive adhesive layer are laminated in this order, and are sheet-like adhesives,
The (A) base material layer is made of a nonwoven fabric having a basis weight of 5 to 200 g / m ² and a porosity of 70 to 95%.   The sheet-like adhesive according to claim 1, wherein the (A) substrate layer is made of glass fiber having a fiber diameter of 5 to 20 µm or a cellulose-based nonwoven fabric.   The sheet-like adhesive according to claim 1 or 2, wherein the (B) thermosetting resin layer contains an epoxy resin, a curing agent, and an inorganic filler as essential components.   The sheet-like adhesive according to any one of claims 1 to 3, wherein the (C) pressure-sensitive adhesive layer is a thermoplastic resin.   A component package formed by sealing a component with the sheet-like adhesive according to any one of claims 1 to 4.

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