JP2010185051A - Resin composition and adhesive for dielectric adhesion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition exhibiting desired dielectric characteristics, flexibility, and adhesion when cured, by containing a predetermined epoxy compound and a dielectric in predetermined amount; and an adhesive for dielectric adhesion including a predetermined epoxy compound and suitable for adhering a dielectric to an electrode or the like. <P>SOLUTION: The resin composition includes one or more epoxy resin (A) represented by the general formula (1) and a dielectric (B), wherein R is an alkylene group, n is an integer of 3 to 13, and assuming that a carbon number of the main chain of the alkylene group is m (m is an integer of 1 or more), (m+1)×n is 9 to 65. The resin composition contains 250 pts.wt. or more of the dielectric (B) when the content of the epoxy resin (A) is 100 pts.wt. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a resin composition and an adhesive for dielectric adhesion, and more specifically, by containing a predetermined amount of a predetermined epoxy compound and a dielectric, when cured, desired dielectric properties, flexibility and The present invention relates to an adhesive for dielectric adhesion, which contains a resin composition capable of exhibiting adhesiveness and a predetermined epoxy compound, and is suitable for adhering a dielectric to an electrode or the like.

  In recent years, wireless communication on mobile terminals has been rapidly increasing because of its simplicity compared with wired communication using fixed terminals. The communication capacity is also increasing from the conventional character information to images, moving images, and real-time high-quality moving images. Various high-speed and large-capacity communication methods have been put to practical use in response to such demands for increasing communication capacity. However, if a plurality of communication methods are to be mounted on one portable terminal, a plurality of high-frequency components are mounted and the terminal may be enlarged. Therefore, the need for downsizing each high-frequency component is very high.

In order to achieve miniaturization of a high-frequency component, a dielectric such as a dielectric ceramic sintered body or a dielectric resin in which a dielectric ceramic powder is mixed in a resin is used. Since these dielectrics have a relative dielectric constant (ε) larger than the relative dielectric constant 1 of air, the wavelength λ in the dielectric is shorter than the wavelength λ _{0 in} air as shown in the following formula (2). It is known that In order to sufficiently reduce the size of the high-frequency component, it is desired that the relative dielectric constant is 15 or more.

λ = λ ₀ · (ε · μ) ^1/2 (2)
However, these dielectrics have a problem that they are difficult to be deformed due to their high tensile elastic modulus, and are easily broken when subjected to an impact such as dropping. For this reason, the expectation for a dielectric in a high-frequency component is high, but the current situation is that it is not sufficient from the viewpoint of compatibility in handling and productivity.

  In order to solve the above-mentioned problems, a technique for providing a laminated structure in which a thermoplastic elastomer is bonded to a circuit structure or the like to achieve both flexibility and desired dielectric properties is disclosed (Patent Document 1). ).

Special Table 2000-506305 (published May 23, 2000)

  However, the styrene-based elastomer and olefin-based elastomer disclosed in Patent Document 1 are excellent in flexibility, but do not have adhesiveness with electrodes, and therefore are fixed using an adhesive separately when applied to electronic components. There is a problem that needs to be done. In addition, even when bonding is performed using an adhesive, there is a problem in that the effect of the dielectric is reduced because a gap is formed between the dielectric and the electrode. Therefore, an alternative technology has been awaited.

  The present invention has been made in view of the above-mentioned problems, and its purpose is to contain a predetermined amount of a predetermined epoxy compound and a dielectric material, so that the desired dielectric properties, flexibility, and flexibility can be obtained when cured. An object of the present invention is to provide a dielectric adhesive that contains a resin composition capable of exhibiting adhesiveness and a predetermined epoxy compound and is suitable for adhering a dielectric to an electrode or the like.

  In view of the above problems, the present inventor has intensively studied a resin composition that has sufficient flexibility even after curing, has impact resistance, can secure desired dielectric properties, and has excellent adhesion. went. As a result, the predetermined bifunctional epoxy compound can satisfactorily adhere the dielectric material in an amount necessary for obtaining desired dielectric properties to the electrode and the like, and the resin composition containing the epoxy compound and the dielectric is The present inventors have found that it has sufficient flexibility even after curing, and have completed the present invention.

  That is, the resin composition according to the present invention has the general formula (1)

(In the formula, R represents an alkylene group, n represents an integer of 3 to 13, and m represents the number of carbons in the main chain of the alkylene group, and (m + 1) × n is 9 to 65).
When the content of the epoxy resin (A) is 100 parts by weight, the dielectric (B) is 250 weight by weight. It is characterized by containing at least part.

  The epoxy resin (A) is a bifunctional epoxy compound having an epoxy ring at both ends, and is excellent in curability because the balance between the density of repeating units in the molecule and the density of the epoxy ring is appropriately adjusted. It is possible to impart strong adhesiveness to the cured resin. In addition, the epoxy resin (A) has a chain structure in molecular structure and contains oxygen atoms in the repeating unit. Oxygen has a valence of 2, and the epoxy resin (A) can easily rotate about the oxygen atom. Therefore, the epoxy resin (A) has excellent flexibility after curing. The “repeating unit” is a portion represented by —RO— in the general formula (1).

  Therefore, the resin composition according to the present invention can greatly improve the adhesion of dielectrics to electrodes and the like, and the impact resistance of dielectrics. Therefore, by curing the resin composition according to the present invention, it has desired dielectric properties resulting from the dielectric (B), has excellent adhesion and impact resistance, and can contribute to downsizing of electronic components. A useful resin cured product can be provided. That is, the resin composition according to the present invention is a very useful raw material for obtaining the cured resin.

  The resin composition according to the present invention may further contain a curing agent. When the resin composition according to the present invention is cured, a curing agent may be blended and cured immediately before use with respect to the resin composition which is a mixture of the epoxy resin (A) and the dielectric (B) (that is, The so-called two-component resin composition may be a so-called one-component resin composition preliminarily blended with a curing agent, for example, occurrence of poor curing due to a light weight mistake during blending, etc. Can be prevented.

  The resin composition according to the present invention has a high proportion of oxygen atoms in the repeating unit of the general formula (1). Therefore, in the general formula (1), the alkylene group is an ethylene group, a propylene group, and a butylene group. It is preferably one or more groups selected from

  In the resin composition according to the present invention, the dielectric (B) is preferably a dielectric ceramic. According to the said structure, it becomes possible to suppress the dielectric loss tangent of the resin cured material which hardened | cured the resin composition concerning this invention low.

  In the resin composition according to the present invention, the dielectric (B) is more preferably barium titanate and / or strontium titanate. Since barium titanate is a typical ferroelectric and strontium titanate is a typical paraelectric, the cured resin obtained by curing the resin composition according to the present invention has a relative dielectric constant of 15 or more. Therefore, it is suitable. Therefore, according to the above configuration, the electronic component can be further reduced in size.

  The resin composition according to the present invention has the general formula (1)

(In the formula, R represents an alkylene group, n represents an integer of 3 to 13, and the number of carbons in the main chain of the alkylene group is m (m is an integer of 1 or more), and (m + 1) × n is 9 or more and 65 or less.)
Containing at least one type of epoxy resin (A), a dielectric (B), and an epoxy resin (C) having a smaller dielectric loss tangent than the epoxy resin (A), and containing the epoxy resin (A) When the total of the amount and the content of the epoxy resin (C) is 100 parts by weight, the dielectric (B) may be contained in an amount of 250 parts by weight or more. According to the said structure, it becomes possible to reduce the dielectric loss tangent of the resin cured material which hardened | cured the said resin composition, and can optimize a dielectric loss tangent more.

  The cured resin according to the present invention is a cured resin obtained by curing the resin composition according to the present invention, and has a relative dielectric constant of 15 or more and a dielectric loss tangent of 0.2 or less. Yes. According to the said structure, since the resin composition concerning this invention is hardened | cured, impact resistance and adhesiveness are enough. Furthermore, since the relative dielectric constant is 15 or more, it can contribute to sufficient miniaturization of electronic parts such as high-frequency parts. Moreover, since the dielectric loss tangent is 0.2 or less, energy loss can be suppressed and efficient radiation intensity can be achieved by using it under an appropriate part design.

  The electronic component according to the present invention includes the cured resin according to the present invention. The cured resin is excellent in impact resistance and adhesiveness, and can achieve downsizing of electronic components. Therefore, according to the above configuration, it is possible to impart impact resistance to the electronic component, and as a result, it is possible to improve the disadvantage of the conventional dielectric that is easily broken when subjected to impact such as dropping. In addition, since the plurality of electronic components can be mounted on the terminal because of the small size, it is possible to provide an electronic component that can sufficiently meet the needs for downsizing.

  The adhesive for dielectric adhesion according to the present invention has the general formula (1)

(In the formula, R represents an alkylene group, n represents an integer of 3 to 13, and the number of carbons in the main chain of the alkylene group is m (m is an integer of 1 or more), and (m + 1) × n is 9 or more and 65 or less.)
It contains 1 or more types of epoxy resins (A) represented by these, It is characterized by the above-mentioned.

  As described above, the epoxy resin (A) is excellent in adhesiveness and excellent in flexibility after curing. Therefore, by curing, the dielectric can be firmly bonded to the electrode and the like, and impact resistance can be imparted to the dielectric. Therefore, application of the dielectric to the electronic component can be facilitated.

  The dielectric adhesive adhesive according to the present invention preferably further contains a curing agent. Thereby, since the trouble of blending the curing agent can be saved, the dielectric can be more easily bonded to the electrode or the like.

  The resin composition according to the present invention includes one or more types of epoxy resin (A) represented by the general formula (1) and a dielectric (B), and the content of the epoxy resin (A) is 100 wt. Part, the dielectric (B) is contained in an amount of 250 parts by weight or more. Therefore, by curing, it is possible to provide a cured resin product having a desired dielectric constant and excellent adhesion and impact resistance.

  The dielectric adhesive adhesive according to the present invention contains one or more types of epoxy resin (A) represented by the general formula (1). Therefore, by curing, the dielectric can be firmly bonded to the electrode and the like, and the impact resistance can be imparted to the dielectric.

It is the schematic diagram which showed how the resin cured material concerning this invention can be utilized in IC package which is an example of the electronic component concerning this invention. It is a schematic diagram which shows the process of obtaining a molded object using a release film.

  An embodiment of the present invention will be described as follows, but the present invention is not limited to this. In the present specification, “A to B” indicating a range indicates that the range is A or more and B or less.

[1. Resin composition]
The resin composition according to the present invention has the general formula (1)

(In the formula, R represents an alkylene group, n represents an integer of 3 to 13, and the number of carbons in the main chain of the alkylene group is m (m is an integer of 1 or more), and (m + 1) × n is 9 or more and 65 or less.)
When the content of the epoxy resin (A) is 100 parts by weight, the dielectric (B) is 250 weight by weight. It is a resin composition containing at least part.

  In the present invention, in the general formula (1), when “n represents an integer of 3 to 13 and the number of carbons in the main chain of the alkylene group is m (m is an integer of 1 or more), (m + 1) × n Is 9 or more and 65 or less "(hereinafter, sometimes referred to simply as" conditions "in this section), the epoxy resin (A) exhibits excellent curability, and the cured resin product after curing It was uniquely found that a strong adhesiveness can be imparted and the cured resin after curing exhibits excellent flexibility. The above “main chain of the alkylene group” means a carbon chain in which carbons at both ends are bonded to oxygen atoms of the main chain in the general formula (1) among the carbon chains of the alkylene group.

The “alkylene group” is a divalent substituent obtained by removing two hydrogens from a chain hydrocarbon (alkane) represented by C _Q H _{2Q + 2} , and is represented by —C _Q H _2Q —. The The alkylene group is not particularly limited. For example, a methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, octylene group, nonylene group, dodecylene group and the like can be mentioned.

  Among these, one or more groups selected from the group consisting of ethylene group, propylene group and butylene group are preferable. The ethylene group may be a 1,1-ethylene group or a 1,2-ethylene group. The propylene group may be a 1,2-propylene group or a 1,3-propylene group. The butylene group may be a 1,2-butylene group or a 1,4-butylene group.

  The epoxy resin (A) has a certain degree of flexibility due to the chain structure of the molecular structure, and becomes more flexible due to the inclusion of oxygen atoms in the repeating unit. Therefore, as long as the main chain of the epoxy resin (A) satisfies the above conditions, the longer the chain length, the higher the flexibility. Further, if the above conditions are satisfied and the main chains are of the same length, the flexibility is almost the same, but if the number of side chain molecules is increased, the molecular motion tends to be suppressed. Therefore, the alkylene group preferably has fewer side chains. Therefore, it is 1,2-ethylene group than 1,1-ethylene group, 1,3-propylene group than 1,2-propylene group, and 1,4-butylene group than 1,2-butylene group. Is preferred.

  The number of alkylene groups contained in one molecule of the epoxy resin (A) may be one, or two or more. For example, in the repeating unit in the general formula (1), when n is 2 or more, all Rs may be the same or different.

  The repeating number n in the general formula (1) represents an integer of 3 or more and 13 or less, preferably 4 or more and 13 or less, and particularly preferably 7 or more and 11 or less. When n is less than 3, the density of the epoxy ring in the molecule increases, so that the dielectric loss tangent of the epoxy resin (A) increases and energy loss increases, which is not preferable. On the other hand, when n is 14 or more, the curing reaction is difficult to proceed, and an uncured product tends to remain, which is not preferable.

  The resin composition concerning this invention contains 1 or more types of epoxy resins (A). Therefore, multiple types of epoxy resin (A) may be contained. Further, the epoxy resin (A) may be a mixture in which epoxy resins having different n are mixed as long as the condition that n is an integer of 3 to 13 is satisfied. In this specification, when the epoxy resin (A) is a mixture obtained by mixing a plurality of types of epoxy resins having different n, n is obtained as an average value of molar ratios. For example, when the molar fraction of the epoxy resin having the repetition number n1 is M1, and the molar fraction of the epoxy resin having the repetition number n2 is M2, the repetition number n of the mixture can be expressed by the following formula (3). .

n = M1 × n1 + M2 × n2 (3)
When this is expanded to a mixture of x types of epoxy resins, n can be expressed by the following equation (4).

  That is, if n obtained as an average value of the molar ratio is an integer of 3 or more and 13 or less, an epoxy compound in which n is less than 3 or more than 14 may be mixed. In addition, when the said molar ratio becomes a value including a decimal point, the value rounded off to the first decimal place is used.

  The epoxy resin (A) is used for imparting flexibility and adhesiveness after curing to the resin composition according to the present invention.

  Since the epoxy resin (A) satisfies the above conditions, the balance between the density of the repeating unit in the general formula (1) in one molecule and the density of the epoxy ring is appropriately adjusted. Therefore, it has excellent curability and can impart strong adhesiveness to the cured resin. In addition, since the molecule has a chain structure and contains oxygen atoms in the main chain, it is excellent in flexibility after curing.

  The above-mentioned “flexibility after curing” means that the cured product has a tensile elastic modulus that is not damaged by an impact at the time of dropping, and can be replaced with words such as “impact resistance” and “flexibility”. Can be used. The tensile elastic modulus is not particularly limited. For example, it is preferable that the tensile elastic modulus measured by a method based on JIS K7161 (Plastic-Tensile Properties Test Method Part 1: General) is 1000 MPa or less. . Further, “adhesiveness” refers to the ability to fix a dielectric that is an adherend to an object (for example, an electrode).

  The dielectric (B) is used for imparting dielectric properties to a cured resin obtained by curing the resin composition according to the present invention. The dielectric (B) is not particularly limited as long as it is a substance that generates dielectric polarization when an electric field is applied. Examples thereof include dielectric ceramics, dielectric resin, metal powder, and magnetic powder. Among these, dielectric ceramics are preferable because they can be easily blended into a resin as a sintered body or powder and the dielectric loss tangent can be kept low.

  The dielectric ceramic is not particularly limited. For example, typical ferroelectrics such as barium titanate and barium zirconate titanate can be used, and typical paraelectrics such as strontium titanate, calcium titanate, barium niobate, and titanium. Barium acid neodynate, titanium oxide, or the like can also be used. Of these, barium titanate and / or strontium titanate are more preferable.

  The content of the dielectric (B) in the resin composition according to the present invention is 250 parts by weight or more when the content of the epoxy resin (A) is 100 parts by weight. In view of using the electronic component for downsizing, the cured resin obtained by curing the resin composition according to the present invention is required to have a relative dielectric constant of 15 or more. If it is the above content, a numerical value that the relative dielectric constant is 15 or more can be achieved.

  Although a dielectric material (B) is not specifically limited, From a viewpoint of workability | operativity improvement at the time of mixing with an epoxy resin (A), it is preferable that it is a powder. Although the upper limit of content of the said dielectric material (B) is not specifically limited, It is preferable that the resin composition concerning this invention is content which can maintain fluidity | liquidity at normal temperature.

  The degree of solidification of the resin composition at room temperature varies depending on the size (particle size, etc.) of the dielectric (B) to be blended. Therefore, although the upper limit of the content of the dielectric (B) cannot be specified unconditionally, for example, when the dielectric (B) is a powder having a particle diameter of 1 μm to 2 μm, the upper limit of the content of the dielectric (B) Is 100 parts by weight of the content of the epoxy resin (A) (when the epoxy resin (C) described later is included, the total content of the epoxy resin (A) and the content of the epoxy resin (C)) Sometimes 450 to 500 parts by weight. “Keeping fluidity” means that the material is not completely solidified, for example, in a liquid, semi-solid, paste, slurry, or viscosity state. Although it is preferable that it is a liquid from a viewpoint of work efficiency of this, it is not specifically limited.

  The resin composition concerning this invention can be manufactured by mixing the said epoxy resin (A) and a dielectric material (B) using a conventionally well-known method. Since the resin composition according to the present invention exhibits appropriate flexibility when cured, it can impart impact resistance to the dielectric. Therefore, the handleability of the dielectric can be improved, and the dielectric properties can be fully utilized. Moreover, since the resin composition concerning this invention also shows strong adhesiveness when it hardens | cures, if it hardens | cures, a dielectric material can fully be fixed to an electrode. Therefore, it is possible to solve the problem of the styrene-based and olefin-based elastomers described in Patent Document 1 that do not have adhesiveness.

  The method for curing the resin composition according to the present invention is not particularly limited. For example, it may be heat curing or UV curing. However, for example, when the dielectric (B) is titanate, there is a possibility that only the surface layer portion is cured because the light shielding property of titanate is high. In such a case, it may be cured only by thermal curing, or a process of thermal curing after UV curing may be taken.

  The method for performing the thermosetting is not particularly limited, and for example, it can be performed by using a conventionally known curing agent and heating in a thermostatic bath. Since the heating temperature and the heating time largely depend on the kind of the curing agent, there is generally no preferable condition. Also, the method for performing UV curing is not particularly limited, and it can be performed by appropriately irradiating with UV using a conventionally known curing agent.

  The curing agent may be mixed with the resin composition immediately before the resin composition according to the present invention is cured, or may be previously mixed with the resin composition according to the present invention. That is, the resin composition according to the present invention may further contain a curing agent. As described above, the resin composition according to the present invention is preferably in a liquid state. However, when the resin composition becomes a solid by containing a curing agent, the resin composition is heated in advance and made liquid before use. What is necessary is just to apply | coat the said resin composition to a target object.

  The curing agent is not particularly limited because the object of the present invention can be achieved as long as the resin composition can be cured. For example, aliphatic amine curing agents (for example, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, diethylaminopropylamine, hexamethylenediamine, mensendiamine, isophoronediamine, bis (4-amino-3- Methylzine cyclohexyl) methane, diaminozine cyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, benzyldimethylamine, tris (dimethylaminomethyl) phenol, etc.), aromatic amine curing agents (for example, metaphenylenediamine, Diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldiphenylmethane, etc.), acid anhydride curing agents (eg phthalic anhydride, maleic anhydride, anhydrous) Decyl succinic acid, hexahydrophthalic anhydride, methyl nadic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, dichlorosuccinic anhydride, chlorendic anhydride, etc.), phenolic curing agent, polyphenolic curing agent, polyphenol It is possible to use a series curing agent, a novolak type phenol curing agent, a polyamide curing agent, dicyandiamide, polythiols (for example, trioxane trimethylene mercaptan, etc.), a bisphenol curing agent, and the like.

  In the resin composition according to the present invention, when the amount of the curing agent is small, curing is insufficient, and when the amount of the curing agent is large, workability is reduced due to high viscosity. Therefore, the epoxy resin (A) (epoxy resin (described later) In the case of containing C), 1 to 30 parts by weight, preferably 1 to 10 parts by weight of the curing agent with respect to 100 parts by weight of the total amount of the epoxy resin (A) and the epoxy resin (C). It is preferable to contain.

  In order to lower the curing temperature, a curing accelerator may be further used. Examples of the curing accelerator include tertiary amine-based curing accelerators (for example, 2,4,6-tris (diaminomethyl) phenol, benzyldimethylamine, 2- (dimethylaminomethyl) phenol), hydrazide-based curing accelerators. Urea derivative-based curing accelerators, imidazole-based curing accelerators (for example, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- 2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2-phenyl Imidazole isocyanuric acid adduct, 2-methylimidazole, 2- Ndecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-phenyl -4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine isocyanuric Acid adducts, 2-phenylimidazole, etc.), azabicyclo compound-based curing accelerators, epoxy resin adduct compounds, and the like. The blending amount of the curing accelerator is 100 parts by weight of the epoxy resin (A) (when the epoxy resin (C) described later is included, the total of the content of the epoxy resin (A) and the content of the epoxy resin (C)). It is preferable that it is 1-30 weight part with respect to hardening accelerator, Preferably it is 1-10 weight part.

  The resin composition according to the present invention may further contain an epoxy resin (C) having a dielectric loss tangent smaller than that of the epoxy resin (A). The hardened | cured material of the said resin composition exists in the tendency for a dielectric loss tangent to become large, so that carbon number of the alkylene group in General formula (1) is small. On the other hand, the dielectric loss tangent of the cured product is required to be 0.2 or less in order to reduce energy loss when the cured product is used for an electronic component such as an antenna.

  Therefore, when the dielectric loss tangent of the cured product is expected to increase due to the structure of the epoxy resin (A) to be used, the resin composition contains an epoxy resin having a dielectric loss tangent smaller than that of the epoxy resin (A). By doing so, the dielectric loss tangent can be lowered and adjusted to 0.2 or less.

  Examples of the epoxy resin (C) include bisphenol-type epoxy resins, biphenyl-type epoxy resins, naphthalene-type epoxy resins, alicyclic epoxy resins, dicyclopentadiene-type epoxy resins, which are general epoxy resins.

  Specifically, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol A ethylene oxide 2 mol adduct diglycidyl ether, bisphenol A-1,2-propylene oxide 2 mol adduct diglycidyl ether, hydrogenated bisphenol A Diglycidyl ether, orthophthalic acid diglycidyl ester, tetrahydroisophthalic acid diglycidyl ester, N, N-diglycidylaniline, N, N-diglycidyltoluidine, N, N-diglycidylaniline-3-glycidyl ether, tetraglycidyl metaxylene Diamine, 1,3-bis (N, N-diglycidylaminomethylene) cyclohexane, tetrabromobisphenol A diglycidyl ether, biphenyl diglycidyl ether, naphtha Emissions diglycidyl ether, dicyclopentadiene diglycidyl ether can be used.

  The amount of the epoxy resin (C) is not particularly limited as long as it does not impair the properties of the resin composition according to the present invention. For example, the total of the content of the epoxy resin (A) and the content of the epoxy resin (C) in the resin composition according to the present invention (the total weight of the epoxy resin (A) and the epoxy resin (C)) is 100. When it is set to parts by weight, an amount capable of setting the dielectric loss tangent of the cured resin obtained by curing the resin composition to 0.2 or less so that the epoxy resin (A) is 10 parts by weight or more. Can be blended.

  When the epoxy resin (C) is used, the content of the dielectric (B) in the resin composition according to the present invention is the sum of the content of the epoxy resin (A) and the content of the epoxy resin (C) being 100. When it is set as a weight part, it is 250 weight part or more. In addition, the mixing | blending of an epoxy resin (C) can be performed using a conventionally well-known method.

  In order to improve the adhesiveness, the resin composition according to the present invention may contain an additive different from the epoxy resin (A) and the epoxy resin (C), for example, a primer, a coupling agent, an adhesive, and the like. good. The blending amount of the additive is not particularly limited as long as it does not impair the characteristics of the resin composition.

  Moreover, you may mix | blend a mold release agent with the resin composition concerning this invention in order to provide mold release property to the hardened | cured material after hardening. The compounding quantity of the said mold release agent will not be specifically limited if it is a range which does not impair the characteristic of the said resin composition.

  Furthermore, you may mix | blend the monofunctional glycidyl ether and modified silicone oil different from an epoxy resin (A) and an epoxy resin (C) for viscosity adjustment. A compounding quantity will not be specifically limited if it is a range which does not impair the characteristic of the said resin composition.

  The resin composition according to the present invention is applied to the target object to which the dielectric (B) is to be bonded and cured, so that the dielectric (B) is firmly bonded to the target with impact resistance. Can be made. The application method is not particularly limited as long as it can be applied in a desired shape, and a conventionally known method can be used. For example, methods such as application using a dispenser, casting, screen printing, and extrusion molding can be used.

  The object may be anything provided with an electrode, and examples thereof include a flexible printed circuit board and a resin molded body by injection molding.

[2. (Hardened resin, electronic parts)
As described above, since the resin composition according to the present invention is cured, the dielectric (B) can be firmly bonded to the target object in a state having impact resistance. Therefore, the dielectric (B) Can fully exhibit the dielectric properties of the. On the other hand, in order to sufficiently reduce the size of the electronic component, it is required that the relative dielectric constant of the cured resin obtained by the above curing is 15 or more. In order to reduce the energy loss of the electronic component, the dielectric loss tangent is required. It is required to be 0.2 or less. Therefore, the cured resin according to the present invention is a cured resin obtained by curing the resin composition according to the present invention, and has a configuration in which the relative dielectric constant is 15 or more and the dielectric loss tangent is 0.2 or less. ing.

  The cured resin according to the present invention can be obtained by curing the resin composition according to the present invention. Regarding the curing method [1. As described in [Resin composition].

  The cured resin according to the present invention can be used as a member constituting an electronic component by appropriately forming as necessary. Therefore, an electronic component provided with the cured resin according to the present invention is also included in the present invention. The electronic component is not particularly limited as long as it includes the cured resin according to the present invention. For example, a high frequency electronic component is mentioned. Since the resin cured product according to the present invention has the characteristics that the relative permittivity is 15 or more, it can be miniaturized, and the dielectric loss tangent is 0.2 or less and the energy loss is small. It can utilize especially suitably as a member which comprises components.

  Examples of the high frequency electronic component include an antenna, a filter, an IC package, and a high frequency relay. Since the electronic component according to the present invention uses the cured resin according to the present invention, the electronic component can be reduced in size. For example, if the cured resin according to the present invention is applied to the metal part of the antenna or filter, the relative dielectric constant of the cured resin is 15 or more, and therefore the antenna and the filter can be remarkably reduced in size. Moreover, since the said resin cured material is provided with impact resistance, the electronic component concerning this invention has tolerance with respect to impacts, such as dropping. Furthermore, since the cured resin according to the present invention has strong adhesiveness, no gap is generated between the dielectric and the electrode unlike the technique described in Patent Document 1. Therefore, the electronic component according to the present invention can sufficiently exhibit the characteristics of the dielectric.

  FIG. 1 is a schematic view showing how the cured resin according to the present invention can be used in an IC package which is an example of an electronic component according to the present invention.

  In FIG. 1, 1 is an IC package, 2 is a cured resin according to the present invention, and 3 is a flexible printed circuit board. FIG. 1A shows a state in which the IC package 1 is bonded to the flexible printed circuit board 3 with the cured resin 2 underfilled between the IC package 1 and the circuit board 3. Thereby, the IC package 1 can be protected from thermal stress and the like, and can be firmly bonded, and the protection and adhesion can be maintained for a long time due to the impact resistance of the cured resin 2. In addition, the said underfill introduce | transduces the resin composition concerning this invention between IC package 1 and the board | substrate 3 by conventionally well-known methods, such as an edge coating underfill process, and thermosets the said resin composition. Can be done by.

  FIG. 1B shows a state where not only the IC package 1 and the flexible printed board 3 but also the entire IC package 1 are potted. Thereby, the IC package 1 can be sufficiently sealed, and the sealing can be maintained for a long time due to the impact resistance of the cured resin 2.

  In this way, by using the resin composition according to the present invention when performing underfill or potting, for example, when a high-frequency component element such as an antenna is included in an IC package, a miniaturization effect can be obtained similarly. Can do. Moreover, the effect as a heat radiating member can also be acquired.

  In addition, the high frequency relay etc. which used the resin cured material concerning this invention as a sealing agent can be mentioned as an example of the electronic component concerning this invention.

  The method for producing the electronic component can be a conventionally known method and is not particularly limited. For example, it can be produced by applying the resin composition according to the present invention to a flexible printed circuit board and curing it. About the method of application | coating and hardening [1. Resin composition].

  In addition, if you want to obtain an electronic component that is molded from a resin cured product in a desired shape, place a conventionally known release film that has been processed into the desired shape on a flexible printed circuit board, etc. to perform masking. Only the resin composition according to the present invention can be applied and cured to produce the electronic component.

  As described above, the cured resin according to the present invention can be obtained as a member constituting an electronic component by applying the resin composition according to the present invention to a flexible substrate or the like and curing it, or according to the present invention. It can also be obtained by curing the resin composition alone without applying it to a flexible substrate or the like. In the latter case, for example, a cured resin obtained by curing and molding using the above-described release film can be fixed to an electrode or the like with an adhesive or a pressure-sensitive adhesive to function.

  FIG. 2 is a schematic diagram illustrating a process of obtaining a molded body using a release film. The same members as those shown in FIG. 1 are given the same numbers as in FIG. (A) of FIG. 2 is a schematic diagram showing how the flexible printed circuit board 3 is masked using the release film 6 and the resin composition 5 according to the present invention is applied by the dispenser 4. (B) of FIG. 2 is the schematic diagram which showed the mode that the resin composition 5 was apply | coated to the part which is not masked of the flexible printed circuit board 3 using the release film 6. FIG. (C) of FIG. 2 is the schematic diagram which showed the mode that the resin composition 5 was hardened and the resin cured material 2 was obtained in the longitudinal cross-section. (D) of FIG. 2 is the schematic diagram which showed the mode that the mold release film 6 is removed after completion | finish of hardening, and the mode that the resin cured | curing material 2 (molded object) shape | molded by the desired shape is obtained.

  By using the release film in this way, a molded body obtained by molding the resin cured product into a desired shape can be easily obtained. In this case, it is preferable to mix a release agent with the resin composition according to the present invention. As the release film, a conventionally known release film can be used. For example, films such as Aflex, Asahi Glass Co., Ltd., Terracy, Kureha Co., Ltd., Lumirror, Toray Industries, Inc. can be used. Moreover, a conventionally well-known board | substrate can be used also for a flexible printed circuit board. For example, a flexible printed board or the like shown in the JPCA standard can be used.

[3. Dielectric adhesive)
As described above, the present inventor has found that the epoxy resin (A) exhibits excellent flexibility and adhesiveness by being cured, and so far imparts impact resistance and adhesiveness simultaneously. It was found that the dielectric (B), which was difficult to adhere to, can be firmly adhered to an electrode or the like, and the adhesion can be kept stable.

  That is, the epoxy resin (A) can be used as an adhesive for dielectric adhesion, and the dielectric (B) is mixed with the epoxy resin (A), applied to a target such as an electrode, and cured. As a result, the dielectric (B) can be bonded to the object.

  The dielectric adhesive adhesive according to the present invention contains one or more types of epoxy resin (A) represented by the general formula (1). For the epoxy resin (A) [1. As described in [Resin composition]. In order to cure the adhesive, a curing agent may be blended and thermally cured. The curing agent may be mixed after the adhesive is mixed with the dielectric (B) and before being applied, or a curing agent may be blended in advance with the adhesive. The dielectric (B) and the curing agent are [1. What was demonstrated by the resin composition] can be used.

  The adhesive contains one or more types of epoxy resin (A) as an essential component, but as other components within a range that does not impair the properties of the adhesive [1. The epoxy resin (C), primer, coupling agent, pressure-sensitive adhesive, release agent, monofunctional glycidyl ether, modified silicone oil and the like described in the resin composition] may be contained. When mixing with the dielectric (B), 250 parts by weight or more of the dielectric (B) is mixed with 100 parts by weight of the epoxy resin (A).

  The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the claims, and embodiments obtained by appropriately combining technical means disclosed in different embodiments. Is also included in the technical scope of the present invention.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this.
〔Test method〕
The cured resin products prepared in the following examples and comparative examples were subjected to the following dielectric property test, flexibility test, and adhesion test.

<Dielectric property test>
The dielectric properties of the cured resin were measured according to IEC60377-2 (Recommended methods for the determination of the dielectric properties of insulating materials at frequencies above 300 MHz-part 2: resonance methods). The relative dielectric constant (ε) is preferably 15 or more and the dielectric loss tangent (tan δ) is preferably 0.2 or less.

<Flexibility test>
As an index of the flexibility of the cured resin, a tensile elastic modulus measured by a method referring to JIS K 7161 (Plastic-Tensile Properties Test Method Part 1: General) was used. The difference from JIS K 7161 is that a thin plate of L30 × W5 × T0.5 (mm) was used as a test piece. This is because JIS K 7161 uses a very large test piece. In order not to be damaged by the impact at the time of dropping, the tensile elastic modulus is preferably 1000 MPa or less. In addition, the said thin plate was produced by printing the resin composition in the shape of a release film, and peeling the said release film, after hardening the said resin composition.

<Adhesion test>
Of the flexible printed circuit board shown in the JPCA standard, that is, a copper-clad laminate for wiring, the base material is 12.5 μm thick polyimide, the copper foil is 18 μm cold rolled copper foil (hereinafter flexible) The breaking stress of the cured resin cured on the abbreviated printed circuit board was measured by a method referring to JIS K 6850 (Testing method for tensile shear bond strength of adhesive). The difference from JIS K 6850 is that a resin of L10 × W10 × T5 (mm) is cured on a flexible printed board and a shear load is applied to the cured resin with the film fixed. In order not to peel off due to the impact at the time of dropping, the breaking stress is preferably 1 MPa or more.

[Example 1]
Polyethylene glycol diglycidyl ether (trade name; Denacol EX-821, n = 4, manufactured by Nagase ChemteX), 100 parts by weight of the epoxy resin (A), barium titanate (product) Name: BT-S, Kyoritsu Material) 350 parts by weight, 5 parts by weight of dicyandiamide as a curing agent, 2-phenylimidazole (trade name: Curesol 2PZ, product of Shikoku Chemicals Co., Ltd.) as an imidazole curing accelerator 5 parts by weight was blended to prepare a resin composition. In addition, the alkylene group contained in the repeating unit of the polyethylene glycol diglycidyl ether is a 1,2-ethylene group.

  Next, this resin composition was cast into a mold and printed on a flexible printed board. Resin curing in a shape suitable for the above test by curing the resin composition by thermosetting reaction for 3 hours in a thermostatic chamber (SH-221, manufactured by Espec Corp.) holding the temperature in the bath at 120 ° C. I got a thing. The structure and composition of the cured resin are shown in Table 1 (the same applies to Examples 2 to 11 and Comparative Example). Moreover, the said dielectric property test, the softness | flexibility test, and the adhesiveness test were done with respect to the obtained resin cured material, and the result was shown in Table 2 (it is the same also about Examples 2-11 and a comparative example).

[Example 2]
A cured resin was prepared in the same manner as in Example 1 except that polyethylene glycol diglycidyl ether (trade name; Denacol EX-839, n = 9, manufactured by Nagase ChemteX) was used as the epoxy resin (A). The test was conducted. In addition, the alkylene group contained in the repeating unit of the polyethylene glycol diglycidyl ether is a 1,2-ethylene group.

Example 3
A cured resin was prepared in the same manner as in Example 1 except that polyethylene glycol diglycidyl ether (trade name; Denacol EX-841, n = 13, manufactured by Nagase ChemteX) was used as the epoxy resin (A). The test was conducted. In addition, the alkylene group contained in the repeating unit of the polyethylene glycol diglycidyl ether is a 1,2-ethylene group.

Example 4
A cured resin product was prepared in the same manner as in Example 1 except that polyisopropylene glycol diglycidyl ether (trade name; Denacol EX-920, n = 3, manufactured by Nagase ChemteX) was used as the epoxy resin (A). A similar test was conducted.

Example 5
A cured resin was prepared in the same manner as in Example 1 except that polyisopropylene glycol diglycidyl ether (trade name; EPOLIGHT 400P, n = 7, manufactured by Kyoeisha Chemical Co., Ltd.) was used as the epoxy resin (A). The test was conducted.

Example 6
A cured resin was produced in the same manner as in Example 1 except that polyisopropylene glycol diglycidyl ether (trade name; Denacol EX-931, n = 11, manufactured by Nagase ChemteX) was used as the epoxy resin (A). A similar test was conducted.

Example 7
A cured resin was prepared in the same manner as in Example 1 except that poly n-butylene glycol diglycidyl ether (n = 9) was used as the epoxy resin (A), and the same test was performed.

Example 8
Polyethylene glycol diglycidyl ether (trade name; Denacol EX-839, n = 9, manufactured by Nagase ChemteX) 50 parts by weight as the epoxy resin (A), and bisphenol A diglycidyl ether (trade name; Using 50 parts by weight of EPICLON 840 (manufactured by DIC), 350 parts by weight of the same dielectric (B) as in Example 1 with respect to the total amount (100 parts by weight) of the epoxy resin (A) and the epoxy resin (C), A resin composition was prepared by blending 5 parts by weight of each of a curing agent and a curing accelerator. Using the resin composition, a cured resin was produced in the same manner as in Example 1, and the same test was performed.

Example 9
Polyethylene glycol diglycidyl ether (trade name; Denacol EX-839, n = 9, manufactured by Nagase ChemteX) as the epoxy resin (A), and naphthalene diglycidyl ether (trade name: EPICLON HP-4032D) as the epoxy resin (C) A cured resin was prepared in the same manner as in Example 8 except that DIC was used, and the same test was performed.

Example 10
Polyethylene glycol diglycidyl ether (trade name; Denacol EX-839, n = 9, manufactured by Nagase ChemteX) is used as the epoxy resin (A), and dicyclopentadiene diglycidyl ether (trade name; Adeka Resin) is used as the epoxy resin (C). A cured resin was produced in the same manner as in Example 8 except that EP-4088S (manufactured by ADEKA) was used, and the same test was performed.

Example 11
A cured resin was prepared in the same manner as in Example 1 except that strontium titanate (trade name; ST-S, manufactured by Kyoritsu Materials Co., Ltd.) was used as the dielectric (B), and the same test was performed.

[Comparative Example 1]
Resin in the same manner as in Example 1 except that polyethylene glycol diglycidyl ether (trade name; Denacol EX-850, n = 2, manufactured by Nagase ChemteX) was used as the diglycidyl ether instead of the epoxy resin (A). Hardened | cured material was produced and the same test was implemented. In addition, the alkylene group contained in the repeating unit of the polyethylene glycol diglycidyl ether is a 1,2-ethylene group.

[Comparative Example 2]
A resin cured product was obtained in the same manner as in Example 1 except that polyethylene glycol diglycidyl ether (Denacol EX-861, n = 22, manufactured by Nagase ChemteX) was used as the diglycidyl ether instead of the epoxy resin (A). A similar test was performed. In addition, the alkylene group contained in the repeating unit of the polyethylene glycol diglycidyl ether is a 1,2-ethylene group.

[Comparative Example 3]
A resin cured product was obtained in the same manner as in Example 1 except that polyethylene glycol diglycidyl ether (Denacol EX-941, n = 2, manufactured by Nagase ChemteX) was used as the diglycidyl ether instead of the epoxy resin (A). A similar test was performed. In addition, the alkylene group contained in the repeating unit of the polyethylene glycol diglycidyl ether is a 1,2-ethylene group.

[Comparative Example 4]
A cured resin was prepared in the same manner as in Example 1 except that bisphenol A type diglycidyl ether (trade name: EPICLON 840, manufactured by DIC) was used as the diglycidyl ether instead of the epoxy resin (A). The test was conducted.

  As shown in Table 2, all of the cured resin products of Examples 1 to 11 exhibited dielectric characteristics having a relative dielectric constant of 15 or more and a dielectric loss tangent of 0.2 or less. Therefore, it turns out that it is a resin hardened | cured material which can contribute to size reduction of an electronic component and there are few energy losses. Moreover, all the tensile elastic moduli are 1000 MPa or less, and it turns out that it is excellent in flexibility. Furthermore, all the breaking stress is 10 MPa or more, and it turns out that it has strong adhesiveness.

  On the other hand, the resin cured product of Comparative Example 2 could not be cured in the first place, and the object of the present invention could not be achieved. About the resin hardened | cured material of the comparative examples 1 and 3, the dielectric loss tangent exceeded 0.2 and it was a thing with a large energy loss. The cured resin of Comparative Example 4 had a very high tensile modulus and insufficient impact resistance.

  As described above, by curing the resin composition according to the present invention, it is possible to achieve both downsizing of electronic parts and reduction of energy loss in any of the characteristics of relative permittivity, dielectric loss tangent, tensile elastic modulus and breaking stress. And sufficient value was obtained in order to provide the resin cured material which is excellent also in flexibility and adhesiveness. On the other hand, when the resin composition according to the present invention was not provided, all of the above characteristics could not be satisfied even when cured.

  Since the resin composition according to the present invention contains a predetermined amount of one or more types of the epoxy resin (A) represented by the general formula (1) and the dielectric (B), the resin composition is cured by curing. It is possible to obtain a cured resin product having dielectric properties, sufficient flexibility, and strong adhesion necessary for downsizing and reduction of energy loss. Therefore, it can be widely used in the entire electronic industry using electronic components, particularly high-frequency electronic components such as antennas, filters, IC packages, and relays.

DESCRIPTION OF SYMBOLS 1 IC package 2 Resin hardened material 3 Flexible printed circuit board 4 Dispenser 5 Resin composition 6 Release film

Claims (10)

General formula (1)

(In the formula, R represents an alkylene group, n represents an integer of 3 to 13, and the number of carbons in the main chain of the alkylene group is m (m is an integer of 1 or more), and (m + 1) × n is 9 or more and 65 or less.)
Including one or more types of epoxy resins (A) represented by: and a dielectric (B),
A resin composition comprising 250 parts by weight or more of the dielectric (B) when the content of the epoxy resin (A) is 100 parts by weight.   The resin composition according to claim 1, further comprising a curing agent.   In the said General formula (1), an alkylene group is 1 or more groups chosen from the group which consists of an ethylene group, a propylene group, and a butylene group, The resin composition of Claim 1 or 2 characterized by the above-mentioned.   The resin composition according to any one of claims 1 to 3, wherein the dielectric (B) is a dielectric ceramic.   5. The resin composition according to claim 4, wherein the dielectric ceramic is barium titanate and / or strontium titanate. General formula (1)

(In the formula, R represents an alkylene group, n represents an integer of 3 to 13, and the number of carbons in the main chain of the alkylene group is m (m is an integer of 1 or more), and (m + 1) × n is 9 or more and 65 or less.)
One or more types of epoxy resins (A) represented by: a dielectric (B), and an epoxy resin (C) having a dielectric loss tangent smaller than that of the epoxy resin (A),
Resin composition containing 250 parts by weight or more of the dielectric (B) when the total content of the epoxy resin (A) and the content of the epoxy resin (C) is 100 parts by weight object.   A cured resin obtained by curing the resin composition according to any one of claims 1 to 6, wherein the relative dielectric constant is 15 or more and the dielectric loss tangent is 0.2 or less. Cured resin.   An electronic component comprising the cured resin product according to claim 7. General formula (1)

(In the formula, R represents an alkylene group, n represents an integer of 3 to 13, and the number of carbons in the main chain of the alkylene group is m (m is an integer of 1 or more), and (m + 1) × n is 9 or more and 65 or less.)
A dielectric adhesive adhesive comprising at least one epoxy resin (A) represented by the formula:   The adhesive for dielectric adhesion according to claim 9, further comprising a curing agent.

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