Adhesive composition, adhesive, adhesive layer, adhesive sheet, laminate and adhesive composition

Abstract

An adhesive that has a low dielectric constant and low dielectric loss tangent, and can form an adhesive with excellent tackiness. A composition is provided. [Solution] Structural site derived from polycarboxylic acids (a1) and polyhydric alcohols (a2) An adhesive composition containing a polyester resin (A) having a structural component derived from, In the structural site derived from the above polycarboxylic acids (a1), aromatic polycarboxylic acids The content of structural sites derived from (a1-1) is 20 mol% or more, In the structural site derived from the above polyhydric alcohols (a2), polydiene diol and / Or, if the content of structural moieties derived from hydrogenated polydienediol (a2-1) is 20 mol% or more An adhesive composition characterized by certain features.

Description

Technical Field

[0001] The present invention relates to an adhesive composition, an adhesive obtained by crosslinking the adhesive composition, an adhesive layer, an adhesive sheet including the adhesive layer, a laminate, and an adhesive composition. More specifically, the present invention relates to an adhesive composition having a low dielectric constant and a low dielectric tangent, excellent adhesive physical properties, and an adhesive obtained by crosslinking the adhesive composition, an adhesive layer, an adhesive sheet including the adhesive layer, a laminate, and an adhesive composition.

Background Art

[0002] Conventionally, polyester resins have been used in a wide range of applications such as films, PET bottles, fibers, toners, electrical components, adhesives, and adhesives because of their excellent heat resistance, chemical resistance, durability, and mechanical strength. In addition, since polyester resins have a high polarity due to their polymer structure, they are known to exhibit excellent adhesiveness to polar polymers such as polyester, polyvinyl chloride, polyimide, and epoxy resin, and metal materials such as copper and aluminum.

[0003] For example, Patent Document 1 aims to obtain a thermosetting adhesive sheet having excellent dimensional stability during curing, excellent adhesiveness, heat resistance, flexibility, electrical insulation, low dielectric constant, and low dielectric tangent after curing. To this end, a reaction functional group capable of reacting with at least one of an organometallic compound or an epoxy group-containing compound, and a functional group having a heteroatom other than halogen, and a resin (for example, a polyester resin) having a total amount of 0.01 mmol / g or more and 9 mmol / g or less, an organometallic compound, and a polyfunctional epoxy group-containing compound have been proposed.

Prior Art Documents

Patent Documents

[0004] [Patent Document 1] Japanese Patent Publication No. 2017-031301 [Overview of the project] [Problems that the invention aims to solve]

[0005] In recent years, with the increasing frequency of transmitted signals, there has been a growing demand for low induction in adhesives used for fixing and bonding devices. Electrical characteristics, particularly low dielectric loss tangent, are becoming increasingly important. For example, in the millimeter-wave band and beyond. For use in the lamination of transparent antenna films for high-frequency radio waves and radio wave reflective films, etc. The adhesive layer that can be used also requires low dielectric properties. However, the technology disclosed in Patent Document 1 above does not achieve low dielectric constant, low dielectric loss tangent, or low water absorption. Although the ester bond concentration is being lowered for this purpose, the demand for low dielectric properties in recent years is very high. Simply lowering the ester bond concentration is insufficient; further improvements are needed. Ta.

[0006] Therefore, in this context, the present invention provides low dielectric constant and low dielectric loss tangent, and viscosity Adhesive composition with excellent adhesion properties, adhesive obtained by crosslinking the above adhesive composition, adhesive layer, the above adhesive The objective is to provide adhesive sheets, laminates, and adhesive compositions having an adhesive layer.

[0007] In addition, adhesives using acrylic resins are widely used as adhesives. Furthermore, acrylic adhesives aimed at low dielectric loss tangent are also known, but The adhesive system had a problem in that its adhesive strength was extremely low due to its design. Also, regarding adhesive strength... While improvement is possible by adding large amounts of tackifier, this would compromise transparency, heat resistance, and durability. There is a problem that durability and other properties deteriorate, and acrylic adhesives have a low dielectric loss tangent and high adhesive properties. It was difficult to achieve both at the same level. In this invention, acrylic adhesives are used because they can achieve a high level of both low dielectric properties and adhesive properties. The objective is to obtain polyester-based adhesives and bonding agents that are superior to conventional adhesives. [Means for solving the problem]

[0008] However, in light of these circumstances, the inventors have conducted extensive research and have found a specific structure By using an adhesive composition made of polyester resin, the objectives of the present invention are met. We discovered this and completed the present invention.

[0009] In other words, the gist of the present invention is as follows: [1] to

[12] . [1] Structural sites derived from polycarboxylic acids (a1) and polyhydric alcohols (a2) An adhesive composition containing a polyester resin (A) having the structural components of, In the structural site derived from the above polycarboxylic acids (a1), aromatic polycarboxylic acids (a 1-1) The content of structural parts derived from 20 mol% or more, In the structural site derived from the above polyhydric alcohols (a2), polydiene diol and / Or, if the content of structural moieties derived from hydrogenated polydienediol (a2-1) is 20 mol% or more A certain adhesive composition. [2] Structural sites derived from the above aromatic polycarboxylic acids (a1-1) and polydiene diols and / or the total of structural sites derived from hydrogenated polydienediol (a2-1) The adhesive composition according to [1], wherein the L-type resin (A) is present in an amount of 90% by weight or more. [3] The above polydienediol and / or hydrogenated polydienediol (a2-1) The adhesive composition described in [1] or [2] having a number average molecular weight of 500 to 10,000. [4] The above polyene diol and / or hydrogenated polyene diol (a2-1) is a polyene diol formed from a conjugated diene having 4 to 9 carbons and / or a hydrogenated product of a polyene diol formed from a conjugated diene having 4 to 9 carbons, which is the adhesive composition described in any one of [1] to [3]. [5] The dielectric tangent of the above polyester resin (A) at a frequency of 10 GHz under the environment of a temperature of 23 °C and a relative humidity of 50% RH is 0.01 or less, which is the adhesive composition described in any one of [1] to [4]. [6] The acid value of the above polyester resin (A) is 10 mgKOH / g or less, which is the adhesive composition described in any one of [1] to [5]. [7] The adhesive composition further containing a crosslinking agent (B), which is the adhesive composition described in any one of [1] to [6]. . [8] An adhesive obtained by crosslinking the adhesive composition described in any one of [1] to [7]. [9] An adhesive layer obtained by crosslinking an adhesive composition containing a polyester resin (A) having a structural site derived from a polyvalent carboxylic acid (a1) and a structural site derived from a polyhydric alcohol (a2) and a crosslinking agent (B), wherein the content of the structural site derived from an aromatic polyvalent carboxylic acid (a1-1) in the structural site derived from the above polyvalent carboxylic acid (a1) is 20 mol% or more, the content of the structural site derived from a polyene diol and / or a hydrogenated polyene diol (a2-1) in the structural site derived from the above polyhydric alcohol (a2) is 20 mol% or more, and the dielectric tangent of the above adhesive layer at a frequency of 10 GHz under the environment of a temperature of 23 °C and a relative humidity of 50% RH is 0.01 or less. ​​​​​​​​

[10] [9] The adhesive layer described above, with a release sheet on one side of the adhesive layer and on the other side An adhesive sheet comprising a base material, wherein the base material is subjected to an environment with a temperature of 23°C and a relative humidity of 50%RH. An adhesive sheet having a dielectric loss tangent of 0.01 or less at a frequency of 10 GHz.

[11] [9] The adhesive layer is provided with a substrate on at least one side of the adhesive layer. A laminate, wherein the above substrate is subjected to a frequency of 10G under conditions of a temperature of 23°C and a relative humidity of 50%RH. A laminate in which the dielectric loss tangent at Hz is 0.01 or less.

[12] Structural sites derived from polycarboxylic acids (a1) and polyhydric alcohols (a2) An adhesive composition containing a polyester resin (A) having a conventional structural component, In the structural site derived from the above polycarboxylic acids (a1), aromatic polycarboxylic acids (a 1-1) The content of structural parts derived from 20 mol% or more, In the structural site derived from the above polyhydric alcohols (a2), polydiene diol and / Or, if the content of structural moieties derived from hydrogenated polydienediol (a2-1) is 20 mol% or more An adhesive composition characterized by a certain feature.

[0010] As described in Patent Document 1 above, typically the water absorption rate, dielectric constant, and dielectric loss tangent are reduced. To achieve this, large quantities of polycarboxylic acids or polyhydric alcohols with long-chain alkyl groups are used in the aesthetics process. Lowering the bond concentration is a possibility, but on the other hand, it would reduce long-term durability in a humid and hot environment. This would result in... Furthermore, simply lowering the ester bond concentration would not lead to further reduction of dielectric constant. Obtaining the specific characteristics is difficult. The present inventors have found that by adjusting the composition of the monomers constituting the polyester resin, Having discovered that it has a low dielectric constant and low dielectric loss tangent, and excellent adhesive properties, the present invention was completed. That is what it was. [Effects of the Invention]

[0011] The adhesive composition or bonding agent of the present invention has a low dielectric constant and a low dielectric loss tangent, and further Because it has excellent adhesive properties, it is used as an adhesive or bonding agent in electronic equipment that transmits and receives high-frequency signals. It is effective as an adhesive. Furthermore, the adhesive layer of the present invention has a low dielectric constant and low dielectric loss tangent, and also exhibits excellent adhesive properties. Therefore, it is effective in adhesive sheets and laminates used in electronic devices that transmit and receive high-frequency signals. That is the case. [Modes for carrying out the invention]

[0012] The configuration of the present invention will be described in detail below, but these are merely examples of desirable embodiments. It is. In this invention, the term "class" appended to the compound name refers to the compound in question, as well as the compound itself. This concept also encompasses derivatives of substances. For example, the term "carboxylic acids" includes carboxylic acids. In addition, carboxylate salts, carboxylic acid anhydrides, carboxylic acid halides, and compounds with approximately 1 to 8 carbon atoms. This also includes carboxylic acid derivatives such as carboxylic acid esters. Furthermore, in the present invention, "y and / or z (y, z are any configuration or component)" This represents three possible combinations: y only, z only, and y and z.

[0013] The adhesive sheet in this specification has a release film on at least one side of the adhesive, and the other side It has a release film or base film laminated on one side and is attached to the substrate. This refers to a product that is attached by peeling off a release film. You may also use a molded plastic with a release agent applied to the back surface. Furthermore, the adhesive sheet in this specification is obtained by coating an adhesive composition onto a base film and then applying a release liner. This refers to a method where the adhesive composition is directly applied to the substrate without layering any film.

[0014] The adhesive composition of the present invention or the adhesive composition of the present invention (hereinafter referred to as "the Composition") , Structural site derived from polycarboxylic acids (a1) and structural site derived from polyhydric alcohols (a2) It contains a polyester resin (A) which includes [the specified component]. First, let's explain polyester resin (A).

[0015] <Polyester resin (A)> Polyester resin (A) consists of structural sites derived from polycarboxylic acids (a1) and polyvalent alcohols. It contains a structural site derived from polycarboxylic acids (a2) in its molecule, and the above polycarboxylic acids (a1 ) contains structural sites derived from aromatic polycarboxylic acids (a1-1) The amount is 20 mol% or more, and in the structural site derived from the above polyhydric alcohols (a2), Lydienediol and / or hydrogenated polydienediol (a2-1) [hereinafter referred to as "polydienediol"] The content of structural parts derived from [sometimes referred to as "endiols (a2-1)] is 20 moles. It is % or more. Furthermore, the above polyester resin (A) is polycarboxylic acid (a1) and poly It is preferable to obtain the product by esterifying it with valence alcohols (a2).

[0016] Generally, polyester resins containing structural components derived from polybutadiene are used as adhesives. It is known that this is possible, and by incorporating a polybutadiene structure, polypropylene It improves adhesion to polyolefins such as [unclear]. On the other hand, in the present invention, a composition derived from aromatic polycarboxylic acids (a1-1) in a specific amount or more Polyester containing a structural site and a specific amount or more of a structural site derived from polydiene diols (a2-1) By using a sterling resin (A), the dielectric properties are uniquely improved (dielectric constant and dielectric loss tangent decrease). I found something to do. Normally, making a resin hydrophobic improves its dielectric properties, but in this invention, surprisingly, , structural sites derived from aromatic polycarboxylic acids (a1-1) which are more hydrophilic than alkyl chains By introducing a specific amount or more of structural sites derived from polydiene diols (a2-1), Polyester resins are generally considered to be materials with poor dielectric properties (high dielectric constant and dielectric loss tangent). We found that the dielectric properties of fats were significantly improved. The reason for this is unclear, but it is thought to be a structural site derived from aromatic polycarboxylic acids (a1-1). By introducing a certain amount or more, the mobility of polymer molecules is suppressed, and furthermore, polydiene By containing many structural sites derived from diols (a2-1), highly polar ester bonds are formed. It is thought that reducing this can lower the polarity. These factors suppress molecular motion and It is presumed that the dielectric properties are improved by the combined effect of the decrease in polarity.

[0017] [Structural site derived from polycarboxylic acids (a1)] Examples of structural sites derived from polycarboxylic acids (a1) include aromatic polycarboxylic acids. (a1-1) Structural site derived from (a1-1), structural site derived from alicyclic polycarboxylic acids, aliphatic polycarboxylic acid Examples of structural parts derived from benzoic acids include: Structure derived from polycarboxylic acids (a1) The ingredients may include one or more different parts.

[0018] Structural sites derived from polycarboxylic acids (a1) are considered to have low dielectric properties, and are aromatic polycarboxylic acids. It contains structural parts derived from carboxylic acids (a1-1). Aromatic polycarboxylic acids (a 1-1) Aromatic polycarboxylic acids (a1-1) that constitute the structural site derived from 1-1 include, for example, For example, terephthalates, dimethyl terephthalates, isophthalates, and dimethyl isophthalates. Orthophthalic acids, naphthalenedicarboxylic acids, dimethyl naphthalenedicarboxylic acids Aromatic dicarboxylic acids such as biphenyldicarboxylic acids, trimellitic acids, trimesin Acids, ethylene glycol bis(anhydrotrimellitates), glycerol tris( Anhydrotrimellites, pyromellitic acids, oxydiphthalic acids, 3,3',4 ,4'-Benzophenonetetracarboxylic acids, 3,3',4,4'-Diphenyltetracarboxylic acids 3,3',4,4'-Diphenylsulfonetetracarboxylic acids, 4,4'-( Xasafloisopropylidene) diphthalates, 2,2'-bis[(dicarboxyphenoxy Examples include trivalent or higher aromatic carboxylic acids such as phenyl]propanes.

[0019] Among these, the use of aromatic dicarboxylic acids, i.e., polyester resins (A) preferably has structural units derived from aromatic dicarboxylic acids, and is particularly preferred These are structural sites derived from terephthalic acids, structural sites derived from isophthalic acids, and naphthalenedicarb. Having structural parts derived from nitrates is even more preferable from the viewpoint of adhesive properties and low dielectric properties. Alternatively, it may involve having structural parts derived from isophthalic acids. Furthermore, in terms of reactivity, it is preferable to use esterified versions of these lower alkyl groups. Specifically, dimethyl terephthalate, dimethyl isophthalate, dimethyl naphthalenedicarb It is preferable to use nic acid.

[0020] Aromatic polycarboxylic acids (a1-1) in the structural site derived from polycarboxylic acids (a1) The content of structural parts derived from ) is 20 mol% or more, more preferably 50 mol% or more. More preferably 70 mol% or more, particularly preferably 82 mol% or more, and especially preferably 90 mol% or more. The amount is 100% or more, most preferably 100 mol%. Aromatic polycarboxylic acids (a1-1) If the content of the original structural components is too low, the dielectric properties will be inferior, and it will be particularly difficult to obtain a low dielectric loss tangent. . Furthermore, poor dielectric properties mean that the dielectric constant and dielectric loss tangent do not decrease, or This means that the value will be large.

[0021] Aromatic polycarboxylic acids (a1) relative to the entire structural site derived from polycarboxylic acids (a1 -1) The content (mol%) of the structural part derived from this product can be calculated using the following formula 1. [Formula 1] Content (mol%) of structural sites derived from aromatic polycarboxylic acids (a1-1) = (aromatic polycarboxylic acids Structural sites (moles) derived from carboxylic acids (a1-1) / derived from polycarboxylic acids (a1) Structural part (moles) × 100

[0022] The composition of the entire polyester resin (A) is derived from aromatic polycarboxylic acids (a1-1). The content of the manufacturing part is preferably 1 to 30% by weight, and more preferably 2 to 20% by weight. More preferably 3 to 10% by weight. Derived from aromatic polycarboxylic acids (a1-1) If the content of structural components is too low, the dielectric properties tend to be inferior, and it is particularly difficult to obtain a low dielectric loss tangent. There is a tendency for this to happen, and if there is too much, the tuck effect tends to be insufficient.

[0023] Furthermore, when imparting an acid value to polyester resin (A), polycarboxylic acids (a1) The original structural site is derived from polycarboxylic acids with 0 or 1 acid anhydride group and a valency of 3 or higher. It is preferable from the viewpoint of adhesiveness that the structural components are present. The number of acid anhydride groups is 0 or 1. The valency of the carboxyl group in the structural site derived from polycarboxylic acids with a valency of 3 or more is preferably It is 3-6 valent, more preferably 3-4 valent. The number of such acid anhydride groups is 0 or 1. The number of acid anhydride groups constituting the structural site derived from polycarboxylic acids with a valency of 3 or more is 0 or 1. Examples of polycarboxylic acids with a valency of 3 or higher include the above-mentioned aromatic polycarboxylic acids with a valency of 3 or higher. Examples of acid anhydrides include those with 0 or 1 acid anhydride group. For example, trimellitic anhydride. Examples include acid anhydrides, trimellitic acids, trimesic acids, etc. Also, the number of acid anhydrides other than those listed above. Examples of polycarboxylic acids with a valency of 0 or 1 include hydrogenated trimellitic acid. Examples include watery substances. Among these, those with 1 acid anhydride group are preferred, and trimelli Structural parts derived from tacin anhydride are particularly preferred.

[0024] As alicyclic polycarboxylic acids that constitute the structural site derived from the above alicyclic polycarboxylic acids Examples include 1,4-cyclohexanedicarboxylic acids and 1,3-cyclohexanedicarboxylic acids. Examples include nic acids and 1,2-cyclohexanedicarboxylic acids.

[0025] The structural sites derived from the above aliphatic polycarboxylic acids are composed of aliphatic polycarboxylic acids. Examples include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and dodecane. Examples include diacides.

[0026] Polyester resin (A) contains structural moieties derived from the above alicyclic polycarboxylic acids, aliphatic polycarboxylic acids If a structural part derived from carboxylic acids is included, the structural part derived from polycarboxylic acids (a1) At this position, the structural site is derived from the above-mentioned alicyclic polycarboxylic acids, and the structural site is derived from aliphatic polycarboxylic acids. The total content of the structural parts is preferably 30 mol% or less, and more preferably 1 The percentage is 8 mol% or less, and more preferably 10 mol% or less.

[0027] Furthermore, the polyester resin (A) contains structural units derived from sulfoterephthalic acid, 5-sulfoterephthalic acid. Structural units derived from foisophthalic acids, structural units derived from 4-sulfophthalic acids, 4-sulfona Structural units derived from phthalene-2,7-dicarboxylic acids, 5(4-sulfophenoxy)isoph Structural units derived from aromatic dicarboxylic acids having sulfonic acid groups, such as structural units derived from taric acids, and aromatic dicarboxylates having sulfonic acid bases such as metal salts and ammonium salts thereof It may contain structural units derived from the resin, but the hygroscopic properties of the polyester resin (A) and the resin From the standpoint of compatibility, the content relative to the total structural unit derived from polycarboxylic acids (a1) is 10 It is preferably 5 mol% or less, more preferably 5 mol% or less, and particularly preferably 3 mol It is less than or equal to %; more preferably less than or equal to 1 mol%; and most preferably 0 mol%.

[0028] [Structural parts derived from polyhydric alcohols (a2)] Examples of structural sites derived from polyhydric alcohols (a2) include polydiene diols ( a2-1) Structural site derived from dimer ols, structural site derived from dimer ols, bisphenol skeleton Structural sites derived from monomers, structural sites derived from aliphatic polyhydric alcohols, alicyclic polyhydric alcohols Examples include structural parts derived from polyhydric alcohols and structural parts derived from aromatic polyhydric alcohols. The structural components derived from the 'L' group (a2) may be present individually or in combination of two or more types.

[0029] In the present invention, polydiene diol is used as the structural site derived from polyhydric alcohols (a2). It contains structural units derived from the 'L' group (a2-1).

[0030] Polydiene diols constituting the structural site derived from the above polydiene diols (a2-1) As for class (a2-1), due to its excellent dielectric properties, it is a conjugated diene having 4 to 9 carbon atoms. From the polydiene diols and / or conjugated dienes having 4 to 9 carbon atoms that are formed It is preferable that the resulting product is a hydrogenated polydiene diol, for example, one in which both ends are hydroxyl groups Polybutadienediol, polyisoprendiol, polyhexadienediol, etc. These hydrogenated substances are examples. They may be used individually or in combination of two or more. Among them, hydrogenated compounds are preferred in terms of suppressing gelation during the manufacturing of polyester resin (A). Furthermore, hydrogenated polybutadiene diol is preferred in terms of versatility.

[0031] The hydroxyl groups at both ends mentioned above are either directly bonded to the polydiene structure or bonded via a bonding chain. It's okay to do so. Examples of such bonding chains include alkylene chains, alkenylene chains, alkynylene chains, and f Hydrocarbons such as phenylene chains and naphthylene chains (these hydrocarbons contain fluorine, chlorine, bromine, etc.) Chains that may be substituted with chlorogen, etc., or -CO-, -COCO-, -CO(CH2)m Examples include CO-(m=1~10), etc. Among these, in terms of not hindering the effects of the present invention, Lukilen chains are preferred. Furthermore, the above-mentioned bonding chains may be present individually or in combination of two or more types. stomach.

[0032] Furthermore, the number-average molecular weight of the above polydiene diols (a2-1) is excellent in dielectric properties. Therefore, it is preferable that it be between 500 and 10000, and more preferably between 1000 and 7000. Preferably, it is between 1500 and 5000.

[0033] The hydrogenation rate of the hydrogenated polybutadienediol is not particularly limited, but preferably hydrogenated The hydrogenation rate is 80% or higher, and particularly preferably 90% or higher. If the hydrogenation rate is low, Due to the presence of unsaturated groups, the appearance of polyester resin (A) deteriorates, and polyester The manufacturing process of tel-based resin (A) is prone to gelation, making it difficult to produce. It has a direction. Also, the upper limit is usually 100%.

[0034] The polybutadiene diols (a2-1) preferably have side chains, and poly The proportion of side chains to the total amount of tadiene diols (a2-1) is preferably 10% or more. More preferably 0% or more, even more preferably 30% or more, and most preferably 40% or more. ru. The proportion (%) of the side chains to the total is calculated by the following equation 2. [Formula 2] Percentage of side chains relative to the total (%) = Number of carbon atoms in side chains / Total number of carbon atoms × 100

[0035] In the polyester resin (A) used in the present invention, from the viewpoint of dielectric properties, polyvalent Polydiene diol (a2-1) derived from the structural site of alcohol (a2) The content of structural components must be 20 mol% or more, preferably 50 to 100 mol%. , particularly preferably 70 to 97 mol%. The composition derived from polydiene diols (a2-1) If the content of the material is too low, it will have poor hygroscopicity, dielectric properties, and tackiness.

[0036] Furthermore, the polydiene diols (a2-1) in relation to the polyester resin (A) The content of the original structural components is preferably 20-99% by weight, and more preferably 30% 98% by weight, more preferably 40-97% by weight. Polydiene diols (a2- 1) If the content of the derived structural components is too low, the material will have poor hygroscopic properties, dielectric properties, and tackiness. There is a tendency for this to happen, and if there is too much, the compatibility with additives tends to worsen.

[0037] Furthermore, in the present invention, from the viewpoint of low dielectric loss tangent, the aromatic polycarboxylic acids (a1 -1) The sum of the structural sites derived from polydiene diols (a2-1) is It is also preferable that the amount of polyester resin (A) be 90% by weight or more. More preferably 95% It is more than % by weight.

[0038] The above-mentioned aromatic polycarboxylic acids (a1-1) and the structural sites derived from polydiene diols (a 2-1) The total number of structural parts derived from these parts can be calculated using the following formula 3. [Formula 3] Structural sites derived from polycarboxylic acids (a1-1) and polydiene diols (a2-1) Total structural parts (weight %) = [Structural parts derived from aromatic polycarboxylic acids (a1-1)] [Weight of (A) + Weight of polydiene diols (a2-1)] / Total weight of polyester resin (A) Amount x 100

[0039] In the present invention, the polyester resin (A) is an aromatic polycarboxylic acid (a1-1) It is preferable to have a good balance of polydiene diols (a2-1) and polyester Aromatic polycarboxylic acids (a1-1) and polydiene diols in tel resins (A) The weight ratio of (a1-1) to (a2-1) [(a1-1) / (a2-1)] is usually between 0.001 and 1. Preferably, it is 0.01 to 0.1.

[0040] Examples of dimer ols that constitute the structural site derived from the aforementioned dimer ols include If the average number of carbon atoms is 10 to 26 (preferably 12 to 24, more preferably 14 to 22), then it is unsaturated. Examples include diols derived from dimer acids of Japanese fatty acid dimers. Specifically, For example, unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid, and erucic acid. Examples of induced diols include:

[0041] The bisphenol skeleton-containing monomer-derived structural part constituting the bisphenol skeleton-containing monomer Examples of monomers include bisphenol A, bisphenol B, and bisphenol E. , bisphenol F, bisphenol AP, bisphenol BP, bisphenol P, bisphenol Sphenol PH, Bisphenol S, Bisphenol Z, 4,4'-Dihydroxybene Zophenone, bisphenol fluorene, and their hydrogenated derivatives, and bisphenols Obtained by adding 1 to several moles of ethylene oxide or propylene oxide to a hydroxyl group. Examples include glycols such as ethylene oxide adducts and propylene oxide adducts. .

[0042] The aliphatic polyhydric alcohols that constitute the structural site derived from the aliphatic polyhydric alcohol are: For example, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol L, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-penta 1,6-Hexanediol, neopentyl glycol, 1,6-Hexanediol, 3-methyl-1,5 -Pentanediol, 1,9-nonanediol, 1,10-decanediol, 2-ethyl -2-Butylpropanediol, 2,4-Diethyl-1,5-Pentanediol, 2,2 Aliphatic diols such as 4-trimethyl-1,3-pentanediol, glycerin, trim Trivalent or higher aliphatic compounds such as tyrolethane, trimethylolpropane, and pentaerythritol. Examples include polyhydric alcohols. Among them, ethylene glycol and trimethylolpropane are particularly noteworthy. n is preferable.

[0043] The alicyclic polyhydric alcohols that constitute the structural site derived from the alicyclic polyhydric alcohol are, For example, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, tri Examples include cyclodecanediol, tricyclodecanedimethanol, and spiroglycol. ru.

[0044] The aromatic polyhydric alcohols that constitute the structural site derived from the aforementioned aromatic polyhydric alcohols are, This excludes the bisphenol skeleton-containing monomers, for example, paraxylene glyco Metaxylene glycol, orthoxylene glycol, 1,4-phenylene glycol Examples include ethylene oxide adducts of 1,4-phenylene glycol.

[0045] Furthermore, the above aromatic polyhydric alcohol is fluorene represented by the following general formula (1). Diol compounds can also be mentioned. [ka]

[0046] Polyester resin (A) contains structural parts derived from dimer ols and a bisphenol skeleton. Structural sites derived from contained monomers, structural sites derived from aliphatic polyhydric alcohols, alicyclic polyhydric alcohols If the structural site is derived from an alcohol or an aromatic polyhydric alcohol, then polyhydric alcohol In the structural site derived from coals (a2), the structural site derived from dimer ols, bisf Structural sites derived from monomers containing an enol skeleton, structural sites derived from aliphatic polyhydric alcohols, alicyclic rings Total content of structural sites derived from polyhydric alcohols and aromatic polyhydric alcohols. However, it is preferably 50 mol% or less, more preferably 30 mol% or less, and particularly preferably The percentage is 20 mol% or less.

[0047] Furthermore, if the polyester resin (A) contains structural parts derived from aliphatic polyhydric alcohols The combination is derived from aliphatic polyhydric alcohols in the structural site of polyhydric alcohols (a2). The content of structural components is preferably 30 mol% or less, and more preferably 20 mol%. The following is particularly preferable: 15 mol% or less.

[0048] The structural sites derived from polyhydric alcohols (a2) are polydiene diols (a2-1) and lipids. The inclusion of aliphatic polyhydric alcohols is preferable in terms of dielectric properties and productivity.

[0049] The polyester resin (A) used in this invention is trivalent or less for the purpose of introducing a branched skeleton. The above structural sites are derived from aromatic polycarboxylic acids and trivalent or higher aliphatic polyhydric alcohols. Having at least one structural part selected from the group consisting of the original structural parts, that is, , as a copolymer component of the polyester resin (A), the above trivalent or higher aromatic polycarboxylic acid It contains at least one selected from the group consisting of aliphatic polyhydric alcohols of the genus and trivalent or higher. It is preferable that it be formed by reacting with the crosslinking agent (B) described later to form a crosslinked structure. By introducing a cross-linked and branched skeleton, the reaction sites of the resin increase, resulting in a high cross-linking density and strong viscosity. A bonding layer can be obtained. In particular, trimellitic acid or its anhydride, It is preferable that limethylolpropane is included. Furthermore, in the depolymerization reaction described later, acid anhydride When using polycarboxylic acids with 0 or 1 group and a valency of 3 or higher, use them in the depolymerization reaction. In addition to the polycarboxylic acids, it is preferable to use aromatic polycarboxylic acids with a valency of 3 or higher. stomach.

[0050] For the purpose of introducing a branched skeleton into polyester resin (A), trivalent or higher aromatic polyvalent carboxymethylcellulose is used. At least one selected from the group consisting of acids and aliphatic polyhydric alcohols with a valency of 3 or higher. When using, use a trivalent or higher aromatic polycarboxylic acid relative to the entire polycarboxylic acid group (a1). The content of acids, or the total amount of polyhydric alcohols (a2) with a value of 3 or higher Content (however, the amount of trivalent or higher acid anhydride used in the depolymerization reaction is 0 or 1) (excluding carboxylic acids) are preferably 0.1 to 10 mol%, more preferably 0 The range is 0.3 to 5 mol%, more preferably 0.5 to 3 mol%. Both or either. If the content of one of the components is too high, the mechanical properties such as the elongation at the breaking point of the coating film formed by the application of the adhesive will be affected. This can lead to a decrease in adhesiveness and a tendency for gelation to occur during polymerization. There is.

[0051] Furthermore, the polyester resin (A) used in the present invention contains oxycarboxylic acid compounds. The structural components may include [the following]. The above-mentioned oxycarboxylic acid compounds are compounds having a hydroxyl group and a carboxyl group in their molecular structure. That is the case. As an oxycarboxylic acid compound constituting the structural site derived from the above oxycarboxylic acid compound For example, 5-hydroxyisophthalic acid, p-hydroxybenzoic acid, p-hydroxy Phenylpropionic acid, p-hydroxyphenylacetic acid, 6-hydroxy-2-naphthoic acid, Examples include 4,4-bis(p-hydroxyphenyl)valeric acid. These can be used individually. Alternatively, it may include two or more types.

[0052] [Glass transition temperature (Tg) of polyester resin (A)] The glass transition temperature (Tg) of the polyester resin (A) used in the present invention is 0°C or lower. Preferably, -70 to -5°C, and especially preferably -60 to -10°C. More preferably -50 to -15°C, especially preferably -40 to -20°C, most preferably The glass transition temperature (Tg) is -35 to -25°C. If the glass transition temperature (Tg) is too low, the dielectric properties tend to be poor. In fact, if the glass transition temperature (Tg) is too high, the tackiness tends to be insufficient.

[0053] The method for measuring the glass transition temperature (Tg) is as follows: The glass transition temperature (Tg) can be determined by measuring it using a differential scanning calorimeter. It is possible. The measurement conditions are a temperature range of -90 to 100°C and a temperature rise rate of 10°C / min. ru.

[0054] [Acid value of polyester resin (A)] The acid value of the polyester resin (A) used in this invention shall be 10 mg KOH / g or less. Preferably, 5 mg KOH / g or less, and especially preferably 3 mg KOH / g or less. More preferably, 2 mg KOH / g or less, and most preferably 1 mg KOH / g or less. The lower limit is usually 0 mgKOH / g. If the acid value is too high, it becomes necessary to add a certain amount of crosslinking agent such as epoxy from the perspective of humid heat resistance. Therefore, it becomes difficult to adjust the gel fraction of the adhesive layer to the desired value, and the desired adhesive properties are not achieved. It tends to become difficult to obtain.

[0055] The definition and measurement method of acid value are as follows: The acid value (mgKOH / g) is calculated by adding 1g of polyester resin (A) to toluene / methanol. Dissolve in 30g of a mixed solvent (for example, toluene / methanol = 7 / 3 by volume), JIS It can be determined by neutralization titration based on K 0070. In this invention, the acid value of the polyester resin (A) is determined by the amount of carboxymethylcellulose in the resin. This is due to the amount of cy group present.

[0056] [Hydroxyl value of polyester resin (A)] Furthermore, the hydroxyl value of the above-mentioned polyether resin (A) must be 1 mg KOH / g or higher. Preferably, more preferably 2-30 mg KOH / g, and even more preferably 3-20 mg KO H / g, particularly preferably 4-15 mg KOH / g. If the hydroxyl value is too low, It becomes difficult to adjust the gel fraction of the adhesive layer to the desired value, making it difficult to obtain the desired adhesive properties. This tends to become difficult. Furthermore, if the hydroxyl value is too high, the dielectric properties, especially the dielectric constant, will be affected. The connection tends to be inferior.

[0057] The hydroxyl value of the above polyester resin (A) was determined by neutralization titration according to JIS K 0070. This is what is required.

[0058] The ester group concentration of the above polyester resin (A) is 3.0 mmol / g or less. Preferably, 0.1 to 2.1 mmol / g, and even more preferably 0.2 to It is 1.0 mmol / g. If the concentration of ester groups is too low, polyester resins ( A) tends to have poor cohesive force because its polarity and elastic modulus decrease, and if it is too high, it negatively affects dielectric properties. It tends to have an influence.

[0059] The above ester group concentration (millimoles / g) refers to the ester group concentration in 1g of polyester resin (A). This refers to the number of moles of the group, and can be calculated, for example, from the amount of ingredients used. The law stipulates that the smaller of the two types of polycarboxylic acids (a1) and polyhydric alcohols (a2) used in the charge is used. This value is obtained by dividing the number of moles by the total weight of the finished product, and an example of the calculation formula is shown below. Note that the amounts of polycarboxylic acids (a1) and polyhydric alcohols (a2) used in the charge are equal in molar amounts. In this case, either of the following calculation formulas may be used. Furthermore, monomers that have both carboxylic acid and hydroxyl groups are used, or caprolactic When preparing polyester from tons or other quantities, the calculation method will need to be adjusted accordingly.

[0060] <When polycarboxylic acids (a1) are low> Ester group concentration (millimoles / g) = [(A1 / α1×m1 + A2 / α2×m2 + A3 / α3×m3···) / Z〕×1000 A: Amount of polycarboxylic acids (a1) to be charged (g) α: Molecular weight of polycarboxylic acids (a1) m: Number of carboxyl groups per molecule of polycarboxylic acids (a1) Z: Finished weight (g)

[0061] <When polyhydric alcohols (a2) are low> Ester group concentration (millimoles / g) = [(B1 / β1×n1+B2 / β2×n2+B3 / β3 × n3···) / Z〕×1000 B: Amount of polyhydric alcohol (a2) added (g) β: Molecular weight of polyhydric alcohols (a2) n: Number of hydroxyl groups per molecule of polyhydric alcohols (a2) Z: Finished weight (g)

[0062] Furthermore, the ester group concentration can also be measured using known methods such as NMR. For example, the determination of the ester group concentration, composition, and composition ratio of polyester resin (A) is done by resonant frequency. Several 400MHz 1 H-NMR measurement (proton-type nuclear magnetic resonance spectroscopy), 13 C-NMR measurement This can be performed using a specific method (carbon-type nuclear magnetic resonance spectroscopy).

[0063] Furthermore, polyester resin (A) possesses other polar groups besides ester groups and reactive functional groups. A lower concentration of the base compound is preferable in terms of low hygroscopicity and long-term durability in humid and hot environments. Other polar groups include, for example, amide groups, imide groups, urethane groups, urea groups, and ethere groups. Examples include the ion group and the carbonate group.

[0064] The concentrations of amide groups, imide groups, urethane groups, and urea groups in polyester resin (A) are as follows: The sum of these is preferably 3 mmol / g or less, and more preferably 2 mmol / g. The following is particularly preferably 1 mmol / g or less, and even more preferably 0.5 mmol / g or less. Yes, and most preferably 0.2 mmol / g or less.

[0065] Examples of the ether groups mentioned above include alkyl ether groups and phenyl ether groups. Furthermore, in terms of low hygroscopicity and long-term durability in humid and hot environments, the concentration of alkyl ether groups is particularly low. It is preferable to do so. The alkyl ether group concentration of polyester resin (A) is 3 mmol / g or less. It is preferable that there be some, more preferably 2 mmol / g or less, and particularly preferably 1.5 mmol / g or less. The amount is less than or equal to 1 mmol / g, more preferably less than or equal to 1 mmol / g, and most preferably 0.5 mmol / g. It is less than 1 / g. Furthermore, the phenyl ether group concentration of polyester resin (A) is 5 mmol / g. It is preferable that the following is the case, more preferably 4 mmol / g or less, and particularly preferably 3 mmol / g or less. The concentration is 1 / mole / g or less, and more preferably 2.5 mmol / g or less.

[0066] The carbonate group concentration of polyester resin (A) is 3 mmol / g or less. Preferably, it is 2 mmol / g or less, and most preferably 1 mmol / g or less. More preferably 0.5 mmol / g or less, and most preferably 0.2 mmol / g It is less than or equal to g.

[0067] [Peak top molecular weight (Mp) and weight-average molecular weight (Mw) of polyester resin (A)] )〕 The peak top molecular weight (Mp) of the polyester resin (A) used in this invention is 5000. ~150,000 is preferred, more preferably 10,000 to 120,000, and particularly preferred The range is 15,000 to 100,000, and more preferably 20,000 to 80,000. If the peak top molecular weight (Mp) is too low, it will have low hygroscopicity, long-term durability in humid and hot environments, and storage The holding power tends to be insufficient. Also, if the peak top molecular weight (Mp) is too high, adhesion occurs. Insufficient force or excessively high viscosity of the solution during application can make it difficult to obtain a uniform coating. There is.

[0068] The weight-average molecular weight (Mw) of the polyester resin (A) used in this invention is 5000 to 5 00000 is preferred, more preferably 10000 to 300000, and particularly preferably 20 000 to 200000, more preferably 30000 to 150000, and especially preferred The range is 50,000 to 130,000. If the weight-average molecular weight (Mw) is too low, it will result in low hygroscopicity, long-term durability in humid and hot environments, and poor retention. This tends to be insufficient. Also, if the weight-average molecular weight (Mw) is too high, the adhesive strength will be insufficient. The solution can become too viscous during application, making it difficult to obtain a uniform coating.

[0069] The methods for measuring peak-top molecular weight (Mp) and weight-average molecular weight (Mw) are as follows: That is the case. Peak-top molecular weight (Mp) and weight-average molecular weight (Mw) are obtained using high-performance liquid chromatography. Using a column (TSKgel Super) (Tosoh Corporation, "HLC-8320GPC") Multipore HZ-M (exclusion limit molecular weight: 2×10 6 Theoretical stages: 16,000 stages / This product, filler material: styrene-divinylbenzene copolymer, filler particle size: 4μm)) The molecular weight can be determined by measuring the molecular weight in series and converting it to the standard polystyrene molecular weight.

[0070] [Water absorption rate (by weight) of polyester resin (A)] The water absorption rate of the polyester resin (A) used in the present invention is preferably 2% by weight or less, and more Preferably 1% by weight or less, particularly preferably 0.8% by weight or less, and even more preferably 0.6% by weight It is less than or equal to a certain percentage by weight. The lower limit is usually 0% by weight. If the water absorption rate is too high, it tends to reduce moisture heat resistance, insulation reliability, and have inferior dielectric properties. .

[0071] The method for measuring the water absorption rate is as follows: A polyester resin (A) solution (without the crosslinking agent (B) described later) is applied to the release film. Apply with an applicator, dry at 120°C for 10 minutes, and dry the polyester resin (A) layer. Prepare a sheet with a dry film thickness of 65 μm. Cut this sheet to a size of 7.5 cm x 11 cm. Then, the polyester resin (A) layer surface of the sheet is placed on a glass plate whose weight has been measured in advance. After lamination, peel off the release film. Laminate six layers of this polyester resin (A). By doing so, a test plate having a polyester resin layer with a thickness of 390 μm on a glass plate was obtained, Measure its weight. After the test plate obtained in this way is immersed in purified water at 23°C for 24 hours, it is removed and After wiping off any moisture from the surface and measuring its weight, it was dried at 70°C for 2 hours, and then the test was performed after drying. Measure the weight of the board. From the weight measured in each of these steps, calculate the water absorption according to formula 4 below. Calculate the percentage (by weight). [Formula 4] Water absorption rate (weight%)=(cd) / (ba)×100 a: Weight of the glass plate alone b: Weight of the initial test board c: Weight of the test plate immediately after removing it from purified water and wiping off the moisture. d: Weight of the test plate after drying at 70°C for 2 hours.

[0072] [Dielectric properties of polyester resin (A)] (Dielectric constant (Dk)) Under conditions of a temperature of 23°C and a relative humidity of 50%RH, the polyester resin (A) used in the present invention The dielectric constant at a frequency of 10 GHz is preferably 2.8 or less, and more preferably 2.5 or less. The dielectric constant is preferably 2.3 or less, and more preferably 2.2 or less. If the signal is too strong, the transmission speed tends to decrease and the transmission loss tends to increase.

[0073] (Dielectric loss tangent (Df)) Under conditions of a temperature of 23°C and a relative humidity of 50%RH, the polyester resin (A) used in the present invention The dielectric loss tangent at a frequency of 10 GHz is preferably 0.01 or less, and more preferably 0. 0.008 or less, more preferably 0.006 or less, particularly preferably 0.005 or less, further Preferably 0.004 or less, especially preferably 0.003 or less, most preferably 0.002 The following applies: Most preferably 0.0015 or less; if the above dielectric loss tangent is too high, the transmission loss will be large. It tends to get worse.

[0074] The above method for measuring dielectric constant and dielectric loss tangent is a cavity resonator using a network analyzer. It can be determined by the perturbation method. Note that polyester resin (A) has strong adhesive properties and can be used alone. If it is difficult to prepare a measurement sample, measure it while it is sandwiched between films, and the film By subtracting the fraction, the dielectric properties of polyester resin (A) alone can also be calculated.

[0075] Furthermore, in the present invention, the polyester resin (A) is an amorphous polyester resin Being a lipid is preferable in terms of solvent solubility, solution stability, tackiness, and transparency. Crystalline materials tend to have insufficient solvent solubility, solution stability, tackiness, and transparency. be. Non-crystalline properties can be confirmed by differential scanning calorimeter, for example, within the measurement temperature range of -9 An endothermic peak due to crystal melting was observed when measured at temperatures ranging from 0 to 400°C with a temperature rise rate of 10°C / min. This refers to items that are not affected. Note that the measurement temperature range and heating rate may be changed as appropriate depending on the sample. It is possible.

[0076] The content of polyester resin (A) in the adhesive composition is 70 wt in terms of dielectric properties. Preferably, it is % by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more. Most preferably, it is 95% by weight or more.

[0077] [Manufacturing of polyester resin (A)] The polyester resin (A) of the present invention comprises the polycarboxylic acids (a1) described above and the above Polyhydric alcohols (a2) are used as raw materials, and a polycondensation reaction is carried out in the presence of a catalyst by a known method. It can be manufactured by the above polyester resin (A), which is a polyvalent compound. Since it is obtained by polycondensation reaction of rubonic acids (a1) and polyhydric alcohols (a2), Structural sites derived from carboxylic acids (a1) and structural sites derived from polyhydric alcohols (a2) This will result in the following: In the above polycondensation reaction, first an esterification reaction or esterification reaction occurs. After the conversion reaction takes place, a polycondensation reaction is carried out. Note that if it is not necessary to increase the molecular weight... It can also be produced solely by esterification or transesterification reactions.

[0078] The mixing ratio of the above polycarboxylic acids (a1) and polyhydric alcohols (a2) is as follows: For every equivalent of carboxylic acid (a1), there should be 1 to 3 equivalents of polyhydric alcohol (a2). Preferably, it is 1.1 to 2.2 equivalents, and even more preferably 1.2 to 1. It is 7 equivalents. If the proportion of polyhydric alcohols (a2) is too low, the acid value will be high and the concentration will be high. It tends to be difficult to increase the quantity of particles, and if the value is too high, the yield tends to decrease.

[0079] [Esterification reaction, or transesterification reaction] In esterification reactions, or transesterification reactions, a catalyst is usually used, and specific Examples of titanium-based coatings include tetraisopropyl titanate and tetrabutyl titanate. Antimony catalysts such as antimony trioxide, germanium-based catalysts such as germanium dioxide Examples of catalysts include those such as ferrite media, zinc acetate, manganese acetate, and dibutyltin oxide. One or more of these can be used. Among these, the catalytic activity is high. Based on the balance between the color of the reactants obtained and the resulting color, antimony trioxide and tetrabutyl titanate are selected. Germanium dioxide and zinc acetate are preferred.

[0080] The amount of the above catalyst added is 1 to 10,000 ppm relative to the total copolymer components (by weight). It is preferable that the concentration be 10 to 5000 ppm, and more preferably 20 to 300 ppm. It is 0 ppm. If the amount of this compound is too low, the polymerization reaction tends not to proceed sufficiently. However, using too much does not offer any advantages such as shortening the reaction time, and tends to increase the likelihood of side reactions.

[0081] The reaction temperature for esterification or transesterification reactions is 200-300°C. The temperature is preferably 210-280°C, and more preferably 220-260°C. If the reaction temperature is too low, the reaction tends not to proceed sufficiently, and if it is too high, decomposition etc. Side reactions tend to occur easily. Also, the pressure during the reaction is usually atmospheric pressure, but when pressurized, It is also preferable to raise the reaction temperature by applying a solution to efficiently advance the reaction.

[0082] The polycondensation reaction that is carried out after the above esterification or transesterification reaction. The required conditions are the same as those used in the esterification or transesterification reactions described above. Further adding a similar amount of catalyst, and setting the reaction temperature preferably to 220-280°C, particularly preferably... The reaction system is gradually depressurized to a temperature of 230-270°C, and the reaction is carried out at a final pressure of 5 hPa or less. It is preferable to do so. If the reaction temperature is too low, the reaction tends not to proceed sufficiently. If the level is too high, side reactions such as decomposition tend to occur more easily.

[0083] Furthermore, when obtaining polyester resins having carboxyl groups in the side chains, polyvalent carboxyl groups are used. By copolymerizing polycarboxylic acids (a1) excluding nic acid anhydrides with polyhydric alcohols (a2) A method in which the resulting hydroxyl group-containing prepolymer is reacted with a polycarboxylic acid anhydride is highly productive. It is preferable in that respect.

[0084] The esterification reaction between polycarboxylic acids (a1) and polyhydric alcohols (a2) is performed at a high temperature. The temperature is typically between 180 and 280°C, and the reaction time is typically between 60 minutes and 8 hours.

[0085] The temperature during polycondensation is typically 200-280°C, and the reaction time is typically 20 minutes to 4 hours. Furthermore, polycondensation is preferably carried out under reduced pressure.

[0086] Furthermore, the polyester resin (A) may be produced by a well-known method other than those described above, for example, polyvalent carbone Acids (a1) and polyhydric alcohols (a2) are esterified, if necessary, in the presence of a catalyst. After obtaining a prepolymer by chemical reaction, the product is manufactured by polycondensation and then depolymerization. It can be made.

[0087] Depolymerization uses polycarboxylic acids with a valency of 3 or higher and having 0 or 1 acid anhydride group. This is preferable in terms of adhesive strength. A polycarboxylic acid with 0 or 1 acid anhydride group and a valency of 3 or higher. As for the type, those described in the above-mentioned polycarboxylic acids (a1) can be used. However, preferably, in order to suppress the decrease in molecular weight, a polyvalent compound with 1 or more acid anhydride groups is used. These are carboxylic acids, and more preferably trimellitic anhydride and hydrogenated trimellitic anhydride. It is a substance, and particularly preferred is trimellitic anhydride from the viewpoint of low dielectric loss tangent. The temperature during depolymerization is typically 200-260°C, and the reaction time is typically 10 minutes to 3 hours. That is the case.

[0088] During depolymerization, when the total amount of polycarboxylic acids (a1) is considered to be 100 mol%, the number of acid anhydride groups When polycarboxylic acids with a valency of 0 or 1, and a valency of 3 or higher, are used in amounts exceeding 20 mol%, the resin The molecular weight may decrease significantly. Therefore, the entire polycarboxylic acid (a1) may decrease by 1 When set to 00 mol%, polycarboxylic acids with 0 or 1 acid anhydride group are trivalent or higher. Depolymerization is preferably carried out using 20 mol% or less, and more preferably 1 to 15 mol%, Preferably, the concentration is 2 to 10 mol%, and more preferably 3 to 8 mol%.

[0089] Thus, a polyester resin (A) with a very small dielectric loss tangent compared to conventional resins can be obtained. It is possible. Furthermore, polyester resins (A) with very low dielectric loss tangents are suitable for transmission in the high-frequency range. Because it can suppress losses, it is very useful as a raw material for adhesives used in bonding electronic material components, etc. This will be useful.

[0090] Furthermore, in this invention, the polyester resin (A) is soluble in a non-halogenated organic solvent. This is preferable in terms of the adhesive composition described later. Solubility in such organic solvents If this is insufficient, it tends to become difficult to prepare the adhesive composition.

[0091] The above non-halogenated organic solvents include, for example, toluene, xylene, solvent naphtha, Aromatic solvents such as Solvesso, methyl ethyl ketone, methyl isobutyl ketone, cyclohexyl ketone Ketone solvents such as xanone, methyl alcohol, ethyl alcohol, isopropyl alcohol Alcohol-based solvents such as isobutyl alcohol, ethyl acetate, n-butyl acetate, etc. Ester solvents, acetate solvents such as cellosolve acetate and methoxyacetate, or a mixture of two or more of those solvents.

[0092] [Crosslinking agent (B)] In order to increase the cohesive force of this composition, it is preferable to crosslink the components. Specifically, it is preferable to further contain a crosslinking agent (B). By doing so, the functional groups in the polyester resin (A) react with the functional groups that react with such functional groups. The crosslinking agent (B) reacts with the material to crosslink, resulting in an adhesive with excellent tackiness, heat resistance, and durability. It is possible to do so. Also, like polyfunctional acrylates, the crosslinking agents react with each other, and the polyester In some cases, pseudo-crosslinking can occur by creating entanglement with resin (A). Examples of such crosslinking agents (B) include polyisocyanate compounds (b1), poly Poxy compounds, polyfunctional (meth)acrylic monomers and polyfunctional urethane (meth)acrylic Examples include hydroxyl groups and carboxymethyl groups contained in polyester resin (A), among others. Compounds having a functional group that reacts with at least one xy group are preferred, and among them, reactive Furthermore, in terms of the ease of adjusting the gel fraction, it is a polyisocyanate compound (b1). preferable.

[0093] Examples of the above polyisocyanate compound (b1) include 2,4-tolylenediiso Tolylene diisocyanate-based crosslinking agents such as cyanate and 2,6-tolylene diisocyanate. xylylene diisocyanate-based crosslinking agents such as 1,3-xylylene diisocyanate, and diphthongs. Diphenylmethane-based crosslinking agents such as phenylmethane-4,4-diisocyanate, 1,5-naphth Aromatic isocyanates such as naphthalene diisocyanates and other naphthalene diisocyanate crosslinking agents Nate-based crosslinking agents; isophorone diisocyanate, 1,4-cyclohexane diisocyanate 4,4'-dicyclohexylmethane diisocyanate, methylcyclohexanediiso Cyanate, isopropylidene dicyclohexyl-4,4'-diisocyanate, 1,3 - Alicyclic compounds such as diisocyanatomethylcyclohexane and norbornane diisocyanate Socyanate-based crosslinking agents; hexamethylene diisocyanate, trimethylhexamethylene di Aliphatic isocyanate crosslinking agents such as isocyanates; the above isocyanate compounds Examples include duct bodies, burette bodies, isocyanurate bodies, etc. Nate compounds are compounds in which the isocyanate portion is blocked by phenols, lactams, etc. However, they can also be used. These polyvalent isocyanate compounds can be used individually. They may be used individually, or two or more may be mixed and used together. In particular, from the viewpoint of compatibility, alicyclic compounds Isocyanate-based crosslinking agents and aliphatic isocyanate-based crosslinking agents are preferred, and in particular, lipid A cyclic isocyanate crosslinking agent is preferred, and moreover, isophorone diisocyanate iso Cyanurate or adductal compounds are preferred.

[0094] The equivalent amount of isocyanate groups to hydroxyl groups is preferably 0.2 to 5, and more preferably 0. 0.3 to 3, particularly preferably 0.5 to 2, even more preferably 0.7 to 1.6, most preferably The range is 0.9 to 1.2. If the equivalent amount is too large, the adhesive strength and the long-term stability of the adhesive sheet may become insufficient. There is a direction. Also, if it is too small, long-term durability and cohesive force in a humid and hot environment will be insufficient. It tends to have inferior dielectric properties.

[0095] Examples of the above polyepoxy compounds include bisphenol A diglycidyl ether. , bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether Difunctional glycidyl ether types such as tel; phenol novolac glycidyl ether, Polyfunctional glycidyl ether types such as cresol novolac glycidyl ether; hexa Glycidyl esters such as hydrophthalate glycidyl esters and dimer glycidyl esters Teltype; Triglycidyl isocyanurate, 3,4-Epoxycyclohexylmethyl Alicyclic or fatty substances such as carboxylates, epoxidized polybutadiene, and epoxidized soybean oil. Examples include polyepoxides. These polyepoxy compounds may be one or more types. These can be used. In particular, from the standpoint of reactivity, glycidyl ether type and glycidyl ether can be used. Lysidyl ester type is preferred, while glycidyl ether type is preferred from the viewpoint of resistance to moist heat. From the viewpoint of heat resistance, a polyfunctional type is preferable.

[0096] Furthermore, it is preferable that the epoxy equivalent of the polyepoxy compound be 500 g / eq or less. More preferably 350 g / eq or less, particularly preferably 250 g / eq or less, even more preferably The amount is less than 200 g / eq. The epoxy equivalent of the polyepoxy compound is too high. This results in a lower crosslink density after crosslinking, leading to poor heat resistance, or requiring a large amount of polymer to increase the crosslink density. Because epoxy compounds need to be added, they tend to have inferior dielectric properties.

[0097] Furthermore, as a polyepoxy compound, a polyepoxy compound containing a nitrogen atom (nitrogen Including an elementary atom-containing polyepoxy compound shortens the aging time of the adhesive layer. This is possible and preferable.

[0098] Examples of nitrogen atom-containing polyepoxy compounds include tetraglycidyldiaminodiph Phenylmethane, Triglycidyl para-aminophenol, Tetraglycidyl bis-aminometh Lucyclohexanone, N,N,N',N'-tetraglycidyl-m-xylenediamine, etc. Examples include glycidylamine compounds.

[0099] The equivalent amount of epoxy group to carboxyl group is preferably 0.8 to 5, and more preferably 0. The values ​​are 0.9 to 3, particularly preferably 1 to 2.5, and even more preferably 1.2 to 2. If the equivalent amount is too large, it can result in insufficient adhesion or low moisture absorption, or inferior dielectric properties. There is a tendency for this to happen. Also, if it is too small, long-term durability and heat resistance in a humid and hot environment will be insufficient. There is a tendency for this to happen.

[0100] The equivalent amount of epoxy groups to carboxyl groups (COOH) is for polyester resin (A). From the acid value and the epoxy equivalent (g / eq) of the compounded polyepoxy, the following formula 5 is used. is required. [Formula 5] Equivalent of epoxy to COOH = (a ÷ WPE) / (AV ÷ 56.1 ÷ 1000 × b ) a: Weight (g) of the polyepoxy compound used in the formulation WPE: Epoxy equivalent (g / eq) of the polyepoxy compound AV: Acid value (mgKOH / g) of the polyester resin (A) b: Weight (g) of the polyester resin (A) used in the formulation

[0101] This composition contains a polyester resin (A) and further a crosslinking agent (B), thereby achieving an effect of being excellent in dielectric properties, having low moisture absorption, high adhesiveness, and excellent long-term durability under a humid and hot environment. exhibits.

[0102] When this composition contains the crosslinking agent (B), the content of the crosslinking agent (B) is preferably 30 parts by weight or less, more preferably 0.1 to 2 0 parts by weight, particularly preferably 0.5 to 10 parts by weight, and even more preferably 1 to 5 parts by weight, based on 100 parts by weight of the polyester resin (A). If the content of the crosslinking agent (B) is too small, the heat resistance, holding power, adhesive strength, and long-term durability under a humid and hot environment tend to be insufficient. If it is too large, the adhesive strength and low moisture absorption tend to be insufficient, and the dielectric properties tend to deteriorate.

[0103] Also, in the present invention, in addition to the polyester resin (A) and the crosslinking agent (B), a urethanization catalyst (C), a hydrolysis inhibitor, an adhesion-imparting resin, an antioxidant, etc. can be blended.

[0104] <Urethanization catalyst (C)> From the viewpoint of the reaction rate, it is more preferable for this composition to contain the urethanization catalyst (C). .

[0105] Examples of urethane catalysts (C) include organometallic compounds and tertiary amine compounds. These can be used individually or in combination of two or more types.

[0106] Examples of the above organometallic compounds include zirconium compounds, iron compounds, and tin compounds. Examples include composites, titanium compounds, lead compounds, cobalt compounds, zinc compounds, etc. can.

[0107] Examples of the above zirconium-based compounds include zirconium naphthenate and zirconium. Examples include acetylacetonate. Examples of the iron-based compounds mentioned above include iron acetylacetonate and iron 2-ethylhexanoate. These are some examples. Examples of the above tin-based compounds include dibutyltin dichloride, dibutyltin oxide, and di Examples include butyltin dilaurate. Examples of the above titanium-based compounds include dibutyltitanium dichloride and tetrabutyl Examples include lutitanate and butoxytitanium trichloride. Examples of the lead-based compounds mentioned above include lead oleate, lead 2-ethylhexanoate, and benzoic acid. Examples include lead and lead naphthenate. Examples of the above cobalt-based compounds include cobalt 2-ethylhexanoate and cobalt benzoate. Barthes and others are examples. Examples of the above zinc-based compounds include zinc naphthenate and zinc 2-ethylhexanoate. It can be listed. Examples of the above tertiary amine compounds include triethylamine, triethylenediamine, Examples include 1,8-diazabicyclo-(5,4,0)-undecene-7.

[0108] Among these urethanization catalysts (C), in terms of reaction rate and pot life of the adhesive layer, organometallic compounds are preferred, and zirconium-based compounds are particularly preferred. Further, it is preferred to use acetylacetone in combination with the urethanization catalyst as a catalyst action inhibitor. Including acetylacetone is preferable in that it suppresses the catalytic action in the solution state and lengthens the pot life.

[0109] The content of the above urethanization catalyst (C) is preferably 0.0001 to 1 part by weight, more preferably 0.001 to 0.1 part by weight, and particularly preferably 0.01 to 0.05 part by weight, based on 100 parts by weight of the polyester resin (A). If such content is too small, the aging time until the completion of the crosslinking reaction tends to be long, and if it is too large, the pot life tends to deteriorate and it becomes difficult to control the physical properties.

[0110] [Hydrolysis inhibitor] The above hydrolysis inhibitor is contained to ensure the long-term durability of the adhesive composition. It is. As the above hydrolysis inhibitor, conventionally known ones can be used. For example, compounds that react and bond with the carboxy group terminals of the above polyester resin (A) can be mentioned. Specifically, for example, compounds containing functional groups such as carbodiimide groups, epoxy groups, oxazoline groups, etc. can be mentioned (however, excluding the above crosslinking agent (B)). Among these, carbodiimide group-containing compounds are preferable in that they have a high effect of disappearing the catalytic activity of protons derived from carboxy group terminals.

[0111] As the above carbodiimide group-containing compound, usually, a carbodiimide group (-N=C=N-) A known carbodiimide having one or more of these molecules can be used, but under higher temperatures and humidity conditions To increase durability, compounds containing two or more carbodiimide groups in the molecule, i.e., multi It is preferably a valence carbodiimide compound, and more particularly a compound with three carbodiimide groups in the molecule. It is preferable that the compound contains one or more of these, more preferably five or more, and especially seven or more. The number of carbodiimide groups in a molecule is usually 50 or less, and if there are many carbodiimide groups... If too much is used, the molecular structure becomes too large, which tends to reduce compatibility. Also, carbodyne High It is also preferable to use molecular weight polycarbodiimides.

[0112] Furthermore, in high molecular weight polycarbodiimides, the terminal isocyanate groups are encapsulated by a encapsulating agent. Those that have good storage stability are preferred. As a sealing agent, those that react with isocyanate groups Examples include compounds having active hydrogen or compounds having an isocyanate group. If, it has one substituent selected from a carboxyl group, an amino group, and an isocyanate group. Examples include monoalcohols, monocarboxylic acids, monoamines, and monoisocyanates. It can be done.

[0113] As such high molecular weight polycarbodiimides, the following diisocyanates are decarboxylated. Examples include those that have undergone a combined reaction.

[0114] Examples of such diisocyanates include 4,4'-diphenylmethane diisocyanate. 3,3'-dimethoxy-4,4'-diphenylmethane diisocyanate, 3,3'- Dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether Diisocyanate, 3,3'-dimethyl-4,4'-diphenyl ether diisocyanate , 2,4-tole diisocyanate, 2,6-tole diisocyanate, 1-methoxy Cyphenyl-2,4-diisocyanate, isophorone diisocyanate, 4,4'-disi Examples include chlorohexylmethane diisocyanate and tetramethylxylylene diisocyanate. These can be used individually or in combination of two or more. Polycarbodiimides can be synthesized or commercially available.

[0115] Examples of commercially available carbodiimide group-containing compounds include, for example, the compound manufactured by Nisshinbo Chemical Co., Ltd. The Lubodilite (registered trademark) series is one example, and among them, Carbodilite V- 01, V-02B, V-03, V-04K, V-04PF, V-05, V-07, V-0 9. V-09GB is preferred because of its excellent compatibility with organic solvents.

[0116] Examples of the epoxy group-containing compounds include glycidyl ester compounds and glycidyl Ether compounds and the like are preferred.

[0117] Specific examples of the above glycidyl ester compounds include, for example, glycidyl benzoate. Lu, t-Bu-glycidyl benzoate, p-glycidyl toluyl ester, cyk Glycidyl hydroxycarboxylic acid, glycidyl pelargonic acid, stearyl carboxylate Glycyl acetate, glycidyl laurate, glycidyl palmitate Glycidyl behenate, glycidyl versatate, glycidyl oleate Lysidyl esters, glycidyl linoleate, glycidyl linolenic acid, ve Glycidyl esters of henolate, glycidyl esters of stearolate, glycidyl esters of terephthalate Lysidyl esters, diglycidyl isophthalate, diglycidyl phthalate naphthalenedicarboxylic acid diglycidyl ester, methyl terephthalate diglycidyl ester Tel, diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate Esters, cyclohexanedicarboxylate diglycidyl esters, diglycidyl adipate Esters, diglycidyl succinate, diglycidyl sebacate, dodecane Diglycidyl dione, diglycidyl octadecanedicarboxylic acid, tri Examples include triglycidyl meritol acid and tetraglycidyl pyromellitic acid. These can be used individually or in combination of two or more types.

[0118] Specific examples of the above glycidyl ether compounds include, for example, phenylglycidyl ether. Lu, o-phenylglycidyl ether, 1,4-bis(β,γ-epoxypropoxy) Tan, 1,6-bis(β,γ-epoxypropoxy)hexane, 1,4-bis(β,γ- Epoxypropoxy)benzene, 1-(β,γ-epoxypropoxy)-2-ethoxyene Tan, 1-(β,γ-epoxypropoxy)-2-benzyloxyethane, 2,2-bis -[р-(β,γ-epoxypropoxy)phenyl]propane, 2,2-bis-(4-Hy) hydroxyphenyl)propane, 2,2-bis-(4-hydroxyphenyl)methane, etc. Examples include bisglycidyl polyethers obtained by the reaction of sphenol and epichlorohydrin. These can be used individually or in combination of two or more types.

[0119] As the oxazoline group-containing compound, bisoxazoline compounds and the like are preferred. Specifically For example, 2,2'-bis(2-oxazoline), 2,2'-bis(4-methyl-2 -Oxazoline), 2,2'-Bis(4,4-dimethyl-2-oxazoline), 2,2'- Bis(4-ethyl-2-oxazoline), 2,2'-bis(4,4'-diethyl-2-oxazoline) Sazoline), 2,2'-bis(4-propyl-2-oxazoline), 2,2'-bis(4- Butyl-2-oxazoline), 2,2'-bis(4-hexyl-2-oxazoline), 2 ,2'-bis(4-phenyl-2-oxazoline), 2,2'-bis(4-cyclohexyl -2-oxazoline), 2,2'-bis(4-benzyl-2-oxazoline), 2,2'- p-phenylenebis(2-oxazoline), 2,2'-m-phenylenebis(2-oxazoline) Zoline), 2,2'-o-phenylenebis(2-oxazoline), 2,2'-p-phenylene 4-methyl-2-oxazoline, 2,2'-p-phenylenebis(4,4-di Methyl-2-oxazoline), 2,2'-m-phenylenebis(4-methyl-2-oxazoline) Zoline), 2,2'-m-phenylenebis(4,4-dimethyl-2-oxazoline), 2 ,2'-ethylenebis(2-oxazoline), 2,2'-tetramethylenebis(2-oxazoline) Zoline), 2,2'-Hexamethylenebis(2-Oxazoline), 2,2'-Octamethylene nbis(2-oxazoline), 2,2'-decamethylenebis(2-oxazoline), 2, 2'-Ethylenebis(4-methyl-2-oxazoline), 2,2'-Tetramethylenebis( 4,4-dimethyl-2-oxazoline), 2,2'-9,9'-diphenoxyethanebis( 2-Oxazoline), 2,2'-Cyclohexylenebis(2-Oxazoline), 2,2'- Examples include diphenylenebis(2-oxazoline), and among these, 2, 2'-bis(2-oxazoline) is the most reactive with polyester resin (A). These are also preferable. Furthermore, these can be used individually or in combination of two or more types.

[0120] These hydrolysis inhibitors are preferably low in volatility, and therefore have a number-average molecular weight. It is preferable to use one with a high number average molecular weight, and the number average molecular weight of the hydrolysis inhibitor is usually 300 to 1 0000, preferably 1000 to 5000. Furthermore, as hydrolysis inhibitors, those with a high weight-average molecular weight are preferred from the viewpoint of hydrolysis resistance. It is preferable to use it. The weight-average molecular weight of the hydrolysis inhibitor is preferably 500 or more. More preferably 1000 or more, and even more preferably 2000 or more. It is particularly preferable that the weight-average molecular weight be 3000 or more. The upper limit for the weight-average molecular weight is usually 5000. It is 0. If the molecular weight of the hydrolysis inhibitor is too small, hydrolysis resistance tends to decrease. On the other hand, If the molecular weight is too large, the compatibility with polyester resin (A) tends to decrease.

[0121] Among hydrolysis inhibitors, it is preferable to use compounds containing a carbodiimide group. In this case, the carbodiimide equivalent is preferably 50 to 10000, and more particularly 100 to 10 00, and more preferably 150-500. Note that carbodiimide equivalent refers to This shows the chemical formula weight per rubodiimide group.

[0122] The amount of the above hydrolysis inhibitor is as follows, per 100 parts by weight of the above polyester resin (A): Preferably, it is 0.01 to 10 parts by weight, particularly preferably 0.1 to 5 parts by weight, and further Preferably, the content is 0.2 to 3 parts by weight. If this content is too high, the polyester resin ( Poor compatibility with A) tends to cause turbidity, and if the amount is too small, sufficient durability cannot be obtained. It tends to be less likely to happen.

[0123] Furthermore, the amount of the hydrolysis inhibitor depends on the acid value of the polyester resin (A). It is preferable to optimize the content of the polyester resin (A) in the adhesive composition. The number of moles of the hydrolysis inhibitor functional group in the adhesive composition relative to the total number of moles of acidic functional groups (x) It is preferable that the molar ratio of the total number of units (y) [(y) / (x)] is 0.5 ≤ (y) / (x). More preferably, 1 ≤ (y) / (x) ≤ 1000, and even more preferably 1.5 ≤ (y) / (x) ≤ 100. If the molar ratio of (y) to (x) is too low, the moisture and heat resistance tends to decrease. If the molar ratio of (y) to (x) is too high, the compatibility with polyester resin (A) will be There is a tendency for these properties to decrease, or for adhesion, cohesiveness, and durability to decline.

[0124] [Adhesion-enhancing resin] In this invention, the adhesive properties can be improved by including a tackifying resin. It is also desirable to do so.

[0125] The tackifying resin mentioned above is not particularly limited and conventionally known resins can be used. This is possible. Examples of the tackifying resins include hydrocarbon-based tackifying resins and terpene-based resins. Resins, phenolic resins, rosin resins, xylene resins, epoxy resins, polyamide resins Examples include resins, ketone resins, and elastomer resins. These can be used alone or in combination. More than one type may be used in combination. Among them, hydrocarbon-based tackifying resins and terpene-based resins are preferred. Furthermore, the tackifying resin contains at least one hydrocarbon-based tackifying resin. It is particularly preferable that the hydrocarbon-based tackifying resin makes up 30% by weight or more of the total tackifying resin. It is preferable that it be present, preferably 50% by weight or more, and preferably 70% by weight or more. It is preferable.

[0126] Examples of the hydrocarbon-based tackifying resins mentioned above include aliphatic hydrocarbon resins and aromatic carbonized hydrocarbon resins. Hydrogen resins, aliphatic cyclic hydrocarbon resins, aliphatic and aromatic petroleum resins (styrene-olefins) Copolymers, aliphatic and alicyclic petroleum resins, hydrogenated hydrocarbon resins, coumarone resins Examples include various hydrocarbon resins such as coumarone-indene resins. In addition, commercially available products include For example, Mitsui Chemicals' "FTR6100", "FTR6110", "FTR61 Examples include "25".

[0127] Examples of the above terpene resins include terpene resins, terpene phenol resins, and aromatic resins. Examples include terpene polymers, specifically α-pinene polymers, β-pinene polymers, Dipentene polymers, and their modification by phenol modification, aromatic modification, hydrogenation modification, hydrocarbon modification, etc. A terpene-based resin can be used. Also, commercially available products include, for example, Yasuha La Chemical's "YS Polystar S145", "YS Resin PX1000", "YS Resin "Zinn PX1250", "YS Polystar T145", "YS Resin TO115", "YS Examples include "Polystar U130" and "Clearon P125," which are nonpolar materials such as polypropylene. Terpene resins are preferred because they have good adhesion to the substrate.

[0128] Examples of the phenolic resins mentioned above include phenol, m-cresol, and 3,5-xyl. Various phenols such as lenol, p-alkylphenol, and resorcinol, and formaldehyde Condensates with hydride can be used. Furthermore, the phenols and formaldehyde and Resols obtained by addition reaction of the aforementioned phenols under alkaline catalyst, and formaldehyde Novolac, unmodified, or modified rosin obtained by condensation reaction with rudehyde under acid catalyst. These rosins, including their derivatives, are subjected to the addition of phenol under acid catalyst conditions and then thermal polymerization. The resulting rosin-modified phenolic resin can be used.

[0129] Examples of the above rosin-based resins include rosin resin, polymerized rosin resin, hydrogenated rosin resin, Rosin ester resin, hydrogenated rosin ester resin, rosin phenol resin, polymerized rosin ester resin Examples include tel, specifically unmodified gum rosin, wood rosin, and tall oil rosin. Rosin (raw rosin) and rosin that has been hydrogenated, disproportionated, polymerized, or otherwise chemically modified. Rosin and its derivatives can be used. Commercially available products include, for example, Lima Chemical's "Hariester TF", "Haritack 8LJA", "Haritack PH", Examples include "Halaltack FK100" and "Halaltack PCJ".

[0130] The tackifying resin preferably has an acid value of 30 mgKOH / g or less, and more preferably The amount is 10 mg KOH / g or less, more preferably 6 mg KOH / g or less, and particularly preferably 3 The concentration is less than or equal to mgKOH / g. When using multiple types of tackifying resins in combination, the average of these resins is as stated above. It is preferable that it be within a range.

[0131] The softening point of the tackifying resin (measured, for example, by the ring-and-ball method) is 80 to 170°C. It is preferable that the temperature be 90 to 160°C, and even more preferably 100 to 1 The temperature is 50°C. If the softening point is within the above range, the adhesive properties (adhesion, cohesive force) will be improved. It can be increased, which is preferable.

[0132] In this invention, the tackifying resin is preferably plant-derived for the sake of protecting the global environment. Examples of plant-derived tackifying resins include terpene resins and rosin resins. Terpene resins are particularly preferred.

[0133] Furthermore, from the viewpoint of compatibility, hydrocarbon-based tackifying resins and terpene-based resins are preferred, and in particular A hydrocarbon-based tackifier is preferred.

[0134] The content of the tackifying resin is 2 to 100 parts by weight of the polyester resin (A). Preferably 100 parts by weight, more preferably 5 to 50 parts by weight, even more preferably The amount is 8 to 30 parts by weight, and particularly preferably 10 to 20 parts by weight. Within the above range, adhesive properties (adhesion strength, cohesive force) can be improved, which is preferable. .

[0135] [Antioxidant] This composition more preferably contains an antioxidant to improve the stability of the resin. .

[0136] Examples of the above antioxidants include hindered phenol antioxidants and amine antioxidants. Examples include antioxidants, sulfur-based antioxidants, and phosphoric acid-based antioxidants. Among them, Hinderdoff A small selection of antioxidants from phenol-based antioxidants, amine-based antioxidants, and phosphate-based antioxidants. Preferably, there is at least one type, and in particular, an oxidation consisting of a hindered phenol compound. A preventative agent is preferred. Examples of hindered phenol antioxidants include those in which the hydroxyl group of phenol is bonded. A tert-butyl group or the like is attached to at least one of the carbon atoms adjacent to a carbon atom on an aromatic ring. Examples include antioxidants having a hindered phenol structure to which a group causing significant bodily harm is attached. .

[0137] The antioxidant content is preferably, per 100 parts by weight of polyester resin (A). The amount is 0.01 to 10 parts by weight, more preferably 0.03 to 8 parts by weight, and even more preferably This is 0.05 to 5 parts by weight. If the amount is too low, adhesive residue is more likely to occur on the adherend, and if it is too high... This tends to reduce the adhesive properties.

[0138] In this composition, the above-mentioned polyester resin (A), crosslinking agent (B), and urethane In addition to catalyst (C), hydrolysis inhibitor, tackifying resin, and antioxidant, other substances that impair the effects of the present invention Within the limits of not containing softeners, plasticizers, low-elasticity agents, UV absorbers, stabilizers, and antistatic agents. Silane coupling agents, fluxes, flame retardants, dispersants, emulsifiers, defoamers, leveling agents ion trapping agents, catalysts, inorganic or organic fillers, metal powders, pigments and other powders and particulate matter Additives such as the above can be incorporated. In addition, the raw materials for the production of the constituent components of this composition are included. It is acceptable if it contains small amounts of impurities. These can be used individually or in combination of two or more types. If this composition contains the above-mentioned additives, the content of these components is preferably 70% by weight. It is less than or equal to %, more preferably 0.05 to 60% by weight, and particularly preferably 0.1 to 50% by weight. %, more preferably 0.2 to 40% by weight.

[0139] This composition is prepared, for example, by preparing the above-mentioned polyester resin (A) and any necessary optional components. Furthermore, by blending and dispersing it during the manufacturing of polyester resin (A), or by using organic solvents The solution of polyester resin (A) dissolved with an agent is mixed and mixed using a mixing roller or the like. It can be obtained by distributing it.

[0140] Furthermore, this composition has an appropriately adjusted viscosity, making it easy to handle when forming a coating film. For this purpose, a solvent may be added. The solvent improves the handling and workability of the composition during molding. It is used to secure resources, and there are no particular restrictions on its use.

[0141] Examples of solvents include acetone, methyl ethyl ketone (MEK), and methyl isobutyl methyl ester. Ketones such as ketones and cyclohexanone; esters such as ethyl acetate; ethylene glyco Ethers such as monomethyl ether; N,N-dimethylformamide, N,N-dimethyl Amides such as acetamide; alcohols such as methanol and ethanol; hexane, sulfate Examples include alkanes such as chlorohexane; aromatics such as toluene and xylene. The listed solvents may be used individually, or two or more may be mixed in any combination and ratio. It may be used in this way.

[0142] <Adhesives, bonding agents> In the present invention, the composition is obtained by crosslinking, and tackiness, adhesiveness, and holding power An adhesive that exhibits excellent effects such as low moisture absorption, long-term durability in humid and hot environments, and low dielectric properties. Alternatively, an adhesive can be obtained. In this invention, "crosslinking" refers to intentionally crosslinking the composition by heat and / or light, etc. This means that the degree of crosslinking can be controlled according to the desired physical properties and application.

[0143] The degree of crosslinking can be confirmed by the gel fraction of the adhesive or bonding agent, preferably The gel fraction is 10-100% by weight, more preferably 15-90% by weight, and especially preferably 20%. ~80% by weight, more preferably 25-70% by weight, and especially preferably 40-65% by weight Yes. If the gel fraction is too low, the heat resistance, holding power, adhesiveness, and long-term durability in humid and hot environments will be insufficient. It tends to be a certain amount, and if it's too high, the adhesive strength tends to be insufficient. The gel fraction mentioned above is an indicator of the degree of crosslinking, and can be calculated, for example, by the following method. In other words, an adhesive layer is formed on the polymer sheet (for example, PET film) that serves as the base material. The adhesive sheet (without a release sheet) is made of 200 mesh stainless steel. Wrapped in a net, immersed in toluene at 23°C for 24 hours, and relative to the weight of the adhesive component before immersion, The gel fraction is defined as the weight percentage of the insoluble adhesive component remaining in the wire mesh after immersion. However, The weight of the base material should be deducted.

[0144] <Adhesive sheets, laminates> Then, the adhesive layer of the present invention is formed from the above adhesive, and having such an adhesive layer This allows you to obtain adhesive sheets or laminates. It is preferable that such an adhesive layer is formed on one or both sides of the support substrate. In this invention, the term "sheet" includes "film" and "tape." This is how it should be written.

[0145] In other words, the adhesive layer of the present invention comprises the aforementioned polyester resin (A) and crosslinking agent (B) An adhesive composition containing is formed from a crosslinked adhesive.

[0146] The adhesive layer of the present invention is used at a frequency of 10 GHz under a temperature of 23°C and a relative humidity of 50% RH. The dielectric loss tangent is 0.01 or less. More preferably 0.008 or less, and particularly preferably is 0.006 or less, more preferably 0.005 or less, especially preferably 0.003 or less, most Preferably, it is 0.0015 or less. If the dielectric loss tangent of such adhesive layer is too high, the transmission loss will be It will grow bigger.

[0147] Furthermore, at a frequency of 10GHz under conditions of 23°C temperature and 50% RH relative humidity in the adhesive layer... The dielectric constant is preferably 2.8 or less, more preferably 2.5 or less, and particularly preferably 2.3. More preferably, the dielectric constant is 2.2 or less. If the dielectric constant is too high, the transmission speed will be reduced or transmission Transmission losses tend to be large.

[0148] The above-mentioned adhesive sheet or laminate can be manufactured, for example, as follows: As a method for manufacturing such an adhesive sheet or laminate, a commonly known method for manufacturing an adhesive sheet is used. It can be manufactured in accordance with the law, for example, by coating the above adhesive composition onto a substrate and drying it. By attaching a release sheet to the adhesive composition layer on the opposite side and curing it as necessary, the adhesive will adhere. An adhesive layer formed from an agent, with a release sheet on one side of the adhesive layer and a substrate on the other side. A laminate comprising an adhesive sheet or adhesive layer and a substrate on one side of the adhesive layer Obtainable. Note that when the above laminate is used, the base material is bonded instead of the release sheet. It may also be a laminate, that is, a laminate having a substrate on both sides of the adhesive layer.

[0149] Furthermore, the adhesive composition is applied to the release sheet and dried, and the substrate is placed on the adhesive layer surface on the opposite side. By bonding these together and applying protective covering as needed, an adhesive sheet or laminate can be obtained.

[0150] Furthermore, an adhesive layer is formed on the release sheet, and the release sheet is attached to the adhesive layer on the opposite side. By doing so, a substrate-less double-sided adhesive sheet can be manufactured.

[0151] The resulting adhesive sheet or substrate-less double-sided adhesive sheet should be used with the above-mentioned release sheet attached. The adhesive layer is peeled off and bonded to the substrate.

[0152] Examples of the above-mentioned substrates include polyethylene naphthalate, polyethylene terephthalate, Polybutylene terephthalate, polyethylene terephthalate / isophthalate copolymer, etc. Polyester resins; polyethylene, polypropylene, polymethylpentene, etc. Refin resins; polyvinyl fluoride, polyvinylidene fluoride, polyethylene fluoride, etc. Refracted ethylene resin; polyamides such as nylon 6, nylon 6,6; polyvinyl chloride Polyvinyl chloride / vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl Vinyl alcohol copolymers, polyvinyl alcohol, vinylon and other vinyl polymers; triacetate cells Cellulose resins such as rosewood and cellophane; polymethyl methacrylate, polymethacrylic acid Acrylic resins such as ethyl polyacrylate, ethyl polyacrylate, and butyl polyacrylate; polystyrene From materials such as polycarbonate, polyarylate, polyimide, and cycloolefin polymers. A sheet made of at least one synthetic resin selected from the group; aluminum, copper, iron Metal foil; paper such as fine paper and glassine paper; textiles made of glass fibers, natural fibers, synthetic fibers, etc. Nonwoven fabrics are an example. These substrates can be used as single layers or as multilayers of two or more layers. It can be used as such.

[0153] Among these, substrates made of polyethylene terephthalate and polyimide are particularly preferred. Polyethylene terephthalate is preferred, particularly because of its excellent adhesion to adhesives.

[0154] Furthermore, the above substrate was tested at a frequency of 10 GHz under conditions of 23°C and 50% RH relative humidity. Using a film with a dielectric loss tangent of 0.01 or less at z is important for adhesive sheets and laminates. This is preferable because it can reduce transmission loss by lowering the overall dielectric loss tangent. More preferably, it is 0.005 or less, and particularly preferably 0.003 or less. Examples include thermoplastic liquid crystal polymer films and low-dielectric polyimide films.

[0155] Furthermore, foam substrates such as polyurethane foam and polyethylene foam can be used as the base material. A foam sheet made of a synthetic resin foam such as foam or polyacrylate foam is used. It is possible to do so. Among these, it is superior in terms of the balance between conformability to the adherend and adhesive strength. Polyethylene foam and polyacrylate foam are preferred.

[0156] The thickness of the above substrate is preferably, for example, 1 to 1000 μm, and is particularly preferred. More preferably, the particle size is 2 to 500 μm, and more preferably 3 to 300 μm.

[0157] Examples of the release sheet include sheets made of various synthetic resins as exemplified in the above-mentioned base material. Paper, cloth, nonwoven fabric, etc., that have been treated with a release agent can be used. It is preferable to use a release sheet made of recon material.

[0158] For example, a gravure roll coater or a reverse roller can be used to coat the above adhesive composition. Roll coater, kiss roll coater, dip roll coater, bar coater, knife coater You can use a coater, spray coater, comma coater, etc.

[0159] The conditions for the above curing treatment are typically: temperature is usually room temperature (23°C) to 70°C, and time is usually 1 to This is for 30 days, specifically, for example, 1 to 20 days at 23°C, preferably 3 to 20 days at 23°C. The process can be carried out under conditions such as 14 days at 40°C for 1 to 10 days.

[0160] Furthermore, as for drying conditions, the drying temperature is preferably 60-140°C, and particularly preferably 80°C. The temperature is 120°C, and the drying time is preferably 0.5 to 30 minutes, and particularly preferably 1 to 5 minutes. be.

[0161] The thickness of the adhesive layer is preferably 2 to 500 μm, and particularly preferably 5 to 2 The thickness is 00 μm, more preferably 10 to 100 μm. If the thickness of such adhesive layer is too thin Furthermore, the adhesive strength tends to decrease, and if it is too thick, it becomes difficult to apply it uniformly, and the coating film There is a tendency for defects such as air bubbles to form. Furthermore, when considering shock absorption... It is preferable that the particle size be 50 μm or larger.

[0162] The thickness of the adhesive layer mentioned above was determined using Mitutoyo's "ID-C112B" adhesive sheet. By subtracting the measured thickness of the components other than the adhesive layer from the measured thickness of the entire structure, It is required.

[0163] Furthermore, such adhesive sheets may be protected by providing a release sheet on the outside of the adhesive layer as needed. It may also be. In addition, in adhesive sheets in which the adhesive layer is formed on one side of the substrate, the substrate By applying a release treatment to the side opposite the adhesive layer, the adhesive layer can be utilized using the released surface. It is also possible to protect it.

[0164] The adhesive, bonding agent, and adhesive sheet of the present invention can be used for bonding various components. In particular, for bonding optical components, fixing components in portable electronic devices, and fixing electronic components. It is suitably used as such, but preferably a low dielectric film with a dielectric loss tangent of 0.01 or less. This combination allows for, for example, transparent antenna filters for millimeter-wave and similarly high-frequency radio waves. It can be suitably used for laminating nuclei and radio wave reflective films.

[0165] Furthermore, the sheet of the present invention is preferably used as an adhesive sheet as described above, It can also be used as an adhesive sheet. Specifically, an adhesive sheet is made by applying this composition to a base material. After coating, forming an adhesive layer, and drying to remove the solvent as needed, apply directly to the substrate. It refers to something that is attached to something. [Examples]

[0166] The present invention will be described in more detail below with reference to examples, but the present invention will not exceed its gist. The following examples are not the only examples. Note that "parts" and "%" in the examples refer to weight. It means a quantity-based standard.

[0167] <Example 1> [Manufacturing of polyester resin (A-1)] In a reaction vessel equipped with a thermometer, stirrer, rectification column, and nitrogen inlet tube, polycarboxylic acids (a1) and Then, 72 parts (1.00 mol) of isophthalic acid (a1-1) and polyhydric alcohols (a2) are used. 26.9 parts (1.00 mol) of ethylene glycol, hydrogenated polypropylene with a number average molecular weight of 2300. Tadienediol (a2-1) [GI-2000 (manufactured by Nippon Soda Co., Ltd.)] 897.0 parts (0. 90 moles), 4 parts (0.07 moles) of trimethylolpropane, and tetrabutyl phosphate as a catalyst. Add 0.1 part of the starter, and raise the temperature over 2.5 hours until the internal temperature reaches 270°C. The esterification reaction was carried out at °C for 1.5 hours. Next, 0.1 parts of tetrabutyl titanate were added as a catalyst, and the system was heated to 2.5 hPa. The polymer reaction was carried out under reduced pressure for 2 hours to obtain a polyester resin (A-1) [the viscosity of Example 1]. A bonding agent composition was obtained. The final composition ratio was as shown in Table 1 below.

[0168] <Examples 2-4> [Manufacturing of polyester resins (A-2) to (A-4)] Except for the fact that the resin composition was changed to match that shown in Table 1 below, following Example 1, Polyester resins (A-2) to (A-4) are prepared in the same manner as polyester resin (A-1). The adhesive compositions of Examples 2 to 4 were each prepared.

[0169] <Comparative Examples 1-5> [Manufacturing of polyester resins (A'-1) to (A'-5)] The resin composition was changed to match that shown in Table 1 below, but otherwise it is a polyester resin. Polyester resins (A'-1) to (A'-5) are prepared in the same manner as A-1) [Comparative Examples 1 to 5] A bonding agent composition was obtained.

[0170] The compositions listed in Table 1 below represent the final composition ratios (resin composition ratios), and the obtained P This is the relative ratio (molar ratio) of the amount of each constituent monomer in the polyester resin. Note that abbreviations in Table 1 refer to the following terms. The following applies: "IPA": Isophthalic acid (a1-1) "DMI": Dimethyl isophthalate (a1-1) "DMT": Dimethyl terephthalate (a1-1) "TMAn": Trimellitus anhydride (a1-1) "AdA": Adipic acid "SebA": Sebacic acid "GI2000": Hydrogenated polybutadiene diol with hydroxyl groups at both ends (manufactured by Nippon Soda Co., Ltd.) , Mn2300)(a2-1) "GI3000": Hydrogenated polybutadiene diol with hydroxyl groups at both ends (manufactured by Nippon Soda Co., Ltd.) , Mn3000)(a2-1) "Prepol 2033": Hydrogenated dimer ol (manufactured by Croda, molecular weight 538) "EG": Ethylene glycol "1,4BG": 1,4-butanediol "NPG": Neopentyl Glycol "1,6HG": 1,6-Hexanediol "TMP": Trimethylolpropane

[0171] The glass transition temperature (°C) and hydroxyl value (mgKOH / g) of the obtained polyester resin are as follows: Acid value (mgKOH / g), peak-top molecular weight (Mp), weight-average molecular weight (Mw), es The tel group concentration (millimoles / g) and dielectric loss tangent were measured according to the description herein. Furthermore, the dielectric loss tangent was evaluated according to the following evaluation criteria. The various physical properties of polyester resins were evaluated. This is shown in Table 2 below.

[0172] (Evaluation criteria for dielectric loss tangent) ◎: Below 0.0020 〇: Greater than 0.0020 and less than or equal to 0.0040 △: Greater than 0.0040 and less than or equal to 0.0100 ×: Exceeds 0.0100

[0173] [Table 1]

[0174] [Table 2]

[0175] The results in Table 2 above show that it contains a large amount of aromatic polycarboxylic acid and hydrogenated polybutadiene diol. Furthermore, the polyester resins of Examples 1 to 4 have a dielectric loss tangent of 0.004 or less, and also, In Examples 1, 3, and 4, which do not contain altha polycarboxylic acids, the dielectric loss tangent is 0.002 or less. The result was lower, and it showed very good dielectric properties. On the other hand, while it contains a lot of hydrogenated polybutadienediol, it also contains a lot of aliphatic polycarboxylic acids, compared to In the polyester resins of Examples 1 and 2, the dielectric loss tangent was 0.01 or higher. Comparative Example 3, a polyester resin containing carboxylic acids and dimer ols, and its dimer ols Comparative Example 5: Polyester system in which part of the diol was replaced with hydrogenated polybutadiene diol While the resin exhibits a reasonably good dielectric loss tangent, it is not comparable to the polyester resins of Examples 1-4. Furthermore, the dielectric properties were inferior. In general polyester resins, which have a large proportion of their constituent parts, One comparative example, 4, had very poor dielectric properties.

[0176] Next, the crosslinking agent (B), urethane catalyst (C), and hindered phenol-based antioxidant are used. So, I prepared the following:

[0177] <Crosslinking agent (B)> (B-1): Trimer of hexamethylene diisocyanate with isocyanurate (Tohs (Manufactured by - Company, "Coronate HX") (B-2): Trimer of isophorone diisocyanate with isocyanurate (ebony (Manufactured by Kudegusa, "Vestanate T-1890") (B-3): 55% acetate of trimethylolpropane tolylene diisocyanate adduct Chill solution (Tosoh Corporation, "Coronate L-55E")

[0178] <Urethane catalyst (C)> (C-1): Zirconium acetylacetonate (manufactured by Matsumoto Fine Chemical Co., Ltd.) (ZC-150 diluted to 1% with acetylacetone.)

[0179] <Hindered phenol-based antioxidants> (D-1): IRGANOX1010 (BASF)

[0180] <Example 5> The polyester resin (A-1) obtained above was diluted with toluene to a solid content concentration of 50%. To this polyester resin (A-1) solution (100 parts as solid content), a crosslinking agent (B -1) (Solid content) is added in 1.5 parts, and further, urethane catalyst (C-1) (active ingredient) 0.02 parts, 0.1 parts of hindered phenol antioxidant (D-1), and further toluene By diluting, stirring, and mixing so that the total solid content is 50%, the adhesive mixture of Example 5 is obtained. We obtained the finished product.

[0181] <Examples 6-10, Comparative Examples 6-10> In Example 5, the same procedure was followed except that the components were blended as shown in Table 3 below. Adhesive compositions for Examples 6-10 and Comparative Examples 6-10 were obtained.

[0182] The adhesive compositions obtained in Examples 5-10 and Comparative Examples 6-10 had a thickness of approximately 25 μm after drying. and polyethylene terephthalate (PET) film (thickness 3 After coating with 8 μm, it was dried at 100°C for 3 minutes to form an adhesive layer. A release-treated PET film (release film) is attached to the adhesive layer, and its surface is maintained. The material was protected and cured for 20 days in an atmosphere at a temperature of 40°C to obtain an adhesive sheet.

[0183] The obtained adhesive sheets were evaluated as follows. The evaluation results are shown in Table 3 below.

[0184] [Gel fraction] The adhesive sheet obtained after curing was cut into 4cm x 4cm pieces. The material was wrapped in 0-mesh stainless steel wire mesh and immersed in toluene at 23°C for 24 hours, and the adhesion before immersion was removed. The gel fraction was defined as the weight percentage of the insoluble adhesive component remaining in the wire mesh relative to the total weight of the adhesive agent.

[0185] [Adhesive strength (peel strength) (compared to SUS-BA)] A SUS-BA plate was prepared as the substrate. The adhesive sheet obtained above was heated at 23°C and 50% After cutting to 25mm x 200mm in an RH environment, peel off the release film and the adhesive layer side The ring was brought into contact with the SUS-BA plate and pressed and attached by moving a 2kg roller back and forth. After leaving it undisturbed in the environment for a specified time (30 minutes or 24 hours), the autograph (manufactured by Shimadzu Corporation) Using an Autograph AGS-H 500N, peeling was performed at a peeling speed of 300 mm / min at a 180-degree angle. The separation strength (N / 25mm) was measured.

[0186] [Adhesion (Peel Strength) (against Glass)] An alkali-free glass plate was prepared as the substrate. The adhesive sheet obtained above was heated at 23°C for 5 minutes. After cutting to 25mm x 200mm in a 0%RH environment, peel off the release film and apply adhesive. The layer side was placed in contact with an alkali-free glass plate, and a 2kg roller was moved back and forth to apply pressure and bond it. Then, after being left to stand for a specified time (30 minutes) in the same environment, the Autograph (manufactured by Shimadzu Corporation) Using a Tograph AGS-H 500N, the peel strength at 180 degrees was measured at a peeling speed of 300 mm / min. (N / 25mm) was measured.

[0187] [Adhesive strength (peel strength) (against PP)] A polypropylene (PP) plate was prepared as the adherend. The adhesive sheet obtained above was 23 After cutting to 25mm x 200mm in an environment of °C and 50%RH, peel off the release film. The adhesive layer side was brought into contact with the PP board, and a 2kg roller was moved back and forth to apply pressure and adhere it. After being left to stand for a specified time (30 minutes) in the environment, Autograph (manufactured by Shimadzu Corporation, Autograph) Using AGS-H 500N, the peel strength at 180 degrees (N / ) was measured at a peeling speed of 300 mm / min. 25mm was measured.

[0188] [Holding force (cohesive force)] The adhesive sheet obtained above is used in accordance with JIS Z-0237, with SUS304 as the substrate. Regarding the results after applying a 25mm x 25mm patch and leaving it to stand at 80°C for 20 minutes: When a 1kg load is applied, the time until it falls, or when left undisturbed for 24 hours, is used to determine which items do not fall. Therefore, the deviation after 24 hours was measured in an 80°C environment and evaluated according to the following criteria. (Evaluation Criteria) ○...After standing for 24 hours, the displacement was within 1 mm. △...Although it did not fall after being left undisturbed for 24 hours, the displacement exceeded 1 mm. ×...It fell while left undisturbed for 24 hours.

[0189] [Dielectric properties] The adhesive layer of the obtained 50 μm thick adhesive sheet was analyzed using a network analyzer. The dielectric properties (dielectric loss tangent Df) were measured using the cavity resonator perturbation method. The evaluation was conducted using the following criteria. (Evaluation Criteria) ◎: Df is 0.0015 or less 〇: Df is greater than 0.0015 and less than or equal to 0.0030. △: Df is greater than 0.0030 and less than or equal to 0.01 ×: Df exceeds 0.01

[0190] [Table 3]

[0191] Based on the results in Table 3 above, adhesive sheets using polyester resins (A-1) to (A-4) Examples 5-10 exhibited excellent adhesion to metal and glass substrates. Furthermore, regarding holding power... Furthermore, the adhesive properties of such adhesive sheets were excellent and could be used effectively as an adhesive. When the dielectric properties of the adhesive layer were measured, the adhesive layer also exhibited dielectric properties, particularly low dielectric loss tangent. It was excellent in that respect. In particular, the polyester resin did not contain aliphatic polycarboxylic acids. Examples 5, 6, and 8-10 showed particularly excellent dielectric loss tangent. In contrast, adhesive sheets using polyester resins (A'-2, 3, 5) (Comparative Example 7) 8, 10) are slightly inferior in dielectric loss tangent compared to the examples, and also, polyester Adhesive sheets using ru-type resins (A'-1, 4) (Comparative Examples 6, 9) exhibited significantly inferior dielectric loss tangent. It became that. [Industrial applicability]

[0192] This composition is an adhesive composition containing a polyester resin, and has a low dielectric constant and low dielectric constant. It has an electro-loss tangent, particularly a low dielectric loss tangent, and forms an adhesive with excellent tackiness. The adhesive composition in question is used as an adhesive in electronic devices that transmit and receive high-frequency signals. It is effective.

Claims

1. Structural site derived from polycarboxylic acids (a1) and structure derived from polyhydric alcohols (a2) An adhesive composition containing a polyester resin (A) having a portion, In the structural site derived from the above polycarboxylic acids (a1), aromatic polycarboxylic acids (a 1-1) The content of structural parts derived from 20 mol% or more, In the structural site derived from the above polyhydric alcohols (a2), polydiene diol and / Or, if the content of structural moieties derived from hydrogenated polydienediol (a2-1) is 20 mol% or more An adhesive composition characterized by certain features.

2. The above-mentioned aromatic polycarboxylic acids (a1-1) and the structural site derived from polydienediol and / or the total of structural parts derived from hydrogenated polydienediol (a2-1) is polysyl-based The adhesive composition according to claim 1, characterized in that the resin (A) is 90% by weight or more. thing.

3. Number average of the above polydienediol and / or hydrogenated polydienediol (a2-1) The adhesive mixture according to claim 1 or 2, characterized in that the molecular weight is 500 to 10000. A finished product.

4. The above polydienediol and / or hydrogenated polydienediol (a2-1) is 4- Polydiene diols and / or 4-9 carbon atoms formed from conjugated dienes having 9 carbon atoms It is characterized by being a hydrogenated polydiene diol formed from a carbon-containing conjugated diene. The adhesive composition according to claim 1 or 2.

5. The above polyester resin (A) under conditions of 23°C and 50% relative humidity, frequency 1 The dielectric loss tangent at 0 GHz is 0.01 or less, as described in claim 1 or 2. The adhesive composition described.

6. The above polyester resin (A) is characterized by having an acid value of 10 mg KOH / g or less. The adhesive composition according to claim 1 or 2.

7. The adhesive composition according to claim 1 or 2, further characterized by containing a crosslinking agent (B). 。

8. An adhesive characterized by being a crosslinked adhesive composition according to claim 1 or 2.

9. Structural site derived from polycarboxylic acids (a1) and structure derived from polyhydric alcohols (a2) An adhesive composition containing a polyester resin (A) having a portion and a crosslinking agent (B) A bridged adhesive layer, In the structural site derived from the above polycarboxylic acids (a1), aromatic polycarboxylic acids (a 1-1) The content of structural parts derived from 20 mol% or more, In the structural site derived from the above polyhydric alcohols (a2), polydiene diol and / Or, if the content of structural moieties derived from hydrogenated polydienediol (a2-1) is 20 mol% or more can be, At a temperature of 23°C and a relative humidity of 50% RH, the above adhesive layer is measured at a frequency of 10 GHz. An adhesive layer characterized by having a dielectric loss tangent of 0.01 or less.

10. The adhesive layer according to claim 9, comprising a release sheet on one side of the adhesive layer and a base material on the other side. An adhesive sheet, wherein the above substrate temperature is 23°C and the relative humidity is 50% RH under conditions of frequency An adhesive sheet characterized by having a dielectric loss tangent of 0.01 or less at 10 GHz.

11. A laminate comprising an adhesive layer according to claim 9 and a substrate on at least one surface of the adhesive layer The above substrate is subjected to a temperature of 23°C and a relative humidity of 50% RH at a frequency of 10 GHz. A laminate characterized by having a dielectric loss tangent of 0.01 or less.

12. Structural site derived from polycarboxylic acids (a1) and structure derived from polyhydric alcohols (a2) An adhesive composition containing a polyester resin (A) having a portion, In the structural site derived from the above polycarboxylic acids (a1), aromatic polycarboxylic acids (a 1-1) The content of structural parts derived from 20 mol% or more, In the structural site derived from the above polyhydric alcohols (a2), polydiene diol and / Or, if the content of structural moieties derived from hydrogenated polydienediol (a2-1) is 20 mol% or more An adhesive composition characterized by a certain feature.

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