TW202309213A - Adhesive composition, adhesive sheet, electromagnetic-wave shielding material, laminate, and printed wiring board - Google Patents

Abstract

To provide an adhesive composition which has high adhesiveness to not only conventional polyimides and liquid-crystal polymers but also metal substrates, can attain high soldering heat resistance, and is excellent in terms of low-dielectric characteristics and laser processability. An adhesive composition comprising a modified polyolefin resin (a), a polyimide resin (b), and a hardener (c), wherein the polyimide resin (b) includes, as a constituent unit, at least one compound selected from the group consisting of polyolefin polyols, dimer diols, dimer diamines, and dimer acids.

Description

Adhesive composition, adhesive sheet, electromagnetic shielding material, laminate, and printed wiring board

The present invention relates to adhesive compositions. More specifically, it relates to an adhesive composition used for bonding a resin substrate to a resin substrate or to a metal substrate. In particular, it relates to an adhesive composition for a flexible printed wiring board (hereinafter referred to as FPC), an adhesive sheet containing the same, an electromagnetic wave shielding material, a laminate, and a printed wiring board.

Flexible printed circuit boards (FPCs) have excellent flexibility and can correspond to the multi-function and miniaturization of personal computers (PCs) and smart phones. Therefore, they are often used to assemble electronic circuit boards into narrow and Complex internal use. In recent years, along with the miniaturization, weight reduction, higher density, and higher output of electronic equipment, the requirements for the performance of wiring boards (electronic circuit boards) have gradually increased. Especially, along with the high-speed transmission signal in FPC, the high frequency of the signal is progressing. Accompanied by this, for FPC, the requirement of low dielectric characteristics (low dielectric constant, low dielectric tangent) in the high-frequency region is increasing. As mentioned above, in order to achieve low dielectric properties, countermeasures have been taken to reduce the dielectric loss of FPC substrates and adhesives. Development using a combination of polyolefin and epoxy (Patent Document 1) and a combination of elastomer and epoxy (Patent Document 2) as an adhesive is progressing. [Prior Art Literature] [Patent Document]

[Patent Document 1] WO2016/047289 Publication [Patent Document 2] WO2014/147903 Publication

[Problem to be Solved by the Invention]

However, in Patent Document 1, it is difficult to say that the heat resistance of the solder used for the reinforcing plate and the interlayer adhesive is excellent. In addition, in Patent Document 2, storage stability after blending, which is important at the time of use, is not sufficient.

In addition, due to the miniaturization of FPC in recent years, the density of circuit boards has become higher. In order to ensure the continuity of the circuit, blind via holes and through holes are drilled by laser processing. In order to establish a high-precision technology for laser processing, processing using UV lasers has been carried out, mainly using a wavelength of 355 nm for hole opening processing, but the above-mentioned documents do not discuss laser processing.

That is, the object of the present invention is to provide a metal substrate that has good adhesion to both various resin substrates such as polyimide and metal substrates, and is also excellent in solder heat resistance, low dielectric properties, and laser processability. adhesive composition. [Means to solve the problem]

As a result of intensive research, the present inventors have found that the above-mentioned problems can be solved by the means shown below, and have achieved the present invention. That is, the present invention consists of the following configurations.

[1] An adhesive composition comprising a modified polyolefin resin (a), a polyimide resin (b) and a hardener (c); The above-mentioned polyimide resin (b) has at least one selected from the group consisting of polyolefin polyol, polyolefin polyamine, polyolefin polycarboxylic acid, dimer glycol, dimer diamine and dimer acid as Structural units.

[2] The adhesive composition according to the above [1], wherein the acid value of the modified polyolefin resin (a) is 5 to 30 mgKOH/g.

[3] The adhesive composition according to the above [1] or [2], wherein the curing agent (c) contains at least one selected from the group consisting of epoxy resin, polyisocyanate, and polycarbodiimide.

[4] The adhesive composition according to any one of the above [1] to [3], wherein, based on 100 parts by mass of the total of the modified polyolefin resin (a) and the polyimide resin (b), Contains 50 to 95 parts by mass of modified polyolefin resin (a).

[5] The adhesive composition according to any one of the above [1] to [4], which has a relative permittivity of less than 3.0 at 10 GHz.

[6] The adhesive composition according to any one of [1] to [5] above, wherein, based on 100 parts by mass of the total of the modified polyolefin resin (a) and the polyimide resin (b), The content of the curing agent (c) is 0.5 to 60 parts by mass.

[7] An adhesive sheet having a layer composed of the adhesive composition according to any one of the above-mentioned [1] to [6].

[8] An electromagnetic wave shielding material having a layer composed of the adhesive composition according to any one of the above [1] to [6].

[9] A laminate having a layer composed of the adhesive composition according to any one of [1] to [6] above.

[10] A printed wiring board comprising the laminate according to the above [9] as a constituent. [Effect of Invention]

The adhesive composition of the present invention has good adhesion to both various resin substrates such as polyimide and metal substrates, and is excellent in solder heat resistance, low dielectric properties, and laser processability .

＜Modified polyolefin resin (a)＞ The modified polyolefin resin (a) used in the present invention (hereinafter also referred to as component (a) for short.) is not limited, and it is preferably obtained by grafting α, β-unsaturated carboxylic acid and its anhydride in polyolefin resin At least one of them is obtained. Polyolefin resin refers to homopolymers of olefin monomers such as ethylene, propylene, butene, butadiene, isoprene, etc., or copolymers with other monomers, and the obtained polymers Hydrides, halides, and other polymers with a hydrocarbon backbone as the main body. That is, the modified polyolefin resin (a) is preferably obtained by grafting at least one of α, β-unsaturated carboxylic acids and their anhydrides in polyethylene, polypropylene and propylene-α-olefin copolymers. 1 kind of winner.

Propylene-α-olefin copolymer is obtained by copolymerizing propylene with α-olefin as the main body. As the α-olefin, for example, one or more of ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene, vinyl acetate and the like can be used. Among these α-olefins, ethylene and 1-butene are preferable. The ratio of the propylene component to the α-olefin component of the propylene-α-olefin copolymer is not limited, and the propylene component is preferably at least 50 mol%, more preferably at least 70 mol%.

At least one kind of α,β-unsaturated carboxylic acid and its anhydride, for example, maleic acid, itaconic acid, citraconic acid, and these anhydrides are mentioned. Among them, acid anhydride is preferable, and maleic anhydride is more preferable. That is, the modified polyolefin resin (a) specifically includes maleic anhydride-modified polypropylene, maleic anhydride-modified propylene-ethylene copolymer, maleic anhydride-modified propylene-butene copolymer, maleic anhydride-modified For the acid anhydride-modified propylene-ethylene-butene copolymer, etc., one of these maleic anhydride-modified polyolefins may be used or two or more of them may be used in combination.

The lower limit of the acid value of the modified polyolefin resin (a) is preferably 5 mgKOH/g or more, more preferably 6 mgKOH/g, from the viewpoint of solder heat resistance and adhesiveness to resin substrates and metal substrates above, more preferably 7 mgKOH/g or above. By setting it as more than the said lower limit, the reactivity with a hardening|curing agent (c) will become favorable, and excellent adhesive strength can be expressed. In addition, the crosslinking density is high and the solder heat resistance becomes good. The upper limit is preferably not more than 30 mgKOH/g, more preferably not more than 28 mgKOH/g, more preferably not more than 25 mgKOH/g. Adhesiveness becomes favorable by setting it as below the said upper limit. In addition, the viscosity and stability of the solution will become better, and it can exhibit excellent pot life characteristics. And the manufacturing efficiency will also be improved.

The number average molecular weight (Mn) of the modified polyolefin resin (a) is preferably in the range of 10,000 to 50,000. The range of 15,000-45,000 is more preferable, the range of 20,000-40,000 is more preferable, and the range of 22,000-38,000 is especially preferable. Cohesion strength becomes favorable by setting it as more than the said lower limit, and excellent adhesiveness can be expressed. Moreover, by setting it as below the said upper limit, fluidity|liquidity becomes excellent and handleability becomes favorable.

The modified polyolefin resin (a) is preferably crystalline. The term "crystallinity" in the present invention means that the temperature is raised from -100°C to 250°C at 20°C/min using a differential scanning calorimeter (DSC), and a clear melting peak is shown during the heating process.

The melting point (Tm) of the modified polyolefin resin (a) is preferably in the range of 50°C to 120°C. It is preferably in the range of 60°C to 100°C, most preferably in the range of 70°C to 90°C. By setting it as more than the said lower limit, the cohesive force derived from a crystal becomes favorable, and excellent adhesiveness and solder heat resistance can be expressed. Moreover, by setting it as below the said upper limit, solution stability and fluidity are excellent, and workability|operativity at the time of adhesion becomes favorable.

The heat of fusion (ΔH) of the modified polyolefin resin (a) is preferably in the range of 5 J/g to 60 J/g. It is preferably in the range of 10J/g-50J/g, most preferably in the range of 20J/g-40J/g. By setting it as more than the said lower limit, the cohesive force derived from a crystal becomes favorable, and excellent adhesiveness and solder heat resistance can be expressed. Moreover, by setting it as below the said upper limit, solution stability and fluidity are excellent, and workability|operativity at the time of adhesion becomes favorable.

The production method of the modified polyolefin resin (a) is not particularly limited, for example, a free radical grafting reaction (that is, a free radical species is generated for the polymer that becomes the main chain, and the free radical species is used as a polymerization initiation point to make unsaturated carboxylic acid and acid anhydride carry out graft polymerization reaction) and so on.

The free radical generator is not particularly limited, but it is preferable to use an organic peroxide. Organic peroxides are not particularly limited, for example: di-tertiary butyl peroxyphthalate, tertiary butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, tertiary butyl peroxybenzoate Esters, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, di-tert-butyl peroxide, lauryl peroxide and other peroxides; azo Azonitriles such as bisisobutyronitrile and azobisisopropionitrile.

＜Polyimide resin (b)＞ The polyimide resin (b) (hereinafter also referred to as (b) component) used in the present invention is obtained by reacting a polycarboxylic acid derivative having an acid anhydride group with a polyisocyanate compound or a polyamine compound. In addition, the polyimide resin (b) used in the present invention is composed of polyolefin polyol, polyolefin polyamine, polyolefin polycarboxylic acid, dimer glycol, dimer diamine and dimer acid. At least one polyimide resin in the group as a structural unit. Here, polyimide resin refers to a polymer having an imide bond, and also includes polyimide resin, polyurethane imide resin, polyester imide resin, polyamide imide resin etc.

The polyimide resin (b) used in the present invention is composed of polyolefin polyol, polyolefin polyamine, polyolefin polycarboxylic acid, dimer glycol, dimer diamine and dimer acid. When at least one of the group is used as a structural unit, the polyimide resin (b) can be made less dielectric, and in addition, the compatibility with the modified polyolefin resin (a) is also improved. The content of the above structural units in the polyimide resin (b) is preferably at least 30% by mass, more preferably at least 40% by mass, more preferably at least 50% by mass. In addition, it is preferably not more than 95% by mass, more preferably not more than 90% by mass, more preferably not more than 85% by mass. By setting it to more than the said lower limit, sufficient low-dielectric characteristics can be ensured, and by setting it below the said upper limit, solder heat resistance and laser processability will become favorable.

The lower limit of the acid value of the polyimide resin (b) used in the present invention is preferably 1 mgKOH from the standpoint of solder heat resistance, adhesion to resin substrates and metal substrates, and low dielectric properties. /g or more, more preferably 1.5 mgKOH/g or more, more preferably 2 mgKOH/g or more. By setting it as more than the said lower limit, the reactivity with a hardening|curing agent (c) becomes favorable, and it becomes possible to express the outstanding adhesive strength. In addition, the crosslink density becomes high and the solder heat resistance becomes good. The upper limit is preferably not more than 25 mgKOH/g, more preferably not more than 23 mgKOH/g, more preferably not more than 20 mgKOH/g. By setting it below the said upper limit, low-dielectric characteristics will become favorable. In addition, the viscosity and stability of the solution will become better, and it can exhibit excellent pot life characteristics. And the manufacturing efficiency is also improved.

For the logarithmic viscosity of the polyimide resin (b) used in the present invention, the lower limit is preferably 0.05 dl/g or more from the viewpoint of adhesion and compatibility with the resin substrate and the metal substrate, It is more preferably at least 0.06 dl/g, more preferably at least 0.07 dl/g. Adhesiveness becomes favorable by setting it as more than the said lower limit. The upper limit is preferably not more than 0.40dl/g, more preferably not more than 0.38dl/g, more preferably not more than 0.35dl/g. By setting it below the said upper limit, the compatibility with a modified olefin resin will become favorable. In addition, the viscosity and stability of the solution will become better, and it can exhibit excellent pot life characteristics. And the manufacturing efficiency is also improved.

＜Polycarboxylic acid derivatives with acid anhydride groups＞ As the polyimide resin (b) used in the present invention, polycarboxylic acid derivatives having acid anhydride groups, for example, aromatic polycarboxylic acid derivatives, aliphatic polycarboxylic acid derivatives or alicyclic polycarboxylic acid derivatives can be used derivative. These may be used individually, and may use 2 or more types together. Among them, aromatic polyhydric carboxylic acid derivatives are preferable. In addition, the valency of the polycarboxylic acid derivative is not particularly limited. It is preferable to have one or two acid anhydride groups in one molecule, and there is no problem in containing one or more carboxyl groups in the polycarboxylic acid derivative having an acid anhydride group.

Aromatic polycarboxylic acid derivatives are not particularly limited, for example, trimellitic anhydride (TMA), 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propionic dianhydride (BisDA ), terephthalic bis(trimellitic anhydride) (TAHQ), 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), 2,2-bis[4-(2,3-dicarboxy Phenoxy)phenyl]propionic dianhydride, pyromelite dianhydride, ethylene glycol bis(dehydrated trimellitate), propylene glycol bis(dehydrated trimellitate), 1,4-butanediol Bis(dehydrated trimellitate), hexanediol bis(dehydrated trimellitate), polyethylene glycol bis(dehydrated trimellitate), polypropylene glycol bis(dehydrated trimellitate), etc. Alkyl glycol bis(dehydrated trimellitate), 3,3'-4,4'-diphenone tetracarboxylic dianhydride, 3,3'-4,4'-biphenyltetracarboxylic dicarboxylic acid anhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,5,6-pyridine tetracarboxylic dianhydride, 3,4 ,9,10-perylenetetracarboxylic dianhydride, 3,3',4,4'-diphenylpyridine tetracarboxylic dianhydride, m-terphenyl-3,3',4,4'-tetracarboxylic dicarboxylic acid anhydride, 4,4'-oxydiphthalic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(2,3- or 3,4-dicarboxyphenyl ) propane dianhydride, 2,2-bis(2,3- or 3,4-dicarboxyphenyl) propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis[ 4-(2,3- or 3,4-dicarboxyphenoxy)phenyl]propane dianhydride, or 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3- Tetramethyldisiloxane dianhydride, etc.

Aliphatic polycarboxylic acid derivatives or alicyclic polycarboxylic acid derivatives are not particularly limited, for example, butane-1,2,3,4-tetracarboxylic dianhydride, pentane-1,2, 4,5-tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, hexahydropyromelite dianhydride, cyclohex-1-ene-2,3,5,6-tetracarboxylic dianhydride, 3 -Ethylcyclohex-1-ene-3-(1,2),5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexane-3-(1,2),5 ,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexane-1-ene-3-(1,2),5,6-tetracarboxylic dianhydride, 1-ethylcyclohexyl Alkane-1-(1,2),3,4-tetracarboxylic dianhydride, 1-propylcyclohexane-1-(2,3),3,4-tetracarboxylic dianhydride, 1,3- Dipropylcyclohexane-1-(2,3),3-(2,3)-tetracarboxylic dianhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride, bicyclo [2,2,1]heptane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2,2,2]octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, hexahydrotrimellitic anhydride, and the like.

These polyhydric carboxylic acid derivatives which have an acid anhydride group may be used individually or in combination of 2 or more types. In consideration of low dielectric properties, cost, etc., aromatic polycarboxylic acid derivatives are preferred, among which trimellitic anhydride and 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl] Propionic dianhydride, terephthalic bis(trimellitic anhydride), 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, pyromelite, ethylene glycol bis(dehydrated trimellitate), 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, or 3,3',4,4'-biphenyltetracarboxylic dianhydride.

The content of the polyhydric carboxylic acid derivative having an acid anhydride group in the polyimide resin (b) is preferably at least 1% by mass, more preferably at least 2% by mass, more preferably at least 3% by mass. In addition, it is preferably not more than 30 mass %, more preferably not more than 35 mass %, more preferably not more than 30 mass %. By setting within the above range, excellent adhesiveness, solder heat resistance, laser processability, and low dielectric properties can be exhibited.

＜Polyolefin polyol components＞ The polyolefin polyol component constituting the polyimide resin (b) used in the present invention functions as a soft component of the polyimide resin (b). Polyolefin polyol is a polymer of polyolefin backbone with a large number of hydroxyl groups. Specific examples of such polyolefin polyols include polyethylene butene diol (polyethylene butene polyol), polybutadiene diol (polybutadiene polyol), and hydrogenated polybutadiene diol (hydrogenated polybutadiene polyol), etc. The polyolefin polyol may be used alone or in combination of two or more. Commercially available products of polyethylene butylene glycol include the product name "POLYTAIL" (manufactured by Mitsubishi Chemical Corporation) and the like. In addition, commercially available polybutadiene diol has a trade name "KRASOL" (manufactured by Cray Valley Co., Ltd.) and the like. Moreover, the commercial item of hydrogenated polybutadiene diol has a brand name "NISSO-PB" (manufactured by Nippon Soda Co., Ltd.) and the like.

＜Dimer glycol component＞ The dimer glycol component constituting the polyimide resin (b) used in the present invention functions as a softening component of the polyimide resin (b). Dimer glycols are preferably reduction reaction products derived from polymeric fatty acids. Polymer fatty acids are also called dimer acids, which are unsaturated fatty acids with 18 carbons (C18) such as oleic acid, linolenic acid, and perilla oleic acid, dry oil fatty acids or semi-dry oil fatty acids, and lower ones of these fatty acids. Monoalcohol ester obtained by dimolecular polymerization (dimer) in the presence or absence of a catalyst. It does not matter that dimer diol has residual unsaturated bond in its molecule, trimer triol etc. are contained as an impurity.

Examples of the dimer glycol component include: Croda Japan Co., Ltd., trade name "Pripol 2033" (mixture with double bond), "Pripol 2030" (mixture without double bond), BASF JAPAN Co., Ltd., trade name " "SOVERMOL 650NS", "SOVERMOL 908", etc. These can be used alone, and there is no harm in combining many of them.

＜Dimer acid component＞ The dimer acid component is a polymer fatty acid which is the starting material of the above-mentioned dimer glycol. The dimer acid may be used alone or in combination of two or more. Examples of commercially available dimer acids include "Pripol 1004," "Pripol 1006," "Pripol 1009," "Pripol 1013," "Pripol 1015," "Pripol 1017," "Pripol 1022," and "Pripol 1025" manufactured by Croda Japan. ", "Pripol 1040"; "Empol 1008", "Empol 1012", "Empol 1016", "Empol 1026", "Empol 1028", "Empol 1043", "Empol 1061", "Empol 1062" manufactured by BASF JAPAN Co., Ltd.

＜Dipolymer diamine component＞ As a dimer diamine component, the compound which converted the carboxyl group of the said dimer acid into an amine group can be mentioned, for example. The above-mentioned conversion method, for example, can be exemplified by amidation of carboxylic acid, amination by Hoffman rearrangement, further distillation and purification. As for the commercially available product of dimer diamine, "Priamine 1071", "Priamine 1073", "Priamine 1074", "Priamine 1075" manufactured by Croda Japan Corporation, "Versamine 551" manufactured by BASF JAPAN Corporation, etc. are mentioned, for example. Dipolymer diamine can be used individually or in combination of 2 or more types.

＜Polyisocyanate compound＞ The polyisocyanate compound constituting the polyimide resin (b) used in the present invention is not particularly limited, and examples thereof include aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, and alicyclic polyisocyanate compounds. Aromatic diisocyanate compounds are preferred. The aromatic polyisocyanate compound is not particularly limited, for example, diphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4,3' - or 5,2'- or 5,3'- or 6,2'- or 6,3'-dimethyldiphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3 '- or 4,2'- or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-diethyldiphenylmethane-2,4' - diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3' -Dimethoxydiphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), diphenylmethane-3,3'-diisocyanate, diphenylmethane Methane-3,4'-diisocyanate, diphenyl-4,4'-diisocyanate ether, benzophenone-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate , toluene-2,4-diisocyanate (TDI), toluene-2,6-diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, naphthalene-2,6-diisocyanate, -4,4'-[ 2,2 bis(4-phenoxyphenyl)propane]diisocyanate, 3,3'- or 2,2'-dimethylbiphenyl-4,4'-diisocyanate, 3,3'- or 2 ,2'-Diethylbiphenyl-4,4'-diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, 3,3'-diethoxybiphenyl- 4,4'-diisocyanate, etc. Considering solder heat resistance, adhesiveness, solubility, cost, etc., it is preferable to use diphenylmethane-4,4'-diisocyanate, toluene-2,4-diisocyanate, m-xylene diisocyanate, 3,3 '- or 2,2'-dimethylbiphenyl-4,4'-diisocyanate, more preferably diphenylmethane-4,4'-diisocyanate, toluene-2,4-diisocyanate. Moreover, these can be used individually or in combination of 2 or more types.

＜Polyamine compound＞ The polyamine compound constituting the polyimide resin (b) used in the present invention is not particularly limited, and examples thereof include diamine compounds and polyamine compounds. Diamine compounds, for example, can be exemplified: 1,4-phenylenediamine, 1,3-phenylenediamine, 1,2-phenylenediamine, 1,5-naphthalene diamine, 1,8-naphthalene diamine, 2 ,3-naphthalenediamine, 2,6-toluenediamine, 2,4-toluenediamine, 3,4-toluenediamine, 4,4'-diaminodiphenylmethane, 3,4'-di Aminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diamino-1,2-diphenylethane, 3,3'-diaminodiphenylmethane, 3,4'-diamine diphenylmethane, 4,4'-diamine diphenyl ketone, 4,4'-diamine diphenyl ketone, 3,3'-diamine diphenyl ketone, 3, Aromatic diamines such as 3'-diamine diphenylene; Ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,7-heptanediamine Alkanediamine, 1,9-nonanediamine, 1,12-dodecanediamine, m-xylylenediamine and other aliphatic diamines; isophoronediamine, norbornanediamine, 1,2 - Alicyclic diamines such as cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-dicyclohexylmethanediamine, and piperhexane, and the like. A polyamine can be used individually or in combination of 2 or more types.

The content of the isocyanate compound and the polyamine compound in the polyimide resin (b) is preferably at least 10% by mass, more preferably at least 13% by mass, and more preferably at least 15% by mass. In addition, it is preferably not more than 50% by mass, more preferably not more than 45% by mass, more preferably not more than 40% by mass.

The method for producing the polyimide resin (b) used in the present invention is not particularly limited, and conventionally known methods for producing polyimide resins can be applied. The usage ratio of each raw material supplied to the polymerization reaction of polyimide resin (b) should be such that the sum of each equivalent of isocyanate group and amine group (B) and the sum of each equivalent of anhydride group, carboxyl group and hydroxyl group (A) The ratio is (B)/(A)=0.7-1.3, preferably 0.8-1.2. By setting it as more than the said lower limit, the molecular weight of a polyimide resin (b) can be made high, and it can prevent that a coating film becomes brittle. Moreover, the viscosity of polyimide resin (b) will be suppressed by making it below the said upper limit, and the leveling property at the time of applying an adhesive solution will become favorable.

The polymerization reaction of the polyimide resin (b) used in the present invention is preferably carried out in the presence of one or more organic solvents. It is ideal that the heat condensation is carried out thereby.

As the polymerization solvent, one having low reactivity with isocyanate groups and amine groups can be used. For example, a solvent that does not contain basic compounds such as amines is preferable. Such organic solvents, for example, can be exemplified: toluene, xylene, ethylbenzene, nitrobenzene, cyclohexane, isophorone, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol methyl ether acetic acid ester, propylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, methyl methoxy propionate, ethyl methoxy propionate, methyl ethoxy propionate, ethyl Ethyl oxypropionate, ethyl acetate, n-butyl acetate, isoamyl acetate, ethyl lactate, acetone, methyl ethyl ketone, cyclohexanone, N,N-dimethylformamide, N,N-dimethylformamide Acetamide, N-methylpyrrolidone, N-ethylpyrrolidone, γ-butyrolactone, dimethylsulfoxide, chloroform and dichloromethane, etc. These may be used individually, and may use 2 or more types together.

Considering the volatility during drying, polymer polymerizability, and good solubility, the polymerization solvent is preferably N,N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, γ -Butyrolactone, cyclohexanone. N-methylpyrrolidone and cyclohexanone are more preferable. In addition, these can also be used as a diluent for the adhesive composition of the present invention.

The amount of solvent used is preferably set at 0.8 to 5.0 times (mass ratio) of the polyimide resin (b) to be produced, more preferably at 1.0 to 3.0 times. By setting the usage-amount to more than the said lower limit, the raise of the viscosity at the time of synthesis|combination is suppressed, and agitation property becomes favorable. Moreover, the fall of a reaction rate can be suppressed by setting it as below the said upper limit.

The reaction temperature is preferably set at 60 to 200°C, more preferably at 100 to 180°C. Reaction time can be shortened by making reaction temperature more than the said lower limit. Moreover, by setting it as below the said upper limit, decomposition|disassembly of a monomer component can be suppressed, and gelation by a three-dimensionalization reaction can be suppressed. The reaction temperature can also be changed in multiple stages. The reaction time can be appropriately selected according to the scale of the batch (Batch) and the reaction conditions adopted, especially according to the reaction concentration.

In order to promote the reaction, it can also be used in triethylamine, lutidine, picoline, undecene, triethylenediamine (1,4-diazabicyclo[2,2,2]octane), DBU(1, 8-diazabicyclo[5,4,0]-7-undecene) and other amines, lithium methoxide, sodium methoxide, sodium ethoxide, potassium butoxide, potassium fluoride, sodium fluoride and other alkali metals, alkaline earth metals The reaction is carried out in the presence of catalysts such as titanium, cobalt, tin, zinc, aluminum and other metals and semi-metal compounds. Among them, if insulation is considered, triethylamine and DBU are suitable.

＜Hardener (c)＞ The resin composition of the present invention contains a curing agent (c). By containing the hardener (c) in the resin composition, adhesiveness and solder heat resistance can be further improved. As the curing agent (c), known ones can be used. Examples of the curing agent (c) include epoxy resins, polyisocyanates, polycarbodiimides, oxazoline crosslinking agents, and aziridine (aziridine) crosslinking agents. Preferably epoxy resin, polyisocyanate, polycarbodiimide. These crosslinking agents may be used alone or in combination of two or more.

＜Epoxy resin＞ The epoxy resin used in the present invention is not particularly limited as long as it has an epoxy group in the molecule, but preferably has two or more epoxy groups in the molecule. Specifically, there are no particular limitations, and examples include: biphenyl type epoxy resin, naphthalene type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, alicyclic ring Oxygen resin, dicyclopentadiene epoxy resin, tetraglycidyl diaminodiphenylmethane, triglycidyl p-aminophenol, tetraglycidyl diaminomethylcyclohexanone, N, N,N',N'-tetraglycidyl-m-xylylenediamine, epoxy-modified polybutadiene, and the like can be used alone or in combination of two or more. Biphenyl type epoxy resin, novolak type epoxy resin and dicyclopentadiene type epoxy resin are preferable. Preferable are novolak type epoxy resins and dicyclopentadiene type epoxy resins.

The epoxy equivalent weight of the epoxy resin is preferably above 50 g/eq, more preferably above 70 g/eq, more preferably above 80 g/eq. Moreover, it is preferably 400 g/eq or less, more preferably 350 g/eq or less, more preferably 300 g/eq or less. By setting it in the said range, excellent solder heat resistance can be expressed.

＜Polycarbodiimide＞ The polycarbodiimide used in the present invention is not particularly limited as long as it has a carbodiimide group in the molecule. It is preferably polycarbodiimide having two or more carbodiimide groups in the molecule. The polycarbodiimide may be any one of an aromatic carbodiimide compound, an alicyclic carbodiimide compound, or an aliphatic carbodiimide compound, and these may be used alone or in combination of two or more. Aromatic carbodiimide compounds, for example: poly-m-phenylene carbodiimide, poly-p-phenylene carbodiimide, polytoluene carbodiimide, poly(diisopropylphenylcarbodiimide), poly(methane Diisopropylphenylcarbodiimide), poly(4,4'-diphenylmethanecarbodiimide), etc. Alicyclic carbodiimide compounds, for example: poly-m-cyclohexylcarbodiimide, poly-p-cyclohexylcarbodiimide, poly(4,4'-dicyclohexylmethanecarbodiimide), poly(3 ,3'-Dicyclohexylmethanecarbodiimide) and so on. The aliphatic carbodiimide compound may be any of linear or branched aliphatic carbodiimide compounds. It is preferably a linear aliphatic carbodiimide compound, specifically, polymethylene carbodiimide, polyethylene carbodiimide, polypropylene carbodiimide, polybutene carbodiimide Amine, polypentylcarbodiimide, polyhexylcarbodiimide, etc. These can be used individually or in combination of 2 or more types. Among them, an aromatic carbodiimide compound or an alicyclic carbodiimide compound is preferable. In addition, when polycarbodiimide and epoxy resin are used together as a curing agent, the effect of further improving solder heat resistance can be expected.

＜Polyisocyanate＞ The polyisocyanate used in the present invention is preferably a polyfunctional isocyanate compound having two or more isocyanate groups in one molecule. In addition, compounds derived from polyfunctional isocyanate compounds can also be used.

The polyisocyanate may be any one of an aromatic isocyanate compound, an alicyclic isocyanate compound, or an aliphatic isocyanate compound, and these may be used alone or in combination of two or more. Among them, aliphatic isocyanate compounds are preferable, and aliphatic diisocyanate compounds are more preferable. Aromatic isocyanate compounds, for example: 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylene diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 1 ,8-naphthalene diisocyanate, 3,3'-biphenyl diisocyanate, 4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, diphenylmethane -3,3'-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, etc., which can be used alone, Or use 2 or more types together. Among them, 3,3'-dimethylbiphenyl-4,4'-diisocyanate is preferable. Alicyclic isocyanate compounds, for example: isophorone diisocyanate, norcamphene diisocyanate, 1,2-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, Isocyanate, dicyclohexylmethane-4,4'-diisocyanate, etc. can be used individually or in combination of 2 or more types. The aliphatic isocyanate compound may be any of linear or branched aliphatic isocyanates. It is preferably a linear aliphatic diisocyanate compound, specifically, 1,3-propane diisocyanate, 1,4-butylene diisocyanate, 1,5-pentylene diisocyanate, 1,6 - Hexylidene diisocyanate, 1,7-heptylene diisocyanate, 1,8-octylene diisocyanate, 1,9-nonylidene diisocyanate, etc. may be used alone or in combination of two or more. Among them, 1,6-hexyl diisocyanate is preferable.

The polyisocyanate may be an isocyanurate form, adduct, biuret form, uretdione form, or allophanate form of the above-mentioned isocyanate compounds. In addition, as the polyisocyanate, blocked isocyanate obtained by blocking an isocyanate group can also be used. These compounds may be used alone or in combination of two or more. Among them, an isocyanurate body or a biuret body is preferable.

In the adhesive composition of the present invention, the content of the hardener (c) is preferably 0.5 parts by mass or more based on 100 parts by mass of the total of the modified polyolefin (a) and the polyimide resin (b), More preferably, it is 1 mass part or more, More preferably, it is 5 mass parts or more, Especially preferably, it is 10 mass parts or more. By setting it as more than the said lower limit, sufficient hardening effect can be acquired, and excellent adhesiveness and solder heat resistance can be expressed. Moreover, it is preferably not more than 60 parts by mass, more preferably not more than 50 parts by mass, and more preferably not more than 40 parts by mass. By setting it below the said upper limit, the low dielectric property of an adhesive composition will become favorable. That is, by setting it within the above-mentioned range, it is possible to obtain an adhesive composition having excellent low dielectric properties in addition to adhesiveness, solder heat resistance, and pot life properties.

＜Adhesive composition＞ The adhesive composition of the present invention can exhibit excellent adhesion to low-polar resin substrates such as liquid crystal polymers (LCP) and metal substrates by containing three of the above-mentioned components (a) to (c). Connectivity, low dielectric properties, solder heat resistance and laser processability. That is, the adhesive composition is coated on the substrate, and the cured adhesive coating film (adhesive layer) can exhibit excellent low dielectric properties, solder heat resistance, and laser processability.

In the adhesive composition of the present invention, the content of the modified polyolefin resin (a) is preferably 50 parts by mass relative to the total of 100 parts by mass of the modified polyolefin resin (a) and the polyimide resin (b). parts by mass or more. More preferably, it is 60 mass parts or more, More preferably, it is 65 mass parts or more. Moreover, it is preferably 95 parts by mass or less, more preferably 90 parts by mass or less, and more preferably 85 parts by mass or less. When the content of the modified polyolefin resin (a) is within the above range, adhesiveness, low dielectric properties, laser processability and compatibility are improved.

The adhesive composition of the present invention may further contain an organic solvent. The organic solvent usable in the present invention is not particularly limited as long as it can dissolve or disperse the modified polyolefin (a), polyimide resin (b) and curing agent (c). Specifically, for example, aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as hexane, heptane, octane, and decane, cyclohexane, cyclohexene, methylcyclohexane, ethyl Alicyclic hydrocarbons such as cyclohexane, halogenated hydrocarbons such as trichlorethylene, dichloroethylene, chlorobenzene, and chloroform, alcohol-based solvents such as methanol, ethanol, isopropanol, butanol, amyl alcohol, hexanol, propylene glycol, and phenol , acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone, acetophenone and other ketone solvents, methyl cellosol, ethyl cellosol and other cellosol , methyl acetate, ethyl acetate, butyl acetate, methyl propionate, butyl formate and other ester solvents, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, ethylene glycol mono-tertiary butyl ether , diethylene glycol mono-n-butyl ether, diethylene glycol mono-isobutyl ether, triethylene glycol mono-n-butyl ether, tetraethylene glycol mono-n-butyl ether, etc. Or use 2 or more types together. In particular, considering the working environment and dryness, methylcyclohexane and toluene are preferable.

The organic solvent is preferably in the range of 100-1000 parts by mass, more preferably 200-900 parts by mass, relative to 100 parts by mass of the total solids of modified olefin (a), polyimide resin (b) and hardener (c). The most desirable range is 300 to 800 parts by mass. By setting it as more than the said lower limit, liquid state and pot life characteristics will become favorable. Moreover, it becomes advantageous in terms of manufacturing cost and transportation cost by setting it as below the said upper limit.

The adhesive composition of the present invention preferably has a relative dielectric constant (ε _c ) of 3.0 or less at a frequency of 10 GHz. It is more preferably 2.6 or less, more preferably 2.3 or less. The lower limit value is not particularly limited, but practically it is 2.0 or more. In addition, the relative permittivity (ε) in the entire frequency range of 1 GHz to 60 GHz is preferably 3.0 or less, more preferably 2.6 or less, and more preferably 2.3 or less.

The adhesive composition of the present invention preferably has a dielectric tangent (tanδ) of 0.02 or less at a frequency of 10 GHz. It is more preferably 0.01 or less, more preferably 0.008 or less. The lower limit is not particularly limited, and is practically 0.0001. In addition, the dielectric tangent (tan δ) in the entire range of frequencies from 1 GHz to 60 GHz is preferably 0.02 or less, more preferably 0.01 or less, and more preferably 0.008 or less.

In the present invention, relative permittivity ( _εc ) and dielectric tangent (tanδ) can be measured as follows. That is, the adhesive composition was applied to the release substrate so that the thickness after drying would be 25 μm, and dried at about 130° C. for about 3 minutes. Then heat treatment was performed at about 140° C. for about 4 hours to harden, and the hardened adhesive composition layer (adhesive layer) was peeled off from the release film. The relative permittivity (ε _c ) of the peeled adhesive composition layer at a frequency of 10 GHz was measured. Specifically, relative permittivity (ε _c ) and dielectric tangent (tan δ) can be calculated from measurements made by the cavity resonator perturbation method.

In addition, the adhesive composition of the present invention may further contain other components as needed within the range of not impairing the effects of the present invention. Specific examples of such components include: flame retardants, tackifiers, fillers, and silane coupling agents.

＜Flame retardant＞ In the adhesive composition of the present invention, a flame retardant may also be blended as needed within the range that does not impair the effect of the present invention. Flame retardancy can be imparted to an adhesive composition by containing a flame retardant. The flame retardant is not particularly limited as long as it exhibits flame retardancy, and is preferably one that does not dissolve in an organic solvent. The flame retardant is preferably a flame retardant filler, for example: an inorganic flame retardant filler and an organic flame retardant filler. Inorganic flame retardant fillers, for example, can be exemplified: metal hydroxide compounds such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, calcium hydroxide, barium hydroxide; basic magnesium carbonate, zinc carbonate, magnesium carbonate-calcium ( The mixture of magnesium carbonate and calcium carbonate), calcium carbonate, barium carbonate and other metal carbonate compounds; magnesium oxide, molybdenum oxide, zirconium oxide, tin oxide, tin oxide water and substances, antimony oxide and other metal oxides; zinc borate, metaboric acid Boric acid metal compounds such as zinc and barium metaborate; inorganic metal compounds such as dolomite, pyrensite and borax; inorganic phosphorus compounds such as red phosphorus, etc. Organic flame retardant fillers, for example, melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, ammonium amide phosphate, ammonium amide polyphosphate, urethane formate, Polyphosphate urethane formate, aluminum diethylphosphinate, aluminum methylethylphosphinate, aluminum diphenylphosphinate, zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, Zinc bis-diphenylphosphinate, titanium diethylphosphinate, titanium diethylphosphinate, titanium bismethylethylphosphinate, titanium tetramethylethylphosphinate, titanium diphenylphosphinate Phosphorus-based flame retardants such as titanyl phosphonate and titanium tetraphenylphosphinate; melamine, melam, melamine cyanurate and other three-series compounds, cyanuric oxy compounds, isocyanuric Oxygen compounds, triazole compounds, tetrazole compounds, diazo compounds, urea and other nitrogen-based flame retardants; silicon-based flame retardants such as silicone resin compounds and silane compounds, etc. The flame retardant is preferably a metal hydroxide compound or a phosphorus compound, and among them, a phosphorus compound is more preferable. For example, phosphorus-based flame-retardant fillers such as aluminum phosphinate can be used. In addition, phosphorus-based flame retardants include types that do not dissolve in organic solvents (phosphorus-based flame-retardant fillers) and types that dissolve in organic solvents (phosphorus-based flame-retardant non-fillers). It is a type that does not dissolve in organic solvents (phosphorus flame retardant filler). The above-mentioned flame-retardant fillers may be used alone or in combination of two or more. When a flame retardant is contained, it is preferably contained in the range of 1 to 200 parts by mass, more preferably in the range of 5 to 150 parts by mass, and most preferably It is the range of 10-100 mass parts. The effect of a tackifier can be exhibited by setting it as more than the said lower limit. Moreover, adhesiveness, solder heat resistance, low-dielectric characteristics, etc. will not fall by setting it as below the said upper limit.

＜Tackifier＞ In the adhesive composition of the present invention, a tackifier may be blended as necessary within the range not impairing the effects of the present invention. Tackifiers, for example: polyterpene resins, rosin resins, aliphatic petroleum resins, alicyclic petroleum resins, copolymerized petroleum resins, styrene resins and hydrogenated petroleum resins, etc., are used to improve viscosity connection strength. These may be used alone or in any combination of two or more. When a tackifier is contained, it is preferably contained in the range of 1 to 200 parts by mass, more preferably in the range of 5 to 150 parts by mass, based on 100 parts by mass of the components (a) to (c) in total. The optimum range is from 10 to 100 parts by mass. The effect of a tackifier can be exhibited by setting it as more than the said lower limit. Moreover, adhesiveness, solder heat resistance, low-dielectric characteristics, etc. will not fall by setting it as below the said upper limit.

＜Filling＞ In the adhesive composition of the present invention, fillers may be blended as necessary within the range not impairing the effects of the present invention. Here, the filler refers to a flame-retardant filler different from those already described in the flame retardant, for example, silicon dioxide and the like can be exemplified. By adding silicon dioxide, the characteristic of solder heat resistance can be improved, so it is very desirable. Silicon dioxide is generally known as hydrophobic silicon dioxide and hydrophilic silicon dioxide. Here, in terms of imparting moisture resistance, dimethyldichlorosilane, hexamethyldisilazane, octane Hydrophobic silica treated with silane or the like is preferred. When silicon dioxide is blended, the blending amount is preferably 0.05 to 30 parts by mass based on 100 parts by mass of the components (a) to (c) in total. By setting it as more than the said lower limit, the effect of improving solder heat resistance can be exhibited. Moreover, by setting it as below the said upper limit, poor dispersion|distribution of silica does not generate|occur|produce, and solution viscosity becomes favorable, and workability becomes favorable. In addition, the adhesiveness will not decrease.

＜Silane coupling agent＞ In the adhesive composition of the present invention, a silane coupling agent may be blended as needed within the range not impairing the effects of the present invention. By adding a silane coupling agent, the characteristics of adhesion to metal and solder heat resistance can be improved, so it is very ideal. The silane coupling agent is not particularly limited, and examples thereof include those having an unsaturated group, those having a glycidyl group, and those having an amine group. Among them, from the viewpoint of solder heat resistance, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β -(3,4-Epoxycyclohexyl)ethyltriethoxysilane and other silane coupling agents with epoxypropyl groups. When blending a silane coupling agent, it is preferable that the compounding quantity is 0.5-20 mass parts with respect to the total 100 mass parts of (a)-(c) component. Excellent solder heat resistance becomes favorable by setting it as 0.5 mass part or more. On the other hand, solder heat resistance and adhesiveness become favorable by setting it as 20 mass parts or less.

＜Laminated body＞ The laminate of the present invention is one in which the adhesive composition is laminated on the substrate (two-layer laminate of substrate/adhesive layer), or one in which the substrate is further bonded (substrate /adhesive layer/substrate 3-layer laminate). Here, the adhesive layer refers to a layer of the adhesive composition obtained by applying the adhesive composition of the present invention to a substrate and drying it. The laminate of the present invention can be obtained by applying the adhesive composition of the present invention to various substrates according to the usual method, drying them, and further laminating other substrates.

＜Substrate＞ In the present invention, the substrate is not particularly limited as long as the adhesive composition of the present invention is coated thereon and dried to form an adhesive layer. Examples include resin substrates such as film-like resins, metal plates, etc. , metal foil and other metal substrates, paper, etc.

Resin substrates, for example: polyester resin, polyamide resin, polyimide resin, polyamide-imide resin, liquid crystal polymer, polyphenylene sulfide, para polystyrene, polyolefin resin and fluororesins, etc. It is preferably a film-like resin (hereinafter also referred to as a base film layer).

As the metal substrate, any conventionally known conductive material for circuit substrates can be used. Examples of the material include various metals such as SUS, copper, aluminum, iron, steel, zinc, and nickel, their alloys, plating, metals treated with other metals such as zinc and chromium compounds, and the like. It is preferably metal foil, more preferably copper foil. The thickness of the metal foil is not particularly limited, and it is preferably more than 1 μm, more preferably more than 3 μm, and more preferably more than 10 μm. In addition, it is preferably not more than 50 μm, more preferably not more than 30 μm, and more preferably not more than 20 μm. If the thickness is too thin, it may be difficult to obtain sufficient electrical performance of the circuit. On the other hand, if the thickness is too thick, the processing efficiency at the time of circuit production may be reduced. Metal foil is usually provided in roll form. The form of the metal foil used when manufacturing the printed wiring board of this invention is not specifically limited. When using the strip-shaped metal foil, its length is not particularly limited. In addition, the width is not particularly limited, but is preferably about 250 to 500 cm.

Examples of paper include wood-free paper, kraft paper, roll paper, cellophane, and the like. In addition, composite materials include glass epoxy and the like.

Considering the adhesion and durability of the adhesive composition, the base material should be polyester resin, polyamide resin, polyimide resin, polyamideimide resin, liquid crystal polymer, polyphenylene sulfide, Side-by-side polystyrene, polyolefin-based resin, fluorine-based resin, SUS steel plate, copper foil, aluminum foil, or glass epoxy.

＜Adhesive sheet＞ In the present invention, the adhesive sheet refers to a laminate obtained by laminating the above-mentioned laminate and the release substrate with an adhesive composition interposed therebetween. The specific structure can be, for example: laminate/adhesive layer/release substrate, or release substrate/adhesive layer/laminate/adhesive layer/release substrate. By laminating the release base material, it functions as a protective layer of the base material. In addition, by using the release base material, the release base material can be released from the adhesive sheet, and the adhesive layer can be transferred to another base material.

The adhesive sheet of the present invention can be obtained by applying the adhesive composition of the present invention to various laminates according to the usual method and drying them. In addition, if the release base material is attached to the adhesive layer after drying, it can be wound without set-off of the base material, excellent in runnability and sticky at the same time. Since the adhesive layer is protected, it is excellent in storage and easy to use. In addition, after coating on the release substrate and drying, if necessary to attach other release substrates, the adhesive layer itself can also be transferred to other substrates.

＜Release base material＞ The release base material is not particularly limited. For example, for example, a coating layer of clay, polyethylene, polypropylene and other interstitial agents is provided on both sides of Dowling paper, kraft paper, roll paper, cellophane, etc., and further on each of them. The coating layer is coated with silicone resin, fluorine, and alkyd release agents. In addition, various olefin films such as polyethylene, polypropylene, ethylene-α-olefin copolymer, and propylene-α-olefin copolymer can be used alone or coated with the above-mentioned release film on a film such as polyethylene terephthalate. Formed by film. Considering the release force of the release base material and the adhesive layer, silicone resin will have adverse effects on the low dielectric properties, etc., it is advisable to perform polypropylene gap filling treatment on both sides of the Daolin paper and use it on it Alkyd-based release agent, or using alkyd-based release agent on polyethylene terephthalate.

In addition, the method of coating the adhesive composition on the substrate in the present invention is not particularly limited, and examples include comma coater, reverse roll coater, and the like. Alternatively, an adhesive layer may be provided on the rolled copper foil or the polyimide film, which is the constituent material of the printed wiring board, directly or by transfer printing as needed. The thickness of the adhesive layer after drying can be appropriately changed according to the needs, and it is preferably in the range of 5-200 μm. If the thickness of the adhesive film is less than 5 μm, the adhesive strength will be insufficient. When it is 200 micrometers or more, drying is insufficient, for example, the residual solvent increases, and there exists a problem that swelling arises at the time of the press which manufactures a printed wiring board. The drying conditions are not particularly limited, and the residual solvent rate after drying is preferably 1% by mass or less. If it exceeds 1% by mass, there is a problem that, for example, the residual solvent foams and swells during pressing of a printed wiring board.

＜Printed Wiring Board＞ The "printed wiring board" in the present invention includes, as constituent elements, a laminate formed of a metal foil forming a conductive circuit and a resin base material. The printed wiring board is manufactured by conventionally known methods such as a subtractive process using a metallized laminate, for example. It is collectively referred to as the so-called flexible circuit board (FPC), flat cable, tape automatic bonding (TAB), etc., which are partially or completely covered with a covering film, screen printing ink, etc., as required. ) for circuit boards, etc.

The printed wiring board of the present invention can have any laminated structure that can be used as a printed wiring board. For example, it can be made into a printed wiring board composed of four layers: a base film layer, a metal foil layer, an adhesive layer, and a cover film layer. In addition, for example, a printed wiring board composed of five layers of a base film layer, an adhesive layer, a metal foil layer, an adhesive layer, and a cover film layer can be produced.

Moreover, it can also be set as the structure which laminated|stacked 2 or more said printed wiring boards as needed.

The adhesive composition of the present invention can be ideally used in each adhesive layer of a printed wiring board. In particular, if the adhesive composition of the present invention is used as an adhesive, it is not only compatible with low-polarity resin bases such as polyimide, polyester film, copper foil, and LCP that constitute printed wiring boards. The material also has high adhesion and can obtain solder heat resistance, and the adhesive layer itself has excellent low dielectric properties. Therefore, it is suitable as an adhesive composition used in coverlay films, laminated boards, copper foil with resin, and bonding sheets.

In the printed wiring board of this invention, arbitrary resin films conventionally used as a base material of a printed wiring board can be used for a base film. The resin of the base film can be exemplified: polyester resin, polyamide resin, polyimide resin, polyamideimide resin, liquid crystal polymer, polyphenylene sulfide, p-polystyrene, polyolefin-based Resins and fluorine-based resins, etc. Especially for low-polar substrates such as liquid crystal polymers, polyphenylene sulfide, polystyrene, and polyolefin resins, it also has excellent adhesion.

＜Covering Mask＞ As the cover film, any conventionally known insulating film can be used as the insulating film for printed wiring boards. For example, polyimide, polyester, polyphenylene sulfide, polyether sulfide, polyether ether ketone, polyaramid, polycarbonate, polyarylate, polyamide imide, Films made of various polymers such as liquid crystal polymers, parapolystyrene, and polyolefin-based resins. Preferably, it is a polyimide film or a liquid crystal polymer film.

The printed wiring board of the present invention can be manufactured using any conventionally known process except for using the materials of the above-mentioned layers.

In an ideal embodiment, a semi-finished product in which an adhesive layer is laminated on a covering film layer (hereinafter referred to as "a semi-finished product on the covering film side") is manufactured. On the other hand, it is a semi-finished product in which a metal foil layer is laminated on a base film layer to form a desired circuit pattern (hereinafter referred to as "2-layer semi-finished product on the base film side") or an adhesive layer is laminated on a base material film layer, and then laminated a metal foil layer on it to form a semi-finished product with a desired circuit pattern (hereinafter referred to as "3-layer semi-finished product on the base film side") (hereinafter referred to as a 2-layer semi-finished product on the base film side and a base film The three layers of semi-finished products on the side are collectively referred to as "substrate film side semi-finished products"). A 4-layer or 5-layer printed wiring board can be obtained by laminating the semi-finished product on the cladding film side and the semi-finished product on the base film side obtained in this way.

The semi-finished product on the base film side can be obtained, for example, by a manufacturing method comprising the following steps: (A) a step of coating the above-mentioned metal foil with a resin solution that becomes the base film, and drying the coating film initially, (B) A step of heat-treating and drying the laminate of the metal foil obtained in (A) and the preliminarily dried coating film (hereinafter referred to as "heat-treating and solvent-removing step").

The circuit in the metal foil layer can be formed using conventionally known methods. Either an additive process or a subtractive process can be used. It should be subtractive method.

The obtained substrate film-side semi-finished product can be directly used for bonding with the covering film-side semi-finished product. In addition, the release film can also be bonded and stored before being used for bonding with the covering film-side semi-finished product.

The semi-finished product on the cladding film side, for example, is manufactured by applying an adhesive to the cladding film. If necessary, crosslinking reaction in the applied adhesive can also be carried out. In an ideal embodiment, the adhesive layer is semi-hardened.

The obtained semi-finished product on the cladding film side can be directly used for lamination with the semi-finished product on the film side of the base material. In addition, the release film can also be laminated and stored before being used for lamination with the semi-finished product on the film side of the base material.

The semi-finished product on the base film side and the semi-finished product on the cladding film side refer to each of them being stored in the form of a roll, and then laminated to produce a printed wiring board. Arbitrary methods can be used for the bonding method, for example, bonding can be performed using a press, a roll, or the like. In addition, the two may be bonded together while heating using a method such as hot pressing or a heating roll device.

The semi-finished product on the reinforcing material side, for example, is a soft and rollable reinforcing material such as a polyimide film, it is suitable to manufacture it by applying an adhesive to the reinforcing material. In addition, for example, when using epoxy resin to harden a metal plate such as SUS, aluminum, or glass fiber, such as a hard and unwindable reinforcement plate, by applying the pre-coated adhesive to the release base It is suitable to manufacture the system by transfer coating. In addition, a crosslinking reaction in the applied adhesive can also be carried out as needed. In an ideal embodiment, the adhesive layer is semi-hardened.

The obtained semi-finished product on the reinforcing material side can be directly used for lamination with the back of the printed wiring board. In addition, the release film can also be laminated and stored before being used for lamination with the semi-finished product on the base film side.

The semi-finished product on the base film side, the semi-finished product on the cladding film side, and the semi-finished product on the reinforcing material side are all laminates for printed wiring boards in the present invention.

＜Electromagnetic wave shielding material＞ The electromagnetic wave shielding material of the present invention is an article provided with an adhesive layer formed using the above-mentioned adhesive composition of the present invention. In the present invention, an ideal aspect is that the adhesive layer is an electromagnetic wave shielding material containing a conductive filler. In this way, it is possible to prevent the malfunction of electronic equipment caused by the noise of electromagnetic waves, the leakage of confidential information caused by the capture of communication waves, etc. The method of manufacturing the electromagnetic wave shielding material of the present invention, for example, can be applied to a method of joining a conductive bonding sheet having an adhesive layer containing a conductive filler and a shielding material. [Example]

The following examples are given to illustrate the present invention in more detail. However, this invention is not limited to an Example. What is abbreviated as "parts" in Examples and Comparative Examples means "parts by mass".

(Physical property evaluation method) (acid value (modified polyolefin resin)) The acid value (mgKOH/g) in the present invention is that the resin sample is dissolved in toluene, and titrated in methanol solution of sodium methoxide with phenolphthalein as indicator.

(acid value (polyimide resin)) The acid value (mgKOH/g) in the present invention is that the resin sample is dissolved in N-methylpyrrolidone (NMP), and titrated in a methanol solution of sodium methoxide with phenolphthalein as an indicator.

(number average molecular weight (Mn)) The number average molecular weight in the present invention is a gel chromatography (hereinafter referred to as GPC) manufactured by Shimadzu Corporation (stock), standard substance: polystyrene resin, mobile phase: tetrahydrofuran, column: Shodex KF-802+KF- 804L+KF-806L, column temperature: 30°C, flow rate: 1.0ml/min, detector: RI detector).

(Determination of melting point and heat of fusion) The melting point (Tm) and heat of fusion (ΔH) in the present invention use a differential scanning calorimeter (hereinafter referred to as DSC, manufactured by TA Instruments Japan, Q-2000) to heat up and melt at a rate of 20°C/min, then cool Resinification, the value obtained by measuring the maximum temperature and area of the melting peak when the temperature is raised and melted again.

(logarithmic viscosity) This was dissolved in NMP so that the polymer concentration of the polyimide resin (b) might become 0.6 g/dl. At 30°C, the solution viscosity and solvent viscosity of the solution were measured with an Ubbelohde-type viscosity tube, and calculated using the following formula. Logarithmic viscosity (dl/g)=[ln(V1/V2)]/V3 V1: Calculated from the time for the solvent (NMP) to pass through the capillary of the Ubbelohde-type viscosity tube V2: Calculated from the time for the polymer solution to pass through the capillary of the Ubbelohde-type viscosity tube V3: polymer concentration (g/dl)

(1) Adhesive strength Apply the adhesive composition described below to a polyimide (PI) film (manufactured by KANEKA Co., Ltd., APICAL (registered trademark)) with a thickness of 12.5 μm so that the thickness after drying becomes 25 μm. , or an LCP film (manufactured by KURARAY Co., Ltd., Vecstar (registered trademark)) with a thickness of 25 μm was dried at 130° C. for 3 minutes. The adhesive film (B-stage product) thus obtained was bonded to a rolled copper foil (manufactured by JX Metal Co., Ltd., BHY series) with a thickness of 18 μm. Lamination is carried out in such a way that the glossy surface of the rolled copper foil is in contact with the adhesive layer, and is pressed at 160°C for 30 seconds under a pressure of 40kgf/cm ² to bond. Then, it heat-processed and hardened at 160 degreeC for 1 hour, and obtained the sample for peeling strength evaluation. The peel strength is to stretch the film at 25°C, and perform a 90° peel test at a tensile speed of 50mm/min, and measure the peel strength. This test indicates the adhesive strength at room temperature. <Evaluation criteria> ◎: 1.0 N/mm or more ○: 0.8 N/mm or more and less than 1.0 N/mm △: 0.5 N/mm or more and less than 0.8 N/mm ×: less than 0.5 N/mm

(2) Solder heat resistance Prepare the sample in the same way as above (1), aging the 2.0cm×2.0cm sample piece at 23°C for 2 days, floating in the solder bath melted at 280°C for 10 seconds, and confirming whether there is expansion or other appearance Variety. ＜Evaluation criteria＞ ◎: No expansion ○: There is some swelling △: There is a lot of swelling ×: Swelling and discoloration

(3) Low dielectric properties (relative permittivity (ε _c ) and dielectric tangent (tanδ)) The adhesive composition described later was coated on Teflon ( Registered trademark) sheet, dried at 130°C for 3 minutes. Then, it was heat-treated at 160° C. for 1 hour to make it harden, and an adhesive resin sheet for testing was obtained. The obtained test adhesive resin sheet was cut into 8 cm x 3 mm strip-shaped samples to obtain test samples. The relative permittivity (εc) and dielectric tangent (tanδ) were measured using a network analyzer (manufactured by Anritsu Corporation) by the cavity resonator perturbation method at a temperature of 23°C and a frequency of 10GHz. The obtained relative permittivity and dielectric tangent were evaluated as follows. <Evaluation criteria for relative dielectric constant> ◎: 2.3 or less ○: More than 2.3 and 2.6 or less △: More than 2.6 and 3.0 or less ×: More than 3.0 <Evaluation criteria for dielectric tangent> ◎: 0.008 or less ○: More than 0.008 and 0.01 or less △: more than 0.01 and 0.02 or less ×: more than 0.02

(4) Absorbance at 355nm The adhesive composition described later was coated on a Teflon (registered trademark) sheet with a thickness of 100 μm so that the thickness after drying and hardening was 25 μm, and dried at 130° C. for 3 minutes. Then, it was heat-treated at 140° C. for 4 hours to make it harden, and an adhesive resin sheet for testing was obtained. Using the obtained adhesive resin sheet, the absorbance at 355 nm was measured with an ultraviolet-visible spectrophotometer V-650 (manufactured by JASCO Corporation). ＜Evaluation criteria＞ ○: Abs 0.3 or more. Δ: Abs 0.2 or more and less than 0.3. ×: Abs is less than 0.2.

(5) Compatibility The adhesive composition described later was applied to a polypropylene film with a thickness of 50 μm so that the thickness after drying and hardening was 25 μm, and dried at 130° C. for 3 minutes. The appearance of the obtained adhesive resin sheet was confirmed visually. ＜Evaluation criteria＞ ○: There is no foreign matter and unevenness. Δ: Slight unevenness is observed. ×: There are foreign substances, unevenness, or coating failure.

(Production example of modified polyolefin resin (a)) (Manufacturing example 1) 100 parts by mass of propylene-butene copolymer (manufactured by Mitsui Chemicals "TAFMER (registered trademark) XM7080"), 150 parts by mass of toluene, 19 parts by mass of maleic anhydride, and di-tert-butyl peroxide were added to a 1 L autoclave. After heating up to 140 degreeC, stirring 6 mass parts, it stirred further for 3 hours. Thereafter, after cooling the obtained reaction liquid, it was poured into a container containing a large amount of methyl ethyl ketone to precipitate a resin. Thereafter, the acid-modified propylene-butene copolymer obtained by graft polymerization of maleic anhydride, (poly) maleic anhydride and low molecular weight substances are separated and purified by centrifuging the liquid containing the resin. Thereafter, by drying at 70° C. for 5 hours under reduced pressure, a maleic anhydride-modified propylene-butene copolymer (a-1, acid value 19 mgKOH/g, number average molecular weight 25,000, Tm80) of a modified polyolefin resin was obtained. ℃, △H35J/g).

(Manufacturing example 2) The feed amount of maleic anhydride was changed to 14 parts by mass, except that, in the same manner as in Production Example 1, the maleic anhydride-modified propylene-butene copolymer ( a-2, acid value 14mgKOH/g, number average molecular weight 30,000, Tm78°C, ΔH25J/g).

(Manufacturing example 3) The feed amount of maleic anhydride was changed to 11 parts by mass, except that, in the same manner as in Production Example 1, a maleic anhydride-modified propylene-butene copolymer ( a-3, acid value 11mgKOH/g, number average molecular weight 33,000, Tm80℃, ΔH25J/g).

(Manufacturing example 4) The charging amount of maleic anhydride was changed to 6 parts by mass, except that, in the same manner as in Production Example 1, the maleic anhydride-modified propylene-butene copolymer ( a-4, acid value 7mgKOH/g, number average molecular weight 35,000, Tm82℃, ΔH25J/g).

(Manufacturing example of polyimide resin (b)) (Manufacturing example 5) Trimellitic anhydride (manufactured by Polynt) 17.3 parts by mass, polybutadiene diol (trade name GI-1000 manufactured by Nippon Soda, molecular weight 1500) 315.0 parts by mass, 4,4'-diphenylmethane diisocyanate (MDI ) (trade name Millionate MT manufactured by Tosoh Corporation) 75.9 parts by mass was placed in a flask, and dissolved in 611.1 parts by mass of cyclohexanone. Furthermore, 0.69 parts by mass of DBU was added as a catalyst. Afterwards, by stirring under a nitrogen flow, it was reacted at 130°C for 5 hours, and then cooled to room temperature to obtain a non-volatile content (solid content) of 40% by mass, an acid value of 4.6mgKOH/g, and a logarithmic viscosity of 0.190dl /g of polyimide resin (b-1) solution.

(Manufacturing example 6) 17.3 parts by mass of trimellitic anhydride (manufactured by Polynt), 117.6 parts by mass of dimer glycol (trade name Pripol2033, manufactured by Croda Japan, molecular weight 560), 4,4'-diphenylmethane diisocyanate (MDI) (Tosoh 75.1 parts by mass of the product (manufactured under the trade name Millionate MT) was placed in a flask, and dissolved in 157.5 parts by mass of cyclohexanone and 157.5 parts by mass of N-methylpyrrolidone. Furthermore, 0.69 parts by mass of DBU was added as a catalyst. Afterwards, by stirring under nitrogen flow, it was reacted at 130° C. for 6 hours, and then cooled to room temperature to obtain 40% by mass of non-volatile content (solid content), acid value 6.7 mgKOH/g, and logarithmic viscosity 0.168 dl /g of polyimide resin (b-2) solution.

(Manufacturing example 7) Feed 210.00 parts by mass of 3,3',4,4'-diphenylketonetetracarboxylic dianhydride (manufactured by Evonik Japan), 1000.80 parts by mass of cyclohexanone, and 201.60 parts by mass of methylcyclohexane, and heat to 60 ℃. Next, 341.67 parts by mass of dimer diamine (trade name Priamine 1075 manufactured by Croda Japan, molecular weight 549) was added dropwise, followed by an imidization reaction at 140°C for 10 hours, and cooled to room temperature to obtain non-volatile components. (solid content) 30% by mass, an acid value of 5.6 mgKOH/g, and a polyimide resin (b-3) solution of a logarithmic viscosity of 0.240 dl/g.

(Manufacturing example 8) 34.6 parts by mass of trimellitic anhydride (manufactured by Polynt), 235.2 parts by mass of dimer acid (trade name Pripol1009, manufactured by Croda Japan, molecular weight 566), 4,4'-diphenylmethane diisocyanate (MDI) (manufactured by Tosoh) as an isocyanate component 145.7 parts by mass of product name Millionate MT) was charged in a flask, and dissolved in 623.1 parts by mass of N-methylpyrrolidone. Furthermore, 1.37 parts by mass of DBU was added as a catalyst. Afterwards, by stirring under nitrogen flow, it was reacted at 130° C. for 5 hours, and then cooled to room temperature to obtain 40% by mass of non-volatile content (solid content), acid value 10.4 mgKOH/g, and logarithmic viscosity 0.318 dl /g of polyimide resin (b-4) solution.

(Manufacturing example 9) 28.8 parts by mass of trimellitic anhydride (manufactured by Polynt), 225.0 parts by mass of polybutadiene diol (trade name GI-1000 manufactured by Nippon Soda), and 4,4'-diphenylmethane diisocyanate (MDI) (To 75.1 parts by mass of (manufactured under the trade name Millionate MT) was placed in a flask, and dissolved in 236.8 parts by mass of cyclohexanone and 236.8 parts by mass of N-methylpyrrolidone. Afterwards, by stirring under a nitrogen stream, react at 130° C. for 5 hours, and then cool to room temperature to obtain 40% by mass of non-volatile content (solid content), acid value 11.8 mgKOH/g, and logarithmic viscosity 0.139 dl /g of polyimide resin (b-5) solution.

(Manufacturing example 10) 17.3 parts by mass of trimellitic anhydride (manufactured by Polynt), 420.0 parts by mass of polyester diol (trade name ODX-2044 manufactured by DIC, molecular weight 2000), 4,4'-diphenylmethane diisocyanate (MDI) as an isocyanate component (Tong 72.8 parts by mass of the product name Millionate MT (manufactured by Cao) was placed in a flask, and dissolved in 765.2 parts by mass of cyclohexanone. Afterwards, by stirring under a nitrogen flow, it was reacted at 130° C. for 8 hours, and then cooled to room temperature to obtain a non-volatile content (solid content) of 40% by mass, an acid value of 8.4 mgKOH/g, and a logarithmic viscosity of 0.250 dl. /g of polyimide resin (b-6) solution.

(Manufacturing example 11) 360.0 parts by mass of polybutadiene diol (trade name GI-1000 manufactured by Nippon Soda), 8.89 parts by mass of 2,2-bis(hydroxymethyl)butyric acid, and 4,4'-diphenylmethane as an isocyanate component 74.2 parts by mass of diisocyanate (MDI) (trade name Millionate MT manufactured by Tosoh) was put in a flask, and dissolved in 664.8 parts by mass of cyclohexanone. Furthermore, 0.69 parts by mass of DBU was added as a catalyst. Afterwards, by stirring under nitrogen flow, it was reacted at 130° C. for 5 hours, and then cooled to room temperature to obtain 40% by mass of non-volatile content (solid content), acid value 5.6 mgKOH/g, and logarithmic viscosity 0.176 dl /g of polyurethane resin (b-7) solution.

The curing agent (c) used in Table 1 is as follows. (epoxy resin) c-1: Dicyclopentadiene type epoxy resin: HP-7200H (manufactured by DIC Corporation, epoxy equivalent 278g/eq) c-2: Cresol novolac type epoxy resin: jER-152 (manufactured by Mitsubishi Chemical, epoxy equivalent 177g/eq) c-3: Epoxypropylamine type epoxy resin: jER-630 (manufactured by Mitsubishi Chemical, epoxy equivalent 98g/eq) (polyisocyanate) c-4: Isocyanurate body of hexylene diisocyanate: SUMIDUR (registered trademark) N-3300 (manufactured by Bayer Corporation) (polycarbodiimide) c-5: Carbodiimide resin: V-09GB (manufactured by Nisshinbo Chemical Co., Ltd. Carbodiimide equivalent weight 216g/eq) c-6: Carbodiimide resin: V-03 (manufactured by Nisshinbo Chemical Co., Ltd. Carbodiimide equivalent weight: 209 g/eq)

<Example 1> The modified polyolefin resin (a-1) was dissolved in an organic solvent (methylcyclohexane/toluene=80/20 (volume ratio)), and a solution having a solid content concentration of 20% by mass was prepared. The curing agent (c-1) (epoxy resin, HP-7200H) was dissolved in an organic solvent (methyl ethyl ketone), and a solution having a solid content concentration of 70% by mass was prepared. Each was blended so that the modified polyolefin resin (a-1) became 80 parts by solid mass, the polyimide resin (b-1) became 20 parts by mass solid, and the curing agent (c-1) became 10 parts by mass solid. solution to obtain an adhesive composition. The evaluation results of adhesive strength, solder heat resistance, low dielectric properties, absorbance at 355 nm and compatibility of the obtained adhesive composition are shown in Table 1.

<Examples 2-23, Comparative Examples 1-5> Change the blending amount (solid mass parts) of modified polyolefin resin (a), polyimide resin (b) and hardener (c) as shown in Table 1, except that, it is based on the same example 1 Carry out Examples 2-21 and Comparative Examples 1-5 in the same manner. The evaluation results of adhesive strength, solder heat resistance, low dielectric properties, 355nm absorbance and compatibility are shown in Table 1.

[Table 1]

As can be seen from Table 1, Examples 1-23, in terms of adhesives, have excellent adhesion with polyimide (PI) and LCP, solder heat resistance, and also have excellent adhesion with copper foil. Adhesiveness, solder heat resistance, and the absorbance at 355nm, which is an index of laser processability, also exhibit good absorption. In contrast, Comparative Example 1 had low absorbance at 355 nm and poor laser processability because no polyimide resin (b) was blended. In Comparative Example 2, since no curing agent (c) was blended, the solder heat resistance was poor. In Comparative Example 3, since the modified polyolefin resin (a) was not blended, the adhesiveness was poor. In Comparative Example 4, since the polyimide resin (b) does not contain polyolefin polyols, dimer acid derivatives, etc., the low dielectric properties and compatibility are poor. In Comparative Example 5, since component (b) is a polyurethane resin that does not contain imide groups, its absorbance at 355 nm is low and its laser processability is poor. [industrial availability]

The adhesive composition of the present invention not only has high adhesion to conventional polyimide, liquid crystal polymer, and metal substrates such as copper foil, but also can obtain high solder heat resistance and low dielectric properties. And laser processing is also excellent. With the adhesive composition of the present invention, an adhesive sheet and a laminate obtained by bonding the same can be obtained. Due to the above characteristics, it is useful in flexible printed wiring board applications, especially in FPC applications that require low dielectric properties (low dielectric constant, low dielectric tangent) in the high-frequency region, and electromagnetic wave shielding materials. it works.

Claims (10)

An adhesive composition comprising modified polyolefin resin (a), polyimide resin (b) and hardener (c); The polyimide resin (b) has at least one selected from the group consisting of polyolefin polyol, polyolefin polyamine, polyolefin polycarboxylic acid, dimer glycol, dimer diamine and dimer acid as Structural units. The adhesive composition according to claim 1, wherein the acid value of the modified polyolefin resin (a) is 5-30 mgKOH/g. The adhesive composition according to claim 1 or 2, wherein the hardener (c) contains at least one selected from the group consisting of epoxy resin, polyisocyanate, and polycarbodiimide. The adhesive composition according to Claim 1 or 2, wherein 50 to 95 parts by mass of modified polyolefin resin (a) and polyimide resin (b) are contained in an amount of 50 to 95 parts by mass relative to the total of 100 parts by mass of modified polyolefin resin (a) and polyimide resin (b). Olefin resin (a). As in the adhesive composition of claim 1 or 2, its relative dielectric constant at 10 GHz is less than 3.0. The adhesive composition according to claim 1 or 2, wherein, relative to the total of 100 parts by mass of the modified polyolefin resin (a) and the polyimide resin (b), the content of the hardener (c) is 0.5 ~60 parts by mass. An adhesive sheet having a layer composed of the adhesive composition according to claim 1 or 2. An electromagnetic wave shielding material having a layer composed of the adhesive composition according to claim 1 or 2. A laminate having a layer composed of the adhesive composition according to claim 1 or 2. A printed wiring board comprising the laminate according to claim 9 as a constituent element.