JP7287545B2 - Low dielectric adhesive composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a low-dielectric adhesive composition which not only has low dielectric properties and good adhesiveness, but also excellent wet-heat solder heat resistance and laser processability. More particularly, the present invention relates to an adhesive composition suitable for use in bonding electronic components and the like, particularly for manufacturing products related to flexible printed wiring boards (hereinafter also referred to as "FPC").

With the miniaturization and weight reduction of electronic devices, the applications for bonding electronic parts and the like are diversifying, and the demand for laminates with adhesive layers is increasing. For example, FPC-related products, which are one of the electronic components, include flexible copper-clad laminates and flexible copper-clad laminates made by bonding copper foil to polyimide film, polyethylene naphthalate film, liquid crystal polymer (LCP) film, etc. Flexible printed wiring board with electronic circuit, flexible printed wiring board with reinforcing plate, flexible printed wiring board and reinforcing plate, multi-layer board, substrate film, flexible copper clad laminate and flexible printed wiring board There is a flexible flat cable (hereinafter, also referred to as "FFC") in which a copper wiring is laminated to a flexible flat cable, etc., and a laminate with an adhesive layer is used when manufacturing these electronic components.

Specifically, when manufacturing the FPC, a laminate with an adhesive layer, which is called a “coverlay film”, is usually used to protect the wiring portion. This coverlay film comprises an insulating resin layer and an adhesive layer formed on the surface thereof, and a polyimide resin composition is widely used for forming the insulating resin layer. Then, a flexible printed wiring board is manufactured by, for example, using a hot press or the like to attach a coverlay film to the surface having the wiring portion via an adhesive layer. At this time, the adhesive layer of the coverlay film must have strong adhesiveness to both the wiring portion and the base film. In addition, mobile communication devices such as mobile phones and information equipment terminals, for which demand has been rapidly increasing in recent years, need to process a large amount of data at high speed, so signal frequencies are increasing. With the increase in signal speed and signal frequency, adhesives used in FPC-related products are required to have electrical properties (low dielectric constant and low dielectric loss tangent) in a high frequency region.

In order to meet the demand for such electrical properties, for example, Patent Document 1 discloses a cover comprising a vinyl compound such as oligophenylene ether, a polystyrene-poly(ethylene/butylene) block copolymer, an epoxy resin, and a curing catalyst. A ray film is disclosed. Further, in Patent Document 2, a styrene-based elastomer containing a carboxyl group and an epoxy resin are included, and the content of the styrene-based elastomer and the epoxy resin is within a predetermined range, and the adhesive cured product measured at a frequency of 1 GHz has been disclosed an adhesive composition having a dielectric constant of less than 3.0. Further, Patent Document 3 discloses a modified polyolefin resin obtained by graft-modifying an unmodified polyolefin resin with a modifier containing an α,β-unsaturated carboxylic acid or a derivative thereof, and an epoxy resin. An adhesive composition is disclosed in which the dielectric constant of the cured adhesive measured at a frequency of 1 GHz is less than 2.5 by setting the content within a predetermined range.

JP 2011-68713 A International Publication No. 2016/017473 International Publication No. 2016/047289

However, although the adhesive coverlay films described in Patent Documents 1 to 3 have relatively good low dielectric properties and adhesiveness, they have the problem of poor wet heat solder heat resistance and laser processability.

The present invention has been made in view of the above problems, and provides a low dielectric adhesive composition that not only has low dielectric properties and good adhesiveness, but also has excellent wet heat solder heat resistance and laser processability. intended to provide

The present inventors found that an adhesive composition containing, as resin components, a polyolefin resin (A), an alicyclic skeleton-containing resin (B), and an epoxy resin (C), the polyolefin resin (A) and By using a resin containing a carboxyl group and/or a derivative thereof as at least one of the alicyclic skeleton-containing resins (B), not only low dielectric properties and good adhesiveness but also wet heat solder heat resistance and laser The inventors have found that an adhesive composition having excellent workability can be obtained, and have completed the present invention.

That is, according to each aspect of the present invention, the following adhesive compositions are provided.
1. containing a polyolefin resin (A), an alicyclic skeleton-containing resin (B), and an epoxy resin (C), at least one of the polyolefin resin (A) and the alicyclic skeleton-containing resin (B) contains a carboxyl group and/or a derivative thereof, and the dielectric constant of the cured product is less than 2.5.
2. The total content of the polyolefin resin (A) and the alicyclic skeleton-containing resin (B) is 50 parts by mass or more with respect to 100 parts by mass of the solid content of the adhesive composition, and the epoxy resin (C ) is 1 to 20 parts by mass per 100 parts by mass of the total content of the polyolefin resin (A) and the alicyclic skeleton-containing resin (B). The adhesive composition according to .
3. The content ratio of the polyolefin resin (A) and the alicyclic skeleton-containing resin (B) is [polyolefin resin (A)]:[alicyclic skeleton-containing resin (B)]=5: 95 to 95:5, the above 1. or 2. The adhesive composition according to .
4. 1. The polyolefin resin (A) contains a carboxyl group and/or a derivative thereof, and has an acid value of 0.1 to 50 mgKOH/g. ~3. The adhesive composition according to any one of .
5. 1. The polyolefin resin (A) is at least one selected from the group consisting of ethylene-propylene copolymers, propylene-butene copolymers and ethylene-propylene-butene copolymers. ~ 4. The adhesive composition according to any one of .
6. 1. The alicyclic skeleton-containing resin (B) contains a carboxyl group and/or a derivative thereof, and the acid value of the alicyclic skeleton-containing resin (B) is 0.1 to 50 mgKOH/g. ~ 5. The adhesive composition according to any one of .
7. The alicyclic skeleton-containing resin (B) has an alicyclic skeleton in the side chain of 1. above. ~6. The adhesive composition according to any one of .
8. 1. above, wherein the epoxy resin (C) is a polyfunctional epoxy resin containing a dicyclopentadiene skeleton. ~7. The adhesive composition according to any one of .
9. 1. The dielectric loss tangent of the cured product measured at a frequency of 1 GHz is less than 0.01. ~8. The adhesive composition according to any one of .
10. 1. The solder heat resistance temperature after humidifying for 12 hours at a temperature of 40° C. and a humidity of 90% is 260° C. or higher. ~ 9. The adhesive composition according to any one of .
11. Furthermore, the above 1. contains an ultraviolet absorber. ~ 10. 1. The adhesive composition according to claim 1.
12. 1. It is for a flexible copper-clad laminate. ~ 11. The adhesive composition according to .
13. 1. It is for a flexible flat cable. ~12. The adhesive composition according to any one of .
14. 1 above. ~ 13. The adhesive layer obtained using the adhesive composition according to any one of the polyimide film, polyether ether ketone film, polyphenylene sulfide film, aramid film, polyethylene naphthalate film, liquid crystal polymer film, polyethylene terephthalate A coverlay film characterized by being formed on at least one side of a film selected from a film, a polyethylene film, a polypropylene film, a TPX film and a fluororesin film.
15. 1 above. ~ 14. A bonding sheet comprising an adhesive layer obtained using the adhesive composition according to any one of 1 above and formed on at least one side of a release film.

The adhesive composition of the present invention contains, as resin components, a polyolefin resin (A), an alicyclic skeleton-containing resin (B), and an epoxy resin (C). Since at least one of the formula skeleton-containing resins (B) contains a carboxyl group and/or a derivative thereof, the dielectric properties are low, the adhesiveness is good, and the wet heat solder heat resistance and laser processability are also excellent. .

An embodiment of the present invention is described below, but the present invention is not limited to this.

1. Adhesive Composition The adhesive composition of the present invention is an adhesive composition containing a polyolefin resin (A), an alicyclic skeleton-containing resin (B), and an epoxy resin (C), At least one of the polyolefin resin (A) and the alicyclic skeleton-containing resin (B) contains a carboxyl group and/or a derivative thereof, and the dielectric constant of the cured product is less than 2.5. . The matters specifying the present invention will be specifically described below.

1-1. Polyolefin resin (A)
The polyolefin resin (A) is one of the main components of the adhesive composition, and is a component that imparts electrical properties in addition to adhesion and flexibility of the cured product. This polyolefin-based resin is not particularly limited as long as it has a structural unit derived from an olefin. Homopolymers or copolymers of 20 or less are preferably used. In the present invention, homopolymers or copolymers of olefins having 2 to 6 carbon atoms are particularly preferred. The content ratio of the structural unit in the polyolefin resin can be arbitrarily selected, but when performing adhesion to difficult-to-adhere adherends, the polyolefin resin is an ethylene-propylene copolymer or a propylene-butene copolymer. Alternatively, it is preferably an ethylene-propylene-butene copolymer. In order to obtain particularly excellent adhesiveness, it is preferable to use a polyolefin resin having a propylene unit content of 50 mol % or more and 98 mol % or less. When the propylene unit content is within the above range, flexibility can be imparted to the bonded portion after the two members are bonded together. Moreover, the molecular weight of the polyolefin resin is not particularly limited. The polyolefin-based resin (A) does not include the alicyclic skeleton-containing resin (B) and the epoxy resin (C) described later.

In order to improve adhesiveness and wet heat soldering heat resistance, the polyolefin resin (A) is preferably acid-modified to contain carboxyl groups and/or derivatives thereof. Here, the above-mentioned "derivatives thereof" include acid anhydrides in which water molecules are removed from two carboxyl groups and are bonded together, as well as other forms derived from carboxyl groups such as acid halides, amides, imides and esters. Forms are also included, but the preferred derivative is the acid anhydride. In this specification, a polyolefin resin containing a carboxyl group and/or a derivative thereof may also be referred to as "acid-modified polyolefin resin", "modified polyolefin resin", or "carboxyl group-containing polyolefin resin". be.
The acid-modified polyolefin resin is a resin having a portion derived from an unmodified polyolefin resin and a graft portion derived from a modifier. It can be obtained by graft polymerizing a modifier containing an unsaturated carboxylic acid or a derivative thereof. A modified polyolefin resin can be produced by graft polymerization by a known method, and a radical initiator may be used in the production. Methods for producing the modified polyolefin resin include, for example, a solution method in which an unmodified polyolefin resin is heated and dissolved in a solvent such as toluene and the modifier and the radical initiator are added, a Banbury mixer, a kneader, an extruder, and the like. is used to melt-knead an unmodified polyolefin resin, a modifier and a radical initiator. The method of using the unmodified polyolefin resin, modifier, and radical initiator is not particularly limited, and they may be added to the reaction system all at once or sequentially.

When producing the above-mentioned modified polyolefin resin, a modification aid for improving the grafting efficiency of the α,β-unsaturated carboxylic acid, a stabilizer for adjusting the resin stability, etc. can be further used. .

Modifiers, radical initiators and modification aids that are described below for the alicyclic skeleton-containing resin (B) can be used in the same manner.

As described above, the modified polyolefin resin has at least a graft portion derived from the modifying agent. The content ratio of the graft portion contained in the modified polyolefin resin (hereinafter also referred to as "graft mass") will be described below.

The modified polyolefin resin has a graft portion derived from α,β-unsaturated carboxylic acid or its derivative. In the modified polyolefin resin, the graft mass of the graft portion derived from α,β-unsaturated carboxylic acid or derivative thereof is, from the viewpoint of adhesion, 0.1 to 20% by mass relative to 100% by mass of the modified polyolefin resin. %, more preferably 0.2 to 18% by mass. When the graft mass is 0.1% by mass or more, the solubility in a solvent is excellent, and the adhesiveness to an adherend made of metal or the like is particularly excellent. Further, when the graft mass is 20% by mass or less, sufficient adhesiveness to an adherend made of resin or the like can be obtained.

The graft mass derived from the α,β-unsaturated carboxylic acid or derivative thereof in the modified polyolefin resin can be determined by alkaline titration, but the α,β-unsaturated carboxylic acid derivative does not have an acid group. In the case of an imide or the like, the graft mass can be determined by Fourier transform infrared spectroscopy.

When the modified polyolefin resin contains a graft portion derived from a (meth)acrylic acid ester represented by the following formula (3), the graft mass is 0.1 to 0.1 to 100% by mass of the modified polyolefin resin. It is preferably 30% by mass, more preferably 0.3 to 25% by mass. When the graft mass is 0.1 to 30% by mass, it has excellent solubility in solvents, excellent compatibility with other resins or elastomers described later, and further improves adhesion to adherends. be able to.

When the modifier contains a (meth)acrylic acid ester represented by the following formula (3), the graft mass in the obtained modified polyolefin resin can be determined by Fourier transform infrared spectroscopy.

The weight average molecular weight (Mw) of the modified polyolefin resin (A) is preferably 30,000 to 250,000, more preferably 50,000 to 200,000. Due to the weight average molecular weight (Mw) of 30,000 to 250,000, it has excellent solubility in solvents and initial adhesion to the adherend, and also has solvent resistance in the adhesion part after adhesion. It can be an excellent adhesive composition.

The acid value of the acid-modified polyolefin resin (A) is preferably 0.1 to 100 mgKOH/g, more preferably 0.5 to 70 mgKOH/g, and more preferably 1.0 to 50 mgKOH/g. It is even more preferable to have When the acid value is 0.1 to 100 mgKOH/g, the adhesive composition is sufficiently cured, and good adhesiveness, heat resistance and resistance to resin bleeding can be obtained.

The total content of the polyolefin resin (A) and the alicyclic skeleton-containing resin (B) is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, relative to 100 parts by mass of the solid content of the adhesive composition. is more preferable. When the content is 50 parts by mass or more, the flexibility of the adhesive layer is improved, and warping of the laminate can be suppressed. The total content of the polyolefin resin (A) and the alicyclic skeleton-containing resin (B) is preferably 99 parts by mass or less per 100 parts by mass of the solid content of the adhesive composition.
In addition, the content ratio of the polyolefin resin (A) and the alicyclic skeleton-containing resin (B) is [polyolefin resin (A)]:[alicyclic skeleton-containing resin (B)]=5: It is preferably 95 to 95:5, more preferably [polyolefin resin (A)]:[alicyclic skeleton-containing resin (B)] = 10:90 to 90:10. When the content ratio is in this range, a high improvement effect of moist heat soldering heat resistance can be obtained.

1-2. Alicyclic skeleton-containing resin (B)
As the alicyclic skeleton-containing resin (B), a polymer containing a compound (b) having an alicyclic skeleton as a monomer unit, in other words, a compound having a saturated or unsaturated cyclic hydrocarbon skeleton (b ), and polymers containing structural units derived from. The polymer may be a homopolymer or a copolymer. When the compound (b) is a compound (b) having an unsaturated cyclic hydrocarbon skeleton such as styrene or norbornene, the alicyclic skeleton of the alicyclic skeleton-containing resin (B) is It is produced by a polymerization reaction or a hydrogenation reaction. The alicyclic skeleton-containing resin (B) may have an alicyclic skeleton in at least one of a main chain and a side chain, preferably a main chain of a linear hydrocarbon chain such as an olefinic polymer and the like. / Alternatively, a resin that has an alicyclic skeleton in its side chain, exhibits thermoplasticity as a single resin, and is amorphous is exemplified. The alicyclic skeleton-containing resin (B) does not include the epoxy resin (C) described later.

Examples of the compound (b) having an alicyclic skeleton include polycyclic cyclic olefins and monocyclic cyclic olefins. Polycyclic cyclic olefins include norbornene, methylnorbornene, dimethylnorbornene, ethylnorbornene, ethylidenenorbornene, butylnorbornene, dicyclopentadiene, dihydrodicyclopentadiene, methyldicyclopentadiene, dimethyldicyclopentadiene, tetracyclododecene, methyltetracyclododecene, dimethylcyclotetradodecene, tricyclopentadiene, tetracyclopentadiene and the like. In addition, monocyclic cyclic olefins include cyclobutene, cyclopentene, cyclooctene, cyclooctadiene, cyclooctatriene, cyclododecatriene and the like.

Examples of the alicyclic skeleton-containing resin (B) having an alicyclic skeleton in the side chain include saturated alicyclic hydrocarbon compounds (vinylcycloalkanes) having a vinyl group, such as vinylcyclohexane and 3-methylisopropenylcyclohexane. and a hydrogenated block copolymer comprising a hydrogenated vinyl aromatic polymer block A obtained by vinyl addition polymerization of and an olefin polymer block B mainly composed of an olefin compound such as ethylene. The hydrogenated vinyl aromatic polymer block A may contain monomer components other than the hydrogenated vinyl aromatic compound in a proportion of 50 mass % or less of the total weight of the block A, for example. The olefin polymer block B may contain monomer components other than the olefin compound at a rate of 50% by mass or less of the total weight of the block B, for example. A hydrogen atom bonded to an alicyclic skeleton such as a cyclohexane ring of the hydrogenated vinyl aromatic polymer block A may be substituted with a methyl group, a butyl group, a chlorine atom, or the like. As the olefin compound, in addition to ethylene, ethylene, propylene, isobutylene, 1-butene, 1-pentene, 4-methyl-1-pentene and the like can also be used.

As the alicyclic skeleton-containing resin (B) having an alicyclic skeleton in the main chain, for example, a block mainly composed of an ethylene or α-olefin polymer and norbornene or and cycloolefin polymers (COPs) or cycloolefin copolymers (COCs) comprising blocks based on polymers of cyclic alkenes such as derivatives thereof. Examples of α-olefins include α-olefins having 3 to 12 carbon atoms.

（式中、ｍ≧１、ｎ≧０、Ｒ_１は水素または炭素数１～１０のアルキル基、Ｒ_２およびＲ_３はそれぞれ独立に水素または炭素数１～６のアルキル基）

(Wherein, m ≥ 1, n ≥ 0, R ₁ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms)

Specific examples of the alicyclic skeleton-containing resin (B) having an alicyclic skeleton in the main chain include, for example, TOPAS (trade name: manufactured by Polyplastics Co., Ltd.), which is a cycloolefin copolymer obtained by copolymerizing norbornene and ethylene. and APEL (trade name: Mitsui Chemicals, Inc.), ARTON (trade name: manufactured by JSR Corporation), which is a cycloolefin copolymer obtained by hydrogenating various cyclic monomers after ring-opening metathesis polymerization, and ZEONEX. (trade name: manufactured by Zeon Corporation) and ZEONOR (trade name: manufactured by Zeon Corporation).

In order to improve adhesiveness and wet heat soldering heat resistance, the alicyclic skeleton-containing resin (B) is preferably modified with an acid to contain a carboxyl group and/or a derivative thereof. In the present invention, at least one of the polyolefin-based resin (A) and the alicyclic skeleton-containing resin (B) may contain a carboxyl group and/or a derivative thereof. Groups and/or derivatives thereof are preferably contained, and it is more preferred that both the polyolefin resin (A) and the alicyclic skeleton-containing resin (B) contain carboxyl groups and/or derivatives thereof. Here, the above-mentioned "derivatives thereof" include acid anhydrides in which water molecules are removed from two carboxyl groups and are bonded together, as well as other forms derived from carboxyl groups such as acid halides, amides, imides and esters. Forms are also included, but the preferred derivative is the acid anhydride. In the present specification, an alicyclic skeleton-containing resin containing a carboxyl group and/or a derivative thereof is referred to as an "acid-modified alicyclic skeleton-containing resin", a "modified alicyclic skeleton-containing resin", or a "carboxyl group-containing resin." It may also be referred to as "resin containing alicyclic skeleton".
The acid-modified alicyclic skeleton-containing resin is a resin having a portion derived from an unmodified alicyclic skeleton-containing resin and a graft portion derived from a modifier, and is preferably a resin containing an unmodified alicyclic skeleton. It can be obtained by graft polymerizing a modifier containing an α,β-unsaturated carboxylic acid or a derivative thereof in the presence of a resin. The modified alicyclic skeleton-containing resin can be produced by graft polymerization by a known method, and a radical initiator may be used during the production. Examples of the method for producing the modified alicyclic skeleton-containing resin include a solution method in which an unmodified alicyclic skeleton-containing resin is heated and dissolved in a solvent such as toluene, and the modifier and the radical initiator are added, or a Banbury mixer. , a kneader, an extruder, or the like to melt-knead the unmodified alicyclic skeleton-containing resin, the modifier, and the radical initiator. The method of using the unmodified alicyclic skeleton-containing resin, modifier, and radical initiator is not particularly limited, and they may be added to the reaction system all at once or sequentially. When producing the modified alicyclic skeleton-containing resin, a modification aid for improving the grafting efficiency of the α,β-unsaturated carboxylic acid, a stabilizer for adjusting the resin stability, etc. are further used. be able to.

Modifiers include α,β-unsaturated carboxylic acids and their derivatives. α,β-unsaturated carboxylic acids include maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, aconitic acid, norbornene dicarboxylic acid and the like. Derivatives of unsaturated polycarboxylic acids include acid anhydrides, acid halides, amides, imides and esters. As the modifier, itaconic anhydride, maleic anhydride, aconitic anhydride and citraconic anhydride are preferable, and itaconic anhydride and maleic anhydride are particularly preferable in terms of adhesion. When a modifier is used, it may be one or more selected from α,β-unsaturated carboxylic acids and derivatives thereof, and a combination of one or more α,β-unsaturated carboxylic acids and one or more derivatives thereof, Combinations of two or more β-unsaturated carboxylic acids or combinations of two or more derivatives of α,β-unsaturated carboxylic acids can be used.

The modifier according to the present invention can contain other compounds (other modifiers) in addition to the α,β-unsaturated carboxylic acid and the like, depending on the purpose. Other compounds (other modifiers) include, for example, (meth)acrylic acid esters represented by the following formula (2), (meth)acrylic acid, other (meth)acrylic acid derivatives, aromatic vinyl compounds, cyclohexyl vinyl ether and the like. These other compounds may be used alone or in combination of two or more.
_CH2 = ^CR1COOR2 ( ² )
(In the formula, R ¹ is a hydrogen atom or a methyl group, and R ² is a hydrocarbon group.)

In formula (2) representing the (meth)acrylic acid ester, R ¹ is a hydrogen atom or a methyl group, preferably a methyl group. R ² is a hydrocarbon group, preferably an alkyl group having 8 to 18 carbon atoms. Examples of the compound represented by the above formula (2) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, (meth)acrylate, hexyl acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylic cyclohexyl acid, benzyl (meth)acrylate, and the like. These compounds may be used alone or in combination of two or more. In the present invention, it is preferable to use a modifier that further contains a (meth)acrylic acid ester having an alkyl group having 8 to 18 carbon atoms, in particular, octyl (meth)acrylate, It preferably contains lauryl (meth)acrylate, tridecyl (meth)acrylate or stearyl (meth)acrylate.

Examples of (meth)acrylic acid derivatives other than (meth)acrylic acid esters include hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, and isocyanate-containing (meth)acrylic acid. Examples of aromatic vinyl compounds include styrene, o-methylstyrene, p-methylstyrene, α-methylstyrene and the like. As the modifier, α,β-unsaturated carboxylic acid or a derivative thereof and another modifier are used in combination to improve the grafting rate of the modifier, improve the solubility in solvents, improve the adhesiveness. can be further improved. In addition, when other modifiers other than the (meth)acrylic acid ester represented by the above formula (2) are used, the amount used is α,β-unsaturated carboxylic acid and its derivatives and (meth)acrylic acid ester It is desirable not to exceed the total amount used.

The radical initiator used for producing the modified alicyclic skeleton-containing resin can be appropriately selected from known ones, such as benzoyl peroxide, dicumyl peroxide, lauroyl peroxide, and di-t-butyl peroxide. , 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and cumene hydroperoxide are preferably used.

Modification aids that can be used in the production of the modified alicyclic skeleton-containing resin include divinylbenzene, hexadiene, dicyclopentadiene, and the like. Stabilizers include hydroquinone, benzoquinone, nitrosophenylhydroxy compounds and the like.

The weight average molecular weight (Mw) of the alicyclic skeleton-containing resin (B) is preferably 10,000 to 200,000, more preferably 20,000 to 150,000, still more preferably 30,000. ~100,000. With a weight average molecular weight (Mw) of 10,000 to 200,000, it has excellent solubility in solvents and initial adhesion to adherends, and also has solvent resistance in the adhesive part after adhesion. It can be an excellent adhesive composition.

The acid value of the acid-modified alicyclic skeleton-containing resin (B) is preferably 0.1 to 50 mgKOH/g, more preferably 1 to 30 mgKOH/g, and 2 to 20 mgKOH/g. is more preferred. When the acid value is 0.1 to 50 mgKOH/g, the adhesive composition is sufficiently cured, and good adhesiveness and wet heat soldering heat resistance can be obtained.

The alicyclic skeleton-containing resin (B) preferably has a glass transition temperature of 60 to 180°C, more preferably 70 to 160°C, even more preferably 80 to 150°C. When the glass transition temperature is within this range, the wet heat soldering heat resistance is improved. The use of the acid-modified alicyclic skeleton-containing resin (B) having such a glass transition temperature is more preferable because the adhesiveness and wet heat soldering heat resistance are further improved.

The content of the alicyclic skeleton-containing resin (B) in the present invention is as described above for the polyolefin resin (A).

1-3. Epoxy resin (C)
Next, the epoxy resin (C), which is another component of the adhesive composition, will be described. The epoxy resin (C) reacts with the carboxyl groups in the carboxyl group-containing polyolefin resin (A) and/or the carboxyl group-containing alicyclic skeleton-containing resin (B), and exhibits high adhesion to adherends and , is a component that develops the heat resistance of the adhesive cured product.

Examples of the epoxy resin (C) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, or hydrogenated products thereof; diglycidyl orthophthalate, diglycidyl isophthalate, diglycidyl terephthalate, p- Glycidyl ester epoxy resins such as glycidyl hydroxybenzoate, diglycidyl tetrahydrophthalate, diglycidyl succinate, diglycidyl adipate, diglycidyl sebacate, and triglycidyl trimellitate; ethylene glycol diglycidyl ether , propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, tetraphenylglycidyl ether ethane, triphenylglycidyl ether Glycidyl ether-based epoxy resins such as ethane, sorbitol polyglycidyl ether, and polyglycerol polyglycidyl ether; glycidylamine-based epoxy resins such as triglycidyl isocyanurate and tetraglycidyldiaminodiphenylmethane; epoxidized polybutadiene, epoxidized soybean oil, etc. Examples include, but are not limited to, aliphatic epoxy resins. Novolac type epoxy resins such as phenol novolak epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, etc. can also be used.

Furthermore, examples of the epoxy resin (C) include brominated bisphenol A type epoxy resin, phosphorus-containing epoxy resin, dicyclopentadiene skeleton-containing epoxy resin, naphthalene skeleton-containing epoxy resin, anthracene-type epoxy resin, tertiary-butylcatechol-type epoxy resin, A triphenylmethane type epoxy resin, a tetraphenylethane type epoxy resin, a biphenyl type epoxy resin, a bisphenol S type epoxy resin, or the like can be used. These epoxy resins may be used alone or in combination of two or more.
Among the above epoxy resins, epoxy resins having no glycidylamino group are preferred. This is because the storage stability of the adhesive layer-attached laminate is improved. In addition, an epoxy resin having an alicyclic skeleton is preferable, and an epoxy resin having a dicyclopentadiene skeleton is more preferable, since an adhesive composition having excellent electrical properties can be obtained.

The epoxy resin used in the present invention preferably has two or more epoxy groups in one molecule. This is because a crosslinked structure can be formed by reaction with the carboxyl group-containing polyolefin resin (A) and/or the carboxyl group-containing alicyclic skeleton-containing resin (B), and high heat resistance can be exhibited. Further, when an epoxy resin having two or more epoxy groups is used, the degree of cross-linking with the carboxyl group-containing polyolefin resin (A) and/or the carboxyl group-containing alicyclic skeleton-containing resin (B) is sufficient. high heat resistance. Therefore, particularly preferred epoxy resins are polyfunctional epoxy resins having a dicyclopentadiene skeleton.

The content of the epoxy resin (C) is preferably 1 to 20 parts by mass per 100 parts by mass of the total content of the polyolefin resin (A) and the alicyclic skeleton-containing resin (B). . More preferably, the content is 3 to 15 parts by mass. When the content is within the above range, sufficient adhesiveness and heat resistance can be obtained, and deterioration of peel adhesive strength and electrical properties can be prevented.

1-4. Electrical Properties of Adhesive Composition The adhesive composition according to the present invention contains a polyolefin resin (A), an alicyclic skeleton-containing resin (B) and an epoxy resin (C), and is measured at a frequency of 1 GHz. It is characterized in that the dielectric constant (ε) of the cured product is less than 2.5. If the dielectric constant is less than 2.5, it is suitable for use in FPC-related products. Moreover, the dielectric loss tangent (tan δ) of the adhesive cured product measured at a frequency of 1 GHz is preferably less than 0.01. If the dielectric loss tangent is less than 0.01, FPC-related products with excellent electrical properties can be manufactured. The dielectric constant and dielectric loss tangent can be adjusted according to the proportions of the polyolefin resin (A), the alicyclic skeleton-containing resin (B) and the epoxy resin (C) in the adhesive composition. can be set. Methods for measuring dielectric constant and dielectric loss tangent will be described later.

1-5. Wet heat soldering heat resistance of adhesive composition The adhesive composition according to the present invention contains a polyolefin resin (A), an alicyclic skeleton-containing resin (B) and an epoxy resin (C), and the polyolefin resin (A ) and the alicyclic skeleton-containing resin (B) contain a carboxyl group and/or a derivative thereof, so that the temperature of the soldering heat resistance after humidification treatment at a temperature of 40° C. and a humidity of 90% for 12 hours is increased. and preferably 240° C. or higher. When both the polyolefin resin (A) and the alicyclic skeleton-containing resin (B) contain a carboxyl group and/or a derivative thereof, the temperature of the solder heat resistance can be further increased. When the content ratio of (A) and the alicyclic skeleton-containing resin (B) [polyolefin resin (A)]:[alicyclic skeleton-containing resin (B)] is 5:95 to 95:5, The solder heat resistance temperature can be set to 240° C. or higher.

1-6. Other Components In addition to the polyolefin resin (A), the alicyclic skeleton-containing resin (B), and the epoxy resin (C), the adhesive composition contains the polyolefin resin (A) and the alicyclic skeleton-containing resin. Thermoplastic resins other than (B), UV absorbers, tackifiers, flame retardants, curing agents, curing accelerators, coupling agents, heat antioxidants, leveling agents, antifoaming agents, inorganic fillers, pigments , and solvent, etc., can be contained to such an extent that the functions of the adhesive composition are not affected.

Examples of other thermoplastic resins include phenoxy resins, polyamide resins, polyester resins, polycarbonate resins, polyphenylene oxide resins, polyurethane resins, polyacetal resins, polyethylene resins, polypropylene resins and polyvinyl resins. These thermoplastic resins may be used alone or in combination of two or more.

Examples of the tackifier include coumarone-indene resin, terpene resin, terpene-phenol resin, rosin resin, pt-butylphenol-acetylene resin, phenol-formaldehyde resin, xylene-formaldehyde resin, petroleum-based hydrocarbon resin, Examples include hydrogenated hydrocarbon resins and turpentine resins. These tackifiers may be used alone or in combination of two or more.

The flame retardant may be either an organic flame retardant or an inorganic flame retardant. Examples of organic flame retardants include melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, amide ammonium phosphate, amide ammonium polyphosphate, carbamate phosphate, and carbamate polyphosphate. , aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, zinc bisdiphenylphosphinate, titanyl bisdiethylphosphinate, titanium tetrakisdiethylphosphinate , Titanyl bismethylethylphosphinate, Titanium tetrakismethylethylphosphinate, Titanyl bisdiphenylphosphinate, Titanium tetrakisdiphenylphosphinate, etc.; , isocyanuric acid compounds, triazole compounds, tetrazole compounds, diazo compounds, urea, and other nitrogen-based flame retardants; silicone compounds, silane compounds, and other silicon-based flame retardants. Inorganic flame retardants include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide, and calcium hydroxide; tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, zinc oxide, Metal oxides such as molybdenum oxide and nickel oxide; zinc carbonate, magnesium carbonate, barium carbonate, zinc borate, hydrated glass and the like. These flame retardants can be used in combination of two or more.

Examples of the curing agent include, but are not limited to, amine-based curing agents, acid anhydride-based curing agents, and the like. Examples of amine curing agents include melamine resins such as methylated melamine resin, butylated melamine resin and benzoguanamine resin, dicyandiamide, 4,4′-diphenyldiaminosulfone and the like. Acid anhydrides include aromatic acid anhydrides and aliphatic acid anhydrides. These curing agents may be used alone or in combination of two or more.
The content of the curing agent is preferably 1 to 100 parts by mass, more preferably 5 to 70 parts by mass, based on 100 parts by mass of the epoxy resin (C).

The curing accelerator is used for the purpose of promoting the reaction between the carboxyl group-containing polyolefin resin (A) and/or the carboxyl group-containing alicyclic skeleton-containing resin (B) and the epoxy resin. Amine-based curing accelerators, tertiary amine salt-based curing accelerators, imidazole-based curing accelerators, and the like can be used.

Tertiary amine curing accelerators include benzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, tetramethylguanidine, triethanolamine, N,N' -dimethylpiperazine, triethylenediamine, 1,8-diazabicyclo[5.4.0]undecene and the like.

Tertiary amine salt curing accelerators include 1,8-diazabicyclo[5.4.0]undecene formate, octylate, p-toluenesulfonate, o-phthalate, phenol salt or Phenolic novolac resin salts, 1,5-diazabicyclo[4.3.0]nonene formate salts, octylate salts, p-toluenesulfonate salts, o-phthalate salts, phenol salts or phenol novolak resin salts, etc. mentioned.

Examples of imidazole curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-methyl-4-ethylimidazole, 2-phenylimidazole, 2-phenyl- 4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2,4-diamino-6-[2′-methylimidazolyl-(1′)]ethyl-s-triazine, 2 ,4-diamino-6-[2′-undecylimidazolyl-(1′)]ethyl-s-triazine, 2,4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′) ] Ethyl-s-triazine, 2,4-diamino-6-[2′-methylimidazolyl-(1′)]ethyl-s-triazine isocyanurate, 2-phenylimidazole isocyanurate, 2-phenyl- 4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole and the like. These curing accelerators may be used alone or in combination of two or more.

When the adhesive composition contains a curing accelerator, the content of the curing accelerator is preferably 0.5 to 10 parts by mass, preferably 1 to 5 parts by mass, with respect to 100 parts by mass of the epoxy resin (C). Part is more preferred. If the content of the curing accelerator is within the above range, excellent adhesiveness and heat resistance can be obtained.

Examples of the coupling agent include vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, N -2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatopropyltriethoxysilane , silane-based coupling agents such as imidazole silane; titanate-based coupling agents; aluminate-based coupling agents; and zirconium-based coupling agents. These may be used alone or in combination of two or more.

Examples of the thermal anti-aging agents include 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionate, Tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenol, triethylene Phenolic antioxidants such as glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate; dilauryl-3,3'-thiodipropionate, dimyristyl-3,3 sulfur-based antioxidants such as '-dithiopropionate; It may be used alone or in combination of two or more.
The content of the thermal anti-aging agent is 0.1 to 10 parts by mass with respect to the total 100 parts by mass of the content of the polyolefin resin (A) and the alicyclic skeleton-containing resin (B). Preferably, it is 0.5 to 5 parts by mass. When the content is within the above range, electrical properties and heat resistance can be improved.

Examples of the inorganic filler include powders of titanium oxide, aluminum oxide, zinc oxide, carbon black, silica, talc, copper, silver, and the like. These may be used alone or in combination of two or more.

The adhesive composition comprises a polyolefin resin (A), an alicyclic skeleton-containing resin (B), an epoxy resin (C) (provided that at least one of the polyolefin resin (A) and the alicyclic skeleton-containing resin (B) must be acid-modified to contain a carboxyl group and/or a derivative thereof) and other ingredients. The mixing method is not particularly limited as long as the adhesive composition becomes uniform. Since the adhesive composition is preferably used in the form of a solution or dispersion, a solvent is also usually used. Examples of solvents include alcohols such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, isobutyl alcohol, n-butyl alcohol, benzyl alcohol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diacetone alcohol. Acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, isophorone and other ketones; toluene, xylene, ethylbenzene, mesitylene and other aromatic hydrocarbons; methyl acetate, ethyl acetate, ethylene glycol monomethyl ether acetate, 3- esters such as methoxybutyl acetate; and aliphatic hydrocarbons such as hexane, heptane, cyclohexane, and methylcyclohexane. These solvents may be used alone or in combination of two or more. When the adhesive composition is a solvent-containing solution or dispersion (resin varnish), coating on the substrate film and formation of the adhesive layer can be performed smoothly, and the adhesive layer can be formed to a desired thickness. can be obtained easily.

When the adhesive composition contains a solvent, the solid content concentration is preferably in the range of 3 to 80% by mass, more preferably 10 to 50% by mass, from the viewpoint of workability including formation of the adhesive layer. When the solid content concentration is 80% by mass or less, the viscosity of the solution is appropriate, and it is easy to apply uniformly.

2. Laminate with Adhesive Layer According to the present invention, a laminate with an adhesive layer comprising an adhesive layer made of the adhesive composition of the present invention and a base film in contact with at least one surface of the adhesive layer. is obtained, and the adhesive layer is preferably B-stage. Here, the adhesive layer being in a B-stage state refers to a semi-cured state in which a part of the adhesive composition has begun to cure, and refers to a state in which curing of the adhesive composition further progresses by heating or the like. .

A cover lay film is mentioned as one aspect|mode of the laminated body with an adhesive bond layer obtained using the adhesive composition of this invention. A coverlay film is a laminate in which an adhesive layer is formed on at least one surface of a base film, and the base film and the adhesive layer are difficult to separate.

When the laminate with an adhesive layer is a coverlay film, the base film includes polyimide film, polyetheretherketone film, polyphenylene sulfide film, aramid film, polyethylene naphthalate film, liquid crystal polymer film, polyethylene terephthalate film, and polyethylene film. , polypropylene film, TPX film, and fluororesin film. Among these, polyimide films, polyethylene naphthalate films, and liquid crystal polymer films are preferred, and polyimide films and liquid crystal polymer films are more preferred, from the viewpoint of adhesiveness and electrical properties.

Such base films are commercially available, and polyimide films include "Kapton (registered trademark)" manufactured by Toray DuPont Co., Ltd., "Xenomax (registered trademark)" manufactured by Toyobo Co., Ltd., Ube Industries ( "Upilex (registered trademark)-S" manufactured by Co., Ltd., "Apical (registered trademark)" manufactured by Kaneka Corporation, etc. can be used. As for the polyethylene naphthalate film, "Teonex (registered trademark)" manufactured by Teijin DuPont Films Limited can be used. Further, as the liquid crystal polymer film, "Vecstar (registered trademark)" manufactured by Kuraray Co., Ltd., "Biac (registered trademark)" manufactured by Primatec Co., Ltd., and the like can be used. The base film can also be used by filming the corresponding resin to a desired thickness.

As a method for producing a coverlay film, for example, a resin varnish containing the adhesive composition and a solvent is applied to the surface of a base film such as a polyimide film to form a resin varnish layer, and then the resin varnish is applied. By removing the solvent from the layer, a coverlay film having a B-staged adhesive layer can be produced.
The drying temperature for removing the solvent is preferably 40 to 250°C, more preferably 70 to 170°C. When the drying temperature is 40° C. or higher, it becomes easier to prevent deterioration of electrical properties due to residual solvent, and when it is 250° C. or lower, it becomes easier to obtain a B-stage adhesive layer. Drying is performed by passing the laminate coated with the adhesive composition through a furnace in which hot air drying, far-infrared heating, high-frequency induction heating, or the like is performed.
If necessary, a release film may be laminated on the surface of the adhesive layer for storage or the like. As the releasable film, publicly known films such as polyethylene terephthalate film, polyethylene film, polypropylene film, silicone release treated paper, polyolefin resin coated paper, polymethylpentene (TPX) film, and fluororesin film are used.

Another aspect of the laminate with an adhesive layer is a bonding sheet. The bonding sheet also has the adhesive layer formed on at least one surface of a substrate film, and the substrate film is a release film. Also, the bonding sheet may be in a mode in which an adhesive layer is provided between two release films. When using the bonding sheet, the release film is peeled off before use. A release film similar to that described above can be used.

Such releasable films are also commercially available, Toray Film Processing Co., Ltd. "Lumirror (registered trademark)", Toyobo Co., Ltd. "Toyobo Ester (registered trademark) Film", Asahi Glass Co., Ltd. " Flux (registered trademark)”, Mitsui Chemicals Tohcello Co., Ltd. “Opulant (registered trademark)”, and the like can be used.

As a method for producing a bonding sheet, for example, there is a method of applying a resin varnish containing the adhesive composition and a solvent to the surface of a release film, and drying in the same manner as in the case of the coverlay film.

The thickness of the base film is preferably from 5 to 100 μm, more preferably from 5 to 50 μm, even more preferably from 5 to 30 μm, in order to make the laminate with the adhesive layer thinner.

The thickness of the B-stage adhesive layer is preferably 5 to 100 μm, more preferably 10 to 70 μm, even more preferably 10 to 50 μm.
The thicknesses of the base film and the adhesive layer are selected depending on the application, but the base film tends to be thinner in order to improve the electrical properties. In general, when the thickness of the base film is thin and the thickness of the adhesive layer is thick, the laminate with the adhesive layer is likely to warp and the workability is reduced, but the laminate with the adhesive layer of the present invention Even when the thickness of the base film is thin and the thickness of the adhesive layer is thick, the laminate hardly warps. In the laminate with an adhesive layer of the present invention, the ratio (A/B) between the thickness (A) of the adhesive layer and the thickness (B) of the base film is 1 or more and 10 or less. It is preferably 1 or more and 5 or less. Furthermore, the thickness of the adhesive layer is preferably thicker than the thickness of the base film.

Since the warp of the adhesive layer-attached laminate affects workability in the manufacturing process of FPC-related products, it is preferable that the warp be as small as possible. Specifically, when a square-shaped laminate with an adhesive layer is placed on a horizontal surface with the adhesive layer facing up, the lift height (H) of the end of the laminate and the laminate The ratio (H/L) to the length (L) of one side is preferably less than 0.05. More preferably, this ratio is less than 0.04, even more preferably less than 0.03. When the ratio (H/L) is less than 0.05, warping or curling of the laminate can be further suppressed, resulting in excellent workability.
The lower limit of H/L is 0 when H is 0.

After curing the adhesive layer of the laminate, the dielectric constant (ε) of the laminate with the adhesive layer measured at a frequency of 1 GHz is less than 3.0, and the dielectric loss tangent (tan δ) is 0.01. It is preferably less than More preferably, the dielectric constant is 2.9 or less, and the dielectric loss tangent is 0.005 or less. If the dielectric constant is less than 3.0 and the dielectric loss tangent is less than 0.01, it can be suitably used for FPC-related products that require strict electrical characteristics. Since the dielectric constant and dielectric loss tangent can be adjusted by adjusting the type and content of the adhesive component, the type of the base film, and the like, it is possible to set laminates having various configurations depending on the application.
Further, after curing the adhesive layer of the laminate, the laminate with the adhesive layer has a dielectric constant (ε) of 2.2 or more measured at a frequency of 1 GHz, and the dielectric loss tangent (tan δ) is 0. It is preferable that it is above.

3. Flexible Copper-Clad Laminate According to the present invention, a flexible copper-clad laminate is obtained by bonding a substrate film and a copper foil together using the laminate with an adhesive layer. That is, the obtained flexible copper-clad laminate is composed of a substrate film, an adhesive layer and a copper foil in this order. Note that the adhesive layer and the copper foil may be formed on both sides of the base film. Since the adhesive composition of the present invention has excellent adhesion to articles containing copper, the flexible copper-clad laminate obtained by the present invention has excellent stability as an integrated product.

As a method for producing the flexible copper-clad laminate, for example, the adhesive layer and copper foil of the laminate are brought into surface contact, thermal lamination is performed at 80 ° C. to 150 ° C., and the adhesive layer is removed by after-curing. There is a way to harden it. The after-cure conditions can be, for example, 100° C. to 200° C. and 30 minutes to 4 hours. Note that the copper foil is not particularly limited, and an electrolytic copper foil, a rolled copper foil, or the like can be used.

4. Flexible Flat Cable (FFC)
According to the present invention, a flexible flat cable is obtained by laminating a substrate film and a copper wiring using the laminate with an adhesive layer. That is, the obtained flexible flat cable is composed of the substrate film, the adhesive layer and the copper wiring in this order. In addition, the adhesive layer and the copper wiring may be formed on both sides of the substrate film. Since the adhesive composition of the present invention has excellent adhesion to articles containing copper, the flexible flat cable obtained by the present invention has excellent stability as an integrated product.

As a method for producing the flexible flat cable, for example, the adhesive layer of the laminate is brought into contact with the copper wiring, thermal lamination is performed at 80 ° C. to 150 ° C., and the adhesive layer is cured by after-curing. There is The after-cure conditions can be, for example, 100° C. to 200° C. and 30 minutes to 4 hours. The shape of the copper wiring is not particularly limited, and any suitable shape may be selected as desired.

The present invention will be described more specifically based on examples, but the present invention is not limited to these. In the following, parts and % are based on mass unless otherwise specified.

1. Evaluation Method (1) Weight Average Molecular Weight GPC measurement was performed under the following conditions to determine the Mw of the polyolefin resin (A) and the alicyclic skeleton-containing resin (B). Mw was obtained by converting the retention time measured by GPC based on the retention time of standard polystyrene.
Apparatus: Alliance 2695 (manufactured by Waters)
Column: TSKgel SuperMultiporeHZ-H 2, TSKgel SuperHZ2500 2, (manufactured by Tosoh Corporation)
Column temperature: 40°C
Eluent: Tetrahydrofuran 0.35 ml/min Detector: RI

(2) Acid value 1 g of polyolefin resin (A) or alicyclic skeleton-containing resin (B) is dissolved in 30 ml of toluene, and an automatic titrator "AT-510" manufactured by Kyoto Electronics Industry Co., Ltd. is used as a buret. 510-20B" was used. Potentiometric titration was performed using a 0.01 mol/L benzyl alcoholic KOH solution as a titration reagent, and the number of mg of KOH per 1 g of resin was calculated.

(3) Glass transition temperature A release polyethylene terephthalate film having a thickness of 38 μm was prepared, and an organic solvent solution of the alicyclic skeleton-containing resin (B) was roll-coated on one surface of the film. Then, the coated film was placed in an oven and dried at 90° C. for 3 minutes to form a coating having a thickness of 25 μm, thereby obtaining a bonding sheet. Next, the PET film was peeled off from the laminated film thus obtained, and this was used as a test piece for measuring the glass transition temperature. This test piece was subjected to measurement in tensile mode with a dynamic viscoelasticity measuring device "EXSTAR DMS6100" (manufactured by SII Nanotechnology) under the conditions of a heating rate of 2°C/min and a frequency of 1 Hz. The maximum value of the loss tangent of the obtained curve was defined as the glass transition temperature (Tg).

(4) Peeling Adhesive Strength A release polyethylene terephthalate film having a thickness of 38 μm was prepared, and the liquid adhesive composition shown in Table 1 was roll-coated on one surface of the film. Then, the film with the coating film was allowed to stand in an oven and dried at 90° C. for 3 minutes to form a coating (adhesive layer) having a thickness of 25 μm to obtain a bonding sheet. Next, a single-sided copper clad laminate (LCP film 50 μm, rolled copper foil 12 μm) having a thickness of 62 μm was prepared, and the LCP surface and the adhesive layer of the bonding sheet were superposed so as to be in surface contact. Lamination was carried out under conditions of a pressure of 0.4 MPa and a speed of 0.5 m/min to obtain a single-sided copper-clad laminate with an adhesive layer. After that, a rolled copper foil having a thickness of 35 μm and an adhesive layer of a single-sided copper-clad laminate with an adhesive layer were superposed so as to be in surface contact, and the temperature was 150° C., the pressure was 0.4 MPa, and the speed was 0.5 m/min. Lamination was carried out under the following conditions. Then, this laminate (single-sided copper-clad laminate/adhesive layer/copper foil) was heat-pressed for 30 minutes at a temperature of 180° C. and a pressure of 3 MPa to obtain a flexible copper-clad laminate A. This flexible copper-clad laminate A was cut to prepare an adhesion test piece having a predetermined size.
In order to evaluate the adhesiveness, in accordance with JIS C 6481 "Testing method for copper-clad laminates for printed wiring boards", under the conditions of a temperature of 23 ° C. and a tensile speed of 50 mm / min, the copper foil of each adhesive test piece was applied to an LCP film. The 90° peel adhesion strength (N/mm) when peeled from the tape was measured. The width of the adhesive test piece during measurement was 10 mm.

(5) Soldering heat resistance Tests were conducted under the following conditions in accordance with JIS C 6481 "Testing methods for copper-clad laminates for printed wiring boards". A flexible copper-clad laminate A was cut into a 20 mm square to prepare a test piece. After that, the test piece was subjected to a wet heat load treatment of 40° C., 90%, and 12 hours. After that, the test piece was placed in a reflow simulator with the single-sided copper-clad laminate facing up, and the temperature at which foaming was observed on the surface of the adhesive test piece was observed.
<Evaluation Criteria>
○: 260°C or higher △: 240 to 260°C
×: 240°C or less

(6) Laser processability For the flexible copper-clad laminate A, UV-YAG laser Model 5335 manufactured by ESI was used to perform via processing from the copper-clad laminate to the boundary between the adhesive layer and the rolled copper foil. After that, the cross section of the via portion was observed with an optical microscope to measure the scratched length of the adhesive layer.
<Evaluation Criteria>
○: Marked length of 10 μm or less ×: Marked length of 10 μm or more

(7) Electrical properties (permittivity and dielectric loss tangent)
A release polyethylene terephthalate film having a thickness of 38 μm was prepared, and the liquid adhesive composition shown in Table 1 was roll-coated on one surface of the film. Then, the coated film was left in an oven and dried at 90° C. for 3 minutes to form a coating (adhesive layer) having a thickness of 50 μm to obtain a bonding sheet. Next, this bonding sheet was placed in an oven and heat-treated at 180° C. for 30 minutes. After that, the release film was peeled off to prepare a test piece (150×120 mm). Permittivity (ε) and dielectric loss tangent (tan δ) are measured using a network analyzer 85071E-300 (manufactured by Agilent) by the split-post dielectric resonator method (SPDR method) at a temperature of 23°C and a frequency of 1 GHz. bottom.

2. Elastomer

(1) Polyolefin resin a1 (olefin elastomer)
100 parts by mass of a propylene-ethylene random copolymer composed of 97 mol% of propylene units and 3 mol% of ethylene units, produced using a metallocene catalyst as a polymerization catalyst, 1.0 parts by mass of maleic anhydride, and 0.5 parts by mass of lauryl methacrylate and 0.8 parts by mass of di-t-butyl peroxide were kneaded and reacted using a twin-screw extruder in which the maximum temperature of the cylinder section was set to 170°C. Thereafter, degassing was performed under reduced pressure in the extruder to remove remaining unreacted substances, thereby producing a modified olefinic elastomer. This modified olefin elastomer had a weight average molecular weight of 150,000 and an acid value of 10 mgKOH/g.
(2) Polyolefin resin a2 (olefin elastomer)
A propylene-ethylene random copolymer composed of 97 mol % of propylene units and 3 mol % of ethylene units, produced using a metallocene catalyst as a polymerization catalyst, was used.
(3) Styrene Elastomer A trade name “Tuftec M1913” (a maleic acid-modified styrene-ethylenebutylene-styrene block copolymer) manufactured by Asahi Kasei Chemicals was used. This copolymer has an acid value of 10 mgKOH/g, a styrene/ethylene butylene ratio of 30/70, and a weight average molecular weight of 150,000.

3. Alicyclic skeleton-containing resin (1) Alicyclic skeleton-containing resin b1
Cyclic olefin resin (manufactured by Nippon Zeon, trade name “Zeonor 1060R” 100 parts by mass was heated and dissolved in 400 parts by mass of xylene in a nitrogen atmosphere in a four-necked flask, and then the temperature in the system was kept at 140 ° C. and stirred. , 8 parts by weight of maleic anhydride and 3 parts by weight of dicumyl peroxide as a radical generator were added over 2 hours, respectively, and then reacted for 6 hours. This resin was further washed with acetone several times to remove unreacted maleic anhydride, and dried under reduced pressure to obtain an alicyclic skeleton-containing resin b1. Resin b1 had an acid value of 10 mgKOH/g and a Tg of 100°C.

(2) Alicyclic skeleton-containing resin b2
Add 400 parts by mass of cyclohexane to 100 parts by mass of Asahi Kasei's "Tuftec H1041" (styrene-ethylenebutylene-styrene block copolymer), and further nickel-alumina catalyst (manufactured by JGC Chemical Co., Ltd.) as a hydrogenation catalyst 7 parts by mass. was added, and the mixture was pressurized to 5 MPa with hydrogen, heated to 200° C. while stirring, and then hydrogenated for 4 hours. Thereafter, the hydrogenation catalyst was removed, and 0.5 parts by mass of an antioxidant (“Irganox 1010” manufactured by Ciba Specialty Chemicals) was added and dissolved. Next, while removing cyclohexane as a solvent and other volatile components, the mixture was extruded in a molten state into strands from an extruder, cooled, pelletized, and pellets were recovered. Then, 4 parts by mass of maleic anhydride, 2 parts by mass of dicumyl peroxide, and 230 parts by mass of tert-butylbenzene are blended with 100 parts by mass of the hydride of the obtained styrene-ethylenebutylene-styrene block copolymer, After the reaction was carried out in an autoclave at 135° C. for 6 hours, the reaction product was poured into a large amount of isopropyl alcohol to precipitate, which was collected by filtration. The collected resin was dried at 100° C. and 1 Torr or less for 48 hours to obtain an alicyclic skeleton-containing resin b2. The alicyclic skeleton-containing resin b2 had an acid value of 10 mgKOH/mg and a Tg of 70°C.

(3) Alicyclic skeleton-containing resin b3
Zeonex 330R (trade name) manufactured by Nippon Zeon was used. This product had an acid value of 0 mgKOH/g and a Tg of 120°C.

4. Raw Materials for Other Adhesive Compositions 4-1. Epoxy resin (1) Epoxy resin c1
DIC's product name "EPICLON HP-7200" (dicyclopentadiene skeleton-containing epoxy resin) was used.
(2) Epoxy resin c2
DIC's product name "EPICLON N-655EXP" (cresol novolak type epoxy resin) was used.

4-2. Additives (1) Curing Accelerator Shikoku Kasei Co., Ltd. trade name “Curesol C11-Z” (imidazole-based curing accelerator) was used.
(2) Thermal anti-aging agent ADEKA's product name "ADEK STAB AO-60" was used.
(3) Ultraviolet absorber BASF trade name "Uvinul3049" was used.

4-3. Organic solvent A mixture of 250 parts by mass of methylcyclohexane, 250 parts by mass of toluene, and 50 parts by mass of methyl ethyl ketone was used.

5. Manufacture of Adhesive Composition A liquid adhesive composition was prepared and evaluated by adding the above raw materials in the proportions shown in Table 1 to a 1000 ml flask equipped with a stirrer and stirring at room temperature for 6 hours to dissolve. Table 1 shows the results.

6. Production and Evaluation of Laminate with Adhesive Layer Using the adhesive composition described above, a laminate with an adhesive layer was produced and evaluated. Table 1 shows the results.

From the results in Table 1 above, it can be seen that the adhesive compositions of Examples 1 to 11 are excellent in adhesiveness, wet heat solder heat resistance, and electrical properties. In addition, from the comparison between Example 1 and Example 11, it can be seen that laser drilling workability is also excellent when an ultraviolet absorber is contained. On the other hand, as in Comparative Example 1, when the adhesive composition does not contain the alicyclic skeleton-containing resin (B), the wet heat soldering heat resistance is poor. Also, as in Comparative Example 2, when the adhesive composition does not contain the polyolefin resin (A), the adhesiveness and wet heat soldering heat resistance are poor. Moreover, as in Comparative Example 3, when the adhesive composition does not contain the epoxy resin (C), the wet heat soldering heat resistance is poor. Also, as in Comparative Example 4, when neither the polyolefin-based resin (A) nor the alicyclic skeleton-containing resin (B) contained in the adhesive composition contains a carboxyl group, the wet heat solder heat resistance is inferior. . Further, as in Comparative Example 5, when the adhesive composition contains a styrene-based elastomer containing a carboxyl group instead of the polyolefin-based resin (A) and the alicyclic skeleton-containing resin (B), the adhesiveness is improved, but the wet heat soldering heat resistance is inferior.

The adhesive composition of the present invention is excellent in adhesiveness, wet heat solder heat resistance, electrical properties, and the like. Therefore, the adhesive composition of the present invention is suitable for manufacturing FPC-related products.

Claims (13)

It contains a polyolefin-based resin (A), an alicyclic skeleton-containing resin (B), and an epoxy resin (C), and the alicyclic skeleton-containing resin (B) has an alicyclic skeleton as a main chain and a side chain. At least one of the polyolefin resin (A) and the alicyclic skeleton-containing resin (B), at least the alicyclic skeleton-containing resin (B) contains a carboxyl group and / or a derivative thereof and the alicyclic skeleton-containing resin (B) has an acid value of 0.1 to 50 mgKOH/g, and the cured product has a dielectric constant of less than 2.5. The total content of the polyolefin resin (A) and the alicyclic skeleton-containing resin (B) is 50 parts by mass or more with respect to 100 parts by mass of the solid content of the adhesive composition,
The content of the epoxy resin (C) is 1 to 20 parts by mass per 100 parts by mass of the total content of the polyolefin resin (A) and the alicyclic skeleton-containing resin (B). 1. The adhesive composition according to 1. The content ratio of the polyolefin resin (A) and the alicyclic skeleton-containing resin (B) is [polyolefin resin (A)]:[alicyclic skeleton-containing resin (B)]=5: The adhesive composition according to claim 1 or 2, which is 95-95:5. 4. The polyolefin resin (A) according to any one of claims 1 to 3, wherein the polyolefin resin (A) contains a carboxyl group and/or a derivative thereof, and has an acid value of 0.1 to 50 mgKOH/g. adhesive composition. 5. Any one of claims 1 to 4, wherein the polyolefin resin (A) is at least one selected from the group consisting of ethylene-propylene copolymers, propylene-butene copolymers and ethylene-propylene-butene copolymers. 1. The adhesive composition according to claim 1. The adhesive composition according to any one of claims 1 to 5, wherein the alicyclic skeleton-containing resin (B) has an alicyclic skeleton in a side chain. The adhesive composition according to any one of claims 1 to 6, wherein the dielectric loss tangent of the cured product measured at a frequency of 1 GHz is less than 0.01. 8. The adhesive composition according to any one of claims 1 to 7, wherein the temperature of solder heat resistance after humidifying for 12 hours at a temperature of 40°C and a humidity of 90% is 260°C or higher. The adhesive composition according to any one of claims 1 to 8, further comprising an ultraviolet absorber. The adhesive composition according to any one of claims 1 to 9, which is for flexible copper-clad laminates. The adhesive composition according to any one of claims 1 to 9, which is for flexible flat cables. The adhesive layer obtained using the adhesive composition according to any one of claims 1 to 11 is a polyimide film, polyetheretherketone film, polyphenylene sulfide film, aramid film, polyethylene naphthalate film, liquid crystal A coverlay film characterized by being formed on at least one side of a film selected from a polymer film, a polyethylene terephthalate film, a polyethylene film, a polypropylene film, a TPX film and a fluororesin film. A bonding sheet comprising an adhesive layer obtained using the adhesive composition according to any one of claims 1 to 11 and formed on at least one side of a release film.