Thermosetting resin composition

Abstract

To provide a thermosetting resin composition which has good adhesion, and is excellent in heat resistance and electric characteristics.SOLUTION: A thermosetting resin composition (Z) contains amino group-modified polyolefin (X) and an epoxy resin (Y). The amino group-modified polyolefin (X) contains polyolefin (A), an unsaturated (poly)carboxylic acid (anhydride) (B), and a compound (b0) having a functional group having reactivity with the carboxylic acid (anhydride) group and an amino group as constituent materials. The polyolefin (A) is polyolefin containing ethylene and α-olefin (3 to 8 carbon atoms) as essential constituent monomers. A weight ratio [ethylene / α-olefin] of the ethylene to the α-olefin (3 to 8 carbon atoms) as the constituent monomers is 5 / 95 to 50 / 50. The amino group-modified polyolefin (X) satisfies all of the following requirements (1) to (3).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a thermosetting resin composition. [Background technology]

[0002] In recent years, as the speed of transmitted signals on printed wiring boards has increased, signals have become increasingly higher in frequency. Accordingly, there is an increasing demand for flexible printed circuit boards (FPCs) with low dielectric properties (low dielectric constant, low dielectric loss tangent) in the high frequency range. In response to these demands, liquid crystal polymers (LCPs), syndiotactic polystyrene (sPS), polyphenylene sulfide (PPS), and other low dielectric materials have been proposed as substrates for flexible printed circuit boards (FPCs) instead of conventional polyimide (PI) and polyethylene terephthalate film. However, because substrates with low dielectric properties have low polarity, when conventional epoxy or acrylic adhesives are used, the adhesive strength is weak, making it difficult to produce FPC components such as coverlay films and laminates. Furthermore, epoxy and acrylic adhesives do not have excellent low dielectric properties and impair the dielectric properties of FPCs. On the other hand, polyolefin resins are known to have low dielectric properties. Therefore, adhesive compositions for FPCs using polyolefin resins have been proposed. For example, Patent Document 1 proposes a modified polyamide adhesive composition incorporating an olefin skeleton to improve the electrical properties of FPCs. Patent Document 2 also proposes an adhesive and a flexible printed wiring board coverlay using an aromatic olefin oligomer-type modifier and an epoxy resin. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-284515 [Patent Document 2] Japanese Patent Application Laid-Open No. 2007-63306 DISCLOSURE OF THE INVENTION [Problem to be solved by the invention]

[0004] However, while the compositions of Patent Documents 1 and 2 are described as having adhesive properties with polyimide, they are difficult to adhere to substrates with low dielectric properties, such as LCP. Furthermore, because they are used as modifiers and the olefin skeleton that accounts for a small portion of the adhesive composition, the dielectric properties of the adhesive are poor. When using an LCP substrate, a method is available in which the LCP is melted without using an adhesive and then laminated to copper foil to produce a two-layer substrate. However, this method has problems such as the need for a high-temperature lamination machine and the tendency for wrinkling during processing, resulting in reduced yield.

[0005] That is, an object of the present invention is to provide a thermosetting resin composition that has good adhesion to both various resin substrates such as polyimide and LCP and metal substrates, and also has excellent heat resistance and electrical properties (low dielectric properties). [Means for solving the problem]

[0006] The present inventors have conducted extensive research to achieve the above-mentioned object and have arrived at the present invention. Specifically, the present invention provides a thermosetting resin composition (Z) comprising an amino group-modified polyolefin (X) and an epoxy resin (Y), wherein the amino group-modified polyolefin (X) comprises, as constituent raw materials, a polyolefin (A), an unsaturated (poly)carboxylic acid (anhydride) (B), and a compound (b0) having an amino group and a functional group reactive with a carboxylic acid (anhydride) group, the polyolefin (A) is a polyolefin containing ethylene and an α-olefin (having 3 to 8 carbon atoms) as essential constituent monomers, and the weight ratio of the ethylene to the α-olefin (having 3 to 8 carbon atoms) as constituent monomers [ethylene / α-olefin] is 5 / 95 to 50 / 50, and the amino group-modified polyolefin (X) satisfies all of the following requirements (1) to (3): (1) Amine value is 1 to 100 mg KOH / g (2) Number average molecular weight (Mn) is 1,000 to 70,000 (3) Isotacticity of the α-olefin moiety is 1 to 50% [Effects of the Invention]

[0007] The thermosetting resin composition (Z) of the present invention has the following effects. (1) Excellent adhesive strength. (2) The cured product has excellent heat resistance and electrical properties (low dielectric properties) [dielectric constant, dielectric dissipation factor]. DETAILED DESCRIPTION OF THE INVENTION

[0008] <Polyolefin (A)> The polyolefin (A) in the present invention contains, as constituent monomers, ethylene and an α-olefin having 3 to 8 carbon atoms. Hereinafter, the "α-olefin having 3 to 8 carbon atoms" may be referred to as "α-olefin". Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene. Although one, two, or more α-olefins may be used in combination, one α-olefin is preferred. Of the above α-olefins, propylene is preferred from the viewpoint of adhesive strength of the cured product and industrial applicability.

[0009] The weight ratio of ethylene to α-olefin, which are constituent monomers of the polyolefin (A) [ethylene / α-olefin], is 5 / 95 to 50 / 50, preferably 10 / 90 to 40 / 60, and more preferably 15 / 85 to 30 / 70. If the weight ratio [ethylene / α-olefin] is less than 2 / 98, the adhesive strength will be poor, and if it exceeds 50 / 50, the heat resistance will be poor. The weight ratio [ethylene / α-olefin] is, for example, 1 It can be calculated using H-MNR (nuclear magnetic resonance spectroscopy).

[0010] The polyolefin (A) may contain other monomers as constituent monomers in addition to ethylene and α-olefins. In such cases, the weight of the other monomers is preferably 10% by weight or less, more preferably 5% by weight or less, and even more preferably 1% by weight or less, based on the weight of all the monomers constituting the polyolefin (A). Examples of the other monomers include 2-butene, isobutene, α-olefins having 9 to 30 carbon atoms (hereinafter sometimes abbreviated as C) (1-decene, 1-dodecene, etc.), and unsaturated monomers having 4 to 30 carbon atoms other than α-olefins (for example, vinyl acetate).

[0011] The number average molecular weight (Mn) of the polyolefin (A) is preferably 800 to 50,000, more preferably 1,500 to 40,000, and even more preferably 2,000 to 30,000, from the viewpoints of adhesive strength and solvent solubility. Among the (A), ethylene / propylene copolymers are preferred.

[0012] In the present invention, the Mn of the polyolefin (A) can be measured by GPC (gel permeation chromatography). The same applies to the amino group-modified polyolefin (X) and acid-modified polyolefin (a) described below.

[0013] In the present invention, the conditions for measuring Mn by GPC are as follows. Apparatus: High temperature gel permeation chromatograph ["AllianceGPCV2000", manufactured by Waters] Detector: Refractive index detector Solvent: orthodichlorobenzene Reference material: polystyrene Sample concentration: 3mg / ml Column stationary phase: PLgel 10 μm, MIXED-B, two columns in series [Polymer Laboratories, Inc.] Column temperature: 135℃

[0014] The number of double bonds per 1,000 carbon atoms in the polyolefin (A) [the number of carbon-carbon double bonds at the molecular terminals and / or in the molecular chain of the polyolefin (A)] is preferably 0.5 to 20, more preferably 1.0 to 18, and even more preferably 1.5 to 15, from the viewpoints of reactivity with the unsaturated (poly)carboxylic acid (anhydride) (B) described below and productivity. Here, the number of double bonds is 1 It can be determined from a H-NMR spectrum. That is, the peaks in the spectrum are assigned, and the relative value between the number of double bonds in polyolefin (A) and the number of carbon atoms in polyolefin (A) is determined from the integral at 4.5 to 6 ppm attributable to the double bonds of polyolefin (A) and the integral attributable to polyolefin (A), and the number of double bonds at the molecular terminals and / or in the molecular chain per 1,000 carbon atoms in polyolefin (A) is calculated. The number of double bonds in the examples described below was determined according to this method.

[0015] The isotacticity of the α-olefin portion of the polyolefin (A) is preferably 1 to 50%, more preferably 5 to 45%, and even more preferably 10 to 40%, from the viewpoints of adhesive strength and solvent solubility. The isotacticity of the α-olefin portion of the polyolefin (A) tends to be directly reflected in the isotacticity of the α-olefin portion of the acid-modified polyolefin (a) and amino group-modified polyolefin (X) described below.

[0016] The isotacticity can be, for example, 13 It can be calculated using C-NMR (nuclear magnetic resonance spectroscopy). Generally, it is known that a side chain methyl group is affected by the configuration (meso or racemo) of the methyl groups on both sides (triad), on both sides of the triad (pentad), and on both sides of the pentad (heptad), and peaks are observed at different chemical shifts. Therefore, the stereoregularity is generally evaluated for the pentad, and the isotacticity in the present invention is also calculated based on the evaluation of the pentad. That is, when the α-olefin is propylene, 13 Regarding the carbon peaks derived from the side chain methyl groups in propylene obtained by C-NMR, when each pentad peak (H) of the α-olefin portion of polyolefin (A) and a peak (Ha) derived from the methyl groups in isotactic propylene in which the pentad is formed only of a mesostructure are taken as the peaks (H), isotacticity can be calculated by the following formula:

[0017] Isotacticity (%) = [(Ha) / Σ(H)] × 100 (2) In the formula, Ha is the peak height of the isotactic signal (pentads are formed only from mesostructures), and H is the height of each peak of the pentad. The isotacticity of the α-olefin portion of the acid-modified polyolefin (a) and amino group-modified polyolefin (X) described below can also be measured in the same manner as above.

[0018] The conditions for measuring isotacticity in the present invention are as follows. Equipment: JEOL Ltd. ECZ400R Measurement mode: Proton decoupling method Pulse width: 8μsec Pulse repetition time: 4.6 seconds Relaxation time: 3.0 seconds Accumulation count: 10,000 times Solvent: orthodichlorobenzene Reference material: tetramethylsilane Sample concentration: 10mg / mL ·Measurement temperature: 120℃

[0019] The polyolefin (A) in the present invention can be produced, for example, by thermally degrading a high molecular weight polyolefin (A0) (preferably having an Mn of 60,000 to 400,000, more preferably having an Mn of 80,000 to 250,000).

[0020] The thermal degradation method includes (1) a method in which the high molecular weight polyolefin (A0) is heated in the absence of an organic peroxide, for example, at 300 to 450°C for 0.5 to 10 hours, and (2) a method in which the high molecular weight polyolefin (A0) is heated in the presence of an organic peroxide [for example, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane], usually at 180 to 300°C for 0.5 to 10 hours. Of these, method (1) is preferred from the industrial viewpoint and from the viewpoint of the modifying properties of the thermosetting resin composition (Z), as it is easy to obtain a product with a larger number of double bonds at the molecular terminals and / or in the molecular chain.

[0021] The weight ratio [ethylene / α-olefin] of ethylene and α-olefin, which are monomers constituting the polyolefin (A), tends to be maintained the same as the weight ratio [ethylene / α-olefin] of these monomers in the high molecular weight polyolefin (A0). Furthermore, the higher the thermal degradation temperature or the longer the thermal degradation time, the greater the number of double bonds per 1,000 carbon atoms tends to be. Furthermore, the smaller the Mn of the high molecular weight polyolefin (A0), the higher the thermal degradation temperature, or the longer the thermal degradation time, the smaller the Mn of the polyolefin (A) tends to be. Furthermore, the higher the isotacticity of the high molecular weight polyolefin (A0), the higher the isotacticity of the polyolefin (A) tends to be. The polyolefin (A) may be used alone or in combination of two or more kinds.

[0022] <Unsaturated (poly)carboxylic acid (anhydride) (B)> The unsaturated (poly)carboxylic acid (anhydride) (B) (hereinafter sometimes referred to as unsaturated carboxylic acid (B)) in the present invention is an unsaturated monocarboxylic acid, an unsaturated polycarboxylic acid and / or an unsaturated polycarboxylic acid anhydride. The unsaturated carboxylic acid (B) is preferably a C3-24 monocarboxylic acid having one polymerizable unsaturated group, a C4-24 polycarboxylic acid having one polymerizable unsaturated group, and / or a C4-24 polycarboxylic acid anhydride having one polymerizable unsaturated group. Among the unsaturated carboxylic acids (B), examples of unsaturated monocarboxylic acids include aliphatic monocarboxylic acids (C3-24, e.g., acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, isocrotonic acid), and alicyclic monocarboxylic acids (C6-24, e.g., cyclohexenecarboxylic acid); examples of unsaturated poly(2-3 or more)carboxylic acids or their anhydrides include unsaturated dicarboxylic acids or their anhydrides [aliphatic dicarboxylic acids or their anhydrides (C4-24, e.g., maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and their anhydrides), and alicyclic dicarboxylic acids or their anhydrides (C8-24, e.g., cyclohexene dicarboxylic acid, cycloheptene dicarboxylic acid, bicycloheptene dicarboxylic acid, methyltetrahydrophthalic acid, and their anhydrides]. The unsaturated carboxylic acids (B) may be used either alone or in combination. Among the above unsaturated carboxylic acids (B), from the viewpoints of reactivity with the polyolefin (A) and productivity of the amino group-modified polyolefin (X), unsaturated dicarboxylic acid anhydrides are preferred, and maleic anhydride is more preferred.

[0023] <Compound (b0) Having an Amino Group and a Functional Group Reactive with a Carboxylic Acid (Anhydride) Group> In the present invention, the compound (b0) having an amino group and a functional group reactive with a carboxylic acid (anhydride) group is, for example, a polyamine compound (b01) having two or more amino groups and at least one type of group selected from the group consisting of a primary amino group and a secondary amino group, and a compound (b02) having a hydroxyl group and a tertiary amino group. That is, examples of functional groups reactive with a carboxylic acid (anhydride) group include a primary amino group, a secondary amino group, and a hydroxyl group.

[0024] Examples of polyamine compounds having two or more amino groups and at least one group selected from the group consisting of primary amino groups and secondary amino groups include those with C2 to C69, such as ethylenediamine, N-methyl or N-ethylethylenediamine, 1,3-propanediamine, N-methyl-, N-ethyl-, or N-butyl-1,3-propanediamine, p-phenylenediamine, N-methyl-, or N-ethyl-p-phenylenediamine, N,N' -dimethylethylenediamine, N,N'-dimethyl-1,3-propanediamine, N,N'-dimethyl-p-phenylenediamine, N,N'-diethylethylenediamine, N,N'-diethyl-1,3-propanediamine, N,N'-diethyl-p-phenylenediamine, N,N'-dibutyl-1,3-propanediamine, N,N-dimethyl-, -diethyl- or -dibutyl-1,3-propanediamine, N,N-dimethyl-p-phenylenediamine, N,N-Diethyl-p-phenylenediamine, N,N,N'-Trimethyl-1,3-propanediamine, Tetramethylenediamine, Hexamethylenediamine, Nonamethylenediamine, Decanemethylenediamine, Undecamethylenediamine, Dodecamethylenediamine, 2,2,4- / 2,4,4-Trimethylhexamethylenediamine, 5-Methylnonamethylenediamine, 2,4-Dimethyloctamethylenediamine, Metaxylylenediamine, Paraxylylene Examples of such an alkyl ether include diamine, 1,3-bis(aminomethyl)cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, isophoronediamine, 3,8-bis(aminomethyl)tricyclodecane, bis(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminopropyl)piperazine, and aminoethylpiperazine. Examples of compounds having a hydroxyl group and a tertiary amino group include those having C4 to C69, such as 2-dimethylaminoethanol, 2-diethylaminoethanol, m-dimethylaminophenol, and N-methyldiethanolamine.

[0025] Among the above (b0), from the viewpoint of the reactivity between the acid-modified polyolefin (a) and (b0), preferred are polyamine compounds having two or more amino groups and at least one group selected from the group consisting of primary amino groups and secondary amino groups, and more preferred are polyamine compounds having at least one group selected from the group consisting of primary amino groups and secondary amino groups and at least one tertiary amino group, polyamine compounds having at least one primary amino group and one secondary amino group, and polyamine compounds having two or more primary amino groups only as amino groups.

[0026] Furthermore, from the viewpoints of adhesiveness and productivity of the amino-modified polyolefin (X), among the above (b0), preferred are hexamethylenediamine, isophoronediamine, 3,3'-diaminodipropylamine, 1,2-diaminobutane, bis(4-aminocyclohexyl)methane, and N,N-dimethyl-1,3propanediamine, and more preferred are hexamethylenediamine, isophoronediamine, bis(4-aminocyclohexyl)methane, and N,N-dimethyl-1,3propanediamine.

[0027] <Amino group modified polyolefin (X)> The amino group-modified polyolefin (X) of the present invention comprises, as constituent raw materials, the polyolefin (A), an unsaturated (poly)carboxylic acid (anhydride) (B), and a compound (b0) having an amino group and a functional group reactive with a carboxylic acid (anhydride) group, wherein the polyolefin (A) is a polyolefin containing ethylene and an α-olefin (having 3 to 8 carbon atoms) as essential constituent monomers, and the weight ratio of the ethylene to the α-olefin (having 3 to 8 carbon atoms) as constituent monomers [ethylene / α-olefin] is 5 / 95 to 50 / 50, and the amino group-modified polyolefin (X) satisfies all of the following requirements (1) to (3): (1) Amine value is 1 to 100 mg KOH / g (2) Number average molecular weight (Mn) is 1,000 to 70,000 (3) Isotacticity of the α-olefin moiety is 1 to 50%

[0028] The amino group-modified polyolefin (X) contains, as constituent materials, the polyolefin (A), an unsaturated (poly)carboxylic acid (anhydride) (B), and a compound (b0) having an amino group and a functional group reactive with a carboxylic acid (anhydride) group. The amino group-modified polyolefin (X) has, for example, the following structure: (A)-<(B)-(b0)>n [where n represents the number of <(B)-(b0)> units per molecule of (A)]

[0029] The amino group-modified polyolefin (X) can be produced, for example, by the following method. (1) React (A), (B), and (b0) (2) (A) and (B) are reacted to obtain an acid-modified polyolefin (a) described below, and the acid-modified polyolefin (a) is reacted with (b0). The acid-modified polyolefin (a) may be further modified with (poly)aminocarboxylic acids and (poly)hydroxycarboxylic acids (m20) reactive with carboxylic acid (anhydride) groups, as described below, lactams and lactones (m21) that are precursors of (m20) [compounds capable of forming (m20)], combinations of carboxy-reactive coupling agents and polycarboxylic acids (meaning acids or their ester-forming derivatives; the same applies hereinafter) (m22), or combinations of two or more of these. The secondary modification may be carried out by (poly)condensation of (m20), ring-opening addition (polymerization) of (m21), or coupling reaction of (m22). Of the above (1) and (2), (2) is preferred.

[0030] The method for producing the amino group-modified polyolefin (X) in the present invention is not particularly limited, but a preferred method is to react the acid-modified polyolefin (a) with a compound (b0) having an amino group and a functional group reactive with a carboxylic acid (anhydride) group in a nitrogen atmosphere at high temperature (e.g., 140 to 280°C) under normal pressure or reduced pressure (e.g., 0.1 to 760 mmHg).

[0031] Requirement (1): The amine value of (X) is 1 to 100 mgKOH / g (hereinafter, only the numerical value may be shown), preferably 3 to 75, and more preferably 5 to 50. If the amine value is less than 1, the resin properties of the thermosetting resin composition (Z) will be poor, and if it exceeds 100, the productivity of the amino group-modified polyolefin (X) will be poor. The amine value can be adjusted appropriately by, for example, the number of double bonds in the polyolefin (A), the weight of the polyolefin (A), the type and weight of the unsaturated carboxylic acid (B), and the type and weight of (b0). The amine value here is a value measured in accordance with JIS K7237:1995.

[0032] Requirement (2): The Mn of the amino group-modified polyolefin (X) is 1,000 to 70,000, preferably 2,000 to 50,000, and more preferably 3,000 to 40,000. If Mn is less than 1,000, the adhesive strength is poor, and if it exceeds 70,000, the resin properties of the thermosetting resin composition (Z) are poor. Furthermore, the Mn of the amino group-modified polyolefin (X) can be appropriately adjusted, for example, by the Mn of the polyolefin (A), the type and amount of the unsaturated carboxylic acid (B), and the type and weight of (b0).

[0033] Requirement (3): The isotacticity of the α-olefin portion of the amino group-modified polyolefin (X) is 1 to 50%, preferably 5 to 40%, and more preferably 10 to 30%. If the isotacticity is less than 1%, the adhesive strength will be poor, and if it exceeds 50%, the compatibility with the epoxy resin (Y) will be poor. The isotacticity (%) of the α-olefin portion of the amino group-modified polyolefin (X) can be appropriately adjusted by the isotacticity (%) of the α-olefin portion of the polyolefin (A).

[0034] <Acid-modified polyolefin (a)> The acid-modified polyolefin (a) contains a polyolefin (A) and an unsaturated (poly)carboxylic acid (anhydride) (B) as constituent materials. The weight ratio of the polyolefin (A) to the unsaturated carboxylic acid (B) in the acid-modified polyolefin (a) [polyolefin (A) / unsaturated carboxylic acid (B)] is preferably 80 / 20 to 99.5 / 0.5, more preferably 90 / 10 to 99 / 1, from the viewpoint of the resin properties and adhesive strength of the cured product.

[0035] Preferably, the acid-modified polyolefin (a) is obtained by reacting the above polyolefin (A) with an unsaturated carboxylic acid (B) in the absence or presence of a radical initiator (C). More preferably, the acid-modified polyolefin (a) can be produced by reacting the polyolefin (A) and the unsaturated carboxylic acid (B) in the presence of a radical initiator (C), optionally adding an appropriate organic solvent [for example, a C3-18 hydrocarbon (hexane, heptane, octane, dodecane, benzene, toluene, xylene, etc.), a C3-18 halogenated hydrocarbon (di-, tri-, or tetrachloroethane, dichlorobutane, etc.), a C3-18 ketone (acetone, methyl ethyl ketone, di-t-butyl ketone, etc.), a C3-18 ether (ethyl-n-propyl ether, di-n-butyl ether, di-t-butyl ether, dioxane, etc.)].

[0036] The radical initiator (C) may be a known one, such as an azo initiator (azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), etc.) or a peroxide initiator (dicumyl peroxide, etc.). Of the above radical initiators (C), peroxide initiators are preferred.

[0037] The reaction temperature is preferably 100 to 270°C, more preferably 120 to 250°C, and even more preferably 130 to 240°C, from the viewpoints of the reactivity of the polyolefin (A) and the unsaturated carboxylic acid (B) and productivity.

[0038] The (poly)aminocarboxylic acids and (poly)hydroxycarboxylic acids (m20) reactive with the above-mentioned carboxylic acid (anhydride) groups, lactams and lactones (m21) which are precursors of (m20) [compounds capable of forming (m20)], and carboxy-reactive coupling agents and polycarboxylic acids (meaning acids or their ester-forming derivatives; the same applies below) (m22) are as follows:

[0039] Examples of the (poly)aminocarboxylic acid (m20) include those with C2 to C12, such as amino acids [glycine, alanine, valine, (iso)leucine, phenylalanine, etc.], ω-aminoalkanoic acids (such as ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, etc.), and aromatic aminocarboxylic acids (such as o-, m-, or p-aminobenzoic acid, etc.).

[0040] Examples of the (poly)hydroxycarboxylic acid (m20) include ω-hydroxycaproic acid, salicylic acid, p- or m-hydroxybenzoic acid, glycolic acid, glyceric acid, tartronic acid, malic acid, tartaric acid, and benzilic acid. Examples of the lactam (m21) include those having 4 to 15 carbon atoms (preferably 6 to 12 carbon atoms), such as ε-caprolactam, enantholactam, laurolactam, and undecanolactam. Examples of lactones (m21) include ε-caprolactone, γ-butyrolactone, and γ-valerolactone.

[0041] Among these, ε-caprolactam and 12-aminododecanoic acid are preferred. The amount of (m21) and (m20) used is 1 to 10 moles or more, preferably 1 to 2 moles, per mole of carboxylic acid group (or anhydride group in the case of a carboxylic acid anhydride) contained in the acid-modified polyolefin (a).

[0042] Examples of the carboxy-reactive coupling agent (m22) include compounds having two or more groups reactive with the carboxy group of polycarboxylic acids, such as polyols.

[0043] Examples of the polyol (m22) include dihydric to octahydric or higher low molecular weight polyols (having a hydroxyl equivalent of less than 250) and mixtures of two or more of these. The hydroxyl equivalent means the molecular weight per hydroxyl group based on the hydroxyl value. Examples of the low molecular weight polyol include polyhydric alcohols.

[0044] Examples of polyhydric alcohols include dihydric alcohols (C2 to C20 or more), such as C2 to C12 aliphatic dihydric alcohols [(di)alkylene glycols, such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,2-, 2,3-, 1,3-, or 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and 3-methylpentanediol (hereinafter abbreviated as EG, DEG, PG, DPG, BD, HD, NPG, and MPD, respectively), and dodecanediol, etc.], C6 to C10 alicyclic dihydric alcohols [1,4-cyclohexanediol, cyclohexanedimethanol, etc.], and C8 to C20 aromatic aliphatic dihydric alcohols [xylylene glycol, bis(hydroxyethyl)benzene, etc.], etc.;trihydric to octahydric or higher polyhydric alcohols, such as (cyclo)alkane polyols and their intramolecular or intermolecular dehydration products [glycerin, trimethylolpropane, pentaerythritol, sorbitol, dipentaerythritol, 1,2,6-hexanetriol, erythritol, cyclohexanetriol, mannitol, xylitol, sorbitan, diglycerin and other polyglycerins, etc.], sugars and their derivatives [for example, sucrose, glucose, fructose, mannose, lactose and glucosides (methyl glucoside, etc.)], nitrogen-containing polyols (tertiary amino group-containing polyols and quaternary ammonium group-containing polyols), such as nitrogen-containing diols, such as C1-12 aliphatic, alicyclic and aromatic primary monoamines [methylamine, ethylamine, 1- or 2-propylamine, (iso)amylamine, hexylamine, 1,3-dimethylamine, methyl ... bishydroxyalkyl (C2-4) compounds of tertiary nitrogen-containing polyols such as butylbutylamine, 3,3-dimethylbutylamine, 1-, 2-, or 3-aminoheptane, nonylamine, decylamine, undecylamine, dodecylamine, cyclopropylamine, cyclopentylamine, cyclohexylamine, aniline, and benzylamine [bis(2-hydroxyethyl) compounds, bis(hydroxypropyl) compounds, and the like, for example, the tertiary nitrogen-containing polyols described in U.S. Pat. No. 4,271,217] and their quaternization products [quaternization products with a quaternizing agent or dialkyl carbonate (dimethyl carbonate, and the like) described in the above U.S. patents], for example, the quaternary nitrogen-containing polyols described in the above U.S. patents; trivalent to octavalent or higher nitrogen-containing polyols such as trialkanol (C2-4) amines (triethanolamine, and the like), and their quaternization products similar to those described above;

[0045] Examples of polycarboxylic acids include dicarboxylic acids and tri-, tetra- or higher-valent polycarboxylic acids. Examples of these include saturated and unsaturated aliphatic polycarboxylic acids having C2 to C30 or more (preferably C2 to C12), such as C2 to C15 dicarboxylic acids (e.g., oxalic acid, succinic acid, malonic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, itaconic acid, etc.), C6 to C20 tricarboxylic acids (e.g., tricarballylic acid, hexanetricarboxylic acid, etc.), C8 to C15 aromatic polycarboxylic acids, such as dicarboxylic acids (e.g., terephthalic acid, isophthalic acid, phthalic acid, etc.), tri- or tetra-carboxylic acids. (for example, trimellitic acid, pyromellitic acid, etc.); C6-40 alicyclic polycarboxylic acids (dimer acid, etc.); sulfo group-containing polycarboxylic acids (those obtained by introducing a sulfo group into the above polycarboxylic acids, such as sulfosuccinic acid, sulfomalic acid, sulfoglutaric acid, sulfoadipic acid, sulfoisophthalic acid, and salts thereof [metal salts, for example, salts of alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.) and Group IIB metals (zinc, etc.); ammonium salts; and amine salts and quaternary ammonium salts, etc.]).

[0046] Examples of ester-forming derivatives of polycarboxylic acids include acid anhydrides, lower alkyl (C1-4) esters, acid halides such as succinic anhydride, maleic anhydride, itaconic anhydride, and phthalic anhydride, dimethyl terephthalate, and malonyl dichloride.

[0047] <Epoxy resin (Y)> The epoxy resin (Y) in the present invention has two or more glycidyl groups in the molecule. As (Y), for example, at least one selected from the group consisting of biphenyl-type epoxy resins, naphthalene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, novolac-type epoxy resins, alicyclic epoxy resins, dicyclopentadiene-type epoxy resins, tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, tetraglycidylbisaminomethylcyclohexanone, and N,N,N',N'-tetraglycidyl-m-xylenediamine can be used. Of the above (Y), bisphenol A type epoxy resins, novolac type epoxy resins, and dicyclopentadiene type epoxy resins are preferred.

[0048] <Thermosetting resin composition (Z)> The thermosetting resin composition (Z) of the present invention is a composition containing the amino group-modified polyolefin (X) and the epoxy resin (Y).

[0049] From the viewpoints of adhesive strength, heat resistance, and electrical properties, the content of the epoxy resin (Y) is preferably 5 to 1,000 parts by weight, more preferably 5 to 500 parts by weight, and particularly preferably 5 to 200 parts by weight, per 100 parts by weight of the amino group-modified polyolefin (X).

[0050] If necessary, a reactive diluent (F16) [for example, a monoepoxide such as 2-ethylhexyl glycyl ether] may be used in addition to (Y). In this case, the amount of (F16) is preferably 1 to 10 parts by weight per 100 parts by weight of (Y).

[0051] The thermosetting resin composition (Z) of the present invention contains components (X) and (Y), which allows it to exhibit excellent electrical properties (low dielectric properties) after curing and high adhesiveness between a low-polarity resin substrate such as an LCP and a metal substrate. Furthermore, the thermosetting resin composition (Z) contains components (X) and (Y), which allows it to exhibit excellent electrical properties after curing and high solder heat resistance between a low-polarity resin substrate such as an LCP and a metal substrate. Furthermore, by including the components (X) and (Y), the thermosetting resin composition (Z) can exhibit excellent adhesion between a low-polarity resin substrate such as an LCP and a metal substrate, as well as solder heat resistance and electrical properties (low dielectric properties) after curing. That is, the thermosetting resin composition (Z) is applied to a substrate, and the resulting adhesive coating (adhesive layer) exhibits excellent low dielectric properties after curing. The thermosetting resin composition (Z) of the present invention can be used for various applications (e.g., as an adhesive), but is particularly suitable as an adhesive for printed wiring boards, and particularly suitable as an adhesive for flexible printed wiring boards.

[0052] <Organic solvent (P)> The thermosetting resin composition (Z) of the present invention may further contain an organic solvent (P). The organic solvent (P) used in the present invention is not particularly limited as long as it can dissolve the amino group-modified polyolefin (X) and the epoxy resin (Y). Specific examples of such solvents include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, and decane; alicyclic hydrocarbons such as cyclohexane, cyclohexene, methylcyclohexane, and ethylcyclohexane; halogenated hydrocarbons such as trichloroethylene, dichloroethylene, chlorobenzene, and chloroform; alcohol solvents such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, and phenol; acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone, and acetophenone. ketone-based solvents, cellosolves such as methyl cellosolve and ethyl cellosolve, ester-based solvents such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate and butyl formate, glycol ether-based solvents such as ethylene glycol mono-n-butyl ether, ethylene glycol mono-iso-butyl ether, ethylene glycol mono-tert-butyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-iso-butyl ether, triethylene glycol mono-n-butyl ether and tetraethylene glycol mono-n-butyl ether, and the like, can be used alone or in combination of two or more thereof. Of the above (P), ketone solvents are preferred.

[0053] The amount of the organic solvent (P) is preferably 10 to 1000 parts by weight, more preferably 50 to 800 parts by weight, and particularly preferably 100 to 500 parts by weight, per 100 parts by weight of the amino group-modified polyolefin (X) from the viewpoints of handling (coating property) and industrial applications.

[0054] Furthermore, in addition to the above-mentioned (X), (Y), and (P), the thermosetting resin composition (Z) of the present invention may further contain various additives (F) as necessary within a range that does not impair the effects of the present invention. The additive (F) may be one or more selected from the group consisting of a flame retardant (F1), a tackifier (F2), a filler (F3), a silane coupling agent (F4), a colorant (F5), a bulking agent (F6), a lubricant (F7), an antistatic agent (F8), a dispersant (F9), an antioxidant (F10), a release agent (F11), an antibacterial agent (F12), a compatibilizer (F13), an ultraviolet absorber (F14), and a curing accelerator (F15).

[0055] The thermosetting resin composition (Z) of the present invention may contain a flame retardant (F1) as needed. Examples of flame retardants include bromine-based, phosphorus-based, nitrogen-based, and metal hydroxide compounds. Among these, phosphorus-based flame retardants are preferred, and known phosphorus-based flame retardants such as phosphate esters (e.g., trimethyl phosphate, triphenyl phosphate, tricresyl phosphate), phosphates (e.g., aluminum phosphinate), and phosphazenes can be used.

[0056] The thermosetting resin composition (Z) of the present invention may contain a tackifier (F2) as needed. Examples of tackifiers include polyterpene resins, rosin resins, aliphatic petroleum resins, alicyclic petroleum resins, copolymer petroleum resins, styrene resins, and hydrogenated petroleum resins.

[0057] The thermosetting resin composition (Z) of the present invention may optionally contain a filler (F3) such as silica. The incorporation of silica is highly preferred because it improves heat resistance. Generally, hydrophobic and hydrophilic silica are known as silica, but in this case, hydrophobic silica treated with dimethyldichlorosilane, hexamethyldisilazane, octylsilane, or the like is preferred to impart moisture absorption resistance.

[0058] The thermosetting resin composition (Z) of the present invention may contain a silane coupling agent (F4) as needed. Adding a silane coupling agent is highly preferred because it improves adhesion to metals and heat resistance. The silane coupling agent is not particularly limited, but examples include those having an unsaturated group, a glycidyl group, and an amino group. Among these, glycidyl group-containing silane coupling agents, such as γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, are more preferred from the standpoint of heat resistance.

[0059] The thermosetting resin composition (Z) of the present invention may contain a colorant (F5) as needed. Examples of the colorant include inorganic pigments (white pigments, cobalt compounds, iron compounds, sulfides, etc.), organic pigments (azo pigments, polycyclic pigments, etc.), and dyes (azo-based, indigoid-based, sulfide-based, alizarin-based, acridine-based, thiazole-based, nitro-based, aniline-based, etc.).

[0060] The thermosetting resin composition (Z) of the present invention may contain a filler (F6) as needed. Examples of the filler include inorganic fillers (calcium carbonate, talc, clay, etc.) and organic fillers (urea, calcium stearate, etc.).

[0061] The thermosetting resin composition (Z) of the present invention may contain a lubricant (F7) as needed, such as calcium stearate, butyl stearate, oleic acid amide, polyolefin wax, and paraffin wax.

[0062] The thermosetting resin composition (Z) of the present invention may contain an antistatic agent (F8) as needed. Examples of the antistatic agent include nonionic, cationic, anionic, or amphoteric surfactants described below and in U.S. Pat. Nos. 3,929,678 and 4,331,447.

[0063] The thermosetting resin composition (Z) of the present invention may optionally contain a dispersant (F9). Examples of dispersants include polymers having an Mn of 1,000 to 20,000, such as vinyl resins, including vinyl resins other than the polyolefin (A) described above (polyvinyl halides (such as polyvinyl chloride and polyvinyl bromide), polyvinyl acetate, polyvinyl alcohol, polymethyl vinyl ether, poly(meth)acrylic acid, poly(meth)acrylic acid esters (such as polymethyl (meth)acrylate), and styrene resins (such as polystyrene and acrylonitrile / styrene (AS) resins)); polyester resins (such as polyethylene terephthalate); polyamide resins (such as 6,6-nylon and 12-nylon); polyether resins (such as polyethersulfone); polycarbonate resins (such as polycondensates of bisphenol A and phosgene), and block copolymers thereof.

[0064] The thermosetting resin composition (Z) of the present invention may contain an antioxidant (F10) as needed. Examples of the antioxidant include phenolic compounds (monocyclic phenols (e.g., 2,6-di-t-butyl-p-cresol), bisphenols (e.g., 2,2'-methylenebis(4-methyl-6-t-butylphenol)), polycyclic phenols (e.g., 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene), sulfur compounds (e.g., dilauryl 3,3'-thiodipropionate), phosphorus compounds (e.g., triphenyl phosphite), and amine compounds (e.g., octylated diphenylamine).

[0065] The thermosetting resin composition (Z) of the present invention may contain a release agent (F11) if necessary. Examples of the release agent include lower (C1-4) alcohol esters of fatty acids (C8-24) (butyl stearate, etc.), polyhydric (dihydric to tetrahydric or higher) alcohol esters of fatty acids (C2-24) (hydrogenated castor oil, etc.), glycol (C2-8) esters of fatty acids (C2-24) (ethylene glycol monostearate, etc.), and liquid paraffin.

[0066] The thermosetting resin composition (Z) of the present invention may contain an antibacterial agent (F12) if necessary. Examples of the antibacterial agent include benzoic acid, sorbic acid, halogenated phenols, organic iodines, nitriles (e.g., 2,4,5,6-tetrachloroisophthalonitrile), thiocyano (methylenebisthianocyanate), N-haloalkylthioimides, copper compounds (e.g., 8-oxyquinoline copper), benzimidazole, benzothiazole, trihaloallyl, triazole, organic nitrogen-sulfur compounds (e.g., Slaof 39), quaternary ammonium compounds, and pyridine-based compounds.

[0067] The thermosetting resin composition (Z) of the present invention may contain a compatibilizer (F13) as needed. Examples of the compatibilizer include modified vinyl polymers having at least one functional group (polar group) selected from the group consisting of an amino group, a hydroxyl group, and a polyoxyalkylene group, such as the polymers described in JP-A-3-258850, modified vinyl polymers having sulfonic acid groups described in JP-A-6-345927, and block polymers having a polyolefin moiety and an aromatic vinyl polymer moiety.

[0068] The thermosetting resin composition (Z) of the present invention may contain an ultraviolet absorber (F14) as needed. Examples of ultraviolet absorbers include benzotriazoles (e.g., 2-(2'-hydroxy-5'-methylphenyl)benzotriazole), benzophenones (e.g., 2-hydroxy-4-methoxybenzophenone), salicylates (e.g., phenyl salicylate), and acrylates (e.g., 2-ethylhexyl-2-cyano-3,3-diphenylacrylate).

[0069] The thermosetting resin composition (Z) of the present invention may contain a curing accelerator (F15) as needed. Examples of the curing accelerator include aliphatic polyamines, aromatic polyamines, secondary amines, tertiary amines (such as diazabicycloundecene), acid anhydrides, imidazole derivatives, organic acid hydrazides, dicyandiamide and its derivatives, and urea derivatives.

[0070] The total content of the additives (F) is, for example, preferably 300% by weight or less based on the total weight of the additives (X) and (Y), and from the viewpoint of the functional expression of each additive (F) and industrial considerations, is more preferably 0.05 to 250% by weight, and even more preferably 0.1 to 200% by weight. The amount of each additive used, based on the total weight of (X) and (Y), is, for example, 200% by weight or less, preferably 10 to 150% by weight; (F2) is, for example, 50% by weight or less, preferably 10 to 40% by weight; (F3) is, for example, 50% by weight or less, preferably 10 to 30% by weight; (F4) is, for example, 30% by weight or less, preferably 10 to 20% by weight; (F5) is, for example, 5% by weight or less, preferably 0.1 to 3% by weight; (F6) is, for example, 5% by weight or less, preferably 0.1 to 1% by weight; (F7) is, for example, 8% by weight or less, preferably 1 to 5% by weight; and (F8) is, for example, (F9) is, for example, 1% by weight or less, preferably 0.1 to 0.5% by weight; (F10) is, for example, 2% by weight or less, preferably 0.05 to 0.5% by weight; (F11) is, for example, 5% by weight or less, preferably 0.01 to 3% by weight; (F12) is, for example, 25% by weight or less, preferably 0.5 to 20% by weight; (F13) is, for example, 15% by weight or less, preferably 0.5 to 10% by weight; (F14) is, for example, 2% by weight or less, preferably 0.05 to 0.5% by weight; and (F15) is, for example, 2% by weight or less, preferably 0.05 to 0.5% by weight.

[0071] When the compounds in (F1) to (F15) are the same and overlap, each compound should not be used in the amount that provides the corresponding additive effect, but should be adjusted according to the purpose of use, taking into consideration that the effects of other additives can also be obtained at the same time.

[0072] <Laminate> The thermosetting resin composition (Z) of the present invention can be used for various purposes, but is preferably used for adhesion, more preferably for adhesion between resin substrates and other resin substrates or metal substrates. The laminate of the present invention is a laminate in which the thermosetting resin composition (Z) is laminated on a substrate (a two-layer laminate of substrate / adhesive layer), or a three-layer laminate of substrate / adhesive layer / substrate). Here, the adhesive layer refers to the layer of adhesive composition remaining after the thermosetting resin composition (Z) of the present invention is applied to a substrate and dried. The laminate of the present invention can be obtained by applying the thermosetting resin composition (Z) of the present invention to various substrates and drying it according to a conventional method, and then laminating another substrate on it.

[0073] <Base material> In the present invention, the substrate is not particularly limited as long as it can be coated with the thermosetting resin composition (Z) of the present invention, dried, and form an adhesive layer. Examples of the substrate include resin substrates such as film-like resins, metal substrates such as metal plates and metal foils, and paper.

[0074] Examples of the resin substrate include polyester resin, polyamide resin, polyimide resin, polyamideimide resin, liquid crystal polymer, polyphenylene sulfide, syndiotactic polystyrene, polyolefin resin, and fluorine-based resin. A film-like resin (hereinafter also referred to as a substrate film layer) is preferred.

[0075] The metal substrate can be any conventionally known conductive material that can be used for circuit boards. Examples of materials include various metals such as SUS, copper, aluminum, iron, steel, zinc, and nickel, as well as their alloys, plated products, and metals treated with other metals such as zinc or chromium compounds. Metal foil is preferred, and copper foil is more preferred. The thickness of the metal foil is preferably 1 μm or more, more preferably 3 μm or more, and even more preferably 10 μm or more. It is also preferably 50 μm or less, more preferably 30 μm or less, and even more preferably 20 μm or less. If the thickness is too thin, it may be difficult to obtain sufficient electrical performance of the circuit, while if the thickness is too thick, the processing efficiency during circuit fabrication may decrease. Metal foil is provided, for example, in a roll form. The shape of the metal foil used in manufacturing the printed wiring board of the present invention is not particularly limited. When a ribbon-shaped metal foil is used, its length is not particularly limited. Its width is also not particularly limited, but is preferably about 250 to 500 cm.

[0076] Examples of the paper include fine paper, kraft paper, roll paper, glassine paper, etc. Examples of the composite material include glass epoxy, etc.

[0077] Of the above-mentioned substrates, polyester resin, polyamide resin, polyimide resin, polyamideimide resin, liquid crystal polymer, polyphenylene sulfide, syndiotactic polystyrene, polyolefin resin, fluorine-based resin, SUS steel plate, copper foil, aluminum foil, and glass epoxy are preferred in terms of adhesion strength with the adhesive composition and durability.

[0078] <Adhesive sheet> The adhesive sheet of the present invention is an adhesive sheet having the laminate. That is, the adhesive sheet is obtained by laminating the laminate and a release substrate via a thermosetting resin composition (Z) [preferably a cured product of (Z)]. Specific configurations include laminate / adhesive layer / release substrate, or release substrate / adhesive layer / laminate / adhesive layer / release substrate. Laminating the release substrate functions as a protective layer for the substrate. Furthermore, by using a release substrate, the release substrate can be released from the adhesive sheet and the adhesive layer can be transferred to another substrate.

[0079] The adhesive sheet of the present invention can be obtained by applying the thermosetting resin composition (Z) of the present invention to various laminates and drying them by known methods. Furthermore, by attaching a release substrate to the adhesive layer after drying, the adhesive can be wound up without causing offset onto the substrate, resulting in excellent operability. Furthermore, the adhesive layer is protected, resulting in excellent storage stability and ease of use. Furthermore, after application to the release substrate and drying, the adhesive layer itself can be transferred to another substrate by attaching another release substrate as needed.

[0080] <Release base material> Examples of release substrates include those in which a coating layer of a filler such as clay, polyethylene, or polypropylene is applied to both sides of paper such as fine paper, kraft paper, roll paper, or glassine paper, and a silicone-based, fluorine-based, or alkyd-based release agent is further applied to each of these coating layers. Other examples include various olefin films such as polyethylene, polypropylene, ethylene-α-olefin copolymer, and propylene-α-olefin copolymer alone, and films such as polyethylene terephthalate to which the release agent is applied. Due to factors such as the release force between the release substrate and the adhesive layer and the adverse effect of silicone on electrical properties, it is preferable to use a polypropylene-sealed coating on both sides of fine paper and an alkyd-based release agent thereon, or to use an alkyd-based release agent on polyethylene terephthalate.

[0081] In the present invention, examples of methods for coating the thermosetting resin composition (Z) onto a substrate include a comma coater and a reverse roll coater. Alternatively, if necessary, an adhesive layer can be formed directly or by transfer onto rolled copper foil or polyimide film, which are materials for forming printed wiring boards. The thickness of the adhesive layer after drying can be appropriately adjusted as necessary, but is preferably in the range of 5 to 200 μm. If the adhesive film thickness is less than 5 μm, the adhesive strength is insufficient. If it is 200 μm or thicker, drying is insufficient, resulting in a large amount of residual solvent, which can cause blisters during pressing in the production of printed wiring boards. The drying conditions are not particularly limited, but the residual solvent content after drying is preferably 1 wt% or less. If it exceeds 1 wt%, the residual solvent tends to foam during pressing of the printed wiring board, causing blisters.

[0082] <Printed wiring board> The term "printed wiring board" as used herein refers to a board that includes, as a component, a laminate formed from a metal foil and a resin substrate that form a conductor circuit. Printed wiring boards are manufactured by conventional methods such as subtractive processes using a metal-clad laminate. The term "printed wiring board" collectively refers to so-called flexible circuit boards (FPCs), flat cables, and circuit boards for tape automated bonding (TAB), in which conductor circuits formed from metal foil are partially or entirely covered with a cover film, screen printing ink, or the like, as needed.

[0083] 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 a printed wiring board consisting of four layers: a base film layer, a metal foil layer, an adhesive layer, and a cover film layer. Alternatively, it can be a printed wiring board consisting of five layers: a base film layer, an adhesive layer, a metal foil layer, an adhesive layer, and a cover film layer.

[0084] Furthermore, if necessary, two or more of the above printed wiring boards may be stacked.

[0085] The thermosetting resin composition (Z) of the present invention can be suitably used in each adhesive layer of a printed wiring board. In particular, when the thermosetting resin composition (Z) of the present invention is used as an adhesive, it has high adhesion not only to conventional polyimide, polyester film, and copper foil constituting printed wiring boards, but also to low-polarity resin substrates such as LCP, and can achieve solder reflow resistance. The adhesive layer itself has excellent low dielectric properties. Therefore, it is suitable as an adhesive composition for use in coverlay films, laminates, resin-coated copper foils, and bonding sheets.

[0086] In the printed wiring board of the present invention, any resin film conventionally used as a substrate for printed wiring boards can be used as the substrate film. Examples of resins for the substrate film include polyester resins, polyamide resins, polyimide resins, polyamideimide resins, liquid crystal polymers, polyphenylene sulfide, syndiotactic polystyrene, polyolefin resins, and fluorine-based resins. In particular, the film has excellent adhesion to low-polarity substrates such as liquid crystal polymers, polyphenylene sulfide, syndiotactic polystyrene, and polyolefin resins.

[0087] <Cover film> The cover film can be any insulating film conventionally known as an insulating film for printed wiring boards. For example, films made from various polymers such as polyimide, polyester, polyphenylene sulfide, polyether sulfone, polyether ether ketone, aramid, polycarbonate, polyarylate, polyimide, polyamide-imide, liquid crystal polymer, polyphenylene sulfide, syndiotactic polystyrene, and polyolefin resin can be used. Polyimide film or liquid crystal polymer film is more preferred.

[0088] The printed wiring board of the present invention may be made of any conventionally known material other than the materials for each layer described above. It can be produced using a process.

[0089] In a preferred embodiment, a semi-finished product is produced in which an adhesive layer is laminated on a cover film layer (hereinafter referred to as a "cover film-side semi-finished product"). On the other hand, a semi-finished product is produced in which a metal foil layer is laminated on a base film layer to form a desired circuit pattern (hereinafter referred to as a "base film-side two-layer semi-finished product"), or a semi-finished product is produced in which an adhesive layer is laminated on a base film layer and a metal foil layer is laminated on top of it to form a desired circuit pattern (hereinafter referred to as a "base film-side three-layer semi-finished product"). Hereinafter, the base film-side two-layer semi-finished product and the base film-side three-layer semi-finished product are collectively referred to as a "base film-side semi-finished product"). By bonding the cover film-side semi-finished product thus obtained and the base film-side semi-finished product together, a four-layer or five-layer printed wiring board can be obtained.

[0090] The substrate film semi-finished product can be obtained, for example, by a manufacturing method including: (1) a step of applying a solution of a resin that will become the substrate film to the metal foil and initially drying the coating; and (2) a step of heat-treating and drying the laminate of the metal foil and the initially dried coating obtained in (1) (hereinafter referred to as the "heat-treatment and desolvation step").

[0091] The circuit can be formed on the metal foil layer by a conventionally known method. Either an active method or a subtractive method may be used. The subtractive method is preferred.

[0092] The obtained semi-finished product on the base film side may be used as it is for bonding to the semi-finished product on the cover film side, or may be used for bonding to the semi-finished product on the cover film side after a release film has been attached and stored.

[0093] The cover film semi-finished product is produced, for example, by applying an adhesive to the cover film. If necessary, a crosslinking reaction can be carried out in the applied adhesive. In a preferred embodiment, the adhesive layer is semi-cured.

[0094] The obtained cover film side semi-finished product may be used as it is for bonding to the substrate side semi-finished product, or may be used for bonding to the substrate film side semi-finished product after a release film is attached and stored.

[0095] The substrate film-side semi-finished product and the cover film-side semi-finished product are stored, for example, in the form of a roll, and then bonded together to produce a printed wiring board. Any bonding method can be used, and for example, they can be bonded together using a press or a roll. They can also be bonded together while heating them using a method such as a hot press or a hot roll device.

[0096] For example, in the case of a reinforcing material that is soft and can be wound up, such as a polyimide film, the reinforcing material semi-finished product is preferably produced by applying an adhesive to the reinforcing material. Furthermore, in the case of a reinforcing plate that is hard and cannot be wound up, such as a metal plate such as SUS or aluminum, or a plate made of glass fiber cured with an epoxy resin, it is preferably produced by transfer coating an adhesive that has been applied in advance to a release substrate. If necessary, a crosslinking reaction can be carried out in the applied adhesive. In a preferred embodiment, the adhesive layer is semi-cured.

[0097] The obtained semi-finished product on the reinforcing material side may be used as it is for bonding to the rear surface of a printed wiring board, or may be used for bonding to a semi-finished product on the base film side after a release film has been attached and stored.

[0098] The substrate film side semi-finished product, the cover film side semi-finished product, and the reinforcing agent side semi-finished product are all laminates for printed wiring boards of the present invention.

[0099] <Cured product> The cured product of the present invention is a cured product obtained by curing the thermosetting resin composition (Z). That is, the cured product can be obtained by, for example, applying and casting the thermosetting resin composition (Z), removing the organic solvent (P) as needed, and then heating (preferably at 90 to 200°C, preferably for 1 minute to 6 hours). The shape of the cured product can be selected appropriately depending on the application, and examples include a coating film (preferably 5 to 1000 μm thick) and a cast product. [Example]

[0100] The present invention will be further described below with reference to examples, but is not limited to these. In the examples, the number average molecular weight (Mn), the number of double bonds of the polyolefin, the isotacticity, the acid value, and the amine value were measured by the methods described above.

[0101] <Production Example 1> A reaction vessel was charged with 1,000 parts by weight of a high molecular weight polyolefin (A0-1) containing 85% by weight of propylene and 15% by weight of ethylene as constituent monomers [trade name "Vistamaxx 6202", manufactured by Exxonmobil, Mn 76,000], and while nitrogen was passed through the liquid phase, the mixture was heated and melted using a mantle heater. Thermal degradation was then carried out with stirring at 375°C for 40 minutes, yielding polyolefin (A-1). The polyolefin (A-1) had an Mn of 6,000, a molecular chain containing 3.0 double bonds per 1,000 carbon atoms, and an isotacticity of 20%.

[0102] <Production Examples 2 to 5, Comparative Production Examples 1 to 2> Each polyolefin (A) was obtained in the same manner as in Production Example 1, except that the polyolefin (A) and thermal degradation conditions in Production Example 1 were according to Table 1. The results are shown in Table 1.

[0103] [Table 1]

[0104] <Production Example 11> A reaction vessel was charged with 100 parts by weight of polyolefin (A-1) and 5 parts by weight of maleic anhydride (B-1). After nitrogen substitution, the mixture was heated to 180°C under nitrogen flow to dissolve uniformly. A solution of 1.3 parts by weight of a radical initiator (dicumyl peroxide, trade name "Percumyl D", manufactured by NOF Corporation) (C-1) dissolved in 5 parts by weight of xylene was added dropwise over 5 minutes, followed by stirring for 1 hour under reflux with xylene. Unreacted maleic anhydride was then distilled off under reduced pressure (1.5 kPa) to obtain acid-modified polyolefin (a-1). The acid-modified polyolefin (a-1) had an acid value (mgKOH / g): 24, Mn: 13,000, and isotacticity (%): 20.

[0105] <Production Examples 12 to 20, Comparative Production Examples 11 to 12> In Production Example 11, the same procedure as in Production Example 11 was carried out except that the raw materials used were those shown in Table 2. Each acid-modified polyolefin (a) was obtained. The results are shown in Table 2.

[0106] [Table 2]

[0107] <Production Example 21> A reaction vessel was charged with 100 parts by weight of acid-modified polyolefin (a-1), 10 parts by weight of 6-aminohexanoic acid (m20-1), and 4.4 parts of N,N-dimethyl-1,3-propanediamine (b0-4) under a nitrogen atmosphere, and the mixture was reacted at 220°C and atmospheric pressure for 8 hours. The water produced by the reaction was then distilled off under reduced pressure (1.0 kPa) for 3 hours to obtain amino-modified polyolefin (X-1). (X-1) had an amine value (mgKOH / g) of 21, an Mn of 15,000, and an isotacticity (%) of the α-olefin moiety of 20.

[0108] <Production Example 22> A reaction vessel was charged with 100 parts by weight of acid-modified polyolefin (a-2), 10 parts by weight of 12-aminododecanoic acid (m20-2), 15 parts by weight of ε-caprolactam (m21-1), and 2.6 parts by weight of bis(4-aminocyclohexyl)methane (b0-3) under a nitrogen atmosphere, and the mixture was reacted at 220°C under pressure (2.0 MPa) for 8 hours. After that, unreacted ε-caprolactam (m21-1), unreacted bis(4-aminocyclohexyl)methane (b0-3), and water produced by the reaction were distilled off under reduced pressure (1.0 kPa) over 3 hours, thereby obtaining an amino group-modified polyolefin (X-2).

[0109] <Production Examples 23 to 30, Comparative Production Examples 21 to 22> Each amino group-modified polyolefin (X) was obtained in the same manner as in Production Example 22, except that the raw materials used (parts by weight) were in accordance with Table 3. The results are shown in Table 3.

[0110] [Table 3]

[0111] Example 1 A 500 ml four-neck flask equipped with a water-cooled reflux condenser and a stirrer was charged with 100 parts by weight of amino-modified polyolefin (X-1), 200 parts by weight of methylcyclohexanone (P-1), and 200 parts by weight of methyl ethyl ketone (P-2). The mixture was heated to 80°C with stirring and dissolved by continuing stirring for 1 hour. The solution was cooled to 50°C, and 10 parts by weight of epoxy resin (Y-1) [YDCN-700-10] was blended to obtain a thermosetting resin composition (Z-1).

[0112] <Examples 2 to 20, Comparative Examples 1 and 2> Each thermosetting resin composition (Z) was obtained in the same manner as in Example 1, except for following Table 4. Each obtained thermosetting resin composition (Z) was evaluated for adhesive strength, solder heat resistance, and electrical properties (frequency 1 MHz). The results are shown in Table 4.

[0113] (1) Peel strength (adhesion strength) The thermosetting resin composition (Z) was applied to a 25 μm thick polyimide film (Apical, manufactured by Kaneka Corporation) so that the thickness after drying would be 25 μm, and then dried at 130° C. for 3 minutes. The adhesive film (B-stage product) thus obtained was laminated to 18 μm rolled copper foil. The lamination was performed at 160°C and 40 kgf / cm with the shiny side of the rolled copper foil in contact with the adhesive. 2 The adhesive was applied for 30 seconds under a pressure of 1000 kJ / cm. The film was then cured by heat treatment at 140°C for 4 hours to obtain a sample for peel strength evaluation. The peel strength was measured by a 90° peel test at 25°C, with the film pulled at a tensile speed of 50 mm / min. This test indicates the adhesive strength at room temperature.

[0114] <Evaluation criteria> ◎:1.5N / mm or more ○: 1.0N / mm or more and less than 1.5N / mm △: 0.8N / mm or more and less than 1.0N / mm ×: Less than 0.8N / mm

[0115] (2) Solder heat resistance (heat resistance) Samples were prepared in the same manner as in (2) above, and 2.5 cm x 2.5 cm sample pieces were dried at 120°C for 30 minutes, and then flowed in a molten solder bath at each temperature for 1 minute, and the temperature at which no changes in appearance such as swelling occurred was measured.

[0116] <Evaluation criteria> ◎: 300℃ or higher ○: 290℃ or higher and lower than 300℃ △: 270℃ or higher but lower than 290℃ ×: Less than 270℃

[0117] (3) Dielectric constant (ε) and dielectric loss tangent (tanδ) [Electrical properties] The thermosetting resin composition (Z) was applied to a release film having a thickness of 50 μm so that the thickness after drying would be 30 μm, and then dried at 130° C. for 3 minutes. The film was then cured by heat treatment at 140°C for 4 hours, and then peeled off from the release film and measured. Measurements were performed using a Precision LCR meter HP-4284A at 22°C, 58% RH, and a frequency of 1 MHz, and the results were evaluated as follows. Similarly, measurements were performed using a Vector Network Analyzer HP8510C, Synthesized Sweeper HP83651A, and Test Set HP8517B at 22°C, 58% RH, and a frequency of 1 GHz, and the results were evaluated as follows.

[0118] <Evaluation criteria for dielectric constant> ◎: 2.3 or less ○: Over 2.3 and 2.6 or less △: Over 2.6 and 3.0 or less ×: Over 3.0 <Evaluation criteria for dielectric loss tangent> ◎: 0.005 or less ○: Over 0.005 and 0.01 or less △: Over 0.01 and 0.02 or less ×: More than 0.02

[0119] [Table 4]

[0120] The results in Tables 1 to 4 show that the thermosetting resin composition (Z) of the present invention has superior adhesive strength compared to the comparative compositions, and the cured product has excellent heat resistance and electrical properties. [Industrial Applicability]

[0121] The thermosetting resin composition (Z) of the present invention has excellent adhesive strength. Furthermore, the cured product has excellent heat resistance and electrical properties (low dielectric properties) [dielectric constant, dielectric loss tangent]. Therefore, it can be used for various applications, preferably for adhesion, and more preferably for adhesion between resin substrates and other resin substrates or metal substrates.

Claims

1. The present invention comprises an amino group-modified polyolefin (X) and an epoxy resin (Y), wherein the amino group-modified polyolefin (X) comprises, as constituent raw materials, a polyolefin (A), an unsaturated (poly)carboxylic acid (anhydride) (B), and a compound (b0) having an amino group and a functional group reactive with a carboxylic acid (anhydride) group, the compound being a polyamine compound having two or more amino groups and having at least one group of at least one kind selected from the group consisting of a primary amino group and a secondary amino group, and the polyolefin (A) is a polyolefin containing ethylene and an α-olefin (having 3 to 8 carbon atoms) as essential constituent monomers, and a polymer of the ethylene and the α-olefin (having 3 to 8 carbon atoms) as constituent monomers. A thermosetting resin composition (Z) (which does not contain water) is an adhesive for printed wiring boards, the composition having a weight ratio [ethylene / α-olefin] of 5 / 95 to 50 / 50, a weight ratio [(A) / (B)] of the polyolefin (A) to the unsaturated (poly)carboxylic acid (anhydride) (B) of 80 / 20 to 99.5 / 0.5, a compound (b0) of 0.3 to 16% by weight based on the total weight of the polyolefin (A) and the unsaturated (poly)carboxylic acid (anhydride) (B), and the amino group-modified polyolefin (X) satisfies all of the following requirements (1) to (3): (1) Amine value is 1 to 100 mg KOH / g (2) Number average molecular weight (Mn) of 1,000 to 70,000 (3) Isotacticity of the α-olefin portion is 1 to 50%

2. 2. The thermosetting resin composition according to claim 1, wherein the organic solvent (P) is contained in an amount of 10 to 1,000 parts by weight per 100 parts by weight of the amino group-modified polyolefin (X).

3. A thermosetting resin composition according to claim 1 or 2, used for bonding a resin substrate to a metal substrate.

4. A laminate comprising a resin substrate and a metal substrate bonded together by the thermosetting resin composition (Z) according to any one of claims 1 to 3.

5. An adhesive sheet comprising the laminate according to claim 4 .

6. A printed wiring board comprising the laminate according to claim 4 or the adhesive sheet according to claim 5 as a constituent element.

7. A cured product obtained by curing the thermosetting resin composition (Z) according to any one of claims 1 to 3.

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