JP7729066B2 - thermosetting resin composition - Google Patents

Description

The present invention relates to a thermosetting resin composition.

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 this demand, liquid crystal polymers (LCPs), syndiotactic polystyrene (sPS), polyphenylene sulfide (PPS), and the like, which have low dielectric properties, have been proposed as substrates for flexible printed circuit boards (FPCs) instead of conventional polyimide (PI) and polyethylene terephthalate films.
However, because substrates with low dielectric properties have low polarity, when conventional epoxy-based or acrylic-based adhesives are used, the adhesive strength is weak, making it difficult to produce FPC components such as coverlay films and laminates. Furthermore, epoxy-based and acrylic-based 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.

Japanese Patent Application Laid-Open No. 2007-284515 Japanese Patent Application Laid-Open No. 2007-63306

However, while the compositions of Patent Documents 1 and 2 are described as having adhesive properties with polyimide, they have difficulty achieving adhesion to substrates with low dielectric properties, such as LCP. Furthermore, because they are used as modifiers and the adhesive composition contains a small amount of olefin backbone, the dielectric properties of the adhesive are poor. When using an LCP substrate, a method exists in which the LCP is melted without an adhesive and then laminated to copper foil to create 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 yields.

In other words, the 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).

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, the weight ratio of the ethylene to the α-olefin (having 3 to 8 carbon atoms) as constituent monomers [ethylene/α-olefin] being 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) of 1,000 to 70,000
(3) Isotacticity of the α-olefin portion is 1 to 50%

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 loss tangent].

<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, it is preferable to use one α-olefin.
Of the above α-olefins, propylene is preferred from the viewpoint of adhesive strength of the cured product and industrial applications.

The weight ratio of ethylene to α-olefin, which are constituent monomers of 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 is poor, and if it exceeds 50/50, the heat resistance is poor.
The weight ratio [ethylene/α-olefin] can be calculated, for example, by ¹ H-MNR (nuclear magnetic resonance spectroscopy).

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 C4 to C30 unsaturated monomers other than α-olefins (for example, vinyl acetate).

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 components (A), ethylene/propylene copolymers are preferred.

In the present invention, the Mn of 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.

In the present invention, the conditions for measuring Mn by GPC are as follows.
Apparatus: High-temperature gel permeation chromatograph ["Alliance GPCV2000", manufactured by Waters Corporation]
Detector: Refractive index detector Solvent: Orthodichlorobenzene Reference material: Polystyrene Sample concentration: 3 mg/ml
Column stationary phase: PLgel 10 μm, MIXED-B (two columns in series) [manufactured by Polymer Laboratories, Inc.]
Column temperature: 135°C

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 can be determined from the ^1H -NMR spectrum of polyolefin (A). That is, 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 integrated value at 4.5 to 6 ppm of polyolefin (A) derived from the double bonds and the integrated value derived from 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 follows this method.

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.

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

Isotacticity (%) = [(Ha) / Σ(H)] × 100 (2)

In the formula, H a 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.

The conditions for measuring isotacticity in the present invention are as follows.
・Device: JEOL Ltd. ECZ400R
Measurement mode: Proton decoupling method Pulse width: 8 μsec
Pulse repetition time: 4.6 seconds
Relaxation time: 3.0 seconds
・Number of measurements: 10,000 ・Solvent: orthodichlorobenzene ・Reference material: tetramethylsilane ・Sample concentration: 10 mg/mL
・Measurement temperature: 120℃

The polyolefin (A) of 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 an Mn of 80,000 to 250,000).

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 composition having a larger number of double bonds at the molecular terminals and/or in the molecular chain.

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.

<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 to C24, e.g., acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, isocrotonic acid), and alicyclic monocarboxylic acids (C6 to C24, e.g., cyclohexenecarboxylic acid); and examples of unsaturated poly(2 to 3 or more)carboxylic acids or their anhydrides include unsaturated dicarboxylic acids or their anhydrides [aliphatic dicarboxylic acids or their anhydrides (C4 to C24, e.g., maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and their anhydrides), and alicyclic dicarboxylic acids or their anhydrides (C8 to C24, 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 of two or more.
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.

<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.

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 2 to 69 carbon atoms, 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, nonanmethylenediamine, decanemethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-/2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, 2,4-dimethyloctamethylenediamine, metaxylylenediamine, paraxylylenediamine Examples of the alkyl esters 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 4 to 69 carbon atoms, such as 2-dimethylaminoethanol, 2-diethylaminoethanol, m-dimethylaminophenol, and N-methyldiethanolamine.

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. 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 as amino groups only.

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

<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) of 1,000 to 70,000
(3) Isotacticity of the α-olefin portion is 1 to 50%

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)]

The amino group-modified polyolefin (X) can be produced, for example, by the following method.
(1) Reacting (A), (B), and (b0) (2) Reacting (A) and (B) to obtain an acid-modified polyolefin (a) described below, and then reacting the acid-modified polyolefin (a) 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)], a combination (m22) of a carboxy-reactive coupling agent and a polycarboxylic acid (meaning an acid or its ester-forming derivative; the same applies hereinafter), or a combination of two or more of these, and then reacted with (b0). The secondary modification may be carried out by (poly)condensation of (m20), ring-opening addition (polymerization) of (m21), or a coupling reaction of (m22).
Of the above (1) and (2), (2) is preferred.

The method for producing the amino group-modified polyolefin (X) in the present invention is not particularly limited, but a preferred method involves reacting 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) and at normal or reduced pressure (e.g., 0.1 to 760 mmHg).

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 appropriately adjusted 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.

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 the 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).

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).

<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.

Preferably, the acid-modified polyolefin (a) is obtained by reacting the polyolefin (A) with an unsaturated carboxylic acid (B) in the absence or presence of a radical initiator (C).
The acid-modified polyolefin (a) can more preferably be produced by reacting the polyolefin (A) and the unsaturated carboxylic acid (B) in the presence of the radical initiator (C), optionally adding an appropriate organic solvent [for example, a C3 to C18 hydrocarbon (hexane, heptane, octane, dodecane, benzene, toluene, xylene, etc.), a C3 to C18 halogenated hydrocarbon (di-, tri-, or tetrachloroethane, dichlorobutane, etc.), a C3 to C18 ketone (acetone, methyl ethyl ketone, di-t-butyl ketone, etc.), a C3 to C18 ether (ethyl-n-propyl ether, di-n-butyl ether, di-t-butyl ether, dioxane, etc.)].

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.

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.

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 hereinafter) (m22) are as follows:

(m20) (poly)aminocarboxylic acids include those having a C2 to C12 chain, 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.).

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 lactams (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.

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).

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

The polyol (m22) may be a dihydric to octahydric or higher low-molecular-weight polyol (having a hydroxyl equivalent of less than 250), or a mixture of two or more of these. The hydroxyl equivalent refers to the molecular weight per hydroxyl group based on the hydroxyl value. Examples of low-molecular-weight polyols include polyhydric alcohols.

Examples of polyhydric alcohols include dihydric alcohols (C2-20 or higher), such as C2-12 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.], C6-10 alicyclic dihydric alcohols [1,4-cyclohexanediol and cyclohexanediol, etc.], xane dimethanol, etc.], C8-20 aromatic aliphatic dihydric alcohols [xylylene glycol, bis(hydroxyethyl)benzene, etc.], etc.; trihydric to octahydric or higher polyhydric alcohols, for example, (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 (such as methyl glucoside)], nitrogen-containing polyols (tertiary amino group-containing polyols and quaternary ammonium group-containing polyols): for example, nitrogen-containing diols, for example, C1-12 aliphatic, alicyclic, and aromatic primary monoamines [methylamine, ethylamine, 1- or 2-propylamine, (iso)amylamine, hexylamine, 1,3-dimethylbutylamine, 3,3-dimethylbutylamine, 1-, 2-, or 3-aminoheptane, nonylamine, decylamine, undecylamine, dodecylamine, cyclopropylamine, cyclopentylamine, cyclohexylamine, aniline, benzylamine, etc.)] and their quaternized derivatives [bis(2-hydroxyethyl) derivatives, bis(hydroxypropyl) derivatives, etc., such as the tertiary nitrogen atom-containing polyols described in U.S. Pat. No. 4,271,217] and their quaternized derivatives [quaternized with a quaternizing agent or dialkyl carbonate (dimethyl carbonate, etc.) described in the above U.S. patents], such as the quaternary nitrogen atom-containing polyols described in the above U.S. patents; trivalent to octavalent or higher nitrogen-containing polyols, such as trialkanol (C2-4) amines (triethanolamine, etc.)] and their quaternized derivatives similar to those described above.

Polycarboxylic acids include dicarboxylic acids and tri-, tetra- or higher-valent polycarboxylic acids. Examples include saturated and unsaturated aliphatic polycarboxylic acids of C2-30 or more (preferably C2-12), such as C2-15 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.) and C6-20 tricarboxylic acids (e.g., tricarballylic acid, hexanetricarboxylic acid, etc.); aromatic polycarboxylic acids of C8-15, such as dicarboxylic acids (e.g., terephthalic acid, isophthalic acid, phthalic acid, etc.), and tri- or tetra-carboxylic acids. (e.g., trimellitic acid, pyromellitic acid, etc.); C6-40 alicyclic polycarboxylic acids (dimer acid, etc.); sulfo group-containing polycarboxylic acids (those obtained by introducing sulfo groups into the above polycarboxylic acids, such as sulfosuccinic acid, sulfomalic acid, sulfoglutaric acid, sulfoadipic acid, sulfoisophthalic acid, and salts thereof [metal salts, such as 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]).

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.

<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-xylylenediamine can be used.
Of the above (Y), bisphenol A type epoxy resins, novolac type epoxy resins, and dicyclopentadiene type epoxy resins are preferred.

<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).

From the viewpoints of adhesive strength, heat resistance, and electrical properties, the content of 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 amino group-modified polyolefin (X).

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).

The thermosetting resin composition (Z) of the present invention contains the components (X) and (Y), which allows the composition 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 the components (X) and (Y), which allows the composition 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 containing the components (X) and (Y), it is possible to exhibit, after curing, all of excellent adhesion between a low-polarity resin substrate such as an LCP and a metal substrate, solder heat resistance, and electrical properties (low dielectric properties). That is, the thermosetting resin composition is applied to a substrate, and the adhesive coating film (adhesive layer) after curing exhibits excellent low dielectric constant properties. The thermosetting resin composition (Z) of the present invention can be used for various applications (for example, as an adhesive), but is suitable as an adhesive for printed wiring boards, and particularly suitable as an adhesive for flexible printed wiring boards.

<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 such as those listed above, 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.

From the viewpoints of handling (applicability) and industrial applications, the amount of organic solvent (P) is preferably 10 to 1,000 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 amino group-modified polyolefin (X).

Furthermore, in addition to the above-described (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).

The thermosetting resin composition (Z) of the present invention may optionally contain a flame retardant (F1). 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), phosphate salts (e.g., aluminum phosphinate), and phosphazenes can be used.

The thermosetting resin composition (Z) of the present invention may optionally contain a tackifier (F2). Examples of tackifiers include polyterpene resins, rosin-based resins, aliphatic petroleum resins, alicyclic petroleum resins, copolymer petroleum resins, styrene resins, and hydrogenated petroleum resins.

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

The thermosetting resin composition (Z) of the present invention may optionally contain a silane coupling agent (F4). Adding a silane coupling agent is highly preferred because it improves adhesion to metals and heat resistance. Silane coupling agents are not particularly limited, but examples include those containing unsaturated groups, glycidyl groups, and amino groups. Of 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.

The thermosetting resin composition (Z) of the present invention may optionally contain a colorant (F5). Examples of colorants 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.).

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

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

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

The thermosetting resin composition (Z) of the present invention may optionally contain a dispersant (F9). Examples of dispersants include polymers with an Mn of 1,000 to 20,000, such as vinyl resins. Examples of dispersants include vinyl resins other than the polyolefin (A) described above, such as 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) resin); 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.

The thermosetting resin composition (Z) of the present invention may optionally contain an antioxidant (F10). Examples of antioxidants 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).

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

The thermosetting resin composition (Z) of the present invention may optionally contain an antibacterial agent (F12). Examples of antibacterial agents 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.

The thermosetting resin composition (Z) of the present invention may optionally contain a compatibilizer (F13). Examples of compatibilizers include modified vinyl polymers having at least one functional group (polar group) selected from the group consisting of amino groups, hydroxyl groups, and polyoxyalkylene groups, 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 portion and an aromatic vinyl polymer portion.

The thermosetting resin composition (Z) of the present invention may optionally contain an ultraviolet absorber (F14). 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).

The thermosetting resin composition (Z) of the present invention may contain a curing accelerator (F15) as needed. Examples of curing accelerators 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.

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 viewpoints of functional expression of each additive (F) and industrial applications, 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, (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.

When the same compound overlaps among the above (F1) to (F15), each compound should not be used in the amount that produces the corresponding additive effect, but rather the amount used should be adjusted according to the intended use, taking into consideration that the effects of other additives can also be obtained at the same time.

<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 according to a conventional method, drying it, and then laminating another substrate on it.

<Base material>
In the present invention, the substrate is not particularly limited as long as it can form an adhesive layer by applying and drying the thermosetting resin composition (Z) of the present invention, and examples thereof include resin substrates such as film-like resins, metal substrates such as metal plates and metal foils, and papers.

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

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 be reduced. The 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.

Examples of paper include fine paper, kraft paper, roll paper, and glassine paper. Examples of composite materials include glass epoxy.

Of the above substrates, polyester resin, polyamide resin, polyimide resin, polyamide-imide 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.

<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.

The adhesive sheet of the present invention can be obtained by applying the thermosetting resin composition (Z) of the present invention to various laminates by known methods and drying them. 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 a release substrate and drying, the adhesive layer itself can be transferred to another substrate by attaching another release substrate as needed.

<Release base material>
Examples of release substrates include those prepared by providing coating layers of a filler such as clay, polyethylene, or polypropylene on both sides of paper such as fine paper, kraft paper, roll paper, or glassine paper, with a silicone-based, fluorine-based, or alkyd-based release agent further coated on 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, as well as films such as polyethylene terephthalate coated with the above-mentioned release agent. 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 polypropylene-sealed coatings on both sides of fine paper and then apply an alkyd-based release agent thereon, or polyethylene terephthalate coated with an alkyd-based release agent.

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 applied directly or by transfer to rolled copper foil or polyimide film, which are materials used to construct printed wiring boards. The thickness of the adhesive layer after drying can be adjusted as needed, 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. Drying conditions are not particularly limited, but a residual solvent content after drying of 1% by weight or less is preferred. If it exceeds 1% by weight, the residual solvent tends to foam during pressing of the printed wiring board, causing blisters.

<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. The printed wiring board is manufactured by a conventionally known method, such as a subtractive method, using a metal-clad laminate. The term "printed wiring board" collectively refers to flexible circuit boards (FPCs), flat cables, circuit boards for tape automated bonding (TAB), and the like, in which a conductor circuit formed from metal foil is partially or entirely covered with a cover film, screen printing ink, or the like, as needed.

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. It can also 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.

Furthermore, if necessary, two or more of the above printed wiring boards can be stacked.

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 exhibits high adhesion not only to the conventional polyimide, polyester film, and copper foil that make up printed wiring boards, but also to low-polarity resin substrates such as LCP, and can achieve solder reflow resistance, and 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 foil, and bonding sheets.

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 resin, polyamide resin, polyimide resin, polyamideimide resin, liquid crystal polymer, polyphenylene sulfide, syndiotactic polystyrene, polyolefin resin, and fluorine-based resin. In particular, the film has excellent adhesion even to low-polarity substrates such as liquid crystal polymer, polyphenylene sulfide, syndiotactic polystyrene, and polyolefin resin.

<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.

The printed wiring board of the present invention can be manufactured by any conventionally known process, except for using the materials for each layer described above.

In a preferred embodiment, a semi-finished product is produced in which an adhesive layer is laminated onto a cover film layer (hereinafter referred to as a "cover film-side semi-finished product"). Alternatively, a semi-finished product is produced in which a metal foil layer is laminated onto 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 onto a base film layer and a metal foil layer is laminated thereon 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 "base film-side semi-finished product"). By bonding the cover film-side semi-finished product and the base film-side semi-finished product thus obtained together, a four-layer or five-layer printed wiring board can be obtained.

The substrate film semi-finished product can be obtained, for example, by a manufacturing method including: (1) a step of applying a solution of the 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/solvent-removal step").

Formation of circuits in the metal foil layer can be achieved using conventional methods. Active or subtractive methods may be used. Subtractive methods are preferred.

The resulting substrate film semi-finished product may be used as is to be bonded to the cover film semi-finished product, or it may be used to bond to the cover film semi-finished product after a release film has been attached and stored.

The cover film side 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.

The resulting cover film semi-finished product may be used as is to be bonded to the substrate semi-finished product, or it may be used to bond to the substrate film semi-finished product after a release film has been attached and stored.

The base film semi-finished product and the cover film semi-finished product are stored, for example, in roll form, and then laminated together to produce a printed wiring board. Any lamination method can be used, and they can be laminated together using a press or roll, for example. They can also be laminated together while heating, using a heated press or heated roll device, for example.

For example, in the case of a reinforcing material that is soft and can be wound up, such as 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 (e.g., SUS or aluminum) or a plate made of glass fiber cured with epoxy resin, it is preferable to produce the reinforcing material semi-finished product 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.

The resulting reinforcing material semi-finished product may be used as is to be bonded to the backside of a printed wiring board, or it may be stored with a release film attached and then used to be bonded to a base film semi-finished product.

The base film side semi-finished product, cover film side semi-finished product, and reinforcing agent side semi-finished product are all laminates for printed wiring boards according to the present invention.

<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 appropriately selected depending on the application, and examples include a coating film (preferably 5 to 1000 μm thick) and a cast product.

The present invention will be further explained below with reference to examples, but the present invention is not limited to these examples. 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 using the methods described above.

<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 aerating nitrogen into the liquid phase, the mixture was heated and melted using a mantle heater. Thermal degradation was 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%.

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

<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 aeration to achieve a uniform solution. 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, and the mixture was then stirred for 1 hour under reflux with xylene. Subsequently, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa) to obtain an acid-modified polyolefin (a-1).
The acid-modified polyolefin (a-1) had an acid value (mgKOH/g): 24, Mn: 13,000, and isotacticity (%): 20.

<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.

<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 normal pressure for 8 hours. The water produced by the reaction was then distilled off under reduced pressure (1.0 kPa) over 3 hours to obtain amino group-modified polyolefin (X-1). (X-1) had an amine value (mg KOH/g) of 21, an Mn of 15,000, and an isotacticity (%) of the α-olefin moiety of 20.

<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. Thereafter, 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).

<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.

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 group-modified polyolefin (X-1), 200 parts by weight of methylcyclohexanone (P-1), and 200 parts by weight of methyl ethyl ketone (P-2), and the mixture was heated to 80°C with stirring and dissolved by continuing stirring for 1 hour. 10 parts by weight of epoxy resin (Y-1) [YDCN-700-10] was blended with the resulting solution cooled to 50°C to obtain a thermosetting resin composition (Z-1).

<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 of the obtained thermosetting resin compositions (Z) was evaluated for adhesive strength, solder heat resistance, and electrical properties (frequency 1 MHz).
The results are shown in Table 4.

(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 by pressing the foil with the shiny side in contact with the adhesive at 160° C. under a pressure of 40 kgf/ ^cm for 30 seconds.
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 pulling rate of 50 mm/min. This test indicates the adhesive strength at room temperature.

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

(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.

<Evaluation criteria>
◎: 300°C or higher ○: 290°C or higher but less than 300°C △: 270°C or higher but less than 290°C ×: Less than 270°C

(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 carried out using a Precision LCRmeter HP-4284A at 22°C, 58% RH, and a frequency of 1 MHz, and the results were evaluated as follows. Similarly, measurements were carried out using a Vector Network Analyzer HP8510C, a Synthesized Sweeper HP83651A, and a Test Set HP8517B at 22°C, 58% RH, and a frequency of 1 GHz, and the results were evaluated as follows.

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

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.

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 dissipation factor]. For this reason, it can be used for a variety of applications, but is preferably used for adhesion, and more preferably for adhesion between resin substrates and other resin substrates or metal substrates.

Claims (7)

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% The thermosetting resin composition according to claim 1, containing 10 to 1,000 parts by weight of organic solvent (P) per 100 parts by weight of the amino group-modified polyolefin (X). The thermosetting resin composition according to claim 1 or 2, which is used for bonding a resin substrate to a metal substrate . 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. An adhesive sheet having the laminate described in claim 4. A printed wiring board comprising the laminate of claim 4 or the adhesive sheet of claim 5 as a component. A cured product obtained by curing the thermosetting resin composition (Z) according to any one of claims 1 to 3.