JP2015165560A - Laminate for printed board and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate for a printed board which strongly adheres between layers and is excellent in foam resistance.SOLUTION: A laminate for a printed board is characterized in that an insulation adhesion layer (A) and layers (B) provided on both surfaces of the insulation adhesion layer (A) are equipped therewith and either bond strength between two layers of the insulation adhesive layer (A) and the layer (B) is 3 N/15 mm or more.

Description

The present invention relates to a laminate for a printed circuit board and a method for producing the same.

In recent years, electrical devices, electronic devices, and communication devices have been remarkably developed. Currently, these devices tend to use higher frequency bands. By the way, usually, various printed circuit boards are used for these devices. Therefore, printed circuit boards are also required to have excellent electrical characteristics corresponding to high-frequency frequencies and excellent heat resistance that can withstand soldering work.

As a material for a flexible printed circuit board known so far, for example, without reducing the glass transition temperature, increasing the linear thermal expansion coefficient, increasing the hygroscopic expansion coefficient, and increasing the elastic modulus, A metal-polyimide composite having excellent adhesion, a polyimide resin from which it is obtained, and a polyamic acid varnish composition are disclosed (for example, see Patent Document 1).

In Patent Document 2, the metal foil and the base material are firmly bonded, and as a metal-clad laminate exhibiting excellent electrical characteristics, the metal foil, and a first resin layer provided on the metal foil, There is disclosed a metal-clad laminate comprising the first resin layer comprising an epoxy resin and a fluorine-containing polymer having a curable functional group.
Patent Document 2 discloses a method for producing the metal-clad laminate, such as a method of bonding a metal foil and a film made of an epoxy resin and a fluorinated polymer having a curable functional group, and an epoxy resin and a metal foil. A method of applying a composition containing a fluorine-containing polymer having a curable functional group is disclosed.

JP 2009-299008 A JP 2012-106491 A

However, there is a need for a laminate for printed circuit boards in which the layers are more firmly bonded than the metal-clad laminate of Patent Document 2.

Further, when the conventional laminated board for printed circuit boards is subjected to a high temperature environment such as soldering, there is a problem that the residual curing agent is decomposed to generate gas and foam to cause defects on the surface.

In view of the above situation, an object of the present invention is to provide a laminate for a printed circuit board in which layers are firmly bonded and has excellent foam resistance.

The present inventors have found that the above problem can be solved brilliantly by bringing the adhesive layer into a specific state, and have completed the present invention.

That is, the present invention includes an insulating adhesive layer (A) and a layer (B) provided on at least one surface of the insulating adhesive layer (A), and the insulating adhesive layer (A) conforms to JIS K5600. A laminate for a printed circuit board, wherein the pencil hardness is softer than 2B or 2B, and the residual solvent ratio is 10% by mass or less.
The insulating adhesive layer (A) is preferably made of a fluorine-containing polymer having a blocked isocyanate and a curable functional group.
The layer (B) is preferably made of at least one material selected from the group consisting of metal, polyimide, polyamideimide, polyethylene terephthalate and polyetheretherketone.
The curable functional group is preferably at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, a glycidyl group, a silyl group, a silanate group, and an isocyanate group.
The insulating adhesive layer (A) preferably contains a urethane bond.
This invention is a manufacturing method of the above-mentioned laminated body for printed circuit boards, Comprising: The composition containing the fluorine-containing polymer which has blocked isocyanate and a curable functional group is apply | coated on a layer (B), and 50-200 degreeC. And a process for forming the insulating adhesive layer (A) by drying for 0.5 to 30 minutes.

The present invention includes an insulating adhesive layer (A) and layers (B) provided on both sides of the insulating adhesive layer (A), and the two layers of the insulating adhesive layer (A) and the layer (B) are provided. The printed circuit board laminate is characterized in that the adhesive strength between the layers is 3 N / 15 mm or more.
The insulating adhesive layer (A) is preferably made of a fluorine-containing polymer having a blocked isocyanate and a curable functional group.
The layer (B) is preferably made of at least one material selected from the group consisting of metal, polyimide, polyamideimide, polyethylene terephthalate and polyetheretherketone.
The curable functional group is preferably at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, a glycidyl group, a silyl group, a silanate group, and an isocyanate group.
The insulating adhesive layer (A) preferably contains a urethane bond.
In the laminate for a printed board of the present invention, the layer (B) is preferably made of a metal and is a metal-clad laminate.
The laminate for a printed board of the present invention is preferably a printed board having a pattern circuit formed by etching the layer (B), wherein the layer (B) is made of metal.
The present invention is a method for producing the laminate for a printed circuit board described above,
On the layer (B), a composition containing a blocked isocyanate and a fluorinated polymer having a curable functional group is applied and dried at 50 to 200 ° C. for 0.5 to 30 minutes to form an insulating adhesive layer (A). Forming, and
Another layer (B) is disposed on the insulating adhesive layer (A), and two layers (B) are interposed through the insulating adhesive layer (A) by hot pressing at 80 to 250 ° C. for 30 to 150 minutes. It is a manufacturing method characterized by including the process of sticking.

The present invention comprises an insulating adhesive layer (A) and a layer (D) made of a woven fabric provided on at least one surface of the insulating adhesive layer (A), and the insulating adhesive layer (A) is a pencil according to JIS K5600. A laminate for a printed circuit board, characterized in that the hardness is softer than 2B or 2B, and the solvent residual ratio is 10% by mass or less.
The printed circuit board laminate further includes a layer (B) provided on the insulating adhesive layer (A), and the layer (B) is made of metal, polyimide, polyamideimide, polyethylene terephthalate, and polyetheretherketone. It is preferably made of at least one material selected from the group.
The insulating adhesive layer (A) preferably contains a urethane bond.
The present invention is a method for producing the laminate for a printed circuit board described above,
After impregnating the layer (D) made of a woven fabric with a composition containing a blocked isocyanate and a fluorinated polymer having a curable functional group, the insulating adhesive layer is dried at 50 to 200 ° C. for 0.5 to 30 minutes. It is a manufacturing method characterized by including the process of forming (A).
The present invention is a method for producing the laminate for a printed circuit board described above,
After impregnating the layer (D) made of a woven fabric with a composition containing a blocked isocyanate and a fluorinated polymer having a curable functional group, the insulating adhesive layer is dried at 50 to 200 ° C. for 0.5 to 30 minutes. Forming (A), and
Including the step of placing the layer (B) on the insulating adhesive layer (A) and bringing the insulating adhesive layer (A) and the layer (B) into close contact by hot pressing at 80 to 250 ° C. for 30 to 150 minutes. This is a featured manufacturing method.
The present invention is described in detail below.

The laminate for a printed circuit board of the present invention is excellent in interlayer adhesion. Moreover, it is excellent in foaming resistance.

The present invention comprises an insulating adhesive layer (A) and a layer (B) provided on at least one surface of the insulating adhesive layer (A), and the insulating adhesive layer (A) has a pencil hardness according to JIS K5600. Is a laminate for a printed circuit board characterized by being softer than 2B or 2B and having a solvent residual ratio of 10% by mass or less.

In the laminate for a printed circuit board of the present invention, the insulating adhesive layer (A) has a pencil hardness according to JIS K5600 of 2B or 2B.
The insulating adhesive layer (A) preferably has a pencil hardness that is softer than 4B, and more preferably softer than 6B.

The insulating adhesive layer (A) has a solvent residual ratio of 10% by mass or less. The insulating adhesive layer (A) preferably has a solvent residual ratio of 5% by mass or less.
The solvent residual ratio is calculated by the following formula.
Residual ratio of solvent (% by mass) = ({mass of the laminate after drying (g) −mass of the laminate before drying (g)} / mass of the laminate before drying (g)) × 100
Drying conditions: 150 ° C., 60-minute formula, the laminated body after drying is a laminated body for a printed circuit board comprising a layer (A) and a layer (B), and the laminated body before drying is the printed circuit board described above For example, it is a laminate for producing a laminate for use, and is, for example, a laminate before drying, obtained by applying a composition described later on the layer (B).

The insulating adhesive layer (A) is preferably made of a fluorine-containing polymer having a curing agent and a curable functional group.
The curing agent is selected according to the functional group of the fluorine-containing polymer having a curable functional group described later. For example, for a hydroxyl group-containing fluorine-containing polymer, an isocyanate-based curing agent, a melamine resin, a silicate compound, an isocyanate group Preferred examples include containing silane compounds. In addition, amino-based curing agents and epoxy-based curing agents are used for carboxyl group-containing fluorine-containing polymers, and carbonyl-group-containing curing agents, epoxy-based curing agents, acid anhydride-based curing agents are used for amino group-containing fluorine-containing polymers. Is usually adopted.
Especially, it is preferable that it is block isocyanate as a hardening | curing agent.
The insulating adhesive layer (A) preferably contains a urethane bond (—OCONH—). The insulating adhesive layer (A) containing a urethane bond can be formed by using a blocked isocyanate and a fluorine-containing polymer having a hydroxyl group as a curable functional group, and reacting both to form a cured product. It can be confirmed by IR analysis that the insulating adhesive layer contains a urethane bond.

Examples of the blocked isocyanate include isocyanate compounds that are blocked with at least one blocking agent.

Examples of the isocyanate compound include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), lysine methyl ester diisocyanate, methylcyclohexyl diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene. Examples thereof include diisocyanate (HDI), n-pentane-1,4-diisocyanate, and the like, trimers thereof, adducts thereof, nurate bodies, and burette bodies.

Examples of the blocking agent include oximes, phenols, alcohols, mercaptans, amides, imides, imidazoles, ureas, amines, imines, pyrazoles, or active methylene compounds. Can be mentioned.

Especially, as said blocked isocyanate, the blocked isocyanate based on hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI) is preferable, and the blocked isocyanate based on hexamethylene diisocyanate (HDI) is more preferable.

The block isocyanate based on the hexamethylene diisocyanate (HDI) is preferably obtained by reacting a polyisocyanate compound derived from hexamethylene diisocyanate (also simply referred to as a polyisocyanate compound) with a blocking agent.

Examples of the polyisocyanate compound derived from hexamethylene diisocyanate include an adduct obtained by addition polymerization of hexamethylene diisocyanate and a trihydric or higher aliphatic polyhydric alcohol, and an isocyanurate structure (nurate) comprising hexamethylene diisocyanate. And a biuret composed of hexamethylene diisocyanate.

Examples of the adduct include the following general formula (1):

(In the formula, R ¹ represents an aliphatic hydrocarbon group having 3 to 20 carbon atoms. K is an integer of 3 to 20).

R ¹ in the general formula (1) is a hydrocarbon group based on the above trivalent or higher aliphatic polyhydric alcohol, more preferably an aliphatic hydrocarbon group having 3 to 10 carbon atoms, and 3 to 6 carbon atoms. The aliphatic hydrocarbon group is more preferable.

The k is a number corresponding to the valence of a trihydric or higher aliphatic polyhydric alcohol. As said k, More preferably, it is an integer of 3-10, More preferably, it is an integer of 3-6.

Examples of the trihydric or higher aliphatic polyhydric alcohol include glycerol, trimethylolpropane (TMP), 1,2,6-hexanetriol, trimethylolethane, 2,4-dihydroxy-3-hydroxymethylpentane, 1 , 1,1-tris (bishydroxymethyl) propane, 2,2-bis (hydroxymethyl) butanol-3, etc .; tetravalent alcohols such as pentaerythritol, diglycerol, etc .; 5 such as arabit, ribitol, xylitol, etc. Hexavalent alcohol (pentit); hexavalent alcohol (hexit) such as sorbit, mannitol, galactitol, and allozulcit. Of these, trimethylolpropane and pentaerythritol are preferable.

The isocyanurate structure has the following general formula (2) in the molecule:

It has 1 or 2 or more isocyanurate rings.
Examples of the isocyanurate structure include a trimer obtained by the trimerization reaction of the isocyanurate, a pentamer obtained by the pentamerization reaction, a heptamer obtained by the heptamization reaction, and the like.

Among them, the following general formula (3):

The trimer represented by these is preferable.

The biuret is represented by the following general formula (4):

And can be obtained by trimerizing hexamethylene diisocyanate under conditions different from the case of obtaining the above isocyanurate structure.

The blocking agent is preferably a compound having active hydrogen.
The compound having active hydrogen is preferably at least one selected from the group consisting of alcohols, oximes, lactams, active methylene compounds, and pyrazole compounds.
Examples of the alcohols include methanol, ethanol, n-propanol, isopropanol, methoxypropanol and the like.
Examples of the oximes include acetone oxime, 2-butanone oxime, and cyclohexanone oxime.
Examples of the lactams include ε-caprolactam.
Examples of the active methylene compound include methyl acetoacetate and ethyl malonate.
Examples of the pyrazole compound include 3-methylpyrazole, 3,5-dimethylpyrazole, 3,5-diethylpyrazole and the like.
Especially, as a compound which has the said active hydrogen, at least 1 sort (s) selected from the group which consists of an active methylene compound and oximes is preferable, and oximes are more preferable.

Commercially available block isocyanates that can be used in the present invention include Duranate (registered trademark) MF-B60B (HDI oxime compound blocked isocyanate), MF-K60X, MF-K60B, K6000 (HDI active methylene compound blocked isocyanate). , TPA-B80E, TPA-B80X, MF-B60X, 17B-60PX, 17B-60P, E402-B80B, SBN-70D, SBB-70P (above, manufactured by Asahi Kasei Chemicals Corporation), Coronate (registered trademark) AP-M Coronate 2503, 2507, 2513, 2515, Millionate (registered trademark) MS-50 (above, manufactured by Nippon Polyurethane Co., Ltd.), Desmodur (registered trademark) BL-3175 (HDI oxime compound block isocyanate) BL-3575, BL-4265, BL1100 / 1, BL1265 / 1 MPa / X, BL3272MPA, BL3475BA / SN, BL5375 / 1 MPa / SN, BL4265SN, BL5375MPA / SN, VPLS2078 / 2 (and above, Sumika Bayer Urethane) Ltd.), Luxate (registered trademark) HC1170, HC2170 (above, manufactured by Olin Chemicals), Takenate (registered trademark) B-830, B-815N, B-820NSU, B-842N, B-846N, B- 870N, B-874N, B-882N (manufactured by Mitsui Chemicals, Inc.) and the like.

The content of the blocked isocyanate is preferably 0.1 to 5.0 equivalents relative to 1 equivalent of the curable functional group in the fluoropolymer having the curable functional group, and preferably 0.5 to 2.0. More preferably, it is equivalent.

The insulating adhesive layer (A) may further contain a curing agent other than the blocked isocyanate. These curing agents may be appropriately selected from generally known ones.

The fluorine-containing polymer having a curable functional group includes a resinous polymer having a clear melting point, an elastomeric polymer exhibiting rubber elasticity, and a thermoplastic elastomeric polymer in between.

The curable functional group is appropriately selected according to the ease of production of the polymer and the curing system. For example, the group consisting of a hydroxyl group, a carboxyl group, an amino group, a glycidyl group, a silyl group, a silanate group, and an isocyanate group. It is preferable that it is at least one functional group selected more.
Especially, it is more preferable that it is at least 1 type of functional group selected from the group which consists of a hydroxyl group, a cyano group, and a silyl group from the point with favorable cure reactivity, and the point and reaction with which an acquisition of a polymer is easy. From the viewpoint of good properties, a hydroxyl group is particularly preferable. These curable functional groups are usually introduced into the fluoropolymer by copolymerizing a monomer having a curable functional group.

The monomer having a curable functional group is, for example, at least selected from the group consisting of a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, and a silicone vinyl monomer. 1 type is preferable, More preferably, it is a hydroxyl-containing monomer.

(1-1) Hydroxyl group-containing monomer:
The hydroxyl group-containing monomer is preferably a hydroxyl group-containing vinyl monomer containing no carboxyl group, more preferably at least one selected from the group consisting of a hydroxyl group-containing vinyl ether and a hydroxyl group-containing allyl ether. More preferred is vinyl ether.

Examples of the hydroxyl group-containing vinyl ether include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether, More preferably, it is at least one selected from the group consisting of 5-hydroxypentyl vinyl ether and 6-hydroxyhexyl vinyl ether. Among these, at least one selected from the group consisting of 4-hydroxybutyl vinyl ether and 2-hydroxyethyl vinyl ether is particularly preferable in terms of excellent polymerization reactivity and functional group curability.

The hydroxyl group-containing allyl ether is preferably at least one selected from the group consisting of 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether.

Examples of the hydroxyl group-containing vinyl monomer include hydroxyalkyl esters of (meth) acrylic acid such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.

(1-2) Carboxyl group-containing monomer:
Examples of the carboxyl group-containing monomer include a formula (5):

（式中、Ｒ^３、Ｒ^４及びＲ^５は同じかまたは異なり、いずれも水素原子、アルキル基、カルボキシル基またはエステル基；ｎは０または１である）で表される不飽和モノカルボン酸、不飽和ジカルボン酸若しくはそのモノエステル、または、式（５）で表される不飽和ジカルボン酸の酸無水物や、多価不飽和カルボン酸ビニルなどの不飽和カルボン酸類；または式（６）：

(Wherein R ³ , R ⁴ and R ⁵ are the same or different and all are hydrogen atoms, alkyl groups, carboxyl groups or ester groups; n is 0 or 1), An unsaturated dicarboxylic acid or a monoester thereof, or an unsaturated carboxylic acid such as an unsaturated dicarboxylic acid anhydride or a polyunsaturated vinyl vinyl represented by formula (5); or formula (6):

（式中、Ｒ^６及びＲ^７は同じかまたは異なり、いずれも飽和または不飽和の直鎖または環状アルキル基；ｎは０または１；ｍは０または１である）で表わされるカルボキシル基含有ビニルエーテル単量体などがあげられる。

(Wherein R ⁶ and R ⁷ are the same or different and both are saturated or unsaturated linear or cyclic alkyl groups; n is 0 or 1; m is 0 or 1) And monomers.

Specific examples of the unsaturated carboxylic acids include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, cinnamic acid, itaconic acid, itaconic acid monoester, maleic acid, maleic acid monoester, maleic anhydride, fumaric acid. , Fumaric acid monoester, vinyl phthalate, and vinyl pyromellitic acid. Among them, at least one selected from the group consisting of crotonic acid, itaconic acid, maleic acid, maleic acid monoester, fumaric acid, and fumaric acid monoester having low homopolymerization property is low in homopolymerization and homopolymeric. It is preferable because union is difficult.

Specific examples of the carboxyl group-containing vinyl ether monomer of the formula (6) include, for example, 3-allyloxypropionic acid, 3- (2-allyloxyethoxycarbonyl) propionic acid, 3- (2-allyloxybutoxycarbonyl) propion Examples thereof include one or more of acid, 3- (2-vinyloxyethoxycarbonyl) propionic acid, 3- (2-vinyloxybutoxycarbonyl) propionic acid and the like. Among these, 3-allyloxypropionic acid, 3- (2-allyloxyethoxycarbonyl) propionic acid and the like are advantageous and preferable in terms of good monomer stability and polymerization reactivity.

(1-3) Amino group-containing monomer:
Examples of the amino group-containing monomer include amino vinyl ethers represented by CH ₂ ═CH—O— (CH ₂ ) _x —NH ₂ (x = 0 to 10); CH ₂ ═CH—O—CO (CH ₂ ) allylamines represented by _{x -NH 2 (x = 1~10)} ; other aminomethylstyrene, vinylamine, acrylamide, vinylacetamide, vinyl formamide and the like.

(1-4) Silicone vinyl monomer:
Examples of the silicone vinyl monomer include CH ₂ ═CHCO ₂ (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CH ₂ ═CHCO ₂ (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , CH ₂ ═C. _{(CH 3) CO 2 (CH} 2) 3 Si (OCH 3) 3, CH 2 = C (CH 3) CO 2 (CH 2) 3 Si (OC 2 H 5) 3, CH 2 = CHCO 2 (CH 2 _{) 3 SiCH 3 (OC 2 H} 5) 2, CH 2 = C (CH 3) CO 2 (CH 2) 3 SiC 2 H 5 (OCH 3) 2, CH 2 = C (CH 3) CO 2 (CH 2 ) ₃ Si (CH ₃ ) ₂ (OC ₂ H ₅ ), CH ₂ ═C (CH ₃ ) CO ₂ (CH ₂ ) ₃ Si (CH ₃ ) ₂ OH, CH ₂ ═CHCO ₂ (CH ₂ ) ₃ Si ( OCOCH ₃ ) ₃ , CH _{2 = C (CH 3) CO 2} (CH 2) 3 SiC 2 H 5 (OCOCH 3) 2, CH 2 = C (CH 3) CO 2 (CH 2) 3 SiCH 3 (N (CH 3) COCH 3) 2 CH ₂ ═CHCO ₂ (CH ₂ ) ₃ SiCH ₃ [ON (CH ₃ ) C ₂ H ₅ ] ₂ , CH ₂ ═C (CH ₃ ) CO ₂ (CH ₂ ) ₃ SiC ₆ H ₅ [ON (CH ₃ ) (Meth) acrylic acid esters such as C ₂ H ₅ ] ₂ ; CH ₂ = CHSi [ON = C (CH ₃ ) (C ₂ H ₅ )] ₃ , CH ₂ = CHSi (OCH ₃ ) ₃ , CH ₂ = CHSi (OC ₂ H ₅ ) ₃ , CH ₂ = CHSiCH ₃ (OCH ₃ ) ₂ , CH ₂ = CHSi (OCOCH ₃ ) ₃ , CH ₂ = CHSi (CH ₃ ) ₂ (OC ₂ H ₅ ), CH ₂ = CHSi (C _{3) 2 SiCH 3 (OCH 3} ) 2, CH 2 = CHSiC 2 H 5 (OCOCH 3) 2, CH 2 = CHSiCH 3 _{[ON (CH 3) C 2 H} 5 ] _2, vinyl trichlorosilane or their partial hydrolysis Examples include vinyl silanes such as decomposition products; vinyl ethers such as trimethoxysilylethyl vinyl ether, triethoxysilylethyl vinyl ether, trimethoxysilylbutyl vinyl ether, methyldimethoxysilylethyl vinyl ether, trimethoxysilylpropyl vinyl ether, and triethoxysilylpropyl vinyl ether. The

It is preferable that the polymerization unit based on the monomer having a curable functional group is 1 to 30 mol% of the total polymerization units constituting the fluorinated polymer having a curable functional group. A more preferred lower limit is 3 mol%, and a more preferred upper limit is 20 mol%.

The content of the polymerized units based on the monomer having a curable functional group in the fluorine-containing polymer having a curable functional group is the amount of all monomers used as a synthetic raw material for the fluorine-containing polymer having a curable functional group. It is calculated by the ratio of the amount of the monomer having a curable functional group to the amount used. In the present specification, the content ratio of other polymerization units can be calculated in the same manner.
The content of the curable functional group can be calculated by appropriately combining NMR, FT-IR, elemental analysis, fluorescent X-ray analysis, and neutralization titration depending on the type of monomer.

The fluorinated polymer having a curable functional group preferably has a polymerized unit based on a fluorinated vinyl monomer.

The fluorine-containing vinyl monomer is selected from the group consisting of tetrafluoroethylene [TFE], vinylidene fluoride (vinylidene fluoride), chlorotrifluoroethylene [CTFE], vinyl fluoride, hexafluoropropylene, and perfluoroalkyl vinyl ether. TFE is preferable in that it is excellent in low dielectric constant, low dielectric loss tangent, dispersibility, moisture resistance, heat resistance, flame retardancy, adhesiveness, copolymerizability, and chemical resistance. More preferably, it is at least one selected from the group consisting of CTFE and vinylidene fluoride, and is excellent in low dielectric constant, low dielectric loss tangent and weather resistance, and also excellent in moisture resistance, from TFE and CTFE. More preferably, it is at least one selected from the group consisting of TFE, and TFE is particularly preferable.

It is preferable that the repeating unit (polymerization unit) based on a fluorine-containing vinyl monomer is 20 to 60 mol% of all the polymerization units constituting the fluorine-containing polymer having a curable functional group. A more preferred lower limit is 30 mol%, and a still more preferred lower limit is 35 mol%. A more preferred upper limit is 47 mol%.

The fluorine-containing polymer having a curable functional group is a repeating polymer based on at least one vinyl monomer selected from the group consisting of carboxylic acid vinyl esters, alkyl vinyl ethers and non-fluorinated olefins (excluding those having a fluorine atom). It is preferable to have a unit. Carboxylic acid vinyl ester has the effect | action which improves compatibility. Examples of vinyl carboxylates include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl cyclohexylcarboxylate, vinyl benzoate, Examples include vinyl para-t-butylbenzoate. Examples of the alkyl vinyl ether include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether and the like. Non-fluorinated olefins include ethylene, propylene, n-butene, inbutene and the like.

The repeating unit based on the above vinyl monomer (excluding those having a fluorine atom) is a repeating unit based on a monomer having a curable functional group among all the polymerized units constituting the fluorinated polymer having a curable functional group. It is preferable to constitute all polymer units other than the polymer units occupied by the units and the repeating units based on the fluorine-containing vinyl monomer.

From the above, the fluorinated polymer having a curable functional group in the present invention is a polymerized unit based on the monomer having the curable functional group, a polymerized unit based on the fluorinated vinyl monomer, and the vinyl monomer. The form which consists of the polymer unit based on and those content ratio is 1-30 / 20-60 / 21-72 in molar ratio is one of the suitable embodiment of this invention. The content ratio (molar ratio) of the above polymerized units is more preferably 3-20 / 30-47 / 33-60.

Examples of the fluorine-containing polymer into which the curable functional group is introduced include the following from the viewpoint of the structural unit.

Examples of the fluorinated polymer having a curable functional group include, for example, a perfluoroolefin polymer mainly composed of a perfluoroolefin unit, a CTFE polymer mainly composed of a chlorotrifluoroethylene (CTFE) unit, and vinylidene fluoride (VdF). Examples thereof include VdF polymers mainly composed of units, and fluoroalkyl group-containing polymers mainly composed of fluoroalkyl units.

(1) Specific examples of perfluoroolefin-based polymers mainly composed of perfluoroolefin units include tetrafluoroethylene (TFE) homopolymer, TFE and hexafluoropropylene (HFP), perfluoro (alkyl vinyl ether) (PAVE). And a copolymer with other monomer copolymerizable with these.

Examples of the other copolymerizable monomers include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, and cyclohexyl. Carboxylic acid vinyl esters such as vinyl carboxylate, vinyl benzoate and vinyl para-t-butylbenzoate; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether and cyclohexyl vinyl ether; ethylene, propylene, n-butene and isobutene Non-fluorinated olefins such as: vinylidene fluoride (VdF), chlorotrifluoroethylene (CTFE), vinyl fluoride (VF), fluorine monomers such as fluorovinyl ether, etc. That is, not limited thereto.

Among these, TFE-based polymers mainly composed of TFE are preferable in terms of excellent pigment dispersibility, weather resistance, copolymerization, and chemical resistance.

Specific examples of the perfluoroolefin polymer include TFE / isobutylene / hydroxybutyl vinyl ether / other monomer copolymer, TFE / vinyl versatate / hydroxybutyl vinyl ether / other monomer copolymer, TFE / VdF / hydroxybutyl vinyl ether / copolymer of other monomers and the like, and in particular, copolymers of TFE / isobutylene / hydroxybutyl vinyl ether / other monomers, and TFE / vinyl versatate / Preference is given to at least one copolymer selected from the group consisting of copolymers of hydroxybutyl vinyl ether / other monomers.

(2) Specific examples of CTFE-based polymers mainly composed of chlorotrifluoroethylene (CTFE) units include, for example, a copolymer of CTFE / hydroxybutyl vinyl ether / other monomers.

(3) Specific examples of VdF polymers mainly composed of vinylidene fluoride (VdF) units include VdF / TFE / hydroxybutyl vinyl ether / copolymers of other monomers.

(4) Specific examples of fluoroalkyl group-containing polymers mainly composed of fluoroalkyl units include CF ₃ CF ₂ (CF ₂ CF ₂ ) _n CH ₂ CH ₂ OCOCH═CH ₂ (mixture of n = 3 and 4) / Examples thereof include 2-hydroxyethyl methacrylate / stearyl acrylate copolymer.

Among these, in consideration of weather resistance and moisture resistance, perfluoroolefin-based polymers are preferable.

The weight average molecular weight of the fluorinated polymer having a curable functional group is preferably 5,000 to 100,000. When the weight average molecular weight of the fluorinated polymer having a curable functional group is in such a range, the insulating adhesive layer (A) and a layer (B) described later can be bonded more firmly. The weight average molecular weight of the fluorinated polymer having a curable functional group is more preferably 20,000 to 40,000.
The weight average molecular weight of the fluorinated polymer having a curable functional group can be measured in the same manner as the weight average molecular weight of the epoxy resin described above.

Specific examples of the commercially available fluorine-containing polymer having the curable functional group include the following.
Examples of the TFE polymer include Zeffle GK series manufactured by Daikin Industries, Ltd.
Examples of the CTFE polymer include Lumiflon manufactured by Asahi Glass Co., Ltd., Fluoronate manufactured by DIC Co., Ltd., Cefral Coat manufactured by Central Glass Co., Ltd., ZAFLON manufactured by Toa Gosei Co., Ltd., and the like.
Examples of the fluoroalkyl group-containing polymer include Unidyne and Ftone manufactured by Daikin Industries, Ltd., and Zonyl manufactured by DuPont.

As the fluorine-containing polymer having the curable functional group,
(A) a perhaloolefin structural unit having 2 carbon atoms,
(B) vinyl acetate structural unit,
(C) formula _{(7): CH 2 = CH} -O- (CH 2) n -OH
(Wherein n is an integer of 2 or more) and a hydroxyl group-containing vinyl monomer structural unit represented by:
Equation (d) ^{(8): R 1 R 2} C = CR 3 - (CH 2) m -COOH
(Wherein R ¹ , R ² and R ³ are the same or different and all are hydrogen atoms or straight-chain or branched alkyl groups having 1 to 10 carbon atoms; m is an integer of 2 or more) It may be a fluorine-containing copolymer comprising a group-containing monomer structural unit.

As the structural unit (a), tetrafluoroethylene (TFE) or chlorotrifluoroethylene (CTFE) is preferable.
As the structural unit (c), hydroxyethyl vinyl ether (HEVE) or hydroxybutyl vinyl ether (HBVE) is preferable.
Examples of the structural unit (d) include pentenoic acid, hexenoic acid, heptenoic acid, octenoic acid, nonenic acid, decenoic acid, undecylenic acid, dodecenoic acid, tridecenoic acid, tetradecenoic acid, pentadecenoic acid, hexadecenoic acid, heptadecenoic acid, Examples include octadecenoic acid, nonadecenoic acid, and eicosenoic acid. Of these, undecylenic acid is preferable.

The fluorine-containing copolymer has a structural unit (a) of 40 mol% to 50 mol%, a structural unit (b) of 20 mol% to 54.9 mol%, and a structural unit (c) of 5 mol. % Or more and 14 mol% or less, the structural unit (d) is 0.1 mol% or more and 5 mol% or less, and the other monomer structural unit (e) is preferably 0 mol% or 25 mol% or less.
The other monomer (e) is not particularly limited as long as it can be copolymerized with the monomers (a) to (d) and does not impair the effects of the present invention.

In addition, as the fluorine-containing polymer having the curable functional group,
Polymerized units based on fluorine-containing monomers,
Polymer units based on vinyl alcohol as optional polymer units, and
Formula (9): —CH ₂ —CH (—O— (L) ₁ —R ^b ) —
(Wherein R ^b is an organic group having at least one terminal double bond, L is a divalent organic group, and l is 0 or 1),
It may be a fluorine-containing polymer characterized by containing.

The fluorine-containing monomer is preferably at least one selected from the group consisting of TFE, CTFE and HFP, and more preferably TFE.

In the general formula (9), R ^b represents the general formula (10):

(In the formula, M is H, Cl, F or CH ₃ , j is an integer of 1 to 20, k is an integer of 1 to 10, and 2j + 1−k is an integer of 0 or more). A group represented by formula (11):

In the formula, R is preferably at least one substituent selected from the group consisting of groups represented by H, Cl, F, CH ₃ or CF ₃ .

L represents the general formula (12):-(C = O) s- (N-H) p-
(In the formula, s is 0 or 1, and p is 0 or 1.)
It is preferable that it is an organic group represented by these.

The molar ratio of the polymerized unit based on the fluorine-containing monomer, the polymerized unit based on vinyl alcohol, and the polymerized unit represented by the general formula (9) is (30 to 70) / (0 to 69) / (1 to 70). Preferably there is.

The content of the fluorinated polymer having a curable functional group is preferably 5 to 100% by mass in the insulating adhesive layer (A), more preferably 20% by mass or more, and still more preferably 50% by mass or more.

The insulating adhesive layer (A) preferably further contains an epoxy resin.
By further including an epoxy resin, interlayer adhesion with the layer (B) can be further strengthened.

The epoxy resin preferably has a weight average molecular weight of 100 to 1,000,000.
When the weight average molecular weight of the epoxy resin is within such a range, the interlayer adhesion with the layer (B) described later can be further improved by including the epoxy resin.
The weight average molecular weight of the epoxy resin is more preferably 1000 or more, further preferably 5000 or more, more preferably 800000 or less, and further preferably 600000 or less.
The weight average molecular weight can be measured by gel permeation chromatography (GPC).

Commercially available epoxy resins include, for example, Epicoat 828 of epibis type compound based on bisphenol A (manufactured by Shell Chemical Co., Ltd.), alkyl-modified EPICLON 800, EPICLON 4050, EPICLON 1121N (manufactured by DIC), Shodyne (Showa Denko) Glycidyl ester compounds such as Araldite CY-183 (manufactured by Ciba Geigy), Novolac-type Epicoat 154 (manufactured by Shell Chemical Co., Ltd.), DEN431, DEN438 (manufactured by Dow Chemical Co., Ltd.), EPICLON850 (manufactured by DIC), Cresol Novolak Examples of the type include ECN1280, ECN1235 (manufactured by Ciba-Geigy), urethane-modified EPU-6, EPU-10 (manufactured by Jyuryu Kagaku Co., Ltd.), and the like.

The content of the epoxy resin is preferably 0 to 95% by mass in the insulating adhesive layer (A), more preferably 85% by mass or less, and further preferably 50% by mass or less.

When the insulating adhesive layer (A) contains the epoxy resin, it is preferable to further contain a curing agent for the epoxy resin.
The curing agent for the epoxy resin is not particularly limited and includes generally known curing agents such as amines, polyaminoamides, polymercaptans, aromatic polyamines, acid anhydrides, phenols, and dicyandiamides. Etc.

When the insulating adhesive layer (A) contains the above epoxy resin, it is preferable to further contain a curing accelerator.
Examples of the curing accelerator include organic tin compounds, acidic phosphate esters, reaction products of acidic phosphate esters and amines, saturated or unsaturated polycarboxylic acids or acid anhydrides thereof, organic titanate compounds, amine compounds, Examples include lead octylate.

1 type may be used for a hardening accelerator and it may use 2 or more types together. The blending ratio of the curing accelerator is preferably about 1.0 × 10 ^{−6 to} 1.0 × 10 ⁻² parts by weight with respect to 100 parts by weight of the fluorinated polymer having a curable functional group, and 5.0 × 10 ^−5. About -1.0 * 10 < ^-3 > weight part is more preferable.

The insulating adhesive layer (A) preferably further contains polytetrafluoroethylene (PTFE). By further including PTFE, a low dielectric constant and a low dielectric loss tangent can be achieved.

The PTFE is a polymer containing only a tetrafluoroethylene (TFE) unit or a TFE unit and a modified monomer unit copolymerizable with the TFE unit. That is, PTFE may be a TFE homopolymer or a modified PTFE.

The modified PTFE means a polymer obtained by copolymerization of TFE and a modified monomer copolymerizable with TFE.

The modified monomer in the modified PTFE is not particularly limited as long as it can be copolymerized with TFE. For example, perfluoroolefin such as hexafluoropropylene [HFP]; chloro such as chlorotrifluoroethylene [CTFE] Examples thereof include fluoroolefins; hydrogen-containing fluoroolefins such as trifluoroethylene and vinylidene fluoride [VDF]; perfluorovinyl ethers; perfluoroalkylethylenes: ethylene. Moreover, the modified | denatured monomer to be used may be 1 type, and multiple types may be sufficient as it.

The perfluorovinyl ether is not particularly limited, and for example, the following general formula (I)
_{CF 2 = CF-ORf (I} )
(Wherein Rf represents a perfluoro organic group), and the like. In the present specification, the “perfluoro organic group” means an organic group in which all hydrogen atoms bonded to carbon atoms are substituted with fluorine atoms. The perfluoro organic group may have ether oxygen.

Examples of the perfluorovinyl ether include perfluoro (alkyl vinyl ether) [PAVE] in which Rf represents a perfluoroalkyl group having 1 to 10 carbon atoms in the general formula (I). The perfluoroalkyl group preferably has 1 to 5 carbon atoms.

Examples of the perfluoroalkyl group in the PAVE include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and a perfluorohexyl group. Purple propyl vinyl ether [PPVE] in which the group is a perfluoropropyl group is preferred.

As the perfluorovinyl ether, in the general formula (I), Rf is a perfluoro (alkoxyalkyl) group having 4 to 9 carbon atoms, and Rf is represented by the following formula:

(Wherein m represents an integer of 0 or 1 to 4), and Rf is a group represented by the following formula:

(In the formula, n represents an integer of 1 to 4).

The perfluoroalkylethylene is not particularly limited, and examples thereof include perfluorobutylethylene (PFBE) and perfluorohexylethylene.

As the modified monomer in the modified PTFE, HFP, CTFE, VDF, PPVE, PFBE, and ethylene are preferable.

In the modified PTFE, the modified monomer unit is preferably 1% by mass or less, more preferably 0.001 to 1% by mass of the total monomer units. In the present specification, the modified monomer unit means a part derived from the modified monomer and part of the molecular structure of the modified PTFE, and the total monomer unit means all the single monomers in the molecular structure of the modified PTFE. It means a part derived from the body. The content of the modified monomer unit is a value measured by performing infrared spectroscopic analysis or NMR (nuclear magnetic resonance).

The PTFE preferably has a number average molecular weight of 600,000 or less. The number average molecular weight is a value measured by gel permeation chromatography (GPC).

The PTFE is preferably a TFE polymer having a melt viscosity of 1 × 10 ^{2 to} 7 × 10 ⁵ (Pa · s) at a melt viscosity of 380 ° C.
The melt viscosity is in accordance with ASTM D 1238, and a 2 g sample heated in advance at 380 ° C. for 5 minutes using a flow tester (manufactured by Shimadzu Corporation) and a 2φ-8L die at a load of 0.7 MPa. It is a value measured while maintaining the above temperature. The number average molecular weight is a value calculated from the melt viscosity measured by the measurement method.

The PTFE is preferably a TFE polymer having a melting point of 324 to 333 ° C.

The PTFE preferably has an average particle size of 1 to 30 μm, more preferably 1 to 20 μm.
The average particle diameter can be determined using a laser diffraction particle size distribution analyzer (manufactured by Nippon Laser Corporation).

The PTFE preferably has a specific surface area of 1 to 30 m ² / g, and more preferably 3 to ²⁰ m ² / g.
The specific surface area is measured by a BET method using a surface analyzer (trade name: MONOSORB, manufactured by QUANTA CHLROME), using a mixed gas of 30% nitrogen and 70% helium as a carrier gas, and liquid nitrogen for cooling. To do.

As a commercial product of the PTFE, Lubron (manufactured by Daikin Industries, Ltd.) and the like can be exemplified.

The content of the PTFE is preferably 1 to 70% by mass in the insulating adhesive layer (A), more preferably 5% by mass or more, further preferably 10% by mass or more, more preferably 60% by mass or less, and 50 A mass% or less is more preferable.

The insulating adhesive layer (A) may further contain other components as necessary.
Examples of the other components include a curing accelerator, a pigment dispersant, an antifoaming agent, a leveling agent, a UV absorber, a light stabilizer, a thickener, an adhesion improver, and a matting agent. Known components can be applied to these components.

The thickness of the insulating adhesive layer (A) is preferably 3 to 3000 μm.
When the thickness is in the range described, low inductivity and low dielectric loss tangent can be ensured.
The thickness is more preferably 5 μm or more, further preferably 10 μm or more, more preferably 2000 μm or less, still more preferably 1500 μm or less.
Further, when the insulating adhesive layer (A) does not include a woven fabric described later and is made of the above-described resin layer, the thickness is preferably 3 to 40 μm, more preferably 5 μm or more, further preferably 10 μm or more, and 30 μm or less. More preferred.

The insulating adhesive layer (A) is formed, for example, by preparing a composition containing the above-mentioned blocked isocyanate, a fluorinated polymer having a curable functional group, and other components as necessary, and using the above-mentioned composition. Can do.

The insulating adhesive layer (A) has an unprecedented characteristic of having a specific hardness. The insulating adhesive layer (A) and the layer (B) are not firmly bonded, but the adhesiveness can be improved by subsequent hot pressing. The specific hardness can be achieved, for example, by using a composition containing a blocked isocyanate and a fluorinated polymer having a curable functional group as described above.
In addition, since a specific hardness can be maintained, another layer (B) is placed on the insulating adhesive layer having a specific hardness and on the opposite surface to which the layer (B) is bonded. Then, the two layers (B) can be firmly bonded via the insulating adhesive layer (A) by hot pressing.
The insulating adhesive layer is obtained by applying a composition containing the above-mentioned blocked isocyanate and a fluorinated polymer having a curable functional group on the layer (B) and drying at 50 to 200 ° C. for 0.5 to 30 minutes. It is preferable that it is a layer formed. The layer thus obtained has a predetermined hardness.

The laminate for a printed circuit board of the present invention further includes a layer (B) provided on at least one surface of the insulating adhesive layer (A).
The layer (B) is preferably made of at least one material selected from the group consisting of metal, polyimide, polyamideimide, polyethylene terephthalate and polyetheretherketone. Especially, it is more preferable to consist of at least 1 type of material selected from the group which consists of a metal and a polyimide.
Since it is necessary to ensure the strength other than the insulating adhesive layer (A), the layer (B) is more preferably made of polyimide.

Examples of the metal layer (B) include a metal foil made of copper, aluminum, iron, nickel, chromium, molybdenum, tungsten, zinc, or an alloy thereof, preferably a copper foil. Further, for the purpose of improving the adhesive force, chemical or mechanical surface treatment may be performed by siding, nickel plating, copper-zinc alloy plating, aluminum alcoholate, aluminum chelate, silane coupling agent, or the like.

The thickness of the layer (B) is preferably 5 to 100 μm.
When the thickness is in the above range, strength and workability can be ensured.
The thickness is more preferably 10 μm or more, further preferably 15 μm or more, more preferably 80 μm or less, and still more preferably 50 μm or less.

As a method for forming the layer (B), a known method may be appropriately selected according to the material for forming the layer (B).

The layer (B) is preferably provided on both surfaces of the insulating adhesive layer (A). By providing the layers (B) on both surfaces of the insulating adhesive layer (A), the layers can be bonded more firmly.

When the layer (B) is provided on both sides of the insulating adhesive layer (A), the adhesive strength between the two layers of the insulating adhesive layer (A) and the layer (B) is 3 N / 15 mm or more. Is preferably 5 N / 15 mm or more.
The adhesive strength is a value obtained by measurement using a Tensilon universal testing machine.

Such an insulating adhesive layer (A) and a layer (B) provided on both sides of the insulating adhesive layer (A) are provided, and between the two layers of the insulating adhesive layer (A) and the layer (B) A laminate for a printed circuit board having an adhesive strength of 3 N / 15 mm or more is also one aspect of the present invention.

In the laminate for a printed board of the present invention, the layer (B) is preferably made of a metal and is a metal-clad laminate.
In this specification, when the laminated body for printed circuit boards of this invention is equipped with the insulating contact bonding layer (A) and the layer (B) which consists of metals, it is also called "a metal-clad laminate."

The laminate for a printed board of the present invention is preferably a printed board having a pattern circuit formed by etching the layer (B), wherein the layer (B) is made of metal.
The printed board may be a rigid printed board or a flexible printed board.

The present invention also includes an insulating adhesive layer (A) and a layer (D) made of a woven fabric provided on at least one surface of the insulating adhesive layer (A), wherein the insulating adhesive layer (A) is JIS K5600. Is a laminate for a printed circuit board having a pencil hardness of 2B or 2B softer and a solvent residual ratio of 10% by mass or less.
The solvent residual ratio is calculated by the following formula.
Residual ratio of solvent (% by mass) = ({mass of the laminate after drying (g) −mass of the laminate before drying (g)} / mass of the laminate before drying (g)) × 100
Drying conditions: 150 ° C., 60-minute formula, the laminated body after drying is a laminated body for a printed circuit board comprising a layer (A) and a layer (D), and the laminated body before drying is the printed circuit board described above For example, a layered product before drying, which is obtained by impregnating the layer (D) with a composition described later.
The insulating adhesive layer (A) is preferably a composite with a layer (D) made of woven fabric, and the composite is a woven composition for forming the above-mentioned insulating adhesive layer (A). It is formed by impregnating the fabric layer (D).

By providing the layer (D) made of woven fabric, the dimensional stability and strength of the insulating adhesive layer (A) can be ensured.
Examples of the woven fabric include those made of flame retardant, low dielectric constant, and high strength materials. Especially, glass fiber is preferable at the point which is a material which has them.

When the layer (D) made of woven fabric is provided, the total thickness of the insulating adhesive layer (A) and the insulating adhesive layer (A) and the layer (D) is preferably 500 to 3000 μm, more preferably 500 to 2000 μm. 500 to 1500 μm is more preferable.

When the layer (D) made of woven fabric is provided, it is preferable that the layer (B) is further provided on the insulating adhesive layer (A). Examples of the insulating adhesive layer (A) and the layer (B) are the same as those described above.

The laminated body for printed circuit boards of the present invention may further include other layers as necessary.
As said other layer, the resin layer etc. which consist of a polyimide, a polyethylene terephthalate, etc. are mentioned, for example.

As a method for producing the laminate for a printed circuit board of the present invention, a composition containing a blocked isocyanate and a fluorinated polymer having a curable functional group is applied onto the layer (B), and the composition is 0.000 at 50 to 200 ° C. It is preferable to include a step of forming the insulating adhesive layer (A) by drying for 5 to 30 minutes.
A method for producing such a laminate for a printed circuit board is also one aspect of the present invention.

The composition is preferably prepared by mixing and dispersing the blocked isocyanate, the fluorinated polymer having the curable functional group, and, if necessary, other components in a solvent.

As the solvent applicable to the above composition, an organic solvent is preferable, for example, esters such as ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, propylene glycol methyl ether acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone , Ketones such as cyclohexanone; cyclic ethers such as tetrahydrofuran and dioxane; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; aromatic hydrocarbons such as toluene and xylene; propylene glycol methyl ether and the like Alcohols; hydrocarbons such as hexane and heptane; and mixed solvents thereof.

The mixing and dispersion may be performed by a known method.
When the composition is a solvent-type composition containing a solvent, the solid content concentration of the composition is 10 to 80% by mass in terms of appropriate viscosity and easy formation of a uniform coating film. Is preferred.

Moreover, when the said composition is a powder type which does not contain a solvent, it is good to prepare by a well-known method, such as mixing and knead | mixing the component mentioned above.

Examples of the method for applying the composition include brush coating, dip coating, spray coating, comma coating, knife coating, die coating, lip coating, roll coater coating, curtain coating, and the like.

Drying is preferably performed at 50 to 200 ° C. for 0.5 to 30 minutes. By drying within the above range, an insulating adhesive layer having a predetermined hardness and containing a predetermined amount of solvent can be formed.

The drying temperature is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, more preferably 190 ° C. or lower, and 180 ° C. or lower in that the solvent can be sufficiently removed. Further preferred.
The drying time is more preferably 1 minute or more, and more preferably 15 minutes or less.

In the laminate for a printed board according to the first aspect of the present invention thus obtained, the insulating adhesive layer (A) has a specific hardness. A laminate in which two layers (B) are firmly adhered to each other via the insulating adhesive layer (A) by further placing the layer (B) on the insulating adhesive layer (A) and performing heat pressing. Can be obtained. Moreover, since the obtained laminated body has the interlayer closely_contact | adhered firmly, it is excellent also in foaming tolerance.

In the laminate for a printed board of the present invention, the layer (B) may be provided on both surfaces of the insulating adhesive layer (A).
As a method for producing a laminate for a printed circuit board in which the layer (B) is provided on both surfaces of the insulating adhesive layer (A), a blocked isocyanate and a curable functional group based on hexamethylene diisocyanate are formed on the layer (B). Applying a composition containing a fluorine-containing polymer having, and forming an insulating adhesive layer (A) by drying at 50 to 200 ° C. for 0.5 to 30 minutes, and on the insulating adhesive layer (A), It is preferable to include the step of bringing the two layers (B) into close contact via the insulating adhesive layer (A) by placing another layer (B) and hot pressing at 80 to 250 ° C. for 30 to 150 minutes.
By such a method, the adhesive strength between the two layers of the insulating adhesive layer (A) and the layer (B) can be 3 N / 15 mm or more.
A method for producing such a laminate for a printed circuit board is also one aspect of the present invention.

The process of forming the said insulating contact bonding layer (A) can be performed similarly to the method mentioned above.
After forming the insulating adhesive layer (A), another layer (B) is arranged on the insulating adhesive layer (A), and the layer (B) / insulating adhesive layer (A) / layer (B) is laminated. By hot pressing the body at 80 to 250 ° C., the two layers (B) are brought into close contact with each other via the insulating adhesive layer (A).
The insulating adhesive layer (A) is in close contact with the layer (B) by hot pressing in the above temperature range.
The temperature of the hot press is more preferably 100 ° C. or higher, more preferably 130 ° C. or higher, more preferably 220 ° C. or lower, and further preferably 200 ° C. or lower in terms of curing.
The hot pressing time is preferably 30 minutes to 150 minutes, and more preferably 50 minutes to 120 minutes.

The pressure during pressing is preferably 0.3 to 3.0 MPa, and more preferably 0.5 to 1.5 MPa.
The hot pressing may be performed by a known method, but is preferably performed under reduced pressure, and more preferably performed under vacuum.

Further, when the insulating adhesive layer (A) contains a fluoropolymer containing a polymer unit represented by the general formula (9), it is photocured by irradiating active energy rays such as ultraviolet rays, electron beams or radiation. be able to. When photocured, the carbon-carbon double bonds in the fluoropolymer polymerize between molecules, and the carbon-carbon double bonds in the fluoropolymer decrease or disappear.

Further, when the laminate for a printed circuit board of the present invention has the layer (D) made of the woven fabric described above, the production method thereof includes a layer (D) made of the woven fabric having a blocked isocyanate and a curable functional group. After impregnating the composition containing the fluoropolymer, it is preferable to have a step of forming the insulating adhesive layer (A) by drying at 50 to 200 ° C. for 0.5 to 30 minutes.
A method for producing such a laminate for a printed circuit board is also one aspect of the present invention.

The composition may be prepared by the same method as described above.
The method for impregnating the woven fabric with the composition may be performed by a known method.
The drying may be performed in the same manner as the step of forming the insulating adhesive layer (A) described above.

Moreover, when the said laminated body for printed circuit boards further has a layer (B), as the manufacturing method, the composition containing the fluorine-containing polymer which has block isocyanate and a curable functional group in the layer (D) which consists of woven fabrics. After the impregnation, the step of forming the insulating adhesive layer (A) by drying at 50 to 200 ° C. for 0.5 to 30 minutes, and arranging the layer (B) on the insulating adhesive layer (A), 80 It is preferable to include a step of bringing the insulating adhesive layer (A) and the layer (B) into close contact with each other by hot pressing at ~ 250 ° C for 30 to 150 minutes.
A method for producing such a laminate for a printed circuit board is also one aspect of the present invention.

The step of forming the insulating adhesive layer (A) may be performed by the same method as described above.
The step of bringing the insulating adhesive layer (A) and the layer (B) into close contact may be performed by the same method as described above.

The printed circuit board laminate of the present invention thus obtained is excellent in interlayer adhesion between the insulating adhesive layer (A) and the layer (B). Moreover, it is excellent in foaming resistance.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Preparation Example 1
30 parts by mass of butyl acetate and 31.8 parts by mass of a block type isocyanate curing agent (Duranate MF-B60B, manufactured by Asahi Kasei Chemicals Co., Ltd.) are added to 100 parts by mass of a hydroxyl group-containing TFE copolymer (Zeffle GK570 manufactured by Daikin Industries, Ltd.) Thus, a curable paint 1 was prepared.

Preparation Example 2
Hydroxyl group-containing TFE copolymer (Zeffle GK570 manufactured by Daikin Industries, Ltd.) 100 parts by mass 30 parts by mass of butyl acetate and block type isocyanate curing agent (Desmodule BL-3175 manufactured by Sumika Bayer) 26.8 parts by mass Was added to prepare a curable coating 2.

Preparation Example 3
Hydroxyl group-containing TFE copolymer (Zeffle GK570 manufactured by Daikin Industries, Ltd.) 100 parts by mass 30 parts by mass of butyl acetate and block type isocyanate curing agent (Desmodule BL-3575 manufactured by Sumika Bayer) 27.8 parts by mass And curable paint 3 was prepared.

Preparation Example 4
Hydroxyl-containing TFE copolymer (Zeffle GK570 manufactured by Daikin Industries, Ltd.) 100 parts by mass, 30 parts by mass of butyl acetate and block type isocyanate curing agent (Desmodule BL-4265, manufactured by Sumika Bayer) 36.0 parts by mass Was added to prepare a curable coating 4.

Preparation Example 5
To 100 parts by mass of a hydroxyl group-containing TFE copolymer (Zeffle GK570 manufactured by Daikin Industries, Ltd.) 30 parts by mass of butyl acetate and 13.8 parts by mass of an isocyanurate type isocyanate curing agent (Sumidule N3300 manufactured by Sumika Bayer) The curable paint 5 was prepared by blending.

Example 1
A laminate in which the curable coating material 1 prepared in Preparation Example 1 was applied to a copper foil (RDPR1, manufactured by JX Nippon Mining & Metals Co., Ltd., 18 μm thick), dried at 150 ° C. for 3 minutes, and a coating film was formed on the copper foil. Was made. Next, a copper foil (RDPR1, manufactured by JX Nippon Mining & Metals Co., Ltd., 18 μm thickness) was placed on the coating surface, and vacuum-pressed at 1 MPa and 160 ° C. for 90 minutes to produce a laminate 1 having a total thickness of 50 μm. Solder heat resistance and adhesion of this laminate 1 were measured. The adhesive strength between the copper foil / adhesive layer was 11.4 (N / 15 mm). Moreover, the pencil hardness and the solvent residual ratio were measured by the following method. The results are shown in Table 1.

(Example 2)
The curable coating material 1 produced in Preparation Example 1 was applied to a polyimide film (Kapton manufactured by Toray DuPont Co., Ltd., 25 μm thickness) and dried at 150 ° C. for 3 minutes to produce a laminate in which a coating film was formed on the polyimide film. . Next, a copper foil (RDPR1, manufactured by JX Nippon Mining & Metals Co., Ltd., 18 μm thickness) was placed on the surface of the coating film and vacuum-pressed at 1 MPa and 160 ° C. for 90 minutes to produce a laminate 2 having a total thickness of 57 μm. Solder heat resistance and adhesion of this laminate 2 were measured. The adhesive strength between the polyimide film / adhesive layer was 7.1 (N / 15 mm), and the adhesive strength between the copper foil / adhesive layer was 11.4 (N / 15 mm). Moreover, the pencil hardness and the solvent residual ratio were measured by the following method. The results are shown in Table 1.

(Example 3)
A laminate in which the curable coating 2 prepared in Preparation Example 2 was applied to a copper foil (RDPR1, manufactured by JX Nippon Mining & Metals, 18 μm thickness), dried at 150 ° C. for 3 minutes, and a coating film was formed on the copper foil. Was made. Next, a copper foil (RDPR1, manufactured by JX Nippon Mining & Metals Co., Ltd., 18 μm thickness) was placed on the coating surface and vacuum-pressed at 1 MPa and 160 ° C. for 90 minutes to produce a laminate 3 having a total thickness of 50 μm. Solder heat resistance and adhesion of this laminate 3 were measured. The adhesive strength between the copper foil / adhesive layer was 11.1 (N / 15 mm). Moreover, the pencil hardness and the solvent residual ratio were measured by the following method. The results are shown in Table 1.

Example 4
The curable paint 2 prepared in Preparation Example 2 was applied to a polyimide film (Kapton manufactured by Toray DuPont, 25 μm thickness) and dried at 150 ° C. for 3 minutes to prepare a laminate in which a coating film was formed on the polyimide film. . Next, a copper foil (RDPR1, manufactured by JX Nippon Mining & Metals Co., Ltd., 18 μm thickness) was placed on the coating surface and vacuum-pressed at 1 MPa and 160 ° C. for 90 minutes to produce a laminate 4 having a total thickness of 57 μm. Solder heat resistance and adhesion of this laminate 4 were measured. The adhesive strength between the polyimide film / adhesive layer was 6.9 (N / 15 mm), and the adhesive strength between the copper foil / adhesive layer was 11.1 (N / 15 mm). Moreover, the pencil hardness and the solvent residual ratio were measured by the following method. The results are shown in Table 1.

(Example 5)
A laminate in which the curable coating material 3 prepared in Preparation Example 3 was applied to a copper foil (RDPR1, manufactured by JX Nippon Mining & Metals Co., Ltd., 18 μm thickness), dried at 150 ° C. for 3 minutes, and a coating film was formed on the copper foil. Was made. Next, a copper foil (RDPR1, manufactured by JX Nippon Mining & Metals Co., Ltd., 18 μm thickness) was placed on the coating surface and vacuum-pressed at 1 MPa and 160 ° C. for 90 minutes to produce a laminate 5 having a total thickness of 50 μm. Solder heat resistance and adhesion of this laminate 5 were measured. The adhesive strength between the copper foil / adhesive layer was 11.9 (N / 15 mm). Moreover, the pencil hardness and the solvent residual ratio were measured by the following method. The results are shown in Table 1.

(Example 6)
A laminate in which the curable coating 4 produced in Preparation Example 4 was applied to a copper foil (RDPR1, manufactured by JX Nippon Mining & Metals Co., Ltd., 18 μm thickness), dried at 150 ° C. for 3 minutes, and a coating film was formed on the copper foil. Was made. Next, a copper foil (RDPR1, manufactured by JX Nippon Mining & Metals Co., Ltd., 18 μm thickness) was placed on the coating surface and vacuum-pressed at 1 MPa and 160 ° C. for 90 minutes to produce a laminate 6 having a total thickness of 50 μm. Solder heat resistance and adhesion of this laminate 6 were measured. The adhesive strength between the copper foil / adhesive layer was 14.1 (N / 15 mm). Moreover, the pencil hardness and the solvent residual ratio were measured by the following method. The results are shown in Table 1.

(Comparative Example 1)
A laminate in which the curable coating material 5 prepared in Preparation Example 5 was applied to a copper foil (RDPR1, manufactured by JX Nippon Mining & Metals Co., Ltd., 18 μm thickness), dried at 150 ° C. for 3 minutes, and a coating film was formed on the copper foil. Was made. Next, a copper foil (RDPR1, manufactured by JX Nippon Mining & Metals Co., Ltd., 18 μm thickness) was placed on the coating surface, and vacuum-pressed at 1 MPa and 160 ° C. for 90 minutes to produce a laminate 7 having a total thickness of 50 μm. Solder heat resistance and adhesion of this laminate 7 were measured. The adhesive strength between the copper foil / adhesive layer was 1 (N / 15 mm) or less. Moreover, the pencil hardness and the solvent residual ratio were measured by the following method. The results are shown in Table 1.

(Comparative Example 2)
The curable coating material 5 produced in Preparation Example 5 was applied to a polyimide film (Kapton manufactured by Toray DuPont Co., Ltd., 25 μm thickness) and dried at 150 ° C. for 3 minutes to produce a laminate in which a coating film was formed on the polyimide film. . Next, a copper foil (RDPR1, manufactured by JX Nippon Mining & Metals Co., Ltd., 18 μm thickness) was placed on the coating surface and vacuum-pressed at 1 MPa and 160 ° C. for 90 minutes to produce a laminate 8 having a total thickness of 57 μm. Solder heat resistance and adhesion of this laminate 8 were measured. The adhesive strength between the polyimide film / adhesive layer and the adhesive strength between the copper foil / adhesive layer were both 1 (N / 15 mm) or less. Moreover, the pencil hardness and the solvent residual ratio were measured by the following method. The results are shown in Table 1.

(Example 7)
The curable coating material 1 produced in Preparation Example 1 was impregnated into a glass cloth (Unitika Ltd., E10T, 90 μm thickness) and dried at 150 ° C. for 3 minutes to produce an impregnated body. Next, a copper foil (RDPR1, manufactured by JX Nippon Mining & Metals Co., Ltd., 18 μm thickness) was superimposed on both surfaces of the impregnated body, and vacuum-pressed at 1 MPa and 160 ° C. for 90 minutes to prepare a laminate 9 having a total thickness of 130 μm.
Solder heat resistance and adhesion of this laminate 9 were measured. Moreover, the pencil hardness and the solvent residual ratio were measured by the following method. The results are shown in Table 1.

<Measurement of solder heat resistance>
Based on JIS standard C6481, a test piece of 25 mm square was prepared and floated on a 300 ° C. molten solder bath for 10 seconds with the copper foil surface down, and repeated 10 times, and the copper foil surface and the laminate were blistered. Visual confirmation was made and the following criteria were evaluated.
No blisters: ○
What causes blisters: ×

<Measurement of interlayer adhesion>
A test piece having a width of 15 mm and a length of 100 mm was prepared, and a 180 ° peel test was performed using a Tensilon universal testing machine (Orientec RTC-1225A), and a copper foil or polyimide film and an insulating adhesive layer or impregnated body were used. The adhesive strength between them was measured in units of N / 15 mm.

<Pencil hardness test>
In each example and comparative example, a curable coating was applied, and a laminate on which a coating film was formed after drying at 150 ° C. for 3 minutes, and the laminate was further heated at 160 ° C. for 90 minutes. The surface of the coating film with the laminate was measured for pencil hardness according to JIS K5600.
Further, in Example 7, the surfaces of the impregnated body impregnated with a curable coating and dried at 150 ° C. for 3 minutes and the impregnated body after the impregnated body was heated at 160 ° C. for 90 minutes were JIS-coated. The pencil hardness was measured according to K5600.
The values in parentheses in the table indicate the pencil hardness after heating at 160 ° C. for 90 minutes.

<Measurement of solvent residual ratio>
The solvent residual ratio is calculated by the following formula.
Residual ratio of solvent (% by mass) = ({mass of the laminate after drying (g) −mass of the laminate before drying (g)} / mass of the laminate before drying (g)) × 100
Drying conditions: 150 ° C., 60 minutes The above-mentioned solvent remaining rate is obtained by taking the mass of the laminate obtained by applying the curable coating 1 to the copper foil as “Example 1” (the mass of the laminate before drying ( g) ”, and the mass of the laminate after drying the laminate at 150 ° C. for 60 minutes can be calculated as“ mass (g) of laminate after drying ”.
Taking Example 7 as an example, the mass of the laminate obtained by impregnating the glass cloth with the curable coating material 1 is “mass (g) of the laminate before drying”, and the laminate is 150 ° C. The mass of the laminate after drying for 60 minutes can be calculated as “the mass (g) of the laminate after drying”.

ADVANTAGE OF THE INVENTION According to this invention, the laminated body for printed circuit boards excellent in interlayer adhesiveness and foaming resistance can be provided.

The insulating adhesive layer (A) has a solvent residual ratio of 10% by mass or less. The insulating adhesive layer (A) preferably has a solvent residual ratio of 5% by mass or less.
The solvent residual ratio is calculated by the following formula.
Residual ratio of solvent (% by mass) = ({mass of the laminate before drying (g) −mass of the laminate after drying (g)} / mass of the laminate before drying (g)) × 100
Drying conditions: 150 ° C, 60 minutes

The present invention also includes an insulating adhesive layer (A) and a layer (D) made of a woven fabric provided on at least one surface of the insulating adhesive layer (A), wherein the insulating adhesive layer (A) is JIS K5600. Is a laminate for a printed circuit board having a pencil hardness of 2B or 2B softer and a solvent residual ratio of 10% by mass or less.
The solvent residual ratio is calculated by the following formula.
Residual ratio of solvent (% by mass) = ({mass of the laminate before drying (g) −mass of the laminate after drying (g)} / mass of the laminate before drying (g)) × 100
Drying conditions: 150 ° C, 60 minutes
Upper Symbol insulating adhesive layer (A) is preferably a complex with a layer consisting of a woven fabric (D), the said complex, a composition for forming the above-mentioned insulating adhesive layer (A) It is formed by impregnating the layer (D) made of woven fabric.

<Measurement of solvent residual ratio>
The solvent residual ratio is calculated by the following formula.
Residual ratio of solvent (% by mass) = ({mass of the laminate before drying (g) −mass of the laminate after drying (g)} / mass of the laminate before drying (g)) × 100
Drying conditions: 150 ° C, 60 minutes

Claims (19)

An insulating adhesive layer (A);
A layer (B) provided on both sides of the insulating adhesive layer (A),
The printed circuit board laminate, wherein the adhesive strength between the two layers of the insulating adhesive layer (A) and the layer (B) is 3 N / 15 mm or more. The laminate for a printed circuit board according to claim 1, wherein the insulating adhesive layer (A) comprises a fluorine-containing polymer having a blocked isocyanate and a curable functional group. The laminate for a printed circuit board according to claim 1 or 2, wherein the layer (B) is made of at least one material selected from the group consisting of metal, polyimide, polyamideimide, polyethylene terephthalate, and polyetheretherketone. The print according to claim 2 or 3, wherein the curable functional group is at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, a glycidyl group, a silyl group, a silanate group, and an isocyanate group. Laminate for substrate. The printed circuit board laminate according to claim 1, wherein the insulating adhesive layer (A) contains a urethane bond. The laminate for a printed board according to claim 1, wherein the layer (B) is made of metal and is a metal-clad laminate. The laminate for a printed circuit board according to claim 1, 2, 3, 4, or 5, wherein the layer (B) is a printed circuit board comprising a pattern circuit formed of a metal and etching the layer (B). A method for producing a laminate for a printed circuit board according to claim 1, 2, 3, 4 or 5,
On the layer (B), a composition containing a blocked isocyanate and a fluorinated polymer having a curable functional group is applied and dried at 50 to 200 ° C. for 0.5 to 30 minutes to form an insulating adhesive layer (A). Forming, and
Another layer (B) is disposed on the insulating adhesive layer (A), and two layers (B) are interposed through the insulating adhesive layer (A) by hot pressing at 80 to 250 ° C. for 30 to 150 minutes. The manufacturing method characterized by including the process of closely_contact | adhering. An insulating adhesive layer (A);
A layer (B) provided on at least one surface of the insulating adhesive layer (A),
The insulating adhesive layer (A) has a pencil hardness according to JIS K5600 that is softer than 2B or 2B, and a residual solvent ratio of 10% by mass or less. The laminate for a printed circuit board according to claim 9, wherein the insulating adhesive layer (A) is made of a fluorine-containing polymer having a blocked isocyanate and a curable functional group. The laminate for a printed circuit board according to claim 9 or 10, wherein the layer (B) is made of at least one material selected from the group consisting of metal, polyimide, polyamideimide, polyethylene terephthalate, and polyetheretherketone. The print according to claim 10 or 11, wherein the curable functional group is at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, a glycidyl group, a silyl group, a silanate group, and an isocyanate group. Laminate for substrate. The printed circuit board laminate according to claim 9, wherein the insulating adhesive layer (A) contains a urethane bond. A method for producing a laminate for a printed circuit board according to claim 9, 10 or 11,
On the layer (B), a composition containing a blocked isocyanate and a fluorinated polymer having a curable functional group is applied and dried at 50 to 200 ° C. for 0.5 to 30 minutes to form an insulating adhesive layer (A). The manufacturing method characterized by including the process to form. An insulating adhesive layer (A);
A layer (D) made of a woven fabric provided on at least one surface of the insulating adhesive layer (A),
The insulating adhesive layer (A) has a pencil hardness according to JIS K5600 that is softer than 2B or 2B, and a residual solvent ratio of 10% by mass or less. Furthermore, it includes a layer (B) provided on the insulating adhesive layer (A),
The laminate for a printed circuit board according to claim 15, wherein the layer (B) is made of at least one material selected from the group consisting of metal, polyimide, polyamideimide, polyethylene terephthalate, and polyetheretherketone. The printed circuit board laminate according to claim 15 or 16, wherein the insulating adhesive layer (A) contains a urethane bond. It is a manufacturing method of the layered product for printed circuit boards according to claim 15 or 17,
After impregnating the layer (D) made of a woven fabric with a composition containing a blocked isocyanate and a fluorinated polymer having a curable functional group, the insulating adhesive layer is dried at 50 to 200 ° C. for 0.5 to 30 minutes. The manufacturing method characterized by including the process of forming (A). A method for producing a laminate for a printed circuit board according to claim 16 or 17,
After impregnating the layer (D) made of a woven fabric with a composition containing a blocked isocyanate and a fluorinated polymer having a curable functional group, the insulating adhesive layer is dried at 50 to 200 ° C. for 0.5 to 30 minutes. Forming (A), and
Including the step of placing the layer (B) on the insulating adhesive layer (A) and bringing the insulating adhesive layer (A) and the layer (B) into close contact by hot pressing at 80 to 250 ° C. for 30 to 150 minutes. A featured manufacturing method.