TW201547333A - Printed circuit board laminate and manufacturing method therefor - Google Patents

Abstract

The purpose of the present invention is to provide a printed circuit board laminate having firmly-bonded layers and excellent foaming resistance. The present invention is a printed circuit board laminate characterized by being provided with an insulating adhesive layer (A), and a layer (B) provided on both surfaces of the insulating adhesive layer (A), and further characterized in that the adhesive strength between the two layers of the layer (B) and the insulating adhesive layer (A) are both 3N/15 mm or above.

Description

Laminate for printed circuit board, and method of producing the same

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

In recent years, electrical equipment, or electronic equipment, and communication equipment have developed very significantly. Currently, in such machines, there is a tendency to use frequencies of higher frequency bands. In other words, various printed substrates are commonly used in such machines. Therefore, excellent electrical characteristics corresponding to the frequency of the high frequency band or excellent heat resistance which can withstand the soldering work are also required for the printed substrate.

The material for a flexible printed circuit board known to date has, for example, disclosed that it does not cause a decrease in glass transition temperature, a high linear thermal expansion coefficient, a high moisture absorption expansion ratio, a high elastic modulus, and is closely adhered to a metal foil. A metal-polyimine composite having excellent properties, and a polyimide/polyamine coating composition for obtaining the same (for example, refer to Patent Document 1).

Patent Document 2 discloses a metal clad laminate which is a metal clad laminate which exhibits excellent electrical properties as a metal foil and a substrate, and is provided with a metal foil and a first tree provided on the metal foil. A metal clad laminate for a grease layer, characterized in that the first resin layer is composed of an epoxy resin and a fluoropolymer having a curable functional group.

Further, in Patent Document 2, as a method of producing the metal clad laminate, a method of bonding a metal foil to a film composed of an epoxy resin and a fluoropolymer having a curable functional group is disclosed; or A method of coating a composition containing an epoxy resin and a fluoropolymer having a curable functional group on a foil.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-299008

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2012-106491

However, it is required to laminate the interlayer of the printed circuit board with the laminate more firmly than the metal clad laminate of Patent Document 2.

In addition, when the conventional laminate for a printed circuit board is exposed to a high-temperature environment such as soldering, there is a problem that the residual curing agent is decomposed to generate a gas, which causes foaming and causes a problem on the surface.

In view of the above-mentioned state, it is an object of the present invention to provide a laminate for a printed circuit board which is excellent in adhesion between layers and which is excellent in foaming resistance.

The inventors of the present invention have found that the above problems can be satisfactorily solved by setting the adhesive layer to a specific state, and completed the present invention.

In other words, the present invention provides a laminate for a printed circuit board comprising: 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). The pencil hardness measured by JIS K5600 is 2B or softer than 2B, and the solvent residual ratio is 10% by mass or less.

The insulating adhesive layer (A) is preferably composed of a blocked isocyanate and a fluoropolymer having a curable functional group.

The layer (B) is preferably composed of at least one material selected from the group consisting of metal, polyimine, polyamidimide, 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 amine group, a glycidyl group, a decyl group, a silanate group, and an isocyanate group.

The insulating back layer (A) preferably contains a urethane bond.

The present invention is a method for producing a laminate for a printed circuit board, which comprises coating a layer (B) with a composition containing a blocked isocyanate and a fluoropolymer having a curable functional group. , drying at 50 to 200 ° C for 0.5 to 30 minutes, thereby forming the step of insulating the layer (A).

The present invention provides a laminate for a printed circuit board comprising: an insulating back layer (A) and a layer (B) provided on both surfaces of the insulating back layer (A), and the insulating back layer (A) and the layer (B) between the 2 layers The strength is 3N/15mm or more.

The insulating adhesive layer (A) is preferably composed of a blocked isocyanate and a fluoropolymer having a curable functional group.

The layer (B) is preferably composed of at least one material selected from the group consisting of metal, polyimine, polyamidimide, 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 amine group, a glycidyl group, a decyl group, a decanoic group, and an isocyanate group.

The insulating back layer (A) preferably contains a urethane bond.

In the laminate for a printed circuit board of the present invention, it is preferable that the layer (B) is made of a metal and the laminated system is a metal clad laminate.

In the laminate for a printed circuit board of the present invention, it is preferable that the layer (B) is made of a metal, and the laminate system includes a printed circuit board having a pattern circuit formed by etching the layer (B).

The present invention relates to a method for producing a laminate for a printed circuit board, characterized in that it comprises

Applying a composition containing a blocked isocyanate and a fluoropolymer having a curable functional group to the layer (B), drying at 50 to 200 ° C for 0.5 to 30 minutes to form an insulating back layer (A), and

The other layer (B) is disposed on the insulating adhesive layer (A), and is heat-pressed at 80 to 250 ° C for 30 to 150 minutes, whereby the two layers (B) are adhered via the insulating back layer (A).

The present invention relates to a laminate for a printed substrate, the characteristics of which are An insulating back layer (A) and a layer (D) composed of a woven fabric provided on at least one side of the insulating back layer (A), the insulating back layer (A) having a pencil hardness system 2B measured by JIS K5600 or It is softer than 2B and has a solvent residual ratio of 10% by mass or less.

The laminate for a printed circuit board preferably further comprises a layer (B) provided on the insulating adhesive layer (A), and the layer (B) is selected from the group consisting of metal, polyimine, and polyamidimide. And at least one material consisting of polyethylene terephthalate and polyether ether ketone.

The insulating back layer (A) preferably contains a urethane bond.

The present invention relates to a method for producing a laminate for a printed circuit board, characterized in that it comprises

After impregnating the layer (D) composed of the woven fabric with a composition containing a blocked isocyanate and a fluoropolymer having a curable functional group, it is dried at 50 to 200 ° C for 0.5 to 30 minutes to form an insulating adhesive layer ( Step A).

The present invention relates to a method for producing a laminate for a printed circuit board, characterized in that it comprises

After impregnating the layer (D) composed of the woven fabric with a composition containing a blocked isocyanate and a fluoropolymer having a curable functional group, it is dried at 50 to 200 ° C for 0.5 to 30 minutes to form an insulating adhesive layer ( The step of A) and the layer (B) disposed on the insulating adhesive layer (A) are heat-pressed at 80 to 250 ° C for 30 to 150 minutes to thereby adhere the insulating adhesive layer (A) to the layer (B). The invention is described in detail below.

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

The present invention provides a laminate for a printed circuit board comprising 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) as JIS K5600 The pencil hardness measured was 2B or softer than 2B, and the solvent residual ratio was 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 of 2B or a softness of 2B as measured by JIS K5600.

The insulating adhesive layer (A) is preferably one in which the pencil hardness is softer than 4B, more preferably softer than 6B.

Further, 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.

Solvent residual ratio (% 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

In the formula, the laminated body after drying means that the layer (A) and the layer (B) are printed. The laminate for a brush substrate, and the laminate before drying, is a laminate for forming the laminate for a printed circuit board, for example, a layer before drying by applying a composition described later on the layer (B). Fit.

Insulating adhesive layer (A), preferably by hardener and hardened A functional group-containing fluoropolymer.

The curing agent can be selected according to the functional group of the fluoropolymer having a curable functional group to be described later. For example, the fluoropolymer containing a hydroxyl group is preferably an isocyanate curing agent, a melamine resin, a phthalic acid ester compound, or the like. A decane compound or the like containing an isocyanate group. Further, an amine-based curing agent or an epoxy-based curing agent is usually used for the carboxyl group-containing fluoropolymer; and for the amine group-containing fluoropolymer, a carbonyl-containing hardener or an epoxy-based hardener or an acid anhydride is usually used. A hardener.

Among them, as the curing agent, a blocked isocyanate is preferred.

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 fluoropolymer having a hydroxyl group as a curable functional group, and reacting the two to form a cured product. It was confirmed by IR analysis that the insulating back layer contained a urethane bond.

The above-mentioned blocked isocyanate may, for example, be at least one isocyanate compound blocked by a blocking agent.

Examples of the above isocyanate compound include methylphenyl diisocyanate (TDI), diphenylmethane diisocyanate (MDI), diphenyl phenyl diisocyanate (XDI), isophorone diisocyanate (IPDI), and lysine. Methyl ester diisocyanate, methylcyclohexyl diisocyanate, trimethyl hexamethylene Diisocyanate, hexamethylene diisocyanate (HDI), n-pentane-1,4-diisocyanate, etc., such trimers, such adducts, triesters, biurets Wait.

Examples of the above blocking agent include anthraquinones, phenols, alcohols, mercaptans, decylamines, quinones, imidazoles, ureas, amines, imines, pyrazoles, or active agents. Methylene compounds and the like.

Wherein the above-mentioned blocked isocyanate, especially a blocked isocyanate derived from hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI); more preferably from hexamethylene diisocyanate (HDI) Segment isocyanate.

The above-mentioned blocked isocyanate derived from 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. By.

The polyisocyanate compound derived from the hexamethylene diisocyanate may, for example, be an adduct obtained by addition polymerization of hexamethylene diisocyanate and a trivalent or higher aliphatic polyol, or a hexamethylene group. A trimeric isocyanate structure (triester structure) composed of an isocyanate and a biuret composed of hexamethylene diisocyanate.

The above adduct preferably has, for example, the following formula (1):

(wherein R ¹ represents an aliphatic hydrocarbon group having 3 to 20 carbon atoms. k is an integer of 3 to 20) represents a structure.

R ¹ in the above formula (1) is derived from the hydrocarbon group of the above-mentioned trivalent or higher aliphatic polyol, more preferably an aliphatic hydrocarbon group having 3 to 10 carbon atoms, and more preferably an aliphatic hydrocarbon group having 3 to 6 carbon atoms. .

The k-series corresponds to the number of valences of the aliphatic polyhydric alcohol of 3 or more. The above k is preferably an integer of 3 to 10, and more preferably an integer of 3 to 6.

Examples of the above trihydric aliphatic polyol include glycerin, trimethylolpropane (TMP), 1,2,6-hexanetriol, trimethylolethane, and 2,4-dihydroxy-3-. a ternary alcohol such as hydroxymethylpentane, 1,1,1-paraxyl (bishydroxymethyl)propane or 2,2-bis(hydroxymethyl)butanol-3; a tetrahydric alcohol such as pentaerythritol or diglycerin a 5-alcohol (pentaerythritol) such as arabitol, ribitol or xylitol; 6-alcohol (hexanol) such as sorbitol, mannitol, galactitol, and allodolcite . Among them, trimethylolpropane and pentaerythritol are preferred.

The trimer isocyanate structure has one or two or more of the following formula (2) in a molecule: [Chemical 2]

Indicates the trimeric isocyanate ring.

Examples of the trimeric isocyanate structure include a trimer obtained by a trimerization reaction of the above trimerization isocyanate, a pentamer obtained by a pentamerization reaction, and a heptamer obtained by a hemerization reaction. Polymer and so on.

Among them, the following general formula (3):

The trimer represented is preferred.

The biuret has the following general formula (4): [Chemical 4]

The compound having the structure shown above can be obtained by trimerizing hexamethylene diisocyanate under conditions different from those obtained when the above-mentioned trimer isocyanate structure is obtained.

The above 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, terpenes, indoleamines, active methylene compounds, and pyrazole compounds.

Examples of the above alcohols include methanol, ethanol, n-propanol, isopropanol, and methoxypropanol.

Examples of the above hydrazines include acetone oxime, 2-butanone oxime, cyclohexanone oxime and the like.

Examples of the above internal guanamines include ε-caprolactam and the like.

The active methylene compound may, for example, be methyl acetacetate or ethyl malonate.

Examples of the pyrazole compound include 3-methylpyrazole, 3,5-dimethylpyrazole, and 3,5-diethylpyrazole.

Among them, the compound having an active hydrogen is preferably at least one selected from the group consisting of an active methylene compound and an anthracene; more preferably an anthracene.

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

The content of the above block isocyanate is relative to the above The amount of the curable functional group in the fluoropolymer of the curable functional group is preferably from 0.1 to 5.0 equivalents, more preferably from 0.5 to 2.0 equivalents per equivalent of the functional group.

The insulating adhesive layer (A) may further contain the above-mentioned embedded layer A hardener other than a segment isocyanate. These hardening agents may be appropriately selected and used by those generally known.

The above fluoropolymer having a curable functional group, comprising a resinous polymer having a clear melting point, an elastomer exhibiting rubber elasticity A polymer, a thermoplastic elastomer in its middle.

The above curable functional group is compatible with the manufacture of the polymer The ease or the hardening is appropriately selected, but is preferably, for example, at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amine group, a glycidyl group, a decyl group, a decanoic group, and an isocyanate group.

In view of the fact that the curing reactivity is good, at least one functional group selected from the group consisting of a hydroxyl group, a cyano group, and a decyl group is more preferable, and a viewpoint of easy availability of the polymer or a good reactivity is preferable. In particular, it is preferably a hydroxyl group. These hardening functional groups are usually introduced into the fluoropolymer by copolymerizing a monomer having a curable functional group.

The above monomer having a hardening functional group is preferably, for example, At least one selected from the group consisting of a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amine group-containing monomer, and a polyoxymethylene-based vinyl monomer is selected, and more preferably a hydroxyl group-containing monomer.

(1-1) Monomers containing hydroxyl groups: The hydroxyl group-containing monomer is preferably a carboxyl group-containing hydroxyl group-containing vinyl monomer, 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 preferably, it is a vinyl ether containing a hydroxyl group.

a vinyl ether containing a hydroxyl group, more preferably selected from a 2-hydroxy group Ethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxyl At least one selected from the group consisting of -2-methylbutyl vinyl ether, 5-hydroxypentyl vinyl ether, and 6-hydroxyhexyl vinyl ether. Special among these At least one selected from the group consisting of 4-hydroxybutyl vinyl ether and 2-hydroxyethyl vinyl ether is preferred from the viewpoint of excellent polymerization reactivity and curability of the functional group.

a hydroxy group-containing allyl ether, preferably selected from the group consisting of 2-hydroxyl At least one selected from the group consisting of ethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerin monoallyl ether.

a vinyl monomer having a hydroxyl group, and an acrylic acid 2- A hydroxyalkyl (meth)acrylate such as hydroxyethyl ester or 2-hydroxyethyl methacrylate.

(1-2) Monomer having a carboxyl group: The monomer having a carboxyl group may, for example, be a formula (5): (wherein R ³ , R ⁴ and R ⁵ are the same or different from each other, and are a hydrogen atom, an alkyl group, a carboxyl group or an ester group; n is 0 or 1) an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid or the same a monoester; or an anhydride of an unsaturated dicarboxylic acid represented by the formula (5) or an unsaturated carboxylic acid such as a polyunsaturated carboxylic acid vinyl ester; or the formula (6): (wherein, R ⁶ and R ⁷ are the same or different, straight or cyclic alkyl groups which are saturated or unsaturated; n is 0 or 1; m is 0 or 1) a vinyl ether monomer having a carboxyl group Wait.

Specific examples of the above unsaturated carboxylic acid include, for example, Acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, cinnamic acid, isaconic acid, isaconic acid monoester, maleic acid, maleic acid monoester, maleic anhydride, fumaric acid, fumaric acid monoester, Vinyl phthalate, vinyl pyromellitate, and the like. Among these, at least one selected from the group consisting of crotonic acid, isaconic acid, maleic acid, maleic acid monoester, fumaric acid, and fumaric acid monoester having low homopolymerization is used. It is preferred because it has low homopolymerity and is difficult to form a homopolymer.

Specific examples of the carboxyl group-containing vinyl ether monomer of the formula (6) For example, 3-allyloxypropionic acid, 3-(2-allyloxyethoxycarbonyl)propionic acid, 3-(2-allyloxybutoxycarbonyl)propionic acid, 3- One or two or more kinds of (2-vinyloxyethoxycarbonyl)propionic acid and 3-(2-vinyloxybutoxycarbonyl)propionic acid. Among them, 3-allyloxypropionic acid, 3-(2-allyloxyethoxycarbonyl)propionic acid, etc. are advantageous from the viewpoint of stability of the monomer or good polymerization reactivity. Preferably.

(1-3) Amino group-containing monomer: an amine group-containing monomer, and examples thereof include an amine vinyl group represented by CH ₂ =CH-O-(CH ₂ ) _x -NH ₂ (x = 0 to 10). Etheramines; CH ₂ =CH-O-CO(CH ₂ ) _x -NH ₂ (x=1~10) allylamines; other aminomethylstyrenes, vinylamines, acrylamides, Vinyl acetamide, vinyl formamide, and the like.

(1-4) Polyoxynized vinyl monomer: polyoxynized vinyl monomer, for example, 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 )C ₂ H ₅ ] ₂ such as (meth) acrylates; 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(CH ₃ ) ₂ SiCH ₃ (OCH ₃ ) ₂ , CH ₂ =CHSiC ₂ H ₅ (OCOC H ₃ ) ₂ , CH ₂ =CHSiCH ₃ [ON(CH ₃ )C ₂ H ₅ ] ₂ , vinyl trichlorodecane or a partial hydrolyzate of such vinyl hydrides; trimethoxy decyl ethyl ethyl Ether, triethoxysulfonylethyl vinyl ether, trimethoxydecyl butyl vinyl ether, methyl dimethoxy decyl ethyl vinyl ether, trimethoxy decyl propyl vinyl ether And vinyl ethers such as triethoxysulfonylpropyl vinyl ether.

a polymerization unit derived from a monomer having a hardenable functional group, It is preferably 1 to 30 mol% of the total polymerization unit of the fluoropolymer having a curable functional group. A more preferred lower limit is 3 mol%, and a more preferred upper limit is 20 mol%.

Among the fluoropolymers having a hardening functional group, The content ratio of the polymerization unit of the monomer having a hardenable functional group is a single having a hardening functional group by using a synthetic raw material of a fluoropolymer having a curable functional group, that is, a total amount of the monomer. The ratio of the amount of the body used is calculated. Further, in the present specification, the content ratio of other polymerization units can also 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 according to the monomer type.

The fluoropolymer having a curable functional group preferably has a polymerization unit derived from a fluorine-containing vinyl monomer.

The fluorine-containing vinyl monomer is preferably selected from the group consisting of tetrafluoroethylene [TFE], vinylidene fluoride, chlorotrifluoroethylene [CTFE], vinyl fluoride, hexafluoropropylene, and perfluoroalkyl vinyl ether. At least one of the groups is excellent in low dielectric constant, low dielectric tangent, dispersibility, moisture resistance, heat resistance, flame retardancy, adhesion, copolymerization, and chemical resistance. From a good point of view, it is more preferably at least one selected from the group consisting of TFE, CTFE, and vinylidene fluoride, and is excellent in low dielectric constant, low dielectric tangent, and weather resistance, and excellent in moisture resistance. In view of the above, it is more preferably at least one selected from the group consisting of TFE and CTFE, and particularly preferably TFE.

a repeating unit (polymerization unit) derived from a fluorine-containing vinyl monomer, It is preferably 20 to 60 mol% of the entire polymerization unit of the fluoropolymer having a curable functional group. A lower limit is preferably 30 mol%, and a lower limit is more preferably 35 mol%. A better upper limit is 47% by mole.

a fluoropolymer having a curable functional group, preferably having There are repeating units derived from at least one vinyl monomer selected from the group consisting of vinyl carboxylate, alkyl vinyl ether, and non-fluorinated olefin (except those having a fluorine atom). The vinyl carboxylate has an effect of improving compatibility. Examples of the vinyl carboxylate include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, trimethyl vinyl acetate, vinyl hexanoate, vinyl versatate, vinyl laurate, and hard. Vinyl fatty acid ester, vinyl cyclohexyl carboxylate, vinyl benzoate, vinyl p-t-butyl benzoate, and the like. Examples of the alkyl vinyl ether include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether. Examples of the non-fluorinated olefin include ethylene, propylene, n-butene, and isobutylene.

The above is derived from a vinyl monomer (except for those having a fluorine atom) The repeating unit is preferably a repeating unit derived from a monomer having a hardening functional group and a repeating unit derived from a fluorine-containing vinyl monomer among all the polymerization units constituting the fluoropolymer having a hardenable functional group. All aggregated units other than the aggregated unit.

From the above, it is known that the present invention has a sclerosing function. The fluoropolymer is composed of the above-mentioned polymerization unit derived from a monomer having a curable functional group, the above-mentioned polymerization unit derived from a fluorine-containing vinyl monomer, and the above-mentioned polymerization unit derived from a vinyl monomer, and The content ratio of the other is a form of 1 to 30/20 to 60/21 to 72 in terms of a molar ratio, which is one of the suitable embodiments of the present invention. The content ratio (molar ratio) of the above polymerization unit is more preferably from 3 to 20/30 to 47/33 to 60.

The fluoropolymer to which the curable functional group is introduced is, for example, the following from the viewpoint of the constituent unit.

Examples of the fluoropolymer having a curable functional group include a perfluoroolefin-based polymer mainly composed of a perfluoroolefin unit, a CTFE-based polymer mainly composed of a chlorotrifluoroethylene (CTFE) unit, and a difluorofluoride. The ethylene (VdF) unit is a main VdF-based polymer, a fluoroalkyl group-based polymer containing a fluoroalkyl group, and the like.

(1) Perfluoroolefin-based polymer mainly composed of perfluoroolefin units

Specific examples thereof include a homopolymer of tetrafluoroethylene (TFE); or a copolymer of TFE and hexafluoropropylene (HFP), perfluoro(alkyl vinyl ether) (PAVE), or the like; Copolymerized copolymer of other monomers, and the like.

Examples of the other monomer which can be copolymerized include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, trimethyl vinyl acetate, vinyl hexanoate, vinyl versatate, and laurel. Vinyl acetate, vinyl stearate, vinyl cyclohexylcarboxylate, ethylene benzoate Ethyl vinyl esters such as esters, p-t-butyl benzoic acid vinyl esters, etc.; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, etc. Non-fluorinated olefins such as ethylene, propylene, n-butene, and isobutylene; fluorine-based singles such as vinylidene fluoride (VdF), chlorotrifluoroethylene (CTFE), vinyl fluoride (VF), and fluorovinyl ether Body, etc., but not limited to this.

Among these, pigment dispersion or weather resistance, copolymerization From the viewpoint of excellent properties and chemical resistance, a TFE polymer mainly composed of TFE is preferred.

Specific examples of the perfluoroolefin-based polymer include, for example, TFE/ Copolymer of isobutylene/hydroxybutyl vinyl ether/other monomer, copolymer of TFE/vinyl versatate/hydroxybutyl vinyl ether/other monomer, TFE/VdF/hydroxybutyl vinyl ether/others Copolymers, etc., particularly preferably copolymers selected from TFE/isobutylene/hydroxybutyl vinyl ether/other monomers, and copolymers of TFE/vinyl versatate/hydroxybutyl vinyl ether/other monomers A copolymer of at least one of the group.

(2) CTFE polymer based on chlorotrifluoroethylene (CTFE) units

Specific examples thereof include a copolymer of CTFE/hydroxybutyl vinyl ether/other monomer.

(3) VdF polymer mainly based on vinylidene fluoride (VdF) units

Specific examples thereof include a copolymer of VdF/TFE/hydroxybutyl vinyl ether/other monomer.

(4) a fluoroalkyl group-containing polymer mainly composed of a fluoroalkyl unit

Specific examples thereof include CF ₃ CF ₂ (CF ₂ CF ₂ ) _n CH ₂ CH ₂ OCOCH=CH ₂ (a mixture of n=3 and 4)/2-hydroxyethyl methacrylate/stearyl acrylate copolymer, and the like. .

Among these, in view of weather resistance and moisture resistance, a perfluoroolefin-based polymer is preferred.

The weight average molecular weight of the above fluoropolymer having a curable functional group is preferably from 5,000 to 100,000. When the weight average molecular weight of the fluoropolymer having a curable functional group is in such a range, the insulating adhesive layer (A) and the layer (B) to be described later can be more firmly adhered. The weight average molecular weight of the fluoropolymer having a hardening functional group is more preferably 20,000 to 40,000.

The weight average molecular weight of the fluoropolymer having a curable functional group can be measured in the same manner as the weight average molecular weight of the above epoxy resin.

Specific examples of the commercially available fluoropolymer having a curable functional group include the followings.

The TFE-based polymer can be exemplified by the Zeffle GK series manufactured by Daikin Industries Co., Ltd., and the like.

Examples of the CTFE-based polymer include Lumiflon manufactured by Asahi Glass Co., Ltd., Fluonate manufactured by DIC Co., Ltd., Cefral Coat manufactured by Central Glass Co., Ltd., and Zaflon manufactured by East Asia Synthetic Co., Ltd.

The fluoroalkyl group-containing polymer may, for example, be Unidyne or Ftone manufactured by Daikin Industries Co., Ltd.; and Zonyl manufactured by DuPont.

The fluoropolymer having a curable functional group may be (a) a perhalo olefin structural unit having a carbon number of 2, (b) a vinyl acetate structural unit, and (c) a formula (7): CH _{2 .} a hydroxyl group-containing vinyl monomer structural unit represented by =CH-O-(CH ₂ ) _n -OH (wherein n is an integer of 2 or more), and (d) formula (8): R ¹ R ² C =CR ³ -(CH ₂ ) _m -COOH (wherein R ¹ , R ² and R ³ are all the same or differently a hydrogen atom or a linear or branched alkyl group having a carbon number of 1 to 10; m is A fluorine-containing copolymer composed of a carboxyl group-containing monomer structural unit represented by an integer of 2 or more.

The above structural unit (a) is preferably tetrafluoroethylene (TFE) or chlorotrifluoroethylene (CTFE).

The above structural unit (c) is preferably hydroxyethyl vinyl ether (HEVE) or hydroxybutyl vinyl ether (HBVE).

Examples of the above structural unit (d) include pentenoic acid, hexenoic acid, heptenoic acid, octenoic acid, decenoic acid, decenoic acid, undecylenic acid, dodecenoic acid, tridecenoic acid, and ten. Teenoic acid, pentadecenoic acid, hexadecenoic acid, heptadecanoic acid, oleic acid, lauric acid, eicosenoic acid and the like. Among them, undecylenic acid is preferred.

The fluorinated copolymer preferably contains 40 mol% or more and 50 mol% or less of the structural unit (a); 20 mol% or more and 54.9 mol% or less of the structural unit (b); and a structural unit (c) 5 mol% or more, 14 mol% or less; containing structural unit (d) 0.1 mol% or more, 5 mol% And; containing other monomer structural units (e) 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 of (a) to (d) without impairing the effects of the present invention.

Further, the fluoropolymer having a curable functional group may be a fluoropolymer characterized by comprising

a polymerization unit derived from a fluorine-containing monomer, a polymerization unit derived from a vinyl alcohol as an arbitrary polymerization unit, and a formula (9): -CH ₂ -CH(-O-(L) ₁ -R ^b )- And R ^b is an organic group having at least one terminal double bond, L is a divalent organic group, and l is a polymerization unit represented by 0 or 1).

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

In the formula (9), R ^{b is} preferably selected from the formula (10):

(wherein, M is H, Cl, F or CH ₃ , j is an integer from 1 to 20, k is an integer from 1 to 10, and 2j+1-k is an integer of 0 or more), and a formula 11):

(wherein R is H, Cl, F, CH ₃ or CF ₃ ) represents at least one substituent group of the group.

L is preferably an organic group represented by the formula (12): -(C=O)s-(N-H)p- (wherein, s is 0 or 1, p is 0 or 1).

The molar ratio of the polymerization unit derived from the fluorine-containing monomer, the polymerization unit derived from the vinyl alcohol, and the polymerization unit represented by the general formula (9) is preferably (30 to 70) / (0 to 69) / (1 to 70) ).

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

The insulating adhesive layer (A) preferably further contains an epoxy resin.

By further containing an epoxy resin, the interlayer adhesion to the layer (B) can be made stronger.

The above epoxy resin preferably has a weight average molecular weight of from 100 to 1,000,000.

When the weight average molecular weight of the epoxy resin is in such a range, by including an epoxy resin, the interlayer adhesion to the layer (B) to be described later can be further improved.

The weight average molecular weight of the above epoxy resin is more preferably 1,000 or more, still more preferably 5,000 or more; more preferably 800,000 or less, still more preferably 600,000 or less.

The above weight average molecular weight can be measured by gel permeation chromatography (GPC).

Commercial products of the above epoxy resins may, for example, be derived from double Epikote 828 (manufactured by Shell Chemical Co., Ltd.) of an epibis type compound such as phenol A, EPICLON 800, EPICLON 4050, EPICLON 1121N (manufactured by DIC Corporation), SHOWDYNE (manufactured by Showa Denko KK), Araldite CY-183 Glyptyl ester-based compound (manufactured by Ciba-Geigy Co., Ltd.), Epikote 154 (made by Shell Chemical Co., Ltd.), DEN431, DEN438 (manufactured by The Dow Chemical Co., Ltd.), EPICLON 850 (manufactured by DIC Corporation), cresol novolac A varnish type ECN1280, ECN1235 (manufactured by Ciba-Geigy Co., Ltd.), a urethane-modified EPU-6, an EPU-10 (manufactured by Dijon Chemical Co., Ltd.), and the like.

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

When the insulating adhesive layer (A) contains the above epoxy resin, it is preferably Further, it contains a hardener for epoxy resin.

The curing agent for the epoxy resin is not particularly limited, and examples thereof include As a general public, for example, amines, polyamine amides, polythiols, aromatic polyamines, acid anhydrides, phenols, dicyandiamides, and the like can be mentioned.

When the insulating adhesive layer (A) contains the above epoxy resin, it is preferably Further containing a hardening accelerator.

Examples of the hardening accelerator include an organotin compound, an acid phosphate, a reactant of an acidic phosphate and an amine, a saturated or unsaturated polycarboxylic acid or an anhydride thereof, an organic titanate compound, an amine compound, lead octoate, and the like.

One type of the hardening accelerator may be used, or two or more types may be used in combination. The blending ratio of the hardening accelerator is preferably from 1.0 × 10 ^-6 to 1.0 × 10 ^-2 parts by weight, more preferably 5.0 × 10, based on 100 parts by weight of the fluoropolymer having a curable functional group. ^-5 ~ 1.0 × 10 ^-3 parts by weight or so.

Further, the insulating back layer (A) preferably further contains Polytetrafluoroethylene (PTFE). By further containing PTFE, low dielectric constant and low dielectric tangent can be performed.

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

The above modified PTFE means that by making TFE The copolymer obtained by copolymerization of TFE copolymerized modified monomers.

The modified monomer in the above modified PTFE, as long as it is compatible with The TFE copolymerization is not particularly limited, and examples thereof include perfluoroolefins such as hexafluoropropylene [HFP]; chlorofluoroolefins such as chlorotrifluoroethylene [CTFE]; trifluoroethylene, vinylidene fluoride [VDF], and the like. Hydrogen-containing fluoroolefin; perfluorovinyl Ether; perfluoroalkyl ethylene: ethylene, and the like. Further, the modified monomers to be used may be one type or plural types.

The perfluorovinyl ether is not particularly limited, and examples thereof include a perfluoro unsaturated compound represented by the following formula (I), CF ₂ =CF-ORf (I) (wherein Rf represents a perfluoroorganic group). In the present specification, the above "perfluoroorgano group" means an organic group in which all hydrogen atoms bonded to a carbon atom are replaced by a fluorine atom. The above perfluoroorganic group may also have ether oxygen.

The perfluorovinyl ether may, for example, be a perfluoro(alkyl vinyl ether) [PAVE] in the above formula (I), and Rf represents a perfluoroalkyl group having 1 to 10 carbon atoms. The carbon number of the above perfluoroalkyl group is preferably from 1 to 5.

The perfluoroalkyl group in the above PAVE may, for example, be a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group or a perfluorohexyl group, and preferably a perfluoroalkyl group. Perfluoropropyl perfluoropropyl vinyl ether [PPVE].

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

(where m is 0 or an integer from 1 to 4), and Rf is the following formula:

(where n is an integer from 1 to 4) indicates the base or the like.

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

The modified monomer in the above modified PTFE is preferably HFP, CTFE, VDF, PPVE, PFBE or ethylene.

In the above modified PTFE, the unit of the modified monomer is preferably 1% by mass or less, more preferably 0.001 to 1% by mass based on the total of the monomer units. In the present specification, the modified monomer unit means a part of the molecular structure of the modified PTFE, and is a part derived from the modified monomer, all monomer units, meaning all of the molecular structures derived from the modified PTFE. Part of the monomer. The content of the modified monomer unit is determined by performing infrared spectrometry The value determined by analysis or NMR (nuclear magnetic resonance).

The above PTFE. Preferably, the number average molecular weight is 600,000 under. The above number average molecular weight is a value measured by gel permeation chromatography (GPC).

The above PTFE is preferably a TFE polymer having a melt viscosity of 380 ° C and a melt viscosity of 1 × 10 ² to 7 × 10 ⁵ (Pa.s).

The melt viscosity is measured by using a flow tester (manufactured by Shimadzu Corporation) and a 2φ-8L mold according to ASTM D 1238, and 2 g of the sample previously heated at 380 ° C for 5 minutes is maintained at the above temperature at a load of 0.7 MPa. value. The number average molecular weight is a value calculated from the melt viscosity measured by the above measurement method.

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

The PTFE preferably has an average particle diameter of 1 to 30 μm. More preferably 1 to 20 μm.

The average particle diameter can be obtained by using a laser diffraction type particle size distribution measuring apparatus (manufactured by Nippon Laser Co., Ltd.).

The PTFE preferably has a specific surface area of from 1 to 30 m ² /g, more preferably from 3 to 20 m ² /g.

The surface area was measured by a surface analyzer (trade name: MONOSORB, manufactured by QUANTA CHLROME Co., Ltd.), and a mixed gas of 30% nitrogen and 氦70% was used as the carrier gas, and liquid nitrogen was used for cooling, and the BET method was used.

Commercial products of the above PTFE can be exemplified by Ruburon Industrial (share) system, etc.

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

Insulating adhesive layer (A), and may further contain other materials as needed ingredient.

Examples of the other components include a curing accelerator, a pigment dispersant, an antifoaming agent, a leveling agent, a UV absorber, a photostabilizer, a tackifier, an adhesion improver, and a matting agent. These ingredients can be applied to known ones.

The thickness of the insulating adhesive layer (A) is preferably from 3 to 3,000 μm. When the thickness is in the above range, low inductivity and low dielectric tangent can be ensured.

The thickness is more preferably 5 μm or more, still more preferably 10 μm or more, more preferably 2000 μm or less, still more preferably 1500 μm or less.

Further, the insulating adhesive layer (A) does not contain a woven fabric to be described later, and when it is composed of the above-mentioned resin layer, the thickness is preferably 3 to 40 μm, more preferably 5 μm or more, still more preferably 10 μm or more; more preferably 30 μm. the following.

The insulating adhesive layer (A) can be formed, for example, by using a composition containing the above-mentioned blocked isocyanate, a fluoropolymer having a curable functional group, and other components as needed, and using the above composition.

The insulating adhesive layer (A) is characterized by the fact that it has a specific hardness. Although the insulating adhesive layer (A) and the layer (B) are not firmly adhered to each other, the adhesiveness can be improved by hot pressing thereafter. The above specific hardness, For example, it can be achieved by using a composition containing a blocked isocyanate and a fluoropolymer having a curable functional group as described above.

Further, since the specific hardness can be maintained, the layer (B) of another layer is provided on the surface opposite to the layer (B) by the insulating adhesive layer having a specific hardness, and hot pressing is performed. The insulating layer (A) is adhered, and the layer (B) of the two layers is firmly followed.

The insulating adhesive layer is preferably formed by coating a composition containing the above-mentioned blocked isocyanate and a fluoropolymer having a curable functional group on the layer (B), and drying at 50 to 200 ° C for 0.5 to 30 minutes. Layer. The layer obtained in this way has a specific hardness.

The laminate for a printed circuit board of the present invention further includes A layer (B) placed on at least one side of the above insulating backing layer (A).

The layer (B) is preferably composed of at least one material selected from the group consisting of metal, polyimine, polyamidimide, polyethylene terephthalate, and polyetheretherketone. More preferably, it is composed of at least one material selected from the group consisting of metals and polyimine.

In addition to the insulating adhesive layer (A), it is necessary to ensure strength, and thus the layer (B) is more preferably composed of polyimine.

The layer (B) composed of the above metal can be exemplified by copper, A metal foil composed of aluminum, iron, nickel, chromium, molybdenum, tungsten, zinc, or the like is preferably a copper foil. Further, for the purpose of improving the adhesion, a chemical or mechanical surface may be applied by siding, nickel plating, copper-zinc alloy, or aluminum alkoxide, aluminum chelate, decane coupling agent or the like. deal with.

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, still more preferably 15 μm or more, more preferably 80 μm or less, still more preferably 50 μm or less.

As a method of forming the layer (B), a known method may be appropriately selected depending on the material forming the layer (B).

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

When the layer (B) is provided on both sides of the insulating adhesive layer (A), the bonding strength between the two layers of the insulating adhesive layer (A) and the layer (B) is preferably 3 N/15 mm or more, more preferably 5 N/ 15mm or more.

The above-mentioned adhesive strength was measured using a TENSILON universal testing machine.

The insulating layer (A) and the layer (B) disposed on both sides of the insulating back layer (A) are provided, and the bonding strength between the two layers of the insulating back layer (A) and the layer (B) is 3N. The laminate for a printed circuit board of /15 mm or more is also one of the inventions.

In the laminate for a printed circuit board of the present invention, it is preferable that the layer (B) is made of a metal and the laminated system is a metal clad laminate.

In the present specification, when the laminate for a printed circuit board of the present invention comprises an insulating back layer (A) and a layer (B) made of a metal, it is also referred to as a "metal clad laminate".

In the laminate for a printed circuit board of the present invention, it is preferable that the layer (B) is made of a metal, and the layered system has an etching layer (B) to form a pattern. The printed substrate of the circuit.

The printed substrate may be a rigid printed substrate or a flexible printed substrate.

The present invention is also a laminate for a printed substrate, which is provided with a tie An insulating backing layer (A), a layer (D) composed of a woven fabric provided on at least one side of the insulating back layer (A), and the insulating backing layer (A), a pencil hardness system 2B measured by JIS K5600 Or softer than 2B, and the solvent residual ratio is 10% by mass or less.

The solvent residual ratio is calculated by the following formula.

Solvent residual ratio (% 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

In the formula, the laminate after drying refers to a laminate for a printed circuit board having a layer (A) and a layer (D), and the laminate before drying refers to a laminate for forming the laminate for a printed substrate. Further, for example, a laminate before drying obtained by impregnating the composition (D) described later with the composition described later.

The insulating backing layer (A) is preferably a composite with a layer (D) composed of a woven fabric, and the composite body refers to a composition for forming the insulating backing layer (A). Formed in the layer (D) formed by the cloth.

Insulation is ensured by having a layer (D) made of woven fabric The dimensional stability and strength of layer (A) is then followed.

The above-mentioned woven fabric can be exemplified by a flame retardant, a low dielectric constant, and a high strength material. The constituents of the materials, etc. Among them, glass fiber is preferred from the viewpoint of having such materials.

Insulating adhesive layer (A) when it has a layer (D) made of woven fabric The thickness is preferably 500 to 3000 μm, more preferably 500 to 2000 μm, still more preferably 500 to 1500 μm, based on the total of the insulating adhesive layer (A) and the layer (D).

When the layer (D) composed of a woven fabric is provided, it is preferable to further A layer (B) is provided over the insulating adhesive layer (A). The insulating adhesive layer (A) and the layer (B) may be the same as described above.

The laminate for a printed circuit board of the present invention can also be used as needed There are other layers in one step.

Examples of the other layer described above include a resin layer composed of polyimide, polyethylene terephthalate or the like.

The method for producing a laminate for a printed circuit board of the present invention Preferably, the composition comprising: a layer of a fluoropolymer having a blocked isocyanate and a curable functional group is coated on the layer (B), and dried at 50 to 200 ° C for 0.5 to 30 minutes to form an insulating adhesive layer (A). The steps.

Such a method of producing a laminate for a printed substrate is also one of the inventions.

The above composition is prepared by the above-mentioned block isocyanic acid The ester, the above-mentioned fluoropolymer having a curable functional group, and other components as needed may be mixed and dispersed in a solvent.

A solvent which can be applied to the above composition, preferably organic solvent The agent may, for example, be ethyl acetate, butyl acetate, isopropyl acetate or acetic acid. Esters of isobutyl ester, ceramide acetate, propylene glycol methyl ether acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; tetrahydrofuran, dioxane, etc. a cyclic ether; an amide such as N,N-dimethylformamide or N,N-dimethylacetamide; an aromatic hydrocarbon such as toluene or xylene; propylene glycol methyl ether; Alcohols; hydrocarbons such as hexane, heptane, etc.; such mixed solvents and the like.

The above mixing or dispersion can be carried out by a known method. When the composition is a solvent-based composition containing a solvent, the viscosity of the composition is appropriate, and a uniform coating film is easily formed. The solid content of the composition is preferably from 10 to 80% by mass.

Further, when the composition is a powder type containing no solvent, It can be prepared by a known method of mixing the above components and kneading.

A method of applying the above composition may, for example, be a brush coating. Methods of cloth, dip coating, spray coating, comma coaring, knife coating, die coating, lip coating, roll coater coating, curtain coating, and the like.

Drying is preferably carried out at 50 to 200 ° C for 0.5 to 30 minutes. borrow Since the above range is dried, an insulating adhesive layer having a specific hardness and containing a solvent in a predetermined range can be formed.

From the viewpoint of sufficiently removing the solvent, the drying temperature is better It is carried out at 80 ° C or higher, more preferably at 100 ° C or higher; more preferably at 190 ° C or lower; more preferably at 180 ° C or lower.

The drying time is more preferably 1 minute or more; more preferably 15 minutes or less. The layer for a printed circuit board of the first invention obtained in this manner Fit, the insulation adhesive layer (A) has a specific hardness. On the insulating backing layer (A), by further arranging the layer (B) and hot pressing, a layer in which two layers (B) are strongly adhered via the insulating backing layer (A) can be obtained. Further, the obtained laminate is excellent in foaming resistance because the layers are strongly adhered to each other.

The laminate for a printed circuit board of the present invention, the layer (B) may also be provided On both sides of the insulating adhesion layer (A).

The method for producing a laminate for a printed circuit board on which the production layer (B) is provided on both surfaces of the insulating adhesive layer (A) preferably comprises: coating a layer (B) with a blocked isocyanate containing hexamethylene diisocyanate. And a composition of a fluoropolymer having a curable functional group, dried at 50 to 200 ° C for 0.5 to 30 minutes to form an insulating back layer (A), and on the insulating back layer (A), another layer (B) A step of heat-pressing at 80 to 250 ° C for 30 to 150 minutes to form a layer (B) of two layers via an insulating back layer (A).

By such a method, the bonding strength between the two layers of the insulating adhesive layer (A) and the layer (B) can be 3 N/15 mm or more.

Such a method of producing a laminate for a printed substrate is also one of the inventions.

The above steps of forming the insulating adhesive layer (A) can be performed with The method is carried out in the same manner.

After the insulating adhesive layer (A) is formed, another layer (B) is disposed on the insulating adhesive layer (A), and the laminate of the layer (B)/insulating adhesive layer (A)/layer (B) is 80 to 250. At a temperature of ° C, the two layers (B) are adhered via the insulating adhesive layer (A).

By hot pressing due to the above temperature range, the insulating adhesive layer (A) will Layer (B) is in close contact.

The temperature of the hot pressing is preferably 100 ° C or higher, more preferably 130 ° C or higher, more preferably 220 ° C or lower, and still more preferably 200 ° C or lower.

The hot pressing time is preferably from 30 minutes to 150 minutes, more preferably from 50 minutes to 120 minutes.

The pressure at the time of pressing is preferably 0.3 to 3.0 MPa, more preferably 0.5~1.5MPa.

The above hot pressing can be carried out by a known method, preferably under reduced pressure, and more preferably under vacuum.

Further, the insulating adhesive layer (A) contains a polymer represented by the formula (9) In the case of a unit of a fluorinated polymer, photocuring can be carried out by irradiating an active energy ray such as an ultraviolet ray, an electron beam or a radiation. When photocuring is performed, the carbon-carbon double bond in the fluoropolymer is polymerized in the molecule, and the carbon-carbon double bond in the fluoropolymer is reduced or eliminated.

Moreover, the laminate for a printed circuit board of the present invention has the above-mentioned When the layer (D) composed of the woven fabric is used as a method for producing the woven fabric, it is preferable to have a composition of a fluoropolymer containing a blocked isocyanate and a curable functional group in the layer (D) composed of the woven fabric. After the object, it is dried at 50 to 200 ° C for 0.5 to 30 minutes to form an insulating back layer (A).

Such a method of producing a laminate for a printed substrate is also one of the inventions.

The preparation of the above composition can be carried out by the same method as the above method.

The method of impregnating the woven fabric with the above composition can be carried out by a known method.

The above drying can be carried out in the same manner as the above step of forming the insulating back layer (A).

Further, the laminate for a printed circuit board further has a layer (B) In the case where the layer (D) composed of the woven fabric is impregnated with a composition containing a blocked isocyanate and a fluoropolymer having a curable functional group, the composition is preferably 50 to 200 ° C. Drying for 0.5 to 30 minutes, thereby forming the insulating adhesive layer (A), and insulating the adhesive layer (A) to arrange the layer (B), and heat-pressing at 80 to 250 ° C for 30 to 150 minutes, thereby making the insulating adhesive layer (A) The step of adhering to the layer (B).

Such a method of producing a laminate for a printed substrate is also one of the inventions.

The step of forming the insulating adhesive layer (A) can be performed by the above The method is the same as the method.

The step of bringing the insulating adhesive layer (A) into contact with the layer (B) can be carried out by the same method as the above method.

Lamination of printed substrate of the present invention obtained in this manner The interlayer of the insulating adhesive layer (A) and the layer (B) is excellent in adhesion. Moreover, the foaming resistance is also excellent.

[Examples]

The present invention will be described in further detail below by way of examples and comparative examples, but the invention is not limited thereto.

Preparation example 1

To 100 parts by mass of a hydroxyl group-containing TFE copolymer (Zeffle GK570, manufactured by Daikin Industries Co., Ltd.), 30 parts by mass of butyl acetate and a block type isocyanate curing agent (Duranate MF-B60B manufactured by Asahi Kasei Chemicals Co., Ltd.) were blended. 37.8 parts by mass, a hardenable coating 1 was prepared.

Preparation example 2

To 100 parts by mass of a hydroxyl group-containing TFE copolymer (Zeffle GK570, manufactured by Daikin Industries Co., Ltd.), 30 parts by mass of butyl acetate and a block type isocyanate curing agent (Desmodur BL-3175 manufactured by Bayer Co., Ltd.) were blended. 26.8 parts by mass, a curable coating 2 was prepared.

Preparation example 3

30 parts by mass of butyl acetate and a block type isocyanate hardener (Desmodur BL-3575 by Bayer Co., Ltd.) were blended with 100 parts by mass of a hydroxyl group-containing TFE copolymer (Zeffle GK570, manufactured by Daikin Industries Co., Ltd.). 27.8 parts by mass, a hardenable coating 3 was prepared.

Preparation example 4

To 100 parts by mass of a hydroxyl group-containing TFE copolymer (Zeffle GK570, manufactured by Daikin Industries Co., Ltd.), 30 parts by mass of butyl acetate and a block type isocyanate curing agent (Desmodur BL-4265 manufactured by Bayer Co., Ltd.) were blended. 36.0 parts by mass, a hardenable coating 4 was prepared.

Preparation Example 5

To 100 parts by mass of a hydroxyl group-containing TFE copolymer (Zeffle GK570, manufactured by Daikin Industries Co., Ltd.), 30 parts by mass of butyl acetate and a isocyanurate type isocyanate curing agent (Sumidur N3300 manufactured by Bayer) 13.8 parts by mass, a curable coating 5 was prepared.

(Example 1)

The curable coating material 1 prepared in the preparation example 1 was applied to a copper foil (RDPR1, thickness of 18 μm, manufactured by J. Nippon Mining & Metal Co., Ltd.), and dried at 150 ° C for 3 minutes to prepare a laminate having a coating film formed on the copper foil. . Subsequently, copper foil (RDPR1, thickness of 18 μm, manufactured by JX Nippon Mining & Metal Co., Ltd.) was laminated on the above-mentioned coating film surface, and vacuum-pressed at 1 MPa and 160 ° C for 90 minutes to prepare a laminate 1 having a total thickness of 50 μm. The solder heat resistance and adhesion of the laminate 1 were measured. The bonding strength between the copper foil and the subsequent layers was 11.4 (N/15 mm). Further, the pencil hardness and the solvent residual ratio were measured by the following methods. The results are shown in Table 1.

(Example 2)

The curable coating material 1 prepared 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 form a coating film on the polyimide film. The laminate. Subsequently, a copper foil (RDPR1, 18 μm thickness manufactured by JX Nippon Mining & Metal Co., Ltd.) was laminated on the above-mentioned coating film surface, and it was carried out at 1 MPa and 160 ° C for 90 minutes. The laminate 2 was formed by hollow pressing to prepare a total thickness of 57 μm. The solder heat resistance and adhesion of the laminate 2 were measured. The adhesion strength between the polyimide film/sublayer was 7.1 (N/15 mm), and the adhesion strength between the copper foil/sublayer was 11.4 (N/15 mm). Further, the pencil hardness and the solvent residual ratio were measured by the following methods. The results are shown in Table 1.

(Example 3)

The curable coating material 2 prepared in Preparation Example 2 was applied to a copper foil (RDPR1, thickness: 18 μm, manufactured by JX Nippon Mining & Metal Co., Ltd.), and dried at 150 ° C for 3 minutes to prepare a laminate having a coating film formed on the copper foil. . Subsequently, copper foil (RDPR1, thickness: 18 μm, manufactured by JX Nippon Mining & Metal Co., Ltd.) was laminated on the above-mentioned coating film surface, and vacuum-pressed at 1 MPa and 160 ° C for 90 minutes to prepare a laminate 3 having a total thickness of 50 μm. The solder heat resistance and adhesion of the laminate 3 were measured. The bonding strength between the copper foil and the subsequent layers was 11.1 (N/15 mm). Further, the pencil hardness and the solvent residual ratio were measured by the following methods. The results are shown in Table 1.

(Example 4)

The curable coating material 2 prepared in Preparation Example 2 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 form a coating film on the polyimide film. The laminate. Subsequently, copper foil (RDPR1, thickness: 18 μm, manufactured by JX Nippon Mining & Metal Co., Ltd.) was laminated on the above-mentioned coating film surface, and vacuum-pressed at 1 MPa and 160 ° C for 90 minutes to prepare a laminate 4 having a total thickness of 57 μm. Measuring the laminate 4 Solder heat resistance and adhesion. The adhesion strength between the polyimide film/sublayer was 6.9 (N/15 mm), and the adhesion strength between the copper foil/sublayer was 11.1 (N/15 mm). Further, the pencil hardness and the solvent residual ratio were measured by the following methods. The results are shown in Table 1.

(Example 5)

The curable coating material 3 prepared in Preparation Example 3 was applied to a copper foil (RDPR1, 18 μm thickness manufactured by JN Nippon Mining & Metal Co., Ltd.), and dried at 150 ° C for 3 minutes to prepare a laminate having a coating film formed on the copper foil. . Subsequently, copper foil (RDPR1, thickness: 18 μm, manufactured by JX Nippon Mining & Metal Co., Ltd.) was laminated on the above-mentioned coating film surface, and vacuum-pressed at 1 MPa and 160 ° C for 90 minutes to prepare a laminate 5 having a total thickness of 50 μm. The solder heat resistance and adhesion of the laminate 5 were measured. The bonding strength between the copper foil and the subsequent layers was 11.9 (N/15 mm). Further, the pencil hardness and the solvent residual ratio were measured by the following methods. The results are shown in Table 1.

(Example 6)

The curable coating material 4 prepared in Preparation Example 4 was applied to a copper foil (RDPR1, thickness: 18 μm, manufactured by JX Nippon Mining & Metal Co., Ltd.), and dried at 150 ° C for 3 minutes to prepare a laminate having a coating film formed on the copper foil. . Subsequently, a copper foil (RDPR1, thickness of 18 μm, manufactured by JX Nippon Mining & Metal Co., Ltd.) was laminated on the above-mentioned coating film surface, and vacuum-pressed at 1 MPa and 160 ° C for 90 minutes to prepare a laminate 6 having a total thickness of 50 μm. The solder heat resistance and adhesion of the laminate 6 were measured. Copper foil / subsequent bonding strength between layers 14.1 (N/15mm). Further, the pencil hardness and the solvent residual ratio were measured by the following methods. The results are shown in Table 1.

(Comparative Example 1)

The curable coating material 5 prepared in Preparation Example 5 was applied to a copper foil (RDPR1, thickness: 18 μm, manufactured by JX Nippon Mining & Metal Co., Ltd.), and dried at 150 ° C for 3 minutes to prepare a laminate having a coating film formed on the copper foil. . Subsequently, copper foil (RDPR1, thickness of 18 μm, manufactured by JX Nippon Mining & Metal Co., Ltd.) was laminated on the above-mentioned coating film surface, and vacuum-pressed at 1 MPa and 160 ° C for 90 minutes to prepare a laminate 7 having a total thickness of 50 μm. The solder heat resistance and adhesion of the laminate 7 were measured. The bonding strength between the copper foil and the subsequent layers was 1 (N/15 mm) or less. Further, the pencil hardness and the solvent residual ratio were measured by the following methods. The results are shown in Table 1.

(Comparative Example 2)

The curable coating material 5 prepared 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 form a coating film on the polyimide film. The laminate. Subsequently, a copper foil (RDPR1, thickness of 18 μm, manufactured by JX Nippon Mining & Metal Co., Ltd.) was laminated on the above-mentioned coating film surface, and vacuum-pressed at 1 MPa and 160 ° C for 90 minutes to prepare a laminate 8 having a total thickness of 57 μm. The solder heat resistance and adhesion of the laminate 8 were measured. The adhesive strength between the polyimide film/sublayer layer and the adhesion strength between the copper foil and the subsequent layer were all 1 (N/15 mm) or less. Further, the pencil hardness and the solvent residual ratio were measured by the following methods. Result In Table 1.

(Example 7)

The curable coating material 1 prepared in Preparation Example 1 was impregnated into a glass cloth (manufactured by UNITIKA Co., Ltd., E10T, thickness: 90 μm), and dried at 150 ° C for 3 minutes to prepare an impregnated body. Then, copper foil (RDPR1, thickness: 18 μm, manufactured by JX Nippon Mining & Metal Co., Ltd.) was laminated 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.

The solder heat resistance and adhesion of the laminate 9 were measured. Further, the pencil hardness and the solvent residual ratio were measured by the following methods. The results are shown in Table 1.

<Measurement of solder heat resistance>

A test piece of 25 mm square was produced in accordance with JIS standard C6481, and the copper foil was faced downward, floated on a molten solder bath at 300 ° C for 10 seconds, and then taken out to visually confirm the presence or absence of foaming of the copper foil surface and the laminate. It is evaluated by the following criteria.

No bubble generation: ○

Produce bubblers: ×

<Measurement of adhesion between layers>

A test piece having a width of 15 mm × a length of 100 mm was produced, and a 180 degree peeling test was performed using a TENSILON universal testing machine (RTC-1225A manufactured by Orientec), and a copper foil or a polyimide film was measured in units of N/15 mm. The strength of the bond between the insulating underlayer or the impregnated body.

<Pencil hardness test>

In each of the examples and the comparative examples, a laminate in which a coating film having a curable coating material and dried at 150 ° C for 3 minutes was formed, and the laminate was further heated directly at 160 ° C for 90 minutes in accordance with JIS K5600 The surface of the coating film of the laminate was measured for pencil hardness.

Further, in Example 7, the impregnated body after impregnating the curable coating material at 150 ° C for 3 minutes and the surface of the impregnated body after the impregnation body was further heated directly at 160 ° C for 90 minutes were measured in accordance with JIS K5600. hardness.

The value in parentheses in the table indicates the pencil hardness after heating at 160 ° C for 90 minutes.

<Measurement of Solvent Residual Rate>

The solvent residual ratio is calculated by the following formula.

Solvent residual ratio (% 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

In the case of the first embodiment, the amount of the laminate obtained by applying the curable coating material 1 to the copper foil can be "the mass (g) of the laminate before drying", and the laminate can be used. After drying at 150 ° C for 60 minutes The laminate quality was calculated as "mass (g) of the laminate after drying".

Further, in the case of the seventh embodiment, the quality of the laminate obtained by impregnating the curable coating material 1 with the glass cloth can be "the mass (g) of the laminate before drying", and the laminate can be dried at 150 ° C. The mass of the laminate after 60 minutes was calculated as "mass (g) of the laminate after drying".

[Industrial availability]

According to the invention, it is possible to provide a laminate for a printed circuit board which is excellent in interlayer adhesion and foaming resistance.

Claims (19)

A laminate for a printed circuit board comprising: an insulating back layer (A) and a layer (B) provided on both surfaces of the insulating back layer (A), and the insulating back layer (A) and the layer (B) The bonding strength between the two layers was 3 N/15 mm or more. The laminate for a printed circuit board according to claim 1, wherein the insulating adhesive layer (A) is composed of a blocked isocyanate and a fluoropolymer having a curable functional group. The laminate for a printed circuit board according to claim 1 or 2, wherein the layer (B) is selected from the group consisting of metals, polyimine, polyamidimide, polyethylene terephthalate, and polyetheretherketone. It consists of at least one material of the group. The laminate for a printed circuit board according to claim 2 or 3, wherein the curable functional group is selected from the group consisting of a hydroxyl group, a carboxyl group, an amine group, a glycidyl group, a decyl group, a silanate group, and an isocyanate group. At least one functional group of the group. The laminate for a printed circuit board according to claim 1, 2, 3 or 4, wherein the insulating adhesive layer (A) contains a urethane bond. The laminate for a printed circuit board according to claim 1, 2, 3, 4 or 5, wherein the layer (B) is made of a metal, and the laminated system 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 made of a metal, and the laminated system has an etching layer (B) And a printed substrate on which the pattern circuit is formed. A method for producing a laminate for a printed circuit board according to claim 1, 2, 3, 4 or 5, which comprises coating a layer (B) with a blocked isocyanate and having a curable function The composition of the fluoropolymer is dried at 50 to 200 ° C for 0.5 to 30 minutes to form an insulating back layer (A), and another layer (B) is disposed on the insulating back layer (A). 80 to 250 ° C hot pressing for 30 to 150 minutes, whereby the two layers (B) are adhered through the insulating back layer (A). A laminate for a printed circuit board comprising: an insulating back layer (A) and a layer (B) provided on at least one side of the insulating back layer (A), and the insulating back layer (A) is JIS K5600 The pencil hardness measured was 2B or softer than 2B, and the solvent residual ratio was 10% by mass or less. The laminate for a printed circuit board according to claim 9, wherein the insulating adhesive layer (A) is composed of a blocked isocyanate and a fluoropolymer having a curable functional group. The laminate for a printed circuit board according to claim 9 or 10, wherein the layer (B) is selected from the group consisting of metals, polyimine, polyamidimide, polyethylene terephthalate, and polyetheretherketone. It consists of at least one material of the group. The laminate for a printed circuit board according to claim 10 or 11, wherein the curable functional group is at least selected from the group consisting of a hydroxyl group, a carboxyl group, an amine group, a glycidyl group, a decyl group, a decanoic group, and an isocyanate group. One functional base. The laminate for a printed circuit board of claim 9, 10, 11 or 12, 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, which comprises coating a layer (B) with a fluorine containing a blocked isocyanate and having a curable functional group. The composition of the polymer is dried at 50 to 200 ° C for 0.5 to 30 minutes to form an insulating back layer (A). A laminate for a printed circuit board comprising: an insulating back layer (A); and a layer (D) composed of a woven fabric provided on at least one surface of the insulating back layer (A), and the insulating back layer (A) The pencil hardness measured by JIS K5600 is 2B or softer than 2B, and the solvent residual ratio is 10% by mass or less. The laminate for a printed circuit board according to claim 15, further comprising a layer (B) provided on the insulating adhesive layer (A), wherein the layer (B) is selected from the group consisting of metal, polyimine, and polyfluorene. At least one material selected from the group consisting of amine sulfoximine, polyethylene terephthalate, and polyether ether ketone. The laminate for a printed circuit board according to claim 15 or 16, wherein the insulating adhesive layer (A) contains a urethane bond. A method for producing a laminate for a printed circuit board according to claim 15 or 17, wherein the layer (D) composed of the woven fabric is impregnated with a blocked isocyanate and After the composition of the fluoropolymer having a curable functional group, it is dried at 50 to 200 ° C for 0.5 to 30 minutes to form an insulating back layer (A). A method for producing a laminate for a printed circuit board according to claim 16 or 17, wherein the layer (D) composed of the woven fabric is impregnated with a blocked isocyanate and has a curable functional group. After the composition of the fluoropolymer, it is dried at 50 to 200 ° C for 0.5 to 30 minutes to form an insulating adhesive layer (A), and a layer (B) is disposed on the insulating adhesive layer (A), at 80 ° The step of heat-pressing at 250 ° C for 30 to 150 minutes to adhere the insulating adhesive layer (A) to the layer (B).