Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
  • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
  • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B29/00—Layered products comprising a layer of paper or cardboard
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/08—Macromolecular additives
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/38—Pressure-sensitive adhesives [PSA]
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2457/00—Electrical equipment
  • B32B2457/08—PCBs, i.e. printed circuit boards

Definitions

• the present invention relates to a polyolefin-based adhesive composition. More specifically, the present invention relates to a polyolefin-based adhesive composition used for adhering a resin base material to a resin base material or a metal base material. In particular, the present invention relates to an adhesive composition for a flexible printed wiring board (hereinafter abbreviated as FPC), and a cover film, a laminated board, a copper foil with a resin, and a bonding sheet containing the same.
• FPC flexible printed wiring board
• the flexible printed wiring board has excellent flexibility, it can be used for multi-functionality and miniaturization of personal computers (PCs) and smartphones, and therefore, an electronic circuit board is incorporated in a narrow and complicated interior. It is often used for.
• electronic devices have become smaller, lighter, higher in density, and have higher output, and due to these trends, the demand for the performance of wiring boards (electronic circuit boards) has become more and more sophisticated.
• the frequency of signals is increasing.
• FPCs having low dielectric properties (low dielectric constant, low dielectric loss tangent) in the high frequency region.
• Patent Document 1 a combination of an acid-modified polyolefin and an epoxy resin
• Patent Document 2 a combination of an acid-modified polyolefin and a polyfunctional isocyanate compound
• Patent Document 3 Thermosetting adhesive compositions containing and the like have been developed (Patent Document 3).
• the maleic anhydride-modified polyolefin has a carboxylic acid anhydride group immediately after production, it has been found that there is a problem that the carboxylic acid anhydride ring opens due to moisture absorption over time. .. Therefore, it was found that the adhesiveness, solder heat resistance, dielectric properties (relative permittivity, dielectric loss tangent) and pot life properties are insufficient when used without any measures for moisture absorption as in Patent Documents 1 to 3. It was.
• the present invention contains an acid-modified polyolefin having a predetermined ratio of carboxylic acid anhydride groups, and is further selected from the group consisting of an epoxy resin, an isocyanate compound and a carbodiimide compound.
• the adhesive composition containing the above exhibits excellent adhesiveness, solder heat resistance, and low dielectric properties (specific dielectric constant, dielectric positive contact) between the resin base material and the metal base material, and further, the pot after blending the curing agent. We have found that it is excellent in life, and have completed the present invention.
• the present invention has good adhesiveness to both various resin substrates such as liquid crystal polymers (LCP) and metal substrates as well as polyimide (PI), and has solder heat resistance, dielectric properties, and a pot. It is an object of the present invention to provide an adhesive composition having excellent life property.
• LCP liquid crystal polymers
• PI polyimide
• Adhesive composition contains an acid-modified polyolefin (A) that satisfies the following (1) to (3), and further contains one or more selected from the group consisting of an epoxy resin (B1), an isocyanate compound (B2), and a carbodiimide compound (B3).
• Adhesive composition (1)
• the bond ratio (molar ratio) of the carboxylic acid anhydride group represented by the formula (a1) and the carboxylic acid group represented by the formula (a2) having an acid value of 5 to 50 mgKOH / g is the formula (molar ratio).
• the epoxy resin (B1) contains a glycidylamine type epoxy resin (B11), and is a mixture of one or more selected from the group consisting of a glycidyl ether type resin (B12) and an alicyclic epoxy resin (B13). Is preferable.
• the isocyanate compound (B2) is preferably a polyfunctional isocyanate compound.
• the carbodiimide compound (B3) is preferably a polyfunctional carbodiimide compound.
• oligophenylene ether C
• organic solvent an organic solvent
• An adhesive composition having a relative permittivity ( ⁇ c ) of 3.0 or less and a dielectric loss tangent (tan ⁇ ) of 0.02 or less at 1 GHz.
• An adhesive sheet or laminate containing the adhesive composition.
• a printed wiring board containing the laminate as a component.
• a cover film containing the printed wiring board as a component.
• the adhesive composition according to the present invention has good adhesiveness not only to polyimide but also to various resin substrates such as liquid crystal polymers and metal substrates, and has solder heat resistance, low dielectric properties and pot life properties. Excellent for.
• the acid-modified polyolefin (A) used in the present invention (hereinafter, also simply referred to as the component (A)) satisfies the following requirements (1) to (3).
• the lower limit of the acid value of the acid-modified polyolefin (A) is required to be 5 mgKOH / g or more from the viewpoint of solder heat resistance and adhesion to a resin base material or a metal base material. Since the compatibility with the epoxy resin (B1), the isocyanate compound (B2) and the carbodiimide compound (B3) is good, excellent adhesive strength can be exhibited, and the crosslink density is high and the solder heat resistance is good. It is preferably 6 mgKOH / g or more, more preferably 7 mgKOH / g or more, and further preferably 8 mgKOH / g or more. Further, the upper limit needs to be 50 mgKOH / g.
• formula (a1) is excessive rather than the formula (a2) because the adhesiveness, the solder heat resistance and the pot life property are good.
• Formula (a1) / formula (a2) less than 100 / more than 0 to more than 50/50, more preferably 99/1 to 55/45, and even more preferably 97/3 to 60/40. It is more preferably 95/5 to 65/35, particularly preferably 93/7 to 70/30, and most preferably 91/9 to 75/25.
• the acid-modified polyolefin (A) has a carboxylic acid anhydride group, but it gradually absorbs moisture through the process of manufacturing, packaging, and storing the acid-modified polyolefin, and the carboxylic acid anhydride group opens to open the carboxylic acid group. Will be. Therefore, in order to keep the bond ratio between the carboxylic acid anhydride group represented by the formula (a1) and the carboxylic acid group represented by the formula (a2) within the above range, for example, after producing the acid-modified polyolefin (A). It is preferable to carry out the dehydration condensation reaction in an organic solvent such as toluene again, or to carry out the dehydration condensation reaction at a high temperature without a solvent.
• the acid-modified polyolefin (A) is preferably obtained by grafting at least one of maleic acid and maleic anhydride on the polyolefin resin.
• the polyolefin resin is a hydrocarbon such as homopolymerization of an olefin monomer exemplified by ethylene, propylene, butene, butadiene, isoprene, or copolymerization with other monomers, and hydrides and halides of the obtained polymer. Refers to a polymer whose main component is the skeleton.
• the acid-modified polyolefin is preferably obtained by grafting at least one of maleic acid and maleic anhydride on at least one of polyethylene, polypropylene and a propylene- ⁇ -olefin copolymer.
• the propylene- ⁇ -olefin copolymer is a copolymer of propylene as a main component and ⁇ -olefin.
• ⁇ -olefin for example, one or several kinds of ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene, vinyl acetate and the like can be used.
• ethylene and 1-butene are preferable, and 1-butene is more preferable.
• the ratio of the propylene component to the ⁇ -olefin component of the propylene- ⁇ -olefin copolymer is not limited, but the propylene component is preferably 50 mol% or more, and more preferably 70 mol% or more.
• Examples of the carboxylic acid component other than maleic acid and maleic anhydride include itaconic acid, citraconic acid and their acid anhydrides, acrylic acid, methacrylic acid and the like.
• Specific examples of the acid-modified polyolefin (A) include maleic anhydride-modified polypropylene, maleic anhydride-modified propylene-ethylene copolymer, maleic anhydride-modified propylene-butene copolymer, and maleic anhydride-modified propylene-ethylene-butene. Examples thereof include copolymers, and these acid-modified polyolefins can be used alone or in combination of two or more. Of these, a maleic anhydride-modified propylene-butene copolymer is preferable.
• the number average molecular weight (Mn) of the acid-modified polyolefin (A) is preferably in the range of 10,000 to 50,000. It is more preferably in the range of 15,000 to 45,000, further preferably in the range of 20,000 to 40,000, and particularly preferably in the range of 22,000 to 38,000.
• Mn number average molecular weight
• the weight average molecular weight (Mw) of the acid-modified polyolefin (A) is preferably in the range of 40,000 to 180,000. It is more preferably in the range of 50,000 to 160,000, further preferably in the range of 60,000 to 150,000, particularly preferably in the range of 70,000 to 140,000, and most preferably in the range of 80. It is in the range of 000 to 130,000.
• Mw weight average molecular weight
• the acid-modified polyolefin (A) is preferably a crystalline acid-modified polyolefin.
• Crystallinity as used in the present invention means that the temperature is raised from -100 ° C to 250 ° C at 20 ° C / min using a differential scanning calorimeter (DSC) and a clear melting peak is shown in the heating process. Point to.
• the melting point (Tm) of the acid-modified polyolefin (A) is preferably in the range of 50 ° C. to 120 ° C. It is more preferably in the range of 60 ° C to 100 ° C, and most preferably in the range of 70 ° C to 90 ° C.
• Tm melting point
• the cohesive force derived from the crystal becomes good, and excellent adhesiveness and solder heat resistance can be exhibited.
• the value is not more than the upper limit, the solution stability and fluidity are excellent, and the operability at the time of adhesion is improved.
• the heat of fusion ( ⁇ H) of the acid-modified polyolefin (A) is preferably in the range of 5 J / g to 60 J / g. It is more preferably in the range of 10 J / g to 50 J / g, and even more preferably in the range of 20 J / g to 40 J / g.
• the cohesive force derived from the crystal becomes good, and excellent adhesiveness and solder heat resistance can be exhibited.
• the value is not more than the upper limit, the solution stability and fluidity are excellent, and the operability at the time of adhesion is improved.
• the method for producing the acid-modified polyolefin (A) is not particularly limited, and for example, a radical graft reaction (that is, a radical species is generated for a polymer serving as a main chain, and the radical species is used as a polymerization initiation point to generate an unsaturated carboxylic acid and (Reaction of graft polymerization of acid anhydride), and the like.
• a radical graft reaction that is, a radical species is generated for a polymer serving as a main chain, and the radical species is used as a polymerization initiation point to generate an unsaturated carboxylic acid and (Reaction of graft polymerization of acid anhydride), and the like.
• the radical generator is not particularly limited, but it is preferable to use an organic peroxide.
• the organic peroxide is not particularly limited, but is not particularly limited, but is di-tert-butylperoxyphthalate, tert-butylhydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butylperoxybenzoate, tert-butylperoxy-.
• Peroxides such as 2-ethylhexanoate, tert-butylperoxypivalate, methylethylketone peroxide, di-tert-butyl peroxide, lauroyl peroxide; azobisisobutyronitrile, azobisisopropionitrile, etc. Examples include azonitriles.
• Epoxy resin (B1) used in the present invention (hereinafter, also simply referred to as the component (B1)) is not particularly limited as long as it has a glycidyl group in the molecule, but preferably two or more in the molecule. It has a glycidyl group.
• the content of the epoxy resin (B1) is preferably 0.5 parts by mass or more with respect to 100 parts by mass of the acid-modified polyolefin (A). Since a sufficient curing effect can be obtained and excellent adhesiveness and solder heat resistance can be exhibited, it is more preferably 1 part by mass or more, further preferably 5 parts by mass or more, and particularly preferably 10 parts by mass. That is all. Further, since it has excellent low dielectric properties in addition to adhesiveness, solder heat resistance and pot life, it is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and further preferably 40 parts by mass. It is 3 parts or less, and particularly preferably 35 parts by mass or less.
• the epoxy equivalent of the epoxy resin (B1) is preferably 50 g / eq or more, more preferably 100 g / eq or more, and further preferably 150 g / eq or more. Further, it is preferably 400 g / eq or less, more preferably 350 g / eq or less, and further preferably 300 g / eq or less. Within the above range, excellent solder heat resistance can be exhibited.
• the epoxy resin (B1) used in the present invention contains a glycidylamine type epoxy resin (B11) from the viewpoint of adhesiveness and solder heat resistance, and is composed of a glycidyl ether type resin (B12) and an alicyclic epoxy resin (B13). It is preferably a mixture of one or more selected from the group. That is, it is preferably a mixture of (B11) and (B12), a mixture of (B11) and (B13), or a mixture of (B11), (B12) and (B13).
• the glycidyl amine type epoxy resin (B11) is not particularly limited as long as it is an amine type epoxy resin having one or more glycidyl groups in one molecule. It is preferable to have two or more glycidyl groups in one molecule of the epoxy resin, more preferably three or more glycidyl groups in one molecule of the epoxy resin, and four or more glycidyl groups in one molecule of the epoxy resin. It is more preferable to have.
• R is an aryl group which may have a substituent, and preferably a phenyl group which may have a substituent.
• the substituent of the aryl group is not particularly limited, but is an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, an amino group, a glycidyl group, a glycidyl amino group, or a glycidyl ether group. Can be mentioned.
• X1 and X2 are linear alkylene groups which may independently have a substituent having 1 or more and 5 or less carbon atoms, and the preferable carbon number is 4 or less, more preferably 3 or less, still more preferable. Is 2 or less.
• the substituent of the alkylene group is not particularly limited, and examples thereof include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and an amino group.
• m is 1 or 2 and n is 1 or 2.
• n is 1 or 2.
• either m or n is 2, and more preferably, both m and n are 2.
• glycidylamine type epoxy resin (B11) are not particularly limited, but tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, tetraglycidylbisaminomethylcyclohexanone, N, N, N', N'-tetraglycidyl-m.
• -Glysidylamine-based materials such as xylene diamine can be mentioned. Of these, N, N, N', N'-tetraglycidyl-m-xylene diamine are preferable.
• These glycidylamine type epoxy resins (B11) can be used alone or in combination of two or more.
• the blending amount of the glycidylamine type epoxy resin (B11) is 0.01 part by mass with respect to 100 parts by mass of the acid-modified polyolefin (A) because the catalytic action is exhibited and the adhesiveness and solder heat resistance are improved. It is preferably 0.03 parts by mass or more, more preferably 0.05 parts by mass or more, particularly preferably 0.08 parts by mass or more, and 0.1 mass by mass. Most preferably, it is more than one part. Further, since the pot life property is improved, it is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, further preferably 40 parts by mass or less, and 30 parts by mass or less. It is more preferably 20 parts by mass or less, and most preferably 15 parts by mass or less.
• the glycidyl ether type epoxy resin (B12) is not particularly limited as long as it is an epoxy resin having a glycidyl ether group in the molecule.
• An epoxy resin having two or more glycidyl groups in one molecule of the epoxy resin is preferable, and an epoxy resin having two or more glycidyl groups in one molecule of the epoxy resin and containing no nitrogen atom is preferable. ..
• the blending amount of the glycidyl ether type epoxy resin (B12) is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and 3 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin (A).
• the above is more preferable, and 4 parts by mass or more is particularly preferable, and 5 parts by mass or more is most preferable. Further, it is preferably 20 parts by mass or less, more preferably 18 parts by mass or less, further preferably 16 parts by mass or less, particularly preferably 14 parts by mass or less, and 12 parts by mass or less. Most preferably. Within the above range, excellent adhesiveness and solder heat resistance can be exhibited.
• glycidyl ether type epoxy resin (B12) are not particularly limited, but examples thereof include a phenol novolac type epoxy resin and a cresol novolac type epoxy resin, which are preferable from the viewpoint of adhesiveness to a metal substrate. These glycidyl ether type epoxy resins (B12) can be used alone or in combination of two or more.
• the alicyclic epoxy resin (B13) is not particularly limited as long as it is an epoxy resin having an alicyclic skeleton in the molecule.
• An alicyclic epoxy resin having two or more glycidyl groups in one molecule of the epoxy resin is preferable, and an alicyclic epoxy resin having two or more glycidyl groups in one molecule of the epoxy resin is more preferable.
• the blending amount of the alicyclic epoxy resin (B13) is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and 3 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin (A).
• the above is more preferable, and 4 parts by mass or more is particularly preferable, and 5 parts by mass or more is most preferable. Further, it is preferably 20 parts by mass or less, more preferably 18 parts by mass or less, further preferably 16 parts by mass or less, particularly preferably 14 parts by mass or less, and 12 parts by mass or less. Most preferably. Within the above range, excellent adhesiveness and solder heat resistance can be exhibited.
• alicyclic epoxy resin (B13) examples include, but are not limited to, a dicyclopentadiene skeleton-containing epoxy resin, hexahydrophthalic acid glycidyl ester, 3,4-epoxycyclohexylmethylcarboxylate, and the like. Of these, a dicyclopentadiene skeleton-containing epoxy resin is preferable. These alicyclic epoxy resins (B13) can be used alone or in combination of two or more.
• Excellent adhesiveness is exhibited by using one or more selected from the group consisting of glycidylamine type epoxy resin (B11), glycidyl ether type resin (B12) and alicyclic epoxy resin (B13) in combination. Can be done. That is, the glycidylamine type epoxy resin (B11) has a reaction and curing action between the acid-modified polyolefin (A) and the glycidyl ether type epoxy resin (B12) and / or the alicyclic epoxy resin (B13).
• the glycidylamine type epoxy resin (B11) includes an acid-modified polyolefin (A) and a glycidylamine type epoxy resin (B11), glycidylamine type epoxy resin (B11) with each other, glycidyl ether type epoxy resin (B12) with each other, and an alicyclic type. It has a reaction and curing catalytic action between epoxy resins (B13) and between glycidylamine type epoxy resin (B11) and glycidyl ether type epoxy resin (B12) and / or alicyclic epoxy resin (B13). Therefore, in addition to polyimide, it is possible to exhibit excellent adhesiveness to a non-polar resin base material such as a liquid crystal polymer or a metal base material.
• a non-polar resin base material such as a liquid crystal polymer or a metal base material.
• the total content thereof is adhesive.
• the amount is preferably 2 to 60 parts by mass, more preferably 5 to 40 parts by mass, based on 100 parts by mass of the acid-modified polyolefin (A). It is more preferably to 20 parts by mass.
• the content of the glycidylamine type epoxy resin (B11) is preferably 1 to 50% by mass, more preferably 2 to 30% by mass, and 3 to 10% by mass of the entire epoxy resin (B1). Is the most preferable.
• the lower limit value or more When it is set to the lower limit value or more, the catalytic action is exhibited, the adhesiveness and the solder heat resistance are improved, and when it is set to the upper limit value or less, the cross-linking reaction does not proceed excessively, so that the rigidity is not too high. , Adhesiveness is good. Further, the cross-linking reaction does not proceed too much during the solution storage of the adhesive composition, and the pot life is also improved.
• epoxy resin (B1) used in the present invention other epoxy resins can also be used.
• examples thereof include cyclic or aliphatic epoxyides, and one type may be used alone or two or more types may be used in combination.
• the isocyanate compound (B2) used in the present invention (hereinafter, also simply referred to as the component (B2)) is preferably a polyfunctional isocyanate compound having two or more isocyanate groups in one molecule.
• compounds derived from polyfunctional isocyanate compounds can also be used.
• the content of the isocyanate compound (B2) is preferably 0.5 parts by mass or more with respect to 100 parts by mass of the acid-modified polyolefin (A). Since a sufficient curing effect can be obtained and excellent adhesiveness and solder heat resistance can be exhibited, it is more preferably 1 part by mass or more, further preferably 5 parts by mass or more, and particularly preferably 10 parts by mass. That is all. Further, since it has excellent low dielectric properties in addition to adhesiveness, solder heat resistance and pot life, it is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and further preferably 40 parts by mass. It is 3 parts or less, and particularly preferably 35 parts by mass or less.
• the isocyanate compound (B2) may be any of an aromatic isocyanate compound, an alicyclic isocyanate compound, or an aliphatic isocyanate compound, and these can be used alone or in combination of two or more. Of these, an aliphatic isocyanate compound is preferable, and an aliphatic diisocyanate compound is more preferable.
• the aromatic isocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-naphthalenedi isocyanate, 1,5-naphthalenedi isocyanate, and 1,8-naphthalene.
• alicyclic isocyanate compound examples include isophorone diisocyanate, norbornene diisocyanate, 1,2-cyclohexanediisocyanate, 1,3-cyclohexanediisocyanate, 1,4-cyclohexanediisocyanate, and dicyclohexylmethane-4,4'-diisocyanate. Can be used alone or in combination of two or more.
• the aliphatic isocyanate compound may be either a linear or branched aliphatic isocyanate compound.
• It is preferably a linear aliphatic diisocyanate compound, and specifically, 1,3-propanediisocyanate, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1 , 7-Heptamethylene diisocyanate, 1,8-octamethylene diisocyanate, 1,9-nonamethylene diisocyanate and the like, and these can be used alone or in combination of two or more. Of these, 1,6-hexamethylene diisocyanate is preferable.
• the isocyanate compound (B2) may be an isocyanurate form, an adduct form, a biuret form, a uretdione form, or an allophanate form of the isocyanate compound. These compounds may be used alone or in combination of two or more. Of these, an isocyanurate form or a biuret form is preferable.
• the carbodiimide compound (B3) used in the present invention (hereinafter, also simply referred to as the component (B3)) is preferably a polyfunctional carbodiimide compound having two or more carbodiimide groups in one molecule.
• the carboxylic acid anhydride group of the acid-modified polyolefin reacts with the carbodiimide to enhance the interaction between the adhesive composition and the substrate, and improve the adhesiveness and solder heat resistance. be able to.
• the content of the carbodiimide compound (B3) is preferably 0.5 parts by mass or more with respect to 100 parts by mass of the acid-modified polyolefin (A). Since a sufficient curing effect can be obtained and excellent adhesiveness and solder heat resistance can be exhibited, it is more preferably 1 part by mass or more, further preferably 5 parts by mass or more, and particularly preferably 10 parts by mass. That is all. Further, since it has excellent low dielectric properties in addition to adhesiveness, solder heat resistance and pot life, it is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and further preferably 40 parts by mass. It is 3 parts or less, and particularly preferably 35 parts by mass or less.
• the carbodiimide compound (B3) may be any of an aromatic carbodiimide compound, an alicyclic carbodiimide compound or an aliphatic carbodiimide compound, and these can be used alone or in combination of two or more.
• the aromatic carbodiimide compound include poly-m-phenylene carbodiimide, poly-p-phenylene carbodiimide, polytrilencarbodiimide, poly (diisopropylphenylene carbodiimide), poly (methyldiisopropylphenylene carbodiimide), and poly (4,4'-diphenylmethanecarbodiimide). ) And so on.
• Examples of the alicyclic carbodiimide compound include poly-m-cyclohexylcarbodiimide, poly-p-cyclohexylcarbodiimide, poly (4,4'-dicyclohexylmethanecarbodiimide, poly (3,3′-dicyclohexylmethanecarbodiimide, etc.) and the like.
• the carbodiimide compound may be either a linear or branched aliphatic carbodiimide compound.
• a linear aliphatic carbodiimide compound is preferable, and specifically, polymethylene carbodiimide, polyethylene carbodiimide, etc.
• Polypropylene carbodiimide, polybutylene carbodiimide, polypentamethylene carbodiimide, polyhexamethylene carbodiimide and the like can be mentioned. These can be used alone or in combination of two or more. Among them, aromatic carbodiimide or alicyclic carbodiimide. It is preferable to have.
• oligophenylene ether (C) By incorporating the oligophenylene ether (C) in the adhesive composition of the present invention, further excellent solder heat resistance can be exhibited.
• the oligophenylene ether (C) used in the present invention (hereinafter, also simply referred to as the component (C)) is not particularly limited, but is a structural unit represented by the following general formula (c1) and / or a structure of the general formula (c2). It is preferably a compound having a unit.
• R 1 , R 2 , R 3 , and R 4 are independently hydrogen atoms, optionally substituted alkyl groups, optionally substituted alkoxy groups, and optionally substituted, respectively. It is preferably a good alkynyl group, an optionally substituted aryl group, an optionally substituted aralkyl group or an optionally optionally substituted alkoxy group.
• the "alkyl group” of the alkyl group which may be substituted is, for example, a linear or branched alkyl group having 1 or more and 6 or less carbon atoms, preferably 1 or more and 3 or less carbon atoms.
• a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group and the like can be mentioned, and a methyl group or an ethyl group can be used. More preferably.
• alkenyl group examples include an ethenyl group, a 1-propenyl group, a 2-propenyl group, a 3-butenyl group, a pentenyl group, a hexenyl group and the like, and an ethenyl group or 1 -It is more preferably a propenyl group.
• alkynyl group examples include ethynyl group, 1-propynyl group, 2-propynyl (propargyl) group, 3-butynyl group, pentynyl group, hexynyl group and the like.
• aryl group of the aryl group which may be substituted include a phenyl group, a naphthyl group and the like, and a phenyl group is more preferable.
• aralkyl group of the aralkyl group which may be substituted include a benzyl group, a phenethyl group, a 2-methylbenzyl group, a 4-methylbenzyl group, an ⁇ -methylbenzyl group, a 2-vinylphenethyl group and a 4-.
• alkoxy group of the optionally substituted alkoxy group is, for example, a linear or branched alkoxy group having 1 or more and 6 or less carbon atoms, preferably 1 or more and 3 or less carbon atoms.
• a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group and the like can be mentioned, and the group may be a methoxy group or an ethoxy group. preferable.
• alkyl group, aryl group, alkenyl group, alkynyl group, aralkyl group, and alkoxy group When the above alkyl group, aryl group, alkenyl group, alkynyl group, aralkyl group, and alkoxy group are substituted, it may have one or more substituents.
• substituents include a halogen atom (for example, a fluorine atom, a chlorine atom and a bromine atom) and an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group).
• R 1 and R 4 are methyl groups
• R 2 and R 3 are hydrogen.
• R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , and R 18 are independently hydrogen atoms, optionally substituted alkyl groups, and substituted, respectively. It is preferably an alkenyl group which may be substituted, an alkynyl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted, or an alkoxy group which may be substituted.
• the definition of each substituent is as described above.
• alkyl group examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group and the like, and a methyl group is preferable. .. Of these, it is preferable that R 13 , R 14 , R 17 and R 18 are methyl groups, and R 11 , R 12 , R 15 and R 16 are hydrogen. Further, —A— is preferably a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms, or oxygen.
• the carbon number of A is more preferably 1 or more and 15 or less, and further preferably 2 or more and 10 or less.
• Examples of the divalent hydrocarbon group of A include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, a cyclohexylene group, a phenylene group and the like, and a phenylene group is preferable. Particularly preferred is oxygen.
• the oligophenylene ether (C) was partially or wholly functionalized with an ethylenically unsaturated group such as a vinylbenzyl group, an epoxy group, an amino group, a hydroxy group, a mercapto group, a carboxyl group, a silyl group and the like. It may be a modified oligophenylene ether. Further, it is preferable that both ends have a hydroxy group, an epoxy group, or an ethylenically unsaturated group.
• an ethylenically unsaturated group such as a vinylbenzyl group, an epoxy group, an amino group, a hydroxy group, a mercapto group, a carboxyl group, a silyl group and the like. It may be a modified oligophenylene ether. Further, it is preferable that both ends have a hydroxy group, an epoxy group, or an ethylenically unsaturated group.
• Examples of the ethylenically unsaturated group include an alkenyl group such as an ethenyl group, an allyl group, a methacrylic group, a propenyl group, a butenyl group, a hexenyl group and an octenyl group, a cycloalkenyl group such as a cyclopentenyl group and a cyclohexenyl group, and a vinylbenzyl group.
• Alkenylaryl groups such as vinylnaphthyl groups can be mentioned.
• both ends may be the same functional group or different functional groups. From the viewpoint of highly controlling the balance between low dielectric loss tangent and reduction of resin residue, it is preferable that both ends are hydroxy groups or vinylbenzyl groups, and both ends are hydroxy groups or vinylbenzyl groups. More preferably.
• n is preferably 3 or more, more preferably 5 or more, preferably 23 or less, more preferably 21 or less, and further preferably 19 or less.
• n is preferably 2 or more, more preferably 4 or more, preferably 23 or less, more preferably 20 or less, still more preferably 18 or less.
• the number average molecular weight of the oligophenylene ether (C) is preferably 3000 or less, more preferably 2700 or less, and further preferably 2500 or less.
• the number average molecular weight of the oligophenylene ether (C) is preferably 500 or more, more preferably 700 or more.
• the content of the oligophenylene ether (C) is preferably 0.05 parts by mass or more with respect to 100 parts by mass of the acid-modified polyolefin (A). Since excellent solder heat resistance can be exhibited, it is more preferably 1 part by mass or more, and further preferably 5 parts by mass or more. Further, it is preferably 200 parts by mass or less. It is more preferably 150 parts by mass or less, further preferably 100 parts by mass or less, and particularly preferably 50 parts by mass or less because it can exhibit excellent adhesiveness and solder heat resistance.
• the adhesive composition of the present invention contains an acid-modified polyolefin (A) that satisfies the above specific requirements, and is further selected from the group consisting of an epoxy resin (B1), an isocyanate compound (B2), and a carbodiimide compound (B3). It is a composition containing at least one kind, and it is preferable to further contain the oligophenylene ether (C).
• the adhesive composition of the present invention has excellent adhesiveness not only to polyimide but also to low-polarity resin base materials such as liquid crystal polymers and metal base materials, and further has solder heat resistance, pot life properties and electrical properties (low dielectric properties). Characteristics) Can be expressed. That is, the adhesive coating film (adhesive layer) after the adhesive composition is applied to the base material and cured can exhibit excellent low dielectric constant characteristics.
• the total amount of maleic acid and maleic anhydride contained in the adhesive composition is preferably 1% by mass or less. It is more preferably 0.8% by mass or less, further preferably 0.6% by mass or less, and particularly preferably 0.4% by mass, because the adhesiveness, solder heat resistance and pot life property are improved. It is as follows. The smaller the total amount of maleic anhydride and maleic acid is, the more preferable it is, but industrially, it may be 0.01% by mass or more, and 0.1% by mass or more may be used.
• the adhesive composition according to the present invention preferably has a relative permittivity ( ⁇ c ) of 3.0 or less at a frequency of 1 GHz. It is more preferably 2.6 or less, and even more preferably 2.3 or less. The lower limit is not particularly limited, but is 2.0 in practice. Further, the relative permittivity ( ⁇ c ) in the entire region of the frequency 1 GHz to 60 GHz is preferably 3.0 or less, more preferably 2.6 or less, and further preferably 2.3 or less.
• the adhesive composition according to the present invention preferably has a dielectric loss tangent (tan ⁇ ) of 0.02 or less at a frequency of 1 GHz. It is more preferably 0.01 or less, and even more preferably 0.008 or less. The lower limit is not particularly limited, but is 0.0001 in practice. Further, the dielectric loss tangent (tan ⁇ ) in the entire region of the frequency 1 GHz to 60 GHz is preferably 0.02 or less, more preferably 0.01 or less, and further preferably 0.008 or less.
• the relative permittivity ( ⁇ c ) and the dielectric loss tangent (tan ⁇ ) can be measured as follows. That is, the adhesive composition is applied to the release base material so that the thickness after drying is 25 ⁇ m, and the adhesive composition is dried at about 130 ° C. for about 3 minutes. Then, it is cured by heat treatment at about 140 ° C. for about 4 hours, and the cured adhesive composition layer (adhesive layer) is peeled off from the release film. The relative permittivity ( ⁇ c ) and the dielectric loss tangent (tan ⁇ ) of the adhesive composition layer after peeling at a frequency of 1 GHz are measured. Specifically, the relative permittivity ( ⁇ c ) and the dielectric loss tangent (tan ⁇ ) can be calculated from the measurement by the cavity resonator perturbation method.
• the adhesive composition of the present invention can further contain an organic solvent.
• the organic solvent used in the present invention is not particularly limited as long as it dissolves an acid-modified polyolefin (A), an epoxy resin (B1), an isocyanate compound (B2), a carbodiimide compound (B3) and an oligophenylene ether (C). ..
• aromatic hydrocarbons such as benzene, toluene and xylene
• aliphatic hydrocarbons such as hexane, heptane, octane and decane
• alicyclic hydrocarbons such as cyclohexane, cyclohexene, methylcyclohexane and ethylcyclohexane.
• Halogenized hydrocarbons such as hydrogen, trichloroethylene, dichloroethylene, chlorobenzene and chloroform
• alcohol solvents such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol and phenol, acetone, methylisobutylketone, Ketone solvents such as methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone, acetophenone
• cell solves such as methyl cellsolve and ethyl cell solve
• ester solvents such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, butyl formate, etc.
• Ethylene glycol mono n-butyl ether ethylene glycol mono iso-butyl ether, ethylene glycol mono tert-butyl ether, diethylene glycol mono n-butyl ether, diethylene glycol mono iso-butyl ether, triethylene glycol mono n-butyl ether, tetraethylene glycol mono n-butyl ether, etc.
• a glycol ether solvent or the like can be used, and one or more of these can be used in combination.
• Methylcyclohexane and toluene are particularly preferable because of their work environment and dryness.
• the organic solvent is preferably in the range of 100 to 1000 parts by mass, more preferably in the range of 200 to 900 parts by mass, and 300 to 800 parts by mass with respect to 100 parts by mass of the acid-modified olefin (A). Most preferably it is in the range. When it is at least the above lower limit value, the liquid and pot life properties are improved. Further, setting the value to the upper limit or less is advantageous in terms of manufacturing cost and transportation cost.
• the organic solvent is one or more selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons and halogenated hydrocarbons from the viewpoint of the solution state and pot life of the adhesive composition.
• a mixed solution of one or more solvents (D2) selected from the group consisting of a solvent (D1), an alcohol solvent, a ketone solvent, an ester solvent and a glycol ether solvent is preferable.
• the solvent (D1) is an aromatic hydrocarbon or an alicyclic hydrocarbon
• the solvent (D2) is a ketone solvent.
• the adhesive composition of the present invention may further contain other components as necessary, as long as the effects of the present invention are not impaired.
• specific examples of such components include flame retardants, tackifiers, fillers, and silane coupling agents.
• a flame retardant may be added to the adhesive composition of the present invention, if necessary, as long as the effects of the present invention are not impaired.
• the flame retardant include bromine-based, phosphorus-based, nitrogen-based, and metal hydroxide compounds.
• a phosphorus-based flame retardant is preferable, and a known phosphorus-based flame retardant such as a phosphate ester such as trimethyl phosphate, triphenyl phosphate, tricresyl phosphate or the like, a phosphate such as aluminum phosphite, or phosphazene can be used. .. These may be used alone or in any combination of two or more.
• the flame retardant When the flame retardant is contained, it is preferably contained in the range of 1 to 200 parts by mass, more preferably in the range of 5 to 150 parts by mass, with respect to 100 parts by mass of the total of the components (A) to (C). The range of 100 parts by mass is most preferable. When it is set to the lower limit value or more, the flame retardancy becomes good. Further, when the value is not more than the above upper limit value, the adhesiveness, solder heat resistance, electrical characteristics and the like are not deteriorated.
• the adhesive composition of the present invention may contain a tackifier, if necessary, as long as the effects of the present invention are not impaired.
• the tackifier include polyterpene resin, rosin resin, aliphatic petroleum resin, alicyclic petroleum resin, copolymer petroleum resin, styrene resin, hydrogenated petroleum resin, and the like for the purpose of improving adhesive strength. Used in. These may be used alone or in any combination of two or more.
• the tackifier is contained, it is preferably contained in the range of 1 to 200 parts by mass, more preferably in the range of 5 to 150 parts by mass, based on 100 parts by mass of the total of the components (A) to (C).
• the range of ⁇ 100 parts by mass is most preferable.
• the value By setting the value to the lower limit or more, the effect of the tackifier can be exhibited. Further, when the value is not more than the above upper limit value, the adhesiveness, solder heat resistance, electrical characteristics and the like are not deteriorated.
• the adhesive composition of the present invention may contain a filler such as silica, if necessary, as long as the effects of the present invention are not impaired. It is very preferable to add silica because the properties of solder heat resistance are improved. Hydrophobic silica and hydrophilic silica are generally known as silica, but here, hydrophobic silica treated with dimethyldichlorosilane, hexamethyldisilazane, octylsilane, etc. in order to impart moisture absorption resistance is used. Is good. When silica is contained, the content thereof is preferably in the range of 0.05 to 30 parts by mass with respect to a total of 100 parts by mass of the components (A) to (C).
• the value By setting the value to the lower limit or more, the effect of improving the solder heat resistance can be obtained. Further, when the value is not more than the upper limit value, poor dispersion of silica does not occur, the solution viscosity is good, and the workability is good. Moreover, the adhesiveness does not decrease.
• a silane coupling agent may be added to the adhesive composition of the present invention, if necessary, as long as the effects of the present invention are not impaired. It is highly preferable to add a silane coupling agent because the properties of adhesion to metal and solder heat resistance are improved.
• the silane coupling agent is not particularly limited, and examples thereof include those having an unsaturated group, those having a glycidyl group, and those having an amino group.
• a silane coupling agent having a glycidyl group is more preferable.
• the silane coupling agent is contained, the content thereof is preferably in the range of 0.5 to 20 parts by mass with respect to 100 parts by mass in total of the components (A) to (C).
• the amount is 0.5 parts by mass or more, excellent solder heat resistance becomes good.
• the amount is 20 parts by mass or less, the solder heat resistance and the adhesiveness are improved.
• the laminate of the present invention is one in which an adhesive composition is laminated on a base material (a two-layer laminate of a base material / adhesive layer), or one in which a base material is further bonded (base material / adhesive layer / It is a three-layer laminate of a base material).
• the adhesive layer refers to a layer of the adhesive composition after the adhesive composition of the present invention is applied to a base material and dried.
• the laminate of the present invention can be obtained by applying and drying the adhesive composition of the present invention to various substrates according to a conventional method, and further laminating other substrates.
• the base material is not particularly limited as long as the adhesive composition of the present invention can be applied and dried to form an adhesive layer, but the base material is a resin base material such as a film-like resin, or a metal. Examples include metal base materials such as plates and metal foils, papers, and the like.
• the resin base material examples include polyester resin, polyamide resin, polyimide resin, polyamide-imide resin, liquid crystal polymer, polyphenylene sulfide, syndiotactic polystyrene, polyolefin resin, and fluorine resin.
• a film-like resin hereinafter, also referred to as a base film layer is preferable.
• any conventionally known conductive material that can be used for the circuit board can be used.
• the material include various metals such as SUS, copper, aluminum, iron, steel, zinc, and nickel, as well as alloys, plated products, and metals treated with other metals such as zinc and chromium compounds.
• a metal leaf is preferable, and a copper foil is more preferable.
• the thickness of the metal foil is not particularly limited, but is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, and further preferably 10 ⁇ m or more. Further, it is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, and further preferably 20 ⁇ m or less.
• the metal leaf is usually provided in roll form.
• the form of the metal foil used in manufacturing the printed wiring board of the present invention is not particularly limited. When a ribbon-shaped metal foil is used, its length is not particularly limited. The width thereof is also not particularly limited, but is preferably about 250 to 500 cm.
• Examples of papers include high-quality paper, kraft paper, roll paper, glassine paper, and the like. Further, as the composite material, glass epoxy or the like can be exemplified.
• polyester resin polyamide resin, polyimide resin, polyamide-imide resin, liquid crystal polymer, polyphenylene sulfide, syndiotactic polystyrene, polyolefin resin, fluorine resin, etc.
• SUS steel plate, copper foil, aluminum foil, or glass epoxy is preferable.
• the adhesive sheet is a laminate of the laminate and a release base material via an adhesive composition.
• Specific configuration embodiments include a laminate / adhesive layer / release base material, or a release base material / adhesive layer / laminate / adhesive layer / release base material.
• the release base material By laminating the release base material, it functions as a protective layer of the base material. Further, by using the release base material, the release base material can be released from the adhesive sheet and the adhesive layer can be transferred to another base material.
• the adhesive sheet of the present invention can be obtained by applying the adhesive composition of the present invention to various laminates and drying them according to a conventional method.
• a release base material is attached to the adhesive layer after drying, it can be wound up without causing set-off to the base material, which is excellent in operability and protects the adhesive layer for storage stability. It is excellent and easy to use.
• the release base material is coated and dried, and then another release base material is attached as needed, the adhesive layer itself can be transferred to another base material.
• the release base material is not particularly limited, but for example, a coating layer of a sealant such as clay, polyethylene, or polypropylene is applied to both sides of paper such as high-quality paper, kraft paper, roll paper, and glassine paper. Examples thereof include those in which a silicone-based, fluorine-based, or alkyd-based mold release agent is coated on each of the coating layers.
• various olefin films such as polyethylene, polypropylene, ethylene- ⁇ -olefin copolymer, and propylene- ⁇ -olefin copolymer alone, and films such as polyethylene terephthalate coated with the above-mentioned release agent can also be mentioned.
• polypropylene sealing treatment is applied to both sides of the woodfree paper, and an alkyd-based release agent is used on top of it.
• an alkyd-based mold release agent on polyethylene terephthalate.
• the method for coating the adhesive composition on the substrate in the present invention is not particularly limited, and examples thereof include a comma coater and a reverse roll coater.
• the adhesive layer may be provided directly or by a transfer method on the rolled copper foil or the polyimide film which is the constituent material of the printed wiring board.
• the thickness of the adhesive layer after drying is appropriately changed as needed, but is preferably in the range of 5 to 200 ⁇ m. If the adhesive film thickness is less than 5 ⁇ m, the adhesive strength is insufficient. If the thickness is 200 ⁇ m or more, drying is insufficient, the amount of residual solvent increases, and there is a problem that blister is generated during pressing for manufacturing a printed wiring board.
• the drying conditions are not particularly limited, but the residual solvent ratio after drying is preferably 1% by mass or less. If it exceeds 1% by mass, there is a problem that the residual solvent foams when the printed wiring board is pressed, causing blisters.
• the "printed wiring board” in the present invention includes a laminate formed of a metal foil forming a conductor circuit and a resin base material as a constituent element.
• the printed wiring board is manufactured by a conventionally known method such as a subtractive method using a metal-clad laminate, for example.
• the printed wiring board of the present invention can have an arbitrary laminated structure that can be adopted as a printed wiring board.
• it can be a printed wiring board composed of four layers, a base film layer, a metal foil layer, an adhesive layer, and a cover film layer.
• it can be a printed wiring board composed of five layers of a base film layer, an adhesive layer, a metal foil layer, an adhesive layer, and a cover film layer.
• two or three or more of the above printed wiring boards may be laminated.
• the adhesive composition of the present invention can be suitably used for each adhesive layer of the printed wiring board.
• the adhesive composition of the present invention when used as an adhesive, it has high adhesiveness not only to the conventional polyimide, polyester film, and copper foil constituting the printed wiring board, but also to a low-polarity resin base material such as LCP. , Solder reflow resistance can be obtained, and the adhesive layer itself has excellent low dielectric properties. Therefore, it is suitable as an adhesive composition used for a cover film, a laminated board, a copper foil with a resin, and a bonding sheet.
• any resin film conventionally used as the base material of the printed wiring board can be used as the base film.
• the resin of the base film include polyester resin, polyamide resin, polyimide resin, polyamide-imide resin, liquid crystal polymer, polyphenylene sulfide, syndiotactic polystyrene, polyolefin resin, and fluorine resin.
• it has excellent adhesiveness to low-polarity substrates such as liquid crystal polymers, polyphenylene sulfide, syndiotactic polystyrene, and polyolefin resins.
• any conventionally known insulating film as an insulating film for a printed wiring board can be used.
• films made from various polymers such as polyimide, polyester, polyphenylene sulfide, polyethersulfone, polyetheretherketone, aramid, polycarbonate, polyarylate, polyamideimide, liquid crystal polymer, syndiotactic polystyrene, and polyolefin resin are used. It is possible. More preferably, it is a polyimide film or a liquid crystal polymer film.
• the printed wiring board of the present invention can be manufactured by any conventionally known process other than using the materials of the above-mentioned layers.
• a semi-finished product in which an adhesive layer is laminated on a cover film layer (hereinafter, referred to as "cover film side semi-finished product") is manufactured.
• a semi-finished product (hereinafter referred to as “base film side two-layer semi-finished product”) in which a metal foil layer is laminated on a base film layer to form a desired circuit pattern, or an adhesive layer is laminated on a base film layer.
• a semi-finished product (hereinafter referred to as “base film side 3-layer semi-finished product”) in which a metal foil layer is laminated on the metal foil layer to form a desired circuit pattern (hereinafter referred to as a base film-side 2-layer semi-finished product).
• the base film side three-layer semi-finished product is collectively referred to as "base film side semi-finished product").
• base film side semi-finished product By laminating the cover film side semi-finished product thus obtained and the base film side semi-finished product, a four-layer or five-layer printed wiring board can be obtained.
• the base film side semi-finished product is, for example, (A) a step of applying a resin solution to be a base film to the metal foil and initially drying the coating film, and (B) the metal foil obtained in (A). It is obtained by a production method including a step of heat-treating and drying the laminate with the initial dry coating film (hereinafter, referred to as "heat treatment / solvent removal step").
• a conventionally known method can be used for forming the circuit in the metal foil layer.
• the active method may be used, or the subtractive method may be used.
• the subtractive method is preferable.
• the obtained base film side semi-finished product may be used as it is for bonding with the cover film side semi-finished product, or for bonding with the cover film side semi-finished product after the release film is bonded and stored. You may use it.
• the cover film side semi-finished product is manufactured by applying an adhesive to the cover film, for example. If necessary, a cross-linking reaction can be carried out on the applied adhesive. In a preferred embodiment, the adhesive layer is semi-cured.
• the obtained cover film side semi-finished product may be used as it is for bonding with the base film side semi-finished product, or may be bonded to the base film side semi-finished product after the release film is bonded and stored. May be used for.
• the base film side semi-finished product and the cover film side semi-finished product are, for example, stored in the form of rolls and then bonded together to manufacture a printed wiring board. Any method can be used as the bonding method, and for example, the bonding can be performed using a press or a roll. It is also possible to bond the two together while heating by a method such as using a heating press or a heating roll device.
• the reinforcing material side semi-finished product is preferably manufactured by applying an adhesive to the reinforcing material.
• an adhesive to the reinforcing material.
• the adhesive previously applied to the release base material is transferred and applied. It is preferable to be manufactured. Further, if necessary, a cross-linking reaction can be carried out in the applied adhesive.
• the adhesive layer is semi-cured.
• the obtained reinforcing material side semi-finished product may be used as it is for bonding with the back surface of the printed wiring board, or may be used for bonding with the base film side semi-finished product after the release film is bonded and stored. You may.
• the base film side semi-finished product, the cover film side semi-finished product, and the reinforcing material side semi-finished product are all laminates for the printed wiring board in the present invention.
• Acid value (mgKOH / g) The acid value (mgKOH / g) in the present invention was determined by dissolving an acid-modified polyolefin in toluene and titrating with a methanol solution of sodium methoxide using phenolphthalein as an indicator.
• the number average molecular weight in the present invention is gel permeation chromatography manufactured by Shimadzu Corporation (hereinafter, GPC, standard substance: polystyrene resin, mobile phase: tetrahydrofuran, column: Shodex KF-802 + KF-804L + KF-806L, column. Temperature: 30 ° C., flow velocity: 1.0 ml / min, detector: RI detector).
• Tm melting point
• ⁇ H heat of melting
• the absorption spectrum (Abs) of the sample solution is measured using an infrared spectrophotometer. Read the maximum absorption intensities around 1780 cm -1 (carboxylic acid anhydride group (a1)) and 1730 cm -1 (carboxylic acid group (a2)) in the absorption spectrum, and read the calibration curve to 1 g of the resin (a1) and (a2). The content per unit (mmol / g) is determined.
• the adhesive composition described later is applied to a 12.5 ⁇ m-thick polyimide film (Kaneka Corporation, Apical (registered trademark)) or a 25 ⁇ m-thick LCP film (Kurare Co., Ltd., Vecstar (registered trademark)). The film was applied so that the thickness after drying was 25 ⁇ m, and dried at 130 ° C. for 3 minutes.
• the adhesive film (B stage product) thus obtained was bonded to a rolled copper foil (manufactured by JX Nippon Mining & Metals Co., Ltd., BHY series) having a thickness of 18 ⁇ m.
• the bonding was performed by pressing the rolled copper foil under a pressure of 40 kgf / cm 2 at 160 ° C. for 30 seconds so that the glossy surface of the rolled copper foil was in contact with the adhesive layer. Then, it was heat-treated at 140 ° C. for 4 hours to be cured to obtain a sample for evaluation of peel strength.
• the peel strength was measured by performing a 90 ° peel test at a film pulling rate of 50 mm / min at 25 ° C. This test shows the adhesive strength at room temperature.
• the relative permittivity ( ⁇ c ) and the dielectric loss tangent (tan ⁇ ) were measured by a cavity resonator perturbation method using a network analyzer (manufactured by Anritsu) under the conditions of a temperature of 23 ° C. and a frequency of 1 GHz.
• the obtained relative permittivity and dielectric loss tangent were evaluated as follows.
• the varnish prepared according to the ratios in Tables 2 to 4 was measured with a dispersion liquid viscosity at 25 ° C. using a Brookfield type viscometer (rotor No. 2, rotation speed 60 rpm) to determine the initial dispersion liquid viscosity ⁇ B0. Then, the varnish was stored at 25 ° C. for 7 days, and the dispersion viscosity ⁇ B was measured at 25 ° C.
• the varnish viscosity was calculated by the following formula and evaluated as follows.
• Solution viscosity ratio solution viscosity ⁇ B / solution viscosity ⁇ B0 ⁇ Evaluation criteria> ⁇ : 0.5 or more and less than 1.5 ⁇ : 1.5 or more and less than 2.0 ⁇ : 2.0 or more and less than 3.0 ⁇ : 3.0 or more or viscosity cannot be measured due to purifying
• Acid-modified polyolefin (A) Production Example 1 (Production of Acid-Modified Polyolefins PO-1a and PO-1b) 100 parts by mass of propylene-butene copolymer (“Toughmer (registered trademark) XM7080” manufactured by Mitsui Chemicals, Inc.), 20 parts by mass of maleic anhydride, 6 parts by mass of di-tert-butyl peroxide, and the maximum temperature of the cylinder part is 170 ° C. The kneading reaction was carried out using the twin-screw extruder set in.
• PO-1a maleic anhydride-modified propylene-butene copolymer
• PO-1a maleic anhydride-modified propylene-butene copolymer
• PO-1a was allowed to stand in a desiccator at 30 ° C. and an RH70% environment for 1 week to obtain P0-1b.
• Production Example 2 (Production of Acid-Modified Polyolefins PO-2a and PO-2b)
• the maleic anhydride-modified propylene-butene copolymer (PO-2a, acid value 48 mgKOH / g, number average molecular weight 17) was used.
• PO-2a was allowed to stand in a desiccator at 30 ° C. and an RH70% environment for 1 week to obtain P0-2b.
• Production Example 3 (Production of Acid-Modified Polyolefins PO-3a and PO-3b)
• the maleic anhydride-modified propylene-butene copolymer (PO-3a, acid value 7 mgKOH / g, number average molecular weight 35) was used.
• PO-3a was allowed to stand in a desiccator at 30 ° C. and an RH70% environment for 1 week to obtain P0-3b.
• Production Example 4 (Production of Acid-Modified Polyolefins PO-4a and PO-4b)
• the maleic anhydride-modified propylene-butene copolymer (PO-4a, acid value 55 mgKOH / g, number average molecular weight 13) was used.
• 000, weight average molecular weight 40,000, Tm70 ° C., ⁇ H25J / g, carboxylic acid anhydride group (a1) / carboxylic acid group binding ratio (a2) 88/12, occupying the total acid component (a1) (A2) total amount 100 mol%) was obtained.
• PO-4b was allowed to stand in a desiccator at 30 ° C. and an RH70% environment for 1 week to obtain P0-4b.
• Production Example 5 (Production of Acid-Modified Polyolefins PO-5a and PO-5b)
• a maleic anhydride-modified propylene-butene copolymer (maleic anhydride-modified propylene-butene copolymer) was prepared in the same manner as in Production Example 1 except that the amount of maleic anhydride charged was changed to 2 parts by mass and the di-tert-butyl peroxide was changed to 0.5 parts by mass.
• PO-5a was allowed to stand in a desiccator at 30 ° C. and an RH70% environment for 1 week to obtain P0-5b.
• PO-6a maleic anhydride-modified propylene-butene copolymer
• PO-6a was allowed to stand in a desiccator at 30 ° C. and an RH70% environment for 1 week to obtain P0-6b.
• Preparation Examples 2 to 9 (cyclization reaction of acid-modified polyolefin PO-1c2 to PO-6c1) The types of acid-modified polyolefins and the reflux time were changed as shown in Table 1, and Preparation Examples 2 to 9 were carried out in the same manner as in Preparation Example 1. The physical characteristics are shown in Table 1.
• Examples 2-35, Comparative Examples 1-15 The blending amounts of the components (A) to (C) were changed as shown in Tables 2 to 4, and Examples 2 to 35 and Comparative Examples 1 to 15 were carried out in the same manner as in Example 1.
• Tables 2 to 4 show the evaluation results of adhesive strength, solder heat resistance, electrical characteristics and pot life.
• the epoxy resin (B1), isocyanate compound (B2), carbodiimide compound (B3), and oligophenylene ether (C) used in Tables 2 to 4 are as follows.
• Comparative Examples 3, 8 and 13 since the acid value of the acid-modified polyolefin (A) was low, the adhesiveness between the liquid crystal polymer and the copper foil and the solder heat resistance were lowered.
• Comparative Examples 4, 9 and 14 since the total amount of the carboxylic acid anhydride group (a1) and the carboxylic acid group (a2) was small, the solder heat resistance and the pot life property were lowered.
• the adhesive composition of the present invention has excellent adhesiveness not only to polyimide but also to a non-polar resin base material such as a liquid crystal polymer and a metal base material such as copper foil. Furthermore, it has excellent solder heat resistance and low dielectric properties, and is also excellent in pot life.
• the adhesive composition of the present invention can obtain an adhesive sheet and a laminate bonded using the adhesive sheet. Due to the above characteristics, it is useful for flexible printed wiring board applications, especially for FPC applications where low dielectric properties (low dielectric constant, low dielectric loss tangent) in a high frequency region are required.

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