WO2021045125A1 - Polyolefin-based adhesive composition - Google Patents
Polyolefin-based adhesive composition Download PDFInfo
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- WO2021045125A1 WO2021045125A1 PCT/JP2020/033325 JP2020033325W WO2021045125A1 WO 2021045125 A1 WO2021045125 A1 WO 2021045125A1 JP 2020033325 W JP2020033325 W JP 2020033325W WO 2021045125 A1 WO2021045125 A1 WO 2021045125A1
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- acid
- adhesive composition
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- epoxy resin
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- 0 *C(CC(O1)=O)C1=O Chemical compound *C(CC(O1)=O)C1=O 0.000 description 1
Classifications
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- 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
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- 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
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- 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
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- 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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Abstract
Description
(1)酸価が5~50mgKOH/gである
(2)式(a1)で示されるカルボン酸無水物基と式(a2)で示されるカルボン酸基の結合比率(モル比)が、式(a1)/式(a2)=100/0~50/50である
(3)酸変性ポリオレフィン(A)に結合する全酸成分を100モル%としたとき、式(a1)と式(a2)の合計量が90モル%以上である
(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). a1) / formula (a2) = 100/0 to 50/50 (3) When the total acid component bonded to the acid-modified polyolefin (A) is 100 mol%, the formulas (a1) and (a2) The total amount is 90 mol% or more
本発明で用いる酸変性ポリオレフィン(A)(以下、単に(A)成分ともいう。)は下記要件(1)~(3)を満足するものである。 <Acid-modified polyolefin (A)>
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).
酸変性ポリオレフィン(A)の酸価は、ハンダ耐熱性および樹脂基材や金属基材との接着性の観点から、下限は5mgKOH/g以上であることが必要である。エポキシ樹脂(B1)、イソシアネート化合物(B2)およびカルボジイミド化合物(B3)との相溶性が良好となり、優れた接着強度を発現することができること、および架橋密度が高くハンダ耐熱性が良好となることから、好ましくは6mgKOH/g以上であり、より好ましくは7mgKOH/g以上であり、さらに好ましくは8mgKOH/g以上である。また、上限は50mgKOH/gであることが必要である。接着性およびハンダ耐熱性が良好となること、および溶液の粘度や安定性が良好となり、優れたポットライフ性を発現できることから、好ましくは40mgKOH/g以下であり、より好ましくは30mgKOH/g以下であり、さらに好ましくは20mgKOH/g以下である。前記範囲内であれば、製造効率も向上する。 <Requirement (1)>
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. It is preferably 40 mgKOH / g or less, more preferably 30 mgKOH / g or less, because the adhesiveness and solder heat resistance are good, the viscosity and stability of the solution are good, and excellent pot life can be exhibited. Yes, more preferably 20 mgKOH / g or less. If it is within the above range, the manufacturing efficiency is also improved.
式(a1)で示されるカルボン酸無水物基と式(a2)で示されるカルボン酸基の結合比率(モル比)が、式(a1)/式(a2)=100/0~50/50であることが必要である。
The bond ratio (molar ratio) between the carboxylic acid anhydride group represented by the formula (a1) and the carboxylic acid group represented by the formula (a2) is formula (a1) / formula (a2) = 100/0 to 50/50. It is necessary to be.
酸変性ポリオレフィン(A)に結合する全酸成分を100モル%としたとき、式(1)と式(2)の合計量が90モル%以上であることが必要である。接着性、ハンダ耐熱性およびポットライフ性が良好となることから、92モル%以上であることが好ましく、より好ましくは95モル%以上であり、さらに好ましくは98モル%以上であり、特に好ましくは99モル%以上であり、100モル%であっても差し支えない。 <Requirement (3)>
When the total acid component bonded to the acid-modified polyolefin (A) is 100 mol%, the total amount of the formula (1) and the formula (2) needs to be 90 mol% or more. From the viewpoint of good adhesiveness, solder heat resistance and pot life, it is preferably 92 mol% or more, more preferably 95 mol% or more, still more preferably 98 mol% or more, and particularly preferably 98 mol% or more. It is 99 mol% or more, and may be 100 mol%.
本発明で用いるエポキシ樹脂(B1)(以下、単に(B1)成分ともいう。)としては、分子中にグリシジル基を有するものであれば、特に限定されないが、好ましくは分子中に2個以上のグリシジル基を有するものである。 <Epoxy resin (B1)>
The 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.
グリシジルアミン型エポキシ樹脂(B11)は、1分子中に1個以上のグリシジル基を有するアミン型エポキシ樹脂であれば特に限定されない。エポキシ樹脂1分子中に2個以上のグリシジル基を有することが好ましく、エポキシ樹脂1分子中に3個以上のグリシジル基を有することがより好ましく、エポキシ樹脂1分子中に4個以上のグリシジル基を有することがさらに好ましい。 <Glysidylamine type epoxy resin (B11)>
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.
グリシジルエーテル型エポキシ樹脂(B12)は、分子内にグリシジルエーテル基を有するエポキシ樹脂であれば特に限定されない。好ましくはエポキシ樹脂1分子中に2個以上のグリシジル基を有するエポキシ樹脂であり、さらに好ましくはエポキシ樹脂1分子中に2個以上のグリシジル基を有し、かつ窒素原子を含有しないエポキシ樹脂である。 <Glysidyl ether type epoxy resin (B12)>
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. ..
脂環型エポキシ樹脂(B13)は、分子内に脂環骨格を有するエポキシ樹脂であれば特に限定されない。好ましくはエポキシ樹脂1分子中に2個以上のグリシジル基を有する脂環型エポキシ樹脂であり、さらに好ましくはエポキシ樹脂1分子中に2個以上のグリシジル基を有する脂環型エポキシ樹脂である。 <Alicyclic epoxy resin (B13)>
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.
本発明で用いるイソシアネート化合物(B2)(以下、単に(B2)成分ともいう。)は、1分子中に2個以上のイソシアネート基を有する多官能イソシアネート化合物であることが好ましい。また、多官能イソシアネート化合物から誘導された化合物も使用することができる。 <Isocyanate compound (B2)>
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. In addition, compounds derived from polyfunctional isocyanate compounds can also be used.
本発明で用いるカルボジイミド化合物(B3)(以下、単に(B3)成分ともいう。)は、1分子中に2個以上のカルボジイミド基を有する多官能カルボジイミド化合物であることが好ましい。カルボジイミド化合物(B3)を使用することによって、酸変性ポリオレフィンのカルボン酸無水物基とカルボジイミドとが反応し、接着剤組成物と基材との相互作用を高め、接着性およびハンダ耐熱性を向上することができる。 <Carbodiimide compound (B3)>
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. By using the carbodiimide compound (B3), 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.
本発明の接着剤組成物にオリゴフェニレンエーテル(C)を含有させることで、さらに優れたハンダ耐熱性を発現することができる。本発明で用いるオリゴフェニレンエーテル(C)(以下、単に(C)成分ともいう。)は特に限定されないが、下記一般式(c1)で表される構造単位および/または一般式(c2)の構造単位を有する化合物であることが好ましい。
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.
本発明の接着剤組成物は、前記特定の要件を満足する酸変性ポリオレフィン(A)を含み、さらにエポキシ樹脂(B1)、イソシアネート化合物(B2)およびカルボジイミド化合物(B3)からなる群より選ばれた1種以上を少なくとも含有する組成物であり、さらに前記オリゴフェニレンエーテル(C)を含有することが好ましい。本発明の接着剤組成物は、ポリイミドのみならず液晶ポリマーなどの低極性樹脂基材や金属基材との優れた接着性を有し、さらにハンダ耐熱性、ポットライフ性および電気特性(低誘電特性)発現することができる。すなわち、接着剤組成物を基材に塗布、硬化後の接着剤塗膜(接着剤層)が優れた低誘電率特性を発現することができる。 <Adhesive composition>
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.
本発明の接着剤組成物は、さらに有機溶剤を含有することができる。本発明で用いる有機溶剤は、酸変性ポリオレフィン(A)、エポキシ樹脂(B1)、イソシアネート化合物(B2)、カルボジイミド化合物(B3)およびオリゴフェニレンエーテル(C)を溶解させるものであれば、特に限定されない。具体的には、例えば、ベンゼン、トルエン、キシレン等の芳香族炭化水素、ヘキサン、ヘプタン、オクタン、デカン等の脂肪族系炭化水素、シクロヘキサン、シクロヘキセン、メチルシクロヘキサン、エチルシクロへキサン等の脂環族炭化水素、トリクロルエチレン、ジクロルエチレン、クロルベンゼン、クロロホルム等のハロゲン化炭化水素、メタノール、エタノール、イソプロピルアルコール、ブタノール、ペンタノール、ヘキサノール、プロパンジオール、フェノール等のアルコール系溶剤、アセトン、メチルイソブチルケトン、メチルエチルケトン、ペンタノン、ヘキサノン、シクロヘキサノン、イソホロン、アセトフェノン等のケトン系溶剤、メチルセルソルブ、エチルセルソルブ等のセルソルブ類、酢酸メチル、酢酸エチル、酢酸ブチル、プロピオン酸メチル、ギ酸ブチル等のエステル系溶剤、エチレングリコールモノn-ブチルエーテル、エチレングリコールモノiso-ブチルエーテル、エチレングリコールモノtert-ブチルエーテル、ジエチレングリコールモノn-ブチルエーテル、ジエチレングリコールモノiso-ブチルエーテル、トリエチレングリコールモノn-ブチルエーテル、テトラエチレングリコールモノn-ブチルエーテル等のグリコールエーテル系溶剤等を使用することができ、これら1種または2種以上を併用することができる。特に作業環境性、乾燥性から、メチルシクロへキサンやトルエンが好ましい。 <Organic solvent>
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). .. Specifically, for example, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane, heptane, octane and decane, and 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.
本発明の接着剤組成物には、本発明の効果を損ねない範囲で、必要に応じて難燃剤を配合しても良い。難燃剤としては、臭素系、リン系、窒素系、水酸化金属化合物等が挙げられる。中でも、リン系難燃剤が好ましく、リン酸エステル、例えば、トリメチルホスフェート、トリフェニルホスフェート、トリクレジルホスフェート等、リン酸塩、例えばホスフィン酸アルミニウム等、ホスファゼン等の公知のリン系難燃剤を使用できる。これらは単独で用いても良いし、2種以上を任意に組み合わせて使用しても良い。難燃剤を含有させる場合、(A)~(C)成分の合計100質量部に対し、1~200質量部の範囲で含有させることが好ましく、5~150質量部の範囲がより好ましく、10~100質量部の範囲が最も好ましい。前記下限値以上とすることで難燃性が良好となる。また、前記上限値以下とすることで接着性、ハンダ耐熱性、電気特性等が低下することがない。 <Flame retardant>
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. Examples of the flame retardant include bromine-based, phosphorus-based, nitrogen-based, and metal hydroxide compounds. Among them, 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. 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.
本発明の接着剤組成物には、本発明の効果を損ねない範囲で、必要に応じて粘着付与剤を配合しても良い。粘着付与剤としては、ポリテルペン樹脂、ロジン系樹脂、脂肪族系石油樹脂、脂環族系石油樹脂、共重合系石油樹脂、スチレン樹脂および水添石油樹脂等が挙げられ、接着強度を向上させる目的で用いられる。これらは単独で用いても良いし、2種以上を任意に組み合わせて使用しても良い。粘着付与剤を含有させる場合、(A)~(C)成分の合計100質量部に対し、1~200質量部の範囲で含有させることが好ましく、5~150質量部の範囲がより好ましく、10~100質量部の範囲が最も好ましい。前記下限値以上とすることで粘着付与剤の効果を奏することができる。また、前記上限値以下とすることで接着性、ハンダ耐熱性、電気特性等が低下することがない。 <Adhesive imparting agent>
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. Examples of 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. When 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. 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.
本発明の接着剤組成物には、本発明の効果を損ねない範囲で、必要に応じてシリカなどのフィラーを配合しても良い。シリカを配合することによりハンダ耐熱性の特性が向上するため非常に好ましい。シリカとしては一般に疎水性シリカと親水性シリカが知られているが、ここでは耐吸湿性を付与する上でジメチルジクロロシランやヘキサメチルジシラザン、オクチルシラン等で処理を行った疎水性シリカの方が良い。シリカを含有させる場合、その含有量は、(A)~(C)成分の合計100質量部に対し、0.05~30質量部の範囲であることが好ましい。前記下限値以上とすることでハンダ耐熱性を向上させる効果を奏することができる。また、前記上限値以下とすることでシリカの分散不良が生じることがなく、溶液粘度が良好であり作業性が良好となる。また接着性も低下しない。 <Filler>
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). 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.
本発明の接着剤組成物には、本発明の効果を損ねない範囲で、必要に応じてシランカップリング剤を配合しても良い。シランカップリング剤を配合することにより金属への接着性やハンダ耐熱性の特性が向上するため非常に好ましい。シランカップリング剤としては特に限定されないが、不飽和基を有するもの、グリシジル基を有するもの、アミノ基を有するものなどが挙げられる。これらのうちハンダ耐熱性の観点からγ-グリシドキシプロピルトリメトキシシランやβ-(3,4-エポキシシクロヘキシル)エチルトリメトキシシランやβ-(3,4-エポキシシクロヘキシル)エチルトリエトキシシラン等のグリシジル基を有したシランカップリング剤がさらに好ましい。シランカップリング剤を含有させる場合、その含有量は(A)~(C)成分の合計100質量部に対して0.5~20質量部の範囲であることが好ましい。0.5質量部以上とすることで優れたハンダ耐熱性が良好となる。一方、20質量部以下とすることでハンダ耐熱性や接着性が良好となる。 <Silane coupling agent>
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. Of these, from the viewpoint of solder heat resistance, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, etc. A silane coupling agent having a glycidyl group is more preferable. When 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). When the amount is 0.5 parts by mass or more, excellent solder heat resistance becomes good. On the other hand, when the amount is 20 parts by mass or less, the solder heat resistance and the adhesiveness are improved.
本発明の積層体は、基材に接着剤組成物を積層したもの(基材/接着剤層の2層積層体)、または、さらに基材を貼り合わせたもの(基材/接着剤層/基材の3層積層体)である。ここで、接着剤層とは、本発明の接着剤組成物を基材に塗布し、乾燥させた後の接着剤組成物の層をいう。本発明の接着剤組成物を、常法に従い、各種基材に塗布、乾燥すること、およびさらに他の基材を積層することにより、本発明の積層体を得ることができる。 <Laminated body>
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). Here, 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.
本発明において基材とは、本発明の接着剤組成物を塗布、乾燥し、接着剤層を形成できるものであれば特に限定されるものではないが、フィルム状樹脂等の樹脂基材、金属板や金属箔等の金属基材、紙類等を挙げることができる。 <Base material>
In the present invention, 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.
本発明において、接着シートとは、前記積層体と離型基材とを接着剤組成物を介して積層したものである。具体的な構成態様としては、積層体/接着剤層/離型基材、または離型基材/接着剤層/積層体/接着剤層/離型基材が挙げられる。離型基材を積層することで基材の保護層として機能する。また離型基材を使用することで、接着シートから離型基材を離型して、さらに別の基材に接着剤層を転写することができる。 <Adhesive sheet>
In the present invention, 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. 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.
離型基材としては、特に限定されるものではないが、例えば、上質紙、クラフト紙、ロール紙、グラシン紙などの紙の両面に、クレー、ポリエチレン、ポリプロピレンなどの目止剤の塗布層を設け、さらにその各塗布層の上にシリコーン系、フッ素系、アルキド系の離型剤が塗布されたものが挙げられる。また、ポリエチレン、ポリプロピレン、エチレン-α-オレフィン共重合体、プロピレン-α-オレフィン共重合体等の各種オレフィンフィルム単独、及びポリエチレンテレフタレート等のフィルム上に上記離型剤を塗布したものも挙げられる。離型基材と接着剤層との離型力、シリコーンが電気特性に悪影響を与える等の理由から、上質紙の両面にポリプロピレン目止処理しその上にアルキド系離型剤を用いたもの、またはポリエチレンテレフタレート上にアルキド系離型剤を用いたものが好ましい。 <Release 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. In addition, various olefin films such as polyethylene, polypropylene, ethylene-α-olefin copolymer, and propylene-α-olefin copolymer alone, and films such as polyethylene terephthalate coated with the above-mentioned release agent can also be mentioned. For reasons such as the release force between the release base material and the adhesive layer, and the fact that silicone adversely affects the electrical characteristics, polypropylene sealing treatment is applied to both sides of the woodfree paper, and an alkyd-based release agent is used on top of it. Alternatively, it is preferable to use an alkyd-based mold release agent on polyethylene terephthalate.
本発明における「プリント配線板」は、導体回路を形成する金属箔と樹脂基材とから形成された積層体を構成要素として含むものである。プリント配線板は、例えば、金属張積層体を用いてサブトラクティブ法などの従来公知の方法により製造される。必要に応じて、金属箔によって形成された導体回路を部分的、或いは全面的にカバーフィルムやスクリーン印刷インキ等を用いて被覆した、いわゆるフレキシブル回路板(FPC)、フラットケーブル、テープオートメーティッドボンディング(TAB)用の回路板などを総称している。 <Printed circuit board>
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. So-called flexible circuit board (FPC), flat cable, tape automated bonding (FPC), flat cable, tape automated bonding (FPC), flat cable, tape automated bonding (FPC), in which a conductor circuit formed of metal foil is partially or wholly coated with a cover film, screen printing ink, or the like as needed. It is a general term for circuit boards for TAB).
カバーフィルムとしては、プリント配線板用の絶縁フィルムとして従来公知の任意の絶縁フィルムが使用可能である。例えば、ポリイミド、ポリエステル、ポリフェニレンスルフィド、ポリエーテルスルホン、ポリエーテルエーテルケトン、アラミド、ポリカーボネート、ポリアリレート、ポリアミドイミド、液晶ポリマー、シンジオタクチックポリスチレン、ポリオレフィン系樹脂等の各種ポリマーから製造されるフィルムが使用可能である。より好ましくは、ポリイミドフィルムまたは液晶ポリマーフィルムである。 <Cover film>
As the cover film, any conventionally known insulating film as an insulating film for a printed wiring board can be used. For example, 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.
以下、実施例を挙げて本発明を更に詳細に説明する。但し、本発明は実施例に限定されない。実施例中および比較例中に単に部とあるのは質量部を示す。 <Example>
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples. In the examples and comparative examples, the term "part" simply indicates a part by mass.
本発明における酸価(mgKOH/g)は、酸変性ポリオレフィンをトルエンに溶解し、ナトリウムメトキシドのメタノール溶液でフェノールフタレインを指示薬として滴定した。 (1) 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.
本発明における数平均分子量は(株)島津製作所製ゲルパーミエーションクロマトグラフィー(以下、GPC、標準物質:ポリスチレン樹脂、移動相:テトラヒドロフラン、カラム:Shodex KF-802 + KF-804L + KF-806L、カラム温度:30℃、流速:1.0ml/分、検出器:RI検出器)によって測定した値である。 (2) Number average molecular weight (Mn), weight average molecular weight (Mw)
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).
本発明における融点、融解熱量は示差走査熱量計(以下、DSC、ティー・エー・インスツルメント・ジャパン製、Q-2000)を用いて、20℃/分の速度で昇温融解、冷却樹脂化して、再度昇温融解した際の融解ピークのトップ温度および面積から測定した値である。 (3) Measurement of melting point (Tm) and heat of melting (ΔH) The melting point and heat of melting in the present invention are measured by using a differential scanning calorimeter (hereinafter, DSC, manufactured by TA Instruments Japan, Q-2000). It is a value measured from the top temperature and area of the melting peak when the temperature is raised and melted at a rate of 20 ° C./min, the resin is converted into a cooling resin, and the temperature is raised and melted again.
[検量線溶液の調製]
無水マレイン酸0.050±0.001gを精秤し、クロロホルムで溶解させ、50mlに定容し、1.000g/lのA溶液を調製する。A溶液を2倍希釈し、0.500g/lのB溶液を調製する。B溶液を4倍希釈し、0.125g/lのC溶液を調製する。
[検量線の作成]
赤外分光光度計(島津製作所社製、FT-IR8200PC)を用い、ブランク溶液(クロロホルム)、C溶液、B溶液、A溶液の順で、吸収スペクトル(Abs)測定する。各スペクトルの1780cm-1付近の最大吸収強度を読み取り、縦軸に無水マレイン酸濃度、横軸に強度を取って検量線を作成し、その傾き(1/a)を求める。
[試料溶液の調製および測定]
試料(酸変性ポリオレフィン(A))0.50±0.01gを精秤し、クロロホルムを6.7ml加えて溶解させて、試料溶液を調製する。赤外分光光度計を用い、試料溶液の吸収スペクトル(Abs)を測定する。吸収スペクトルの1780cm-1付近(カルボン酸無水物基(a1))と1730cm-1付近(カルボン酸基(a2))の最大吸収強度を読み取り、検量線より(a1)および(a2)の樹脂1gあたりの含量(mmol/g)を求める。
[計算]
計算式1:カルボン酸無水物基(a1)含量(mmol/g)=H1×(1/a)/C÷99×1000
計算式2:カルボン酸基(a2)の含量((mmol/g)=H2×2.08×(1/a)/C÷117×1000
H1:1780cm-1付近の最大吸収の強度(Abs)
H2:1730cm-1付近の最大吸収の強度(Abs)
2.08:マレイン酸の吸収を無水マレイン酸の吸収に置き換える換算係数
1/a:検量線の傾き
C:試料溶液中の酸変性ポリオレフィン(A)の濃度(質量%) (4) Measurement of binding ratio of carboxylic acid anhydride group (a1) and carboxylic acid group (a2) [Preparation of calibration curve solution]
0.050 ± 0.001 g of maleic anhydride is precisely weighed, dissolved in chloroform, and the volume is adjusted to 50 ml to prepare 1.000 g / l A solution. Dilute solution A 2-fold to prepare 0.500 g / l solution B. The B solution is diluted 4-fold to prepare a 0.125 g / l C solution.
[Create calibration curve]
Using an infrared spectrophotometer (FT-IR8200PC, manufactured by Shimadzu Corporation), the absorption spectrum (Abs) is measured in the order of blank solution (chloroform), C solution, B solution, and A solution. Read the maximum absorption intensity near 1780 cm -1 of each spectrum, take the maleic anhydride concentration on the vertical axis and the intensity on the horizontal axis to create a calibration curve, and obtain the slope (1 / a).
[Preparation and measurement of sample solution]
0.50 ± 0.01 g of the sample (acid-modified polyolefin (A)) is precisely weighed, and 6.7 ml of chloroform is added and dissolved to prepare a sample solution. 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.
[Calculation]
Calculation formula 1: Carboxylic acid anhydride group (a1) content (mmol / g) = H1 × (1 / a) / C ÷ 99 × 1000
Calculation formula 2: Content of carboxylic acid group (a2) (( mmol / g) = H2 × 2.08 × (1 / a) / C ÷ 117 × 1000
Maximum absorption intensity (Abs) around H1: 1780 cm -1
H2: Maximum absorption intensity around 1730 cm -1 (Abs)
2.08: Conversion coefficient that replaces the absorption of maleic acid with the absorption of maleic anhydride 1 / a: Slope of the calibration curve C: Concentration (mass%) of the acid-modified polyolefin (A) in the sample solution
400MHzの1H-核磁気共鳴スペクトル装置(1H-NMR)を用い、酸変性ポリオレフィン(A)のカルボン酸無水物基(a1)、カルボン酸基(a2)およびその他の酸(アクリル酸等)のモル比定量を行った。溶媒には重クロロホルムを使用した。 (5) Measurement of the total amount of (a1) and (a2) in the total acid component bound to the acid-modified polyolefin (A) Acid-modified using a 400 MHz 1 H-nuclear magnetic resonance spectroscope ( 1 H-NMR). The molar ratio of the carboxylic acid anhydride group (a1), the carboxylic acid group (a2) and other acids (acrylic acid, etc.) of the polyolefin (A) was quantified. Deuterated chloroform was used as the solvent.
後述する接着剤組成物を厚さ12.5μmのポリイミドフィルム(株式会社カネカ製、アピカル(登録商標))、または、厚さ25μmのLCPフィルム(クラレ株式会社製、ベクスター(登録商標))に、乾燥後の厚みが25μmとなるように塗布し、130℃で3分乾燥した。この様にして得られた接着性フィルム(Bステージ品)を厚さ18μmの圧延銅箔(JX金属株式会社製、BHYシリーズ)と貼り合わせた。貼り合わせは、圧延銅箔の光沢面が接着剤層と接する様にして、160℃で40kgf/cm2の加圧下に30秒間プレスし、接着した。次いで140℃で4時間熱処理して硬化させて、剥離強度評価用サンプルを得た。剥離強度は、25℃において、フィルム引き、引張速度50mm/minで90°剥離試験を行ない、剥離強度を測定した。この試験は常温での接着強度を示すものである。
<評価基準>
◎:1.0N/mm以上
○:0.8N/mm以上1.0N/mm未満
△:0.5N/mm以上0.8N/mm未満
×:0.5N/mm未満 (6) Peeling strength (adhesiveness)
The adhesive composition described later is applied to a 12.5 μm-thick polyimide film (Kaneka Corporation, Apical (registered trademark)) or a 25 μm-thick LCP film (Kurare Co., Ltd., Vecstar (registered trademark)). The film was applied so that the thickness after drying was 25 μm, 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 μm. 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.
<Evaluation criteria>
⊚: 1.0 N / mm or more ○: 0.8 N / mm or more and less than 1.0 N / mm Δ: 0.5 N / mm or more and less than 0.8 N / mm ×: 0.5 N / mm or less
上記と同じ方法でサンプルを作製し、2.0cm×2.0cmのサンプル片を23℃で2日間エージング処理を行い、280℃で溶融したハンダ浴に10秒フロートし、膨れなどの外観変化の有無を確認した。
<評価基準>
◎:膨れ無し
○:一部膨れ有
△:多くの膨れ有
×:膨れ、かつ変色有 (7) Solder heat resistance A sample was prepared by the same method as above, and a 2.0 cm × 2.0 cm sample piece was aged at 23 ° C for 2 days and floated in a solder bath melted at 280 ° C for 10 seconds. It was confirmed whether there was any change in appearance such as swelling.
<Evaluation criteria>
⊚: No swelling ○: Partially swelling △: Many swelling ×: Swelling and discoloration
後述する接着剤組成物を厚さ100μmのテフロン(登録商標)シートに、乾燥硬化後の厚みが25μmとなるように塗布し、130℃で3分乾燥した。次いで140℃で4時間熱処理して硬化させた後、テフロン(登録商標)シートを剥離して試験用の接着剤樹脂シートを得た。得られた試験用接着剤樹脂シートを8cm×3mmの短冊状にサンプルを裁断し、試験用サンプルを得た。比誘電率(εc)及び誘電正接(tanδ)は、ネットワークアナライザー(アンリツ社製)を使用し、空洞共振器摂動法で、温度23℃、周波数1GHzの条件で測定した。得られた比誘電率、誘電正接について、以下の通りに評価した。
<比誘電率の評価基準>
◎:2.3以下
○:2.3を超え2.6以下
△:2.6を超え3.0以下
×:3.0を超える
<誘電正接の評価基準>
◎:0.008以下
○:0.008を超え0.01以下
△:0.01を超え0.02以下
×:0.02を超える (8) Relative permittivity (ε c ) and dielectric loss tangent (tan δ)
The adhesive composition described below was applied to a Teflon (registered trademark) sheet having a thickness of 100 μm so as to have a thickness of 25 μm after drying and curing, and dried at 130 ° C. for 3 minutes. Then, after heat-treating at 140 ° C. for 4 hours to cure, the Teflon (registered trademark) sheet was peeled off to obtain an adhesive resin sheet for testing. The obtained test adhesive resin sheet was cut into strips of 8 cm × 3 mm to obtain test samples. The relative permittivity (ε c ) and the dielectric loss tangent (tan δ) 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.
<Evaluation criteria for relative permittivity>
⊚: 2.3 or less ○: More than 2.3 and 2.6 or less Δ: More than 2.6 and 3.0 or less ×: More than 3.0 <Evaluation criteria for dielectric loss tangent>
⊚: 0.008 or less ○: 0.008 or more and 0.01 or less Δ: 0.01 or more and 0.02 or less ×: 0.02 or more
ポットライフ性とは、(A)成分、(B)成分、および必要に応じて(C)成分、並びにメチルシクロヘキサン、メチルエチルケトンおよびトルエンの混合溶媒(メチルシクロヘキサン/メチルエチルケトン/トルエン=72/8/20(v/v))を固形分濃度が20質量%となるように配合して樹脂溶液(ワニス)を調製し、その配合直後または配合後一定時間経過後の該ワニスの安定性を指す。ポットライフ性が良好な場合は、ワニスの粘度上昇が少なく長期間保存が可能であることを指し、ポットライフ性が不良な場合は、ワニスの粘度が上昇(増粘)し、ひどい場合にはゲル化現象を起こし、基材への塗布が困難となり、長期間保存が不可能であることを指す。
表2~4の比率に従い調製したワニスを、ブルックフィールド型粘度計(ローターNo.2、回転数60rpm)を用いて25℃の分散液粘度測定し、初期分散液粘度ηB0を求めた。その後、ワニスを25℃下7日間貯蔵し、25℃下で分散粘度ηBを測定した。ワニス粘度を下記式にて算出を行い、以下の通りに評価した。
溶液粘度比=溶液粘度ηB/溶液粘度ηB0
<評価基準>
◎:0.5以上1.5未満
○:1.5以上2.0未満
△:2.0以上3.0未満
×:3.0以上、またはプリン化により粘度測定不可 (9) Pot-life property Pot-life property means component (A), component (B), and component (C) if necessary, and a mixed solvent of methylcyclohexane, methylethylketone, and toluene (methylcyclohexane / methylethylketone / toluene =). 72/8/20 (v / v)) is blended so that the solid content concentration is 20% by mass to prepare a resin solution (varnish), and the varnish is stable immediately after blending or after a certain period of time has passed after blending. Refers to sex. If the pot life is good, it means that the viscosity of the varnish does not increase so much that it can be stored for a long time. If the pot life is poor, the viscosity of the varnish increases (thickening), and in severe cases, it means that the varnish can be stored for a long time. It means that a gelation phenomenon occurs, it becomes difficult to apply it to a base material, and it cannot be stored for a long period of time.
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 ηB0. Then, the varnish was stored at 25 ° C. for 7 days, and the dispersion viscosity ηB was measured at 25 ° C. The varnish viscosity was calculated by the following formula and evaluated as follows.
Solution viscosity ratio = solution viscosity ηB / solution viscosity ηB0
<Evaluation criteria>
⊚: 0.5 or more and less than 1.5 ○: 1.5 or more and less than 2.0 Δ: 2.0 or more and less than 3.0 ×: 3.0 or more or viscosity cannot be measured due to purifying
製造例1(酸変性ポリオレフィンPO-1a、PO-1bの製造)
プロピレン-ブテン共重合体(三井化学社製「タフマー(登録商標)XM7080」)100質量部、無水マレイン酸20質量部、ジ-tert-ブチルパーオキサイド6質量部をシリンダー部の最高温度を170℃に設定した二軸押出機を用いて混錬反応した。その後、押出機内にて減圧脱気を行い、残留する未反応物を除去して、無水マレイン酸変性プロピレン-ブテン共重合体(PO-1a、酸価25mgKOH/g、数平均分子量25,000、重量平均分子量80,000、Tm75℃、△H30J/g、カルボン酸無水物基(a1)/カルボン酸基の結合比率(a2)=89/11、全酸成分に占める(a1)と(a2)の合計量100モル%)を得た。
次いで、PO-1aを30℃、RH70%環境下のデシケータ内に1週間静置し、P0-1bを得た。PO-1bは、カルボン酸無水物基(a1)/カルボン酸基の結合比率(a2)=15/85であった。 (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. Then, degassing under reduced pressure is performed in the extruder to remove the residual unreacted material, and the maleic anhydride-modified propylene-butene copolymer (PO-1a, acid value 25 mgKOH / g, number average molecular weight 25,000, Weight average molecular weight 80,000, Tm75 ° C., ΔH30J / g, carboxylic acid anhydride group (a1) / carboxylic acid group bond ratio (a2) = 89/11, occupying total acid components (a1) and (a2) The total amount of 100 mol%) was obtained.
Then, PO-1a was allowed to stand in a desiccator at 30 ° C. and an RH70% environment for 1 week to obtain P0-1b. PO-1b had a carboxylic acid anhydride group (a1) / carboxylic acid group bond ratio (a2) = 15/85.
無水マレイン酸の仕込み量を25質量部に変更した以外は製造例1と同様にすることにより、無水マレイン酸変性プロピレン-ブテン共重合体(PO-2a、酸価48mgKOH/g、数平均分子量17,000、重量平均分子量50,000、Tm75℃、△H25J/g、カルボン酸無水物基(a1)/カルボン酸基の結合比率(a2)=88/12、全酸成分に占める(a1)と(a2)の合計量100モル%)を得た。
次いで、PO-2aを30℃、RH70%環境下のデシケータ内に1週間静置し、P0-2bを得た。PO-2bは、カルボン酸無水物基(a1)/カルボン酸基の結合比率(a2)=13/87であった。 Production Example 2 (Production of Acid-Modified Polyolefins PO-2a and PO-2b)
By carrying out the same procedure as in Production Example 1 except that the amount of maleic anhydride charged was changed to 25 parts by mass, the maleic anhydride-modified propylene-butene copolymer (PO-2a, acid value 48 mgKOH / g, number average molecular weight 17) was used. 000, weight average molecular weight 50,000, Tm75 ° C., ΔH25J / 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.
Then, PO-2a was allowed to stand in a desiccator at 30 ° C. and an RH70% environment for 1 week to obtain P0-2b. PO-2b had a carboxylic acid anhydride group (a1) / carboxylic acid group bond ratio (a2) = 13/87.
無水マレイン酸の仕込み量を6質量部に変更した以外は製造例1と同様にすることにより、無水マレイン酸変性プロピレン-ブテン共重合体(PO-3a、酸価7mgKOH/g、数平均分子量35,000、重量平均分子量130,000、Tm82℃、△H25J/g、カルボン酸無水物基(a1)/カルボン酸基の結合比率(a2)=90/10、全酸成分に占める(a1)と(a2)の合計量100モル%)を得た。
次いで、PO-3aを30℃、RH70%環境下のデシケータ内に1週間静置し、P0-3bを得た。PO-3bは、カルボン酸無水物基(a1)/カルボン酸基の結合比率(a2)=17/83であった。 Production Example 3 (Production of Acid-Modified Polyolefins PO-3a and PO-3b)
By carrying out the same procedure as in Production Example 1 except that the amount of maleic anhydride charged was changed to 6 parts by mass, the maleic anhydride-modified propylene-butene copolymer (PO-3a, acid value 7 mgKOH / g, number average molecular weight 35) was used. 000, weight average molecular weight 130,000, Tm82 ° C., ΔH25J / g, carboxylic acid anhydride group (a1) / carboxylic acid group binding ratio (a2) = 90/10, occupying the total acid component (a1) (A2) total amount 100 mol%) was obtained.
Then, PO-3a was allowed to stand in a desiccator at 30 ° C. and an RH70% environment for 1 week to obtain P0-3b. PO-3b had a carboxylic acid anhydride group (a1) / carboxylic acid group bond ratio (a2) = 17/83.
無水マレイン酸の仕込み量を30質量部に変更した以外は製造例1と同様にすることにより、無水マレイン酸変性プロピレン-ブテン共重合体(PO-4a、酸価55mgKOH/g、数平均分子量13,000、重量平均分子量40,000、Tm70℃、△H25J/g、カルボン酸無水物基(a1)/カルボン酸基の結合比率(a2)=88/12、全酸成分に占める(a1)と(a2)の合計量100モル%)を得た。
次いで、PO-4bを30℃、RH70%環境下のデシケータ内に1週間静置し、P0-4bを得た。PO-4bは、カルボン酸無水物基(a1)/カルボン酸基の結合比率(a2)=12/88であった。 Production Example 4 (Production of Acid-Modified Polyolefins PO-4a and PO-4b)
By carrying out the same procedure as in Production Example 1 except that the amount of maleic anhydride charged was changed to 30 parts by mass, 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., ΔH25J / 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.
Then, PO-4b was allowed to stand in a desiccator at 30 ° C. and an RH70% environment for 1 week to obtain P0-4b. PO-4b had a carboxylic acid anhydride group (a1) / carboxylic acid group bond ratio (a2) = 12/88.
無水マレイン酸の仕込み量を2質量部、ジ-tert-ブチルパーオキサイドを0.5質量部に変更した以外は製造例1と同様にすることにより、無水マレイン酸変性プロピレン-ブテン共重合体(PO-5a、酸価3mgKOH/g、数平均分子量60,000、重量平均分子量200,000、Tm80℃、△H25J/g、カルボン酸無水物基(a1)/カルボン酸基の結合比率(a2)=90/10、全酸成分に占める(a1)と(a2)の合計量100モル%)を得た。
次いで、PO-5aを30℃、RH70%環境下のデシケータ内に1週間静置し、P0-5bを得た。PO-5bは、カルボン酸無水物基(a1)/カルボン酸基の結合比率(a2)=18/82であった。 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, acid value 3 mgKOH / g, number average molecular weight 60,000, weight average molecular weight 200,000, Tm80 ° C., ΔH25J / g, carboxylic acid anhydride group (a1) / carboxylic acid group bond ratio (a2) = 90/10, the total amount of (a1) and (a2) in the total acid component was 100 mol%).
Then, PO-5a was allowed to stand in a desiccator at 30 ° C. and an RH70% environment for 1 week to obtain P0-5b. PO-5b had a carboxylic acid anhydride group (a1) / carboxylic acid group bond ratio (a2) = 18/82.
プロピレン-ブテン共重合体(三井化学社製「タフマー(登録商標)XM7080」)100質量部、無水マレイン酸20質量部、アクリル酸5質量部、ジ-tert-ブチルパーオキサイド6質量部をシリンダー部の最高温度を170℃に設定した二軸押出機を用いて混錬反応した。その後、押出機内にて減圧脱気を行い、残留する未反応物を除去して、無水マレイン酸アクリル酸変性プロピレン-ブテン共重合体(PO-6a、酸価30mgKOH/g、数平均分子量25,000、重量平均分子量80,000、Tm75℃、△H30J/g、カルボン酸無水物基(a1)/カルボン酸基の結合比率(a2)=89/11、全酸成分に占める(a1)と(a2)の合計量70モル%)を得た。
次いで、PO-6aを30℃、RH70%環境下のデシケータ内に1週間静置し、P0-6bを得た。PO-6bは、カルボン酸無水物基(a1)/カルボン酸基の結合比率(a2)=14/86であった。 Production Example 6 (Production of Acid-Modified Polyolefin PO-6a)
100 parts by mass of propylene-butene copolymer (“Toughmer (registered trademark) XM7080” manufactured by Mitsui Chemicals, Inc.), 20 parts by mass of maleic anhydride, 5 parts by mass of acrylic acid, 6 parts by mass of di-tert-butyl peroxide in the cylinder part The kneading reaction was carried out using a twin-screw extruder in which the maximum temperature of the above was set to 170 ° C. Then, degassing under reduced pressure was performed in the extruder to remove the residual unreacted material, and the maleic anhydride-modified propylene-butene copolymer (PO-6a, acid value 30 mgKOH / g, number average molecular weight 25, 000, weight average molecular weight 80,000, Tm75 ° C., ΔH30J / g, carboxylic acid anhydride group (a1) / carboxylic acid group binding ratio (a2) = 89/11, occupying the total acid component (a1) and ( The total amount of a2) was 70 mol%).
Then, PO-6a was allowed to stand in a desiccator at 30 ° C. and an RH70% environment for 1 week to obtain P0-6b. PO-6b had a carboxylic acid anhydride group (a1) / carboxylic acid group bond ratio (a2) = 14/86.
ディーンスターク装置と撹拌機を備えた4つ口フラスコに、PO-1bを100質量部、トルエンを500質量部仕込み、還流下5時間反応した。冷却後、多量のメチルエチルケトンが入った容器に注ぎ、樹脂(PO-1c1)を析出させた。PO-1c1は、酸価25mgKOH/g、数平均分子量25,000、重量平均分子量80,000、Tm75℃、△H30J/g、カルボン酸無水物基(a1)/カルボン酸基の結合比率(a2)=100/0、全酸成分に占める(a1)と(a2)の合計量100モル%であった。 Preparation Example 1 (Cyclation reaction of acid-modified polyolefin PO-1c1)
In a four-necked flask equipped with a Dean-Stark apparatus and a stirrer, 100 parts by mass of PO-1b and 500 parts by mass of toluene were charged and reacted under reflux for 5 hours. After cooling, it was poured into a container containing a large amount of methyl ethyl ketone to precipitate the resin (PO-1c1). PO-1c1 has an acid value of 25 mgKOH / g, a number average molecular weight of 25,000, a weight average molecular weight of 80,000, Tm75 ° C., ΔH30J / g, and a carboxylic acid anhydride group (a1) / carboxylic acid group binding ratio (a2). ) = 100/0, the total amount of (a1) and (a2) in the total acid component was 100 mol%.
酸変性ポリオレフィンの種類および還流時間を表1に示すとおりに変更し、調製例1と同様な方法で調製例2~9を行った。物性を表1に示す。 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.
(A)成分として、PO-1c1を100質量部、(B1)成分として、B11-1を0.1質量部、B12-1を8質量部、有機溶媒(メチルシクロヘキサン/メチルエチルケトン/トルエン=72/8/20(v/v))を432質量部(固形分濃度で20質量%)配合し、接着剤組成物を得た。配合量、接着強度、ハンダ耐熱性、ポットライフ性および電気特性を表1に示す。 Example 1
As component (A), PO-1c1 is 100 parts by mass, as component (B1), B11-1 is 0.1 parts by mass, B12-1 is 8 parts by mass, and an organic solvent (methylcyclohexane / methylethylketone / toluene = 72 /). 8/20 (v / v)) was blended in an amount of 432 parts by mass (20% by mass in terms of solid content concentration) to obtain an adhesive composition. Table 1 shows the blending amount, adhesive strength, solder heat resistance, pot life property and electrical characteristics.
(A)~(C)成分の配合量を表2~4に示すとおりに変更し、実施例1と同様な方法で実施例2~35、比較例1~15を行った。接着強度、ハンダ耐熱性、電気特性およびポットライフの評価結果を表2~4に示す。なお、有機溶媒(メチルシクロヘキサン/メチルエチルケトン/トルエン=72/8/20(v/v))は固形分濃度が20質量%となるように調整した。 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 organic solvent (methylcyclohexane / methylethylketone / toluene = 72/8/20 (v / v)) was adjusted so that the solid content concentration was 20% by mass.
<エポキシ樹脂(B1)>
<グリシジルアミン型エポキシ樹脂(B11)>
B11-1:N,N,N’,N’-テトラグリシジル-m-キシレンジアミン:TETRAD(登録商標)-X(三菱ガス化学社製)
<グリシジルエーテル型エポキシ樹脂(B12)>
B12-1:フェノールノボラック型エポキシ樹脂:jER(登録商標)152(三菱化学社製)
B12-2:o-クレゾールノボラック型エポキシ樹脂:YDCN-700-3(新日鉄住金化学社製)
<脂環型エポキシ樹脂(B13)>
B13-1:ジシクロペンタジエン型エポキシ樹脂:HP-7200H(DIC社製 エポキシ当量 278g/eq)
<イソシアネート化合物(B2)>
B21:ヘキサメチレンジイソシアネートのイソシアヌレート体:スミジュール(登録商標)N-3300(バイエル社製)
B22:ヘキサメチレンジイソシアネートのビウレット体:デュラネート(登録商標)24A-100(旭化成ケミカルズ社製)
<カルボジイミド化合物(B3)>
B31:多官能カルボジイミド:カルボジライト(登録商標)V-09(日清紡ケミカル社製)
B32:多官能カルボジイミド:カルボジライト(登録商標)V-03(日清紡ケミカル社製)
<オリゴフェニレンエーテル(C)>
C1:オリゴフェニレンエーテルスチレン変性品:OPE-2St 2200(三菱ガス化学社製 Mn2000の一般式(4)の構造を有する化合物)
C2:オリゴフェニレンエーテル:SA90(SABIC社製 Mn1800の一般式(3)の構造を有する化合物) The epoxy resin (B1), isocyanate compound (B2), carbodiimide compound (B3), and oligophenylene ether (C) used in Tables 2 to 4 are as follows.
<Epoxy resin (B1)>
<Glysidylamine type epoxy resin (B11)>
B11-1: N, N, N', N'-tetraglycidyl-m-xylene diamine: TETRAD (registered trademark) -X (manufactured by Mitsubishi Gas Chemical Company, Inc.)
<Glysidyl ether type epoxy resin (B12)>
B12-1: Phenolic novolac type epoxy resin: jER (registered trademark) 152 (manufactured by Mitsubishi Chemical Corporation)
B12-2: o-cresol novolac type epoxy resin: YDCN-700-3 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
<Alicyclic epoxy resin (B13)>
B13-1: Dicyclopentadiene type epoxy resin: HP-7200H (DIC Epoxy equivalent 278 g / eq)
<Isocyanate compound (B2)>
B21: Isocyanurate of hexamethylene diisocyanate: Sumijour (registered trademark) N-3300 (manufactured by Bayer)
B22: Biuret of hexamethylene diisocyanate: Duranate (registered trademark) 24A-100 (manufactured by Asahi Kasei Chemicals)
<Carbodiimide compound (B3)>
B31: Polyfunctional carbodiimide: Carbodilite (registered trademark) V-09 (manufactured by Nisshinbo Chemical Co., Ltd.)
B32: Polyfunctional carbodiimide: Carbodilite (registered trademark) V-03 (manufactured by Nisshinbo Chemical Co., Ltd.)
<Oligoxyphenylene ether (C)>
C1: Oligophenylene ether styrene modified product: OPE-2St 2200 (Compound having the structure of the general formula (4) of Mn2000 manufactured by Mitsubishi Gas Chemical Company, Inc.)
C2: Oligophenylene ether: SA90 (compound having the structure of the general formula (3) of Mn1800 manufactured by SABIC)
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.
Claims (11)
- 下記(1)~(3)を満足する酸変性ポリオレフィン(A)を含み、さらにエポキシ樹脂(B1)、イソシアネート化合物(B2)およびカルボジイミド化合物(B3)からなる群より選ばれた1種以上を含有する接着剤組成物。
(1)酸価が5~50mgKOH/gである
(2)式(a1)で示されるカルボン酸無水物基と式(a2)で示されるカルボン酸基の結合比率(モル比)が、式(a1)/式(a2)=100/0~50/50である
(3)酸変性ポリオレフィン(A)に結合する全酸成分を100モル%としたとき、式(a1)と式(a2)の合計量が90モル%以上である
(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). a1) / formula (a2) = 100/0 to 50/50 (3) When the total acid component bonded to the acid-modified polyolefin (A) is 100 mol%, the formulas (a1) and (a2) The total amount is 90 mol% or more
- エポキシ樹脂(B1)が、グリシジルアミン型エポキシ樹脂(B11)を含み、さらにグリシジルエーテル型樹脂(B12)および脂環型エポキシ樹脂(B13)からなる群より選ばれた1種以上の混合物である請求項1に記載の接着剤組成物。 Claimed that the epoxy resin (B1) is a mixture of one or more selected from the group consisting of a glycidyl amine type epoxy resin (B11), and further consisting of a glycidyl ether type resin (B12) and an alicyclic epoxy resin (B13). Item 2. The adhesive composition according to Item 1.
- イソシアネート化合物(B2)が、多官能イソシアネート化合物である請求項1に記載の接着剤組成物。 The adhesive composition according to claim 1, wherein the isocyanate compound (B2) is a polyfunctional isocyanate compound.
- カルボジイミド化合物(B3)が、多官能カルボジイミド化合物である請求項1に記載の接着剤組成物。 The adhesive composition according to claim 1, wherein the carbodiimide compound (B3) is a polyfunctional carbodiimide compound.
- さらにオリゴフェニレンエーテル(C)を含有する請求項1~4のいずれかに記載の接着剤組成物。 The adhesive composition according to any one of claims 1 to 4, further containing an oligophenylene ether (C).
- さらに有機溶媒を含有する請求項1~5のいずれかに記載の接着剤組成物。 The adhesive composition according to any one of claims 1 to 5, further containing an organic solvent.
- 1GHzにおける比誘電率(εc)が3.0以下、誘電正接(tanδ)が0.02以下である請求項1~6のいずれかに記載の接着剤組成物。 The adhesive composition according to any one of claims 1 to 6, wherein the relative permittivity (ε c ) at 1 GHz is 3.0 or less and the dielectric loss tangent (tan δ) is 0.02 or less.
- 請求項1~7のいずれかに記載の接着剤組成物を含有する接着シート。 An adhesive sheet containing the adhesive composition according to any one of claims 1 to 7.
- 請求項1~7のいずれかに記載の接着剤組成物を含有する積層体。 A laminate containing the adhesive composition according to any one of claims 1 to 7.
- 請求項9に記載の積層体を構成要素として含むプリント配線板。 A printed wiring board containing the laminate according to claim 9 as a component.
- 請求項10に記載のプリント配線板を構成要素として含むカバーフィルム。
A cover film comprising the printed wiring board according to claim 10 as a component.
Priority Applications (3)
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JP2021544010A JPWO2021045125A1 (en) | 2019-09-06 | 2020-09-02 | |
KR1020227008542A KR20220057549A (en) | 2019-09-06 | 2020-09-02 | Polyolefin-based adhesive composition |
CN202080055038.2A CN114207068B (en) | 2019-09-06 | 2020-09-02 | Polyolefin adhesive composition |
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JP2019-162725 | 2019-09-06 | ||
JP2019162725 | 2019-09-06 | ||
JP2019171597 | 2019-09-20 | ||
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JP2019171596 | 2019-09-20 | ||
JP2019-171596 | 2019-09-20 |
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PCT/JP2020/033325 WO2021045125A1 (en) | 2019-09-06 | 2020-09-02 | Polyolefin-based adhesive composition |
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JP (1) | JPWO2021045125A1 (en) |
KR (1) | KR20220057549A (en) |
CN (1) | CN114207068B (en) |
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WO (1) | WO2021045125A1 (en) |
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WO2022210672A1 (en) * | 2021-03-30 | 2022-10-06 | リンテック株式会社 | Adhesive sheet |
WO2022210671A1 (en) * | 2021-03-30 | 2022-10-06 | リンテック株式会社 | Curable adhesive composition and cured product |
WO2022210673A1 (en) * | 2021-03-30 | 2022-10-06 | リンテック株式会社 | Curable adhesive composition, cured product, and method for manufacturing cured product |
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KR20220057549A (en) | 2022-05-09 |
CN114207068B (en) | 2024-04-02 |
JPWO2021045125A1 (en) | 2021-03-11 |
TW202116959A (en) | 2021-05-01 |
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