WO2022196586A1 - 接着剤組成物、ならびにこれを含有する接着シート、積層体およびプリント配線板 - Google Patents
接着剤組成物、ならびにこれを含有する接着シート、積層体およびプリント配線板 Download PDFInfo
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- WO2022196586A1 WO2022196586A1 PCT/JP2022/011090 JP2022011090W WO2022196586A1 WO 2022196586 A1 WO2022196586 A1 WO 2022196586A1 JP 2022011090 W JP2022011090 W JP 2022011090W WO 2022196586 A1 WO2022196586 A1 WO 2022196586A1
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- compound
- acid
- adhesive composition
- resin
- modified
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- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
- ROEHNQZQCCPZCH-UHFFFAOYSA-N tert-butyl 2-tert-butylperoxycarbonylbenzoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)OC(C)(C)C ROEHNQZQCCPZCH-UHFFFAOYSA-N 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
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- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- 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
- 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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- 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
- C09J123/30—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 by oxidation
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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
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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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
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C09J171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C09J171/12—Polyphenylene oxides
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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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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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
- 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
Definitions
- the present invention relates to adhesive compositions. More particularly, it relates to an adhesive composition used for bonding a resin base material and a resin base material or a metal base material. In particular, it relates to an adhesive composition for flexible printed wiring boards (hereinafter abbreviated as FPC), and adhesive sheets, laminates and printed wiring boards containing the same.
- FPC flexible printed wiring boards
- FPC has excellent flexibility, so it can be used for multi-functionality and miniaturization of personal computers (PCs) and smartphones.
- PCs personal computers
- electronic devices have become smaller, lighter, denser, and higher in output, and the demand for the performance of wiring boards (electronic circuit boards) has become more and more sophisticated.
- high-frequency signals are being used to increase the transmission speed in FPC.
- FPCs are increasingly required to have low dielectric properties (low dielectric constant, low dielectric loss tangent) in a high frequency region. In order to achieve such low dielectric properties, measures have been taken to reduce the dielectric loss of FPC substrates and adhesives.
- the adhesive described in Patent Document 1 has high polarity because it contains an epoxy resin and an epoxy resin curing agent, and cannot satisfy the high requirements for dielectric loss tangent in particular.
- the adhesive described in Patent Document 2 has excellent heat resistance as an FPC adhesive, and its dielectric properties are also insufficient.
- an object of the present invention is to provide an adhesive composition having excellent heat resistance, adhesive strength, low dielectric constant and dielectric loss tangent, and excellent dielectric properties, and an adhesive sheet, a laminate and a printed wiring board containing the same. It is to be.
- the present invention consists of the following configurations.
- An adhesive composition comprising an acid-modified resin, compound A and compound B.
- Compound A a compound having a terminal unsaturated hydrocarbon group and a 5% weight loss temperature of 260°C or higher
- Compound B a compound having an epoxy group and a terminal unsaturated hydrocarbon group
- acid-modified resin The adhesive composition of [1] above, containing at least one resin selected from acid-modified polyolefins, acid-modified polystyrene resins and acid-modified cycloolefin polymers.
- [4] The adhesive composition of [1] or [2] above, wherein the compound A is a polyphenylene ether or phenolic resin having a terminal unsaturated hydrocarbon group.
- [5] The adhesive composition according to [1] to [4], wherein the compound B is a compound having an isocyanuric ring.
- An adhesive sheet having an adhesive layer comprising the adhesive composition of [1] to [5].
- [7] A laminate having an adhesive layer comprising the adhesive composition of [1] to [5].
- [8] A printed wiring board comprising the laminate of [7] as a component.
- the adhesive composition of the present invention is excellent in dielectric properties, adhesive strength, and solder heat resistance. Therefore, it is suitable for printed wiring board adhesives, adhesive sheets, laminates and printed wiring boards in the high frequency range.
- the acid-modified resin used in the present invention is a resin modified with an acid component.
- an acid-modified resin it has excellent adhesion to metal substrates such as copper foil, and an adhesive layer having excellent solder heat resistance can be formed by a cross-linking reaction with an epoxy group of compound B described later.
- the acid-modified resin used in the present invention can be prepared, for example, by modifying a base resin with an unsaturated carboxylic acid component, or by copolymerizing an unsaturated carboxylic acid component during polymerization of the base resin.
- the unsaturated carboxylic acid component is not particularly limited, and includes acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, maleic anhydride, itaconic anhydride, and fumaric anhydride.
- the lower limit of the acid value of the acid-modified resin used in the present invention is preferably 10 equivalents/10 6 g or more, more preferably 20 equivalents, from the viewpoint of heat resistance and adhesiveness to resin substrates and metal substrates. /10 6 g or more, more preferably 30 equivalents/10 6 g or more. When it is at least the above value, the compatibility with the compound B and the like is improved, the adhesive strength is improved, and the crosslink density is increased, so that the heat resistance can be improved.
- the upper limit is preferably 1000 equivalents/10 6 g or less, more preferably 700 equivalents/10 6 g or less, and even more preferably 500 equivalents/10 6 g or less. When it is the above value or less, adhesiveness and low dielectric properties become better.
- the number average molecular weight (Mn) of the acid-modified resin used in the present invention is preferably in the range of 10,000 to 50,000. It is more preferably in the range of 15,000 to 45,000, still more preferably in the range of 20,000 to 40,000, and particularly preferably in the range of 22,000 to 38,000. By making it more than the said lower limit, cohesive force becomes favorable and can express the outstanding adhesiveness. Further, when the content is equal to or less than the above upper limit, excellent fluidity and good operability can be obtained.
- the acid-modified resin used in the present invention is preferably an acid-modified resin obtained by acid-modifying a resin mainly composed of hydrocarbons, since it has good low dielectric properties. Olefin polymers and acid-modified polyolefins are preferred. Furthermore, from the viewpoint of pot life, acid-modified polystyrene resins and acid-modified cycloolefin polymers are preferred.
- the acid-modified resin can be used singly or in combination of two or more.
- the acid-modified resin of the present invention preferably has a dielectric constant ( ⁇ c) of 2.7 or less at a frequency of 10 GHz. It is more preferably 2.6 or less, still more preferably 2.3 or less. Although the lower limit is not particularly limited, it is practically 2.0. Also, the dielectric constant ( ⁇ c) in the entire frequency range of 1 GHz to 60 GHz is preferably 2.7 or less, more preferably 2.6 or less, and even more preferably 2.3 or less.
- the acid-modified resin of the present invention preferably has a dielectric loss tangent (tan ⁇ ) of 0.003 or less at a frequency of 10 GHz. It is more preferably 0.0025 or less, and still more preferably 0.002 or less. Although the lower limit is not particularly limited, it is practically 0.0001 or more. Further, the dielectric loss tangent (tan ⁇ ) in the entire frequency range of 1 GHz to 60 GHz is preferably 0.003 or less, more preferably 0.0025 or less, and even more preferably 0.002 or less.
- the content of the acid-modified resin in the adhesive composition of the present invention is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 40% by mass or more. Moreover, it is preferably 99% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less. Within the above range, the adhesiveness and heat resistance are improved, which is preferable.
- acid-modified polyolefin can be preferably used as the acid-modified resin.
- the acid-modified polyolefin used in the present invention is not limited, it is preferably obtained by grafting at least one of an ⁇ , ⁇ -unsaturated carboxylic acid and its acid anhydride to a polyolefin resin.
- Polyolefin resin refers to homopolymerization of olefin monomers exemplified by ethylene, propylene, butene, butadiene, isoprene, etc., or copolymerization with other monomers, and hydrocarbons such as hydrides and halides of the resulting polymers.
- the acid-modified polyolefin is preferably obtained by grafting at least one of ⁇ , ⁇ -unsaturated carboxylic acid and its acid anhydride to at least one of polyethylene, polypropylene and propylene- ⁇ -olefin copolymer. .
- the propylene- ⁇ -olefin copolymer is mainly composed of propylene and is copolymerized with an ⁇ -olefin.
- the ⁇ -olefin for example, one or several of ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene, vinyl acetate and the like can be used. Among these ⁇ -olefins, ethylene and 1-butene are preferred.
- the ratio of the propylene component to the ⁇ -olefin component in the propylene- ⁇ -olefin copolymer is not limited, but the propylene component is preferably 50 mol% or more, more preferably 70 mol% or more.
- Examples of at least one ⁇ , ⁇ -unsaturated carboxylic acid and its acid anhydride include maleic acid, itaconic acid, citraconic acid and acid anhydrides thereof. Among these, acid anhydrides are preferred, and maleic anhydride is more preferred.
- the acid-modified polyolefins include maleic anhydride-modified polypropylene, maleic anhydride-modified propylene-ethylene copolymer, maleic anhydride-modified propylene-butene copolymer, and maleic anhydride-modified propylene-ethylene-butene copolymer. Such acid-modified polyolefins can be used singly or in combination of two or more.
- the lower limit of the acid value of the acid-modified polyolefin is preferably 89 equivalents/10 6 g or more, more preferably 107 equivalents/10 6 g, from the viewpoint of heat resistance and adhesiveness to resin substrates and metal substrates. or more, more preferably 125 equivalents/10 6 g or more.
- the upper limit is preferably 713 equivalents/10 6 g or less, more preferably 534 equivalents/10 6 g or less, and even more preferably 356 equivalents/10 6 g or less. Adhesiveness becomes favorable by making it below the said upper limit.
- the viscosity and stability of the solution are improved, and excellent pot life can be exhibited. Furthermore, manufacturing efficiency is also improved.
- the acid-modified polyolefin is preferably crystalline acid-modified polyolefin.
- the crystallinity referred to in the present invention means that a temperature is raised from ⁇ 100° C. to 250° C. at a rate of 20° C./min using a differential scanning calorimeter (DSC), and a clear melting peak is exhibited during the heating process. Point.
- DSC differential scanning calorimeter
- the melting point (Tm) of the acid-modified polyolefin 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 content is at least the above lower limit, the cohesive force derived from the crystals is improved, and excellent adhesiveness and solder heat resistance can be exhibited. Further, when the content is equal to or less than the upper limit, excellent solution stability and fluidity are obtained, and operability at the time of adhesion is improved.
- the heat of fusion ( ⁇ H) of the acid-modified polyolefin is preferably in the range of 5 J/g to 60 J/g. More preferably in the range of 10 J/g to 50 J/g, most preferably in the range of 20 J/g to 40 J/g.
- the content is at least the above lower limit, the cohesive force derived from the crystals is improved, and excellent adhesiveness and solder heat resistance can be exhibited. Further, when the content is equal to or less than the upper limit, excellent solution stability and fluidity are obtained, and operability at the time of adhesion is improved.
- the method for producing the acid-modified polyolefin is not particularly limited. reaction to graft polymerize), and the like.
- an acid-modified polystyrene resin can be preferably used as the acid-modified resin.
- the acid-modified polystyrene resin is not limited, but an aromatic vinyl compound alone or a copolymer mainly composed of block and/or random structure of an aromatic vinyl compound and a conjugated diene compound, and its hydrogenated product, It is preferably modified with a saturated carboxylic acid.
- aromatic vinyl compounds include, but are not limited to, styrene, t-butylstyrene, ⁇ -methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N,N-diethyl-p-aminoethyl.
- Styrene, vinyl toluene, p-tert-butyl styrene and the like can be mentioned.
- conjugated diene compounds include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like.
- copolymers of these aromatic vinyl compounds and conjugated diene compounds include styrene-ethylene-butylene-styrene block copolymers (SEBS), styrene-ethylene-propylene-styrene block copolymers (SEPS), Styrene-ethylene-ethylene/propylene-styrene block copolymer (SEEPS) and the like are included.
- SEBS styrene-ethylene-butylene-styrene block copolymers
- SEPS styrene-ethylene-propylene-styrene block copolymers
- SEEPS Styrene-ethylene-ethylene/propylene-styrene block copolymer
- ⁇ Acid-modified cycloolefin polymer> it is also preferable to use an acid-modified cycloolefin polymer as the acid-modified resin.
- the acid-modified cycloolefin polymer is obtained by introducing a carboxy group into the cycloolefin polymer by acid modification, and the cycloolefin polymer is a homopolymer (COP) produced from only one type of cycloolefin monomer, or one or more types. Any copolymer (COC) composed of cycloolefin monomers and comonomers can be used.
- cycloolefin monomer examples include bicyclics such as norbornene and norbornadiene, tricyclics such as dicyclopentadiene and dihydroxypentadiene, tetracyclics such as tetracyclododecene, and pentacyclics such as cyclopentadiene trimer.
- Heptacyclics such as tetracyclopentadiene, or polycyclics thereof substituted with alkyl (methyl, ethyl, propyl, butyl, etc.), alkenyl (vinyl, etc.), alkylidene (ethylidene, etc.), aryl (phenyl, tolyl, naphthyl, etc.) substituted products.
- alkyl methyl, ethyl, propyl, butyl, etc.
- alkenyl vinyl, etc.
- alkylidene ethylidene, etc.
- aryl phenyl, tolyl, naphthyl, etc.
- norbornene-based monomers selected from the group consisting of norbornene, tetracyclododecene, and alkyl-substituted products thereof are particularly preferred.
- the comonomer may be any monomer that can be copolymerized with the cycloolefin monomer described above, and is preferably an alkene monomer, for example.
- alkene monomers include ⁇ -olefins such as ethylene, propylene, 1-butene and 1-hexene, and isobutene.
- Alkene monomers may be linear or branched.
- the cycloolefin monomer 50% by mass or more of the monomer component constituting the acid-modified cycloolefin polymer is the cycloolefin monomer, and more preferably 60% by mass or more is the cycloolefin monomer.
- the cycloolefin monomer accounts for 50% by mass or more of the total monomer components, good solder heat resistance can be obtained.
- the polymerization method, polymerization conditions, and the like for polymerizing the monomer components are not particularly limited, and may be appropriately set in accordance with conventional methods.
- Compound A in the present invention is a compound having a terminal unsaturated hydrocarbon group and a 5% weight loss temperature of 260° C. or higher.
- a terminal unsaturated hydrocarbon group By having a terminal unsaturated hydrocarbon group, it is possible to increase crosslink density and improve solder heat resistance by reaction with compound B described later.
- the adhesive can have excellent dielectric properties.
- Having two or more terminal unsaturated hydrocarbon groups in one molecule is preferable because the crosslink density can be further increased.
- the 5% weight loss temperature of compound A must be 260°C or higher. It is preferably 270° C. or higher, more preferably 280° C. or higher, and still more preferably 290° C. or higher. When the 5% weight loss temperature is equal to or higher than the above value, soldering can be performed without causing poor appearance even at a temperature exceeding the melting point of solder.
- Compound A preferably has an aromatic ring structure or an alicyclic structure as a structural unit.
- solder heat resistance can be improved, and dielectric properties are also excellent.
- polyphenylene ethers having terminal unsaturated hydrocarbon groups include SA-9000 from SABIC and OPE-2St from Mitsubishi Gas Chemical.
- As the phenolic resin having a terminal unsaturated hydrocarbon group Resitop FTC-809AE manufactured by Gun Ei Chemical Industry Co., Ltd. is exemplified.
- the number average molecular weight of compound A is preferably 500 or more, more preferably 1000 or more. Also, it is preferably 100,000 or less, more preferably 10,000 or less. Within the above range, the solubility in a solvent is good, and a uniform adhesive coating film can be formed.
- the content of the compound A in the adhesive composition of the present invention is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and still more preferably 10 parts by mass or more with respect to 100 parts by mass of the acid-modified resin. is. Also, it is preferably 100 parts by mass or less, more preferably 70 parts by mass or less, and even more preferably 50 parts by mass or less. Within the above range, both excellent adhesiveness and soldering heat resistance can be achieved.
- Compound B in the present invention is a compound having an epoxy group and a terminal unsaturated hydrocarbon group.
- an epoxy group By having an epoxy group, it can be reacted with an acid-modified resin or polycarbodiimide described later, and by having a terminal unsaturated hydrocarbon group, it can be reacted with compound A, so that the crosslink density is increased between these compounds.
- the compound B preferably has a ring structure.
- the ring structure of compound B is preferably an aromatic ring structure or an isocyanuric ring structure from the viewpoint of heat resistance.
- Specific examples of such compound B include diallyl monoglycidyl isocyanurate and diglycidyl monoallyl isocyanurate. By using these, the crosslink density can be increased and the solder heat resistance can be improved.
- the molecular weight of compound B is preferably 500 or less. It is more preferably 400 or less. When the molecular weight is equal to or less than the above value, the solubility in solvents and the reactivity with compound A, acid-modified resin, and polycarbodiimide are improved, the crosslink density is increased, and solder heat resistance can be improved.
- the content of compound B in the adhesive composition of the present invention is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and still more preferably 100 parts by mass of the acid-modified resin. It is 1 part by mass or more. Also, it is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less. Within the above range, both excellent adhesiveness and soldering heat resistance can be achieved. Moreover, the content of the compound B is preferably 1 equivalent or more of the terminal unsaturated hydrocarbon group with respect to the terminal unsaturated hydrocarbon group of the compound A. When the amount is 1 equivalent or more, the crosslink density can be increased and excellent solder heat resistance can be exhibited.
- the adhesive composition of the present invention is an adhesive composition comprising an acid-modified resin, compound A and compound B.
- compound A and compound B are the following compounds, respectively.
- Compound A a compound having a terminal unsaturated hydrocarbon group and a 5% weight loss temperature of 260°C or higher
- Compound B a compound having an epoxy group and a terminal unsaturated hydrocarbon group Terminals of compound A and compound B Since the unsaturated hydrocarbon groups react with each other to cure without generating hydroxyl groups that deteriorate the dielectric properties, both excellent solder heat resistance and dielectric properties can be achieved.
- the adhesive composition of the present invention preferably has a dielectric constant ( ⁇ c) of 2.7 or less at a frequency of 10 GHz. It is more preferably 2.6 or less, still more preferably 2.3 or less. Although the lower limit is not particularly limited, it is practically 2.0. Also, the dielectric constant ( ⁇ c) in the entire frequency range of 1 GHz to 60 GHz is preferably 2.7 or less, more preferably 2.6 or less, and even more preferably 2.3 or less.
- the adhesive composition of the present invention preferably has a dielectric loss tangent (tan ⁇ ) of 0.003 or less at a frequency of 10 GHz. It is more preferably 0.0025 or less, and still more preferably 0.002 or less. Although the lower limit is not particularly limited, it is practically 0.0001 or more. Further, the dielectric loss tangent (tan ⁇ ) in the entire frequency range of 1 GHz to 60 GHz is preferably 0.003 or less, more preferably 0.0025 or less, and even more preferably 0.002 or less.
- the adhesive composition of the present invention also preferably contains a radical generator.
- a radical generator In the adhesive composition of the present invention, compound A and compound B can be reacted by heating, but the radicals generated by the radical generator cause the terminal unsaturated hydrocarbon groups of compound A and compound B to efficiently react with each other. By increasing the crosslink density, solder heat resistance and dielectric properties can be improved.
- the radical generator is not particularly limited, it is preferable to use an organic peroxide.
- organic peroxides include, but are not limited to, di-tert-butyl peroxyphthalate, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy- 2-ethylhexanoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, di-tert-butyl peroxide, lauroyl peroxide, 2,5-dimethyl-2,5-di(tertiarybutylperoxy)hexane and azonitriles such as azobisisobutyronitrile and azobisisopropionitrile.
- azonitriles such as azobisisobutyronitrile and azobisisopropionitrile.
- the one-minute half-life temperature of the radical generator used in the present invention is preferably 140°C or higher.
- the temperature is 140° C. or higher, the solvent of the adhesive composition varnish is volatilized to prevent the radical reaction from starting when the adhesive sheet is produced, and excellent adhesiveness can be exhibited.
- the blending amount of the radical generator in the adhesive composition of the present invention is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, relative to 100 parts by mass of compound A. Also, it is preferably 50 parts by mass or less, more preferably 20 parts by mass or less. By setting it within the above range, it is possible to obtain an optimum cross-linking density and achieve both adhesion and soldering heat resistance.
- the adhesive composition of the invention can contain polycarbodiimide.
- Polycarbodiimide is not particularly limited as long as it has two or more carbodiimide bonds in the molecule.
- the epoxy group of the acid-modified polystyrene elastomer or compound B reacts with the carbodiimide bond, and heat resistance and adhesiveness can be improved.
- the content of polycarbodiimide is preferably 1 part by mass or more, more preferably 3 parts by mass or more, relative to 100 parts by mass of the acid-modified resin.
- a crosslink density can be raised and solder heat resistance becomes favorable.
- it is preferably 20 parts by mass or less, more preferably 10 parts by mass or less.
- the adhesive composition of the present invention can contain an epoxy resin different from compound B.
- the epoxy resin used in the present invention is not particularly limited as long as it has an epoxy group in the molecule, but preferably has two or more epoxy groups in the molecule.
- N,N,N',N'-tetraglycidyl-m-xylenediamine biphenyl type epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin and epoxy-modified polybutadiene. More preferred is N,N,N',N'-tetraglycidyl-m-xylenediamine, which can exhibit excellent adhesiveness.
- the content of the epoxy resin is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, relative to 100 parts by mass of the acid-modified resin. More preferably, it is 1 part by mass or more.
- the content is preferably 10 parts by mass or less, more preferably 5 parts by mass or less.
- 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 the acid-modified resin, compound A and compound B.
- aromatic hydrocarbons such as benzene, toluene and xylene
- aliphatic hydrocarbons such as hexane, heptane, octane and decane
- alicyclic hydrocarbons such as cyclohexane, cyclohexene, methylcyclohexane and ethylcyclohexane.
- Halogenated hydrocarbons such as hydrogen, trichlorethylene, dichloroethylene, chlorobenzene, and chloroform
- alcoholic solvents such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, and phenol, acetone, methyl isobutyl ketone, ketone solvents such as methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone and acetophenone
- cellosolves such as methyl cellosolve and ethyl cellosolve
- ester solvents such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate and butyl formate
- Ethylene glycol mono-n-butyl ether ethylene glycol mono-iso-butyl ether, ethylene glycol mono-tert-butyl
- the organic solvent is preferably in the range of 100 to 1000 parts by mass with respect to 100 parts by mass of the acid-modified resin. By making it more than the said lower limit, liquid state and pot-life property become favorable. Moreover, setting the content to the above upper limit or less is advantageous in terms of manufacturing costs and transportation costs.
- the adhesive composition of the present invention may further contain other components as necessary.
- specific examples of such components include flame retardants, tackifiers, fillers, and silane coupling agents.
- the adhesive composition of the present invention may optionally contain a flame retardant.
- flame retardants include bromine-based, phosphorus-based, nitrogen-based, and metal hydroxide compounds.
- phosphorus-based flame retardants are preferable, and known phosphorus-based flame retardants such as phosphate esters such as trimethyl phosphate, triphenyl phosphate, tricresyl phosphate, etc., phosphates such as aluminum phosphinate, and phosphazenes can be used. . These may be used alone, or may be used in any combination of two or more.
- a flame retardant When containing a flame retardant, it is preferable to contain a flame retardant in the range of 1 to 200 parts by mass, more preferably 5 to 150 parts by mass, based on a total of 100 parts by mass of the acid-modified resin, compound A and compound B. Preferably, the range of 10 to 100 parts by weight is most preferred. By setting the content within the above range, it is possible to exhibit flame retardancy while maintaining adhesiveness, solder heat resistance, and electrical properties.
- a tackifier may be added to the adhesive composition of the present invention, if necessary.
- tackifiers include polyterpene resins, rosin resins, aliphatic petroleum resins, alicyclic petroleum resins, copolymer petroleum resins, styrene resins and hydrogenated petroleum resins. used in These may be used alone, or may be used in any combination of two or more.
- a tackifier is contained, it is preferably contained in the range of 1 to 200 parts by mass, more preferably 5 to 150 parts by mass, with respect to the total 100 parts by mass of the acid-modified resin, compound A and compound B.
- a range of 10 to 100 parts by weight is most preferred.
- the adhesive composition of the present invention may optionally contain a filler.
- organic fillers include powders of heat-resistant resins such as polyimide, polyamideimide, fluororesin, and liquid crystal polyester.
- inorganic fillers include silica (SiO 2 ), alumina (Al 2 O 3 ), titania (TiO 2 ), tantalum oxide (Ta 2 O 5 ), zirconia (ZrO 2 ), silicon nitride (Si 3 N 4 ), boron nitride (BN), calcium carbonate ( CaCO3 ), calcium sulfate ( CaSO4 ), zinc oxide (ZnO), magnesium titanate (MgO- TiO2 ), barium sulfate ( BaSO4 ), organic bentonite, clay , mica, aluminum hydroxide, magnesium hydroxide, etc.
- silica is preferable from the viewpoint of ease of dispersion and effect of improving heat resistance.
- Hydrophobic silica and hydrophilic silica are generally known as silica, but here, hydrophobic silica treated with dimethyldichlorosilane, hexamethyldisilazane, octylsilane, etc. is used to impart moisture absorption resistance. is good.
- the blending amount is preferably 0.05 to 30 parts by mass with respect to 100 parts by mass of the acid-modified resin, compound A and compound B in total. Further heat resistance can be expressed by making it more than the said lower limit.
- the content is equal to or less than the above upper limit, poor dispersion of silica and excessive increase in solution viscosity are suppressed, and workability is improved.
- a silane coupling agent may be added to the adhesive composition of the present invention, if necessary. Addition of a silane coupling agent is very preferable because it improves adhesion to metals and heat resistance.
- the silane coupling agent is not particularly limited, examples thereof include those having an unsaturated group, those having an epoxy group, and those having an amino group.
- epoxy such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and ⁇ -(3,4-epoxycyclohexyl)ethyltriethoxysilane is used from the viewpoint of heat resistance.
- a silane coupling agent having a group is more preferred.
- the blending amount is preferably 0.5 to 20 parts by mass per 100 parts by mass of the acid-modified resin, compound A and compound B in total. Soldering heat resistance and adhesiveness can be improved by making it into the said range.
- the laminate of the present invention is obtained by laminating an adhesive composition on a base material (two-layer laminate of base material/adhesive layer), or further laminating a base material (base material/adhesive layer/ A three-layer laminate of substrates).
- the adhesive layer refers to a layer of the adhesive composition after the adhesive composition of the present invention has been applied to a substrate and dried.
- the laminate of the present invention can be obtained by applying the adhesive composition of the present invention to various substrates, drying it, and further laminating another substrate in accordance with conventional methods.
- the substrate is not particularly limited as long as the adhesive composition of the present invention can be applied and dried to form an adhesive layer.
- Examples include metal substrates such as plates and metal foils, papers, and the like.
- resin substrates examples include polyester resins, polyamide resins, polyimide resins, polyamideimide resins, liquid crystal polymers, polyphenylene sulfides, syndiotactic polystyrene, polyolefin resins, fluorine resins, and the like.
- 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 circuit boards can be used as the metal base material.
- materials include various metals such as SUS, copper, aluminum, iron, steel, zinc, and nickel, and their alloys, plated products, and metals treated with other metals such as zinc and chromium compounds.
- Metal foil is preferred, and copper foil is more preferred.
- the thickness of the metal foil is not particularly limited, it is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, and still more preferably 10 ⁇ m or more. Also, it is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, and still more preferably 20 ⁇ m or less. If the thickness is too thin, it may be difficult to obtain sufficient electrical performance of the circuit.
- Metal foils are 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.
- the length is not particularly limited.
- the width is not particularly limited, but it is preferably about 250 to 500 cm.
- the surface roughness of the substrate is not particularly limited, but is preferably 3 ⁇ m or less, more preferably 2 ⁇ m or less, and still more preferably 1.5 ⁇ m or less. Moreover, it is practically preferably 0.3 ⁇ m or more, more preferably 0.5 ⁇ m or more, and still more preferably 0.7 ⁇ m or more.
- Examples of papers include high-quality paper, kraft paper, roll paper, and glassine paper. Moreover, glass epoxy etc. can be illustrated as a composite material.
- polyester resin Based on adhesive strength and durability with the adhesive composition, polyester resin, polyamide resin, polyimide resin, polyamideimide resin, liquid crystal polymer, polyphenylene sulfide, syndiotactic polystyrene, polyolefin resin, fluororesin, A SUS steel plate, copper foil, aluminum foil, or glass epoxy is preferred.
- the adhesive sheet is obtained by laminating the laminate and the release substrate via an adhesive composition.
- Specific configuration modes include laminate/adhesive layer/release substrate, or release substrate/adhesive layer/laminate/adhesive layer/release substrate.
- the release base material By laminating the release base material, it functions as a protective layer for the 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 applied to the adhesive layer after drying, it is possible to wind up the product without set-off to the base material, resulting in excellent workability and preservability due to the protection of the adhesive layer. excellent and easy to use.
- the adhesive layer itself is applied to a release base material and dried, and if necessary, another release base material is applied, the adhesive layer itself can be transferred to another base material.
- the release substrate is not particularly limited, but for example, a coated layer of filler such as clay, polyethylene, polypropylene, etc. is applied to both sides of paper such as woodfree paper, kraft paper, roll paper, and glassine paper. and a silicone type, fluorine type or alkyd type release agent is applied on each coating layer.
- a coated layer of filler such as clay, polyethylene, polypropylene, etc.
- paper such as woodfree paper, kraft paper, roll paper, and glassine paper.
- a silicone type, fluorine type or alkyd type release agent is applied on each coating layer.
- Other examples include various olefin films such as polyethylene, polypropylene, ethylene- ⁇ -olefin copolymer and propylene- ⁇ -olefin copolymer alone, and films such as polyethylene terephthalate coated with the release agent.
- both sides of high-quality paper are filled with polypropylene and an alkyd-based release agent is used on top of it.
- an alkyd release agent on polyethylene terephthalate.
- the method of coating the substrate with the adhesive composition in the present invention is not particularly limited, but includes a comma coater, a reverse roll coater, and the like.
- an adhesive layer can be provided directly or by a transfer method on the rolled copper foil or polyimide film, which are the constituent materials of the printed wiring board.
- the thickness of the adhesive layer after drying may be changed as required, but is preferably in the range of 5 to 200 ⁇ m. Sufficient adhesive strength can be obtained by setting the thickness of the adhesive film to 5 ⁇ m or more. Further, by setting the thickness to 200 ⁇ m or less, it becomes easier to control the amount of residual solvent in the drying process, and blisters are less likely to occur during pressing in the manufacture of printed wiring boards.
- the drying conditions are not particularly limited, but the residual solvent rate after drying is preferably 1% by mass or less. When the amount is 1% by mass or less, foaming of the residual solvent is suppressed during pressing of the printed wiring board, and blisters are less likely to occur.
- the printed wiring board in the present invention includes, as constituent elements, a laminate formed of a metal foil forming a conductive circuit and a resin base material, and examples thereof include flexible substrates, rigid substrates, package substrates, and the like.
- a printed wiring board is manufactured, for example, by a conventionally known method such as a subtractive method using a metal-clad laminate. If necessary, so-called flexible circuit boards (FPC), flat cables, tape automated bonding ( It is a general term for circuit boards for TAB).
- FPC flexible circuit boards
- TAB tape automated bonding
- the printed wiring board of the present invention can have any laminated structure that can be employed 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.
- a printed wiring board can be made up of five layers: a base film layer, an adhesive layer, a metal foil layer, an adhesive layer, and a cover film layer.
- the adhesive composition of the present invention can be suitably used for each adhesive layer of printed wiring boards.
- the adhesive composition of the present invention when used as an adhesive, it has high adhesiveness not only to conventional polyimides, polyester films, and copper foils constituting printed wiring boards, but also to low-polarity resin substrates 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 coverlay films, laminates, resin-coated copper foils and bonding sheets.
- any resin film conventionally used as a base material for printed wiring boards can be used as the base film.
- resins for the base film include polyester resins, polyamide resins, polyimide resins, polyamideimide resins, liquid crystal polymers, polyphenylene sulfides, syndiotactic polystyrene, polyolefin resins, fluorine resins, and the like.
- it has excellent adhesion even to low-polarity substrates such as liquid crystal polymers, polyphenylene sulfide, syndiotactic polystyrene, and polyolefin resins.
- any insulating film conventionally known as an insulating film for printed wiring boards 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. Polyimide films or liquid crystal polymer films are more preferred.
- the printed wiring board of the present invention can be manufactured using any conventionally known process except for using the materials for each layer described above.
- 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 in which a desired circuit pattern is formed by laminating a metal foil layer on a base film layer (hereinafter referred to as a "two-layer semi-finished product on the base film side"), or a semi-finished product in which an adhesive layer is laminated on a base film layer.
- a semi-finished product having a desired circuit pattern formed by laminating a metal foil layer thereon (hereinafter referred to as “base film side 3-layer semi-finished product”) (hereinafter referred to as “base film side 2-layer semi-finished product”). Together with the base film side three-layer semi-finished product, it is referred to as the “base film side semi-finished product”).
- base film side semi-finished product By laminating the semi-finished product on the cover film side and the semi-finished product on the base film side thus obtained, a printed wiring board having four or five layers can be obtained.
- the semi-finished product on the substrate film side includes, for example, (A) a step of applying a solution of a resin that will be the substrate film to the metal foil and initially drying the coating film, and (B) the metal foil obtained in (A) and It is obtained by a production method including a process of heat-treating and drying the laminate with the initially dried coating film (hereinafter referred to as "heat-treatment/solvent removal process").
- a conventionally known method can be used to form a circuit in the metal foil layer.
- An additive method may be used, or a subtractive method may be used.
- a subtractive method is preferred.
- the semi-finished product on the base film side thus obtained may be used as it is for lamination with the semi-finished product on the cover film side. may be used.
- the semi-finished product on the cover film side is manufactured, for example, by applying an adhesive to the cover film. If desired, a cross-linking reaction in the applied adhesive can be performed. In a preferred embodiment, the adhesive layer is semi-cured.
- the semi-finished product on the cover film side thus obtained may be used as it is for bonding to the semi-finished product on the base film side. may be used for
- the semi-finished product on the base film side and the semi-finished product on the cover film side are each stored, for example, in the form of a roll, and then laminated 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. Also, both can be bonded together while being heated by a method such as using a hot press or a hot roll device.
- the semi-finished product on the reinforcing material side for example, in the case of a soft and windable reinforcing material such as a polyimide film, it is preferable to manufacture it by applying an adhesive to the reinforcing material.
- an adhesive to the reinforcing material.
- the adhesive applied in advance to the release base material can be transferred and applied. It is preferably manufactured. Also, if necessary, a cross-linking reaction in the applied adhesive can be carried out.
- the adhesive layer is semi-cured.
- the semi-finished product on the reinforcing material side thus obtained may be used as it is for bonding to the back surface of the printed wiring board, or it may be used for bonding to the semi-finished product on the base film side after being stored after being bonded with a release film. You may
- the semi-finished product on the base film side, the semi-finished product on the cover film side, and the semi-finished product on the reinforcing material side are all printed wiring board laminates in the present invention.
- the acid value (equivalent/10 6 g) in the present invention was obtained by dissolving the acid-modified resin 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 determined by Shimadzu Corporation Gel Permeation Chromatography (hereinafter referred to as GPC, standard substance: polystyrene resin, mobile phase: tetrahydrofuran, column: Shodex KF-802 + KF-804L + KF-806L, column temperature: 30°C, flow rate: 1.0 ml/min, detector: RI detector).
- GPC Shimadzu Corporation Gel Permeation Chromatography
- the melting point and the heat of fusion in the present invention are measured using a differential scanning calorimeter (hereinafter referred to as DSC, Q-2000 manufactured by TA Instruments Japan) at a rate of 20 ° C. / min. It is a value measured from the top temperature and area of the melting peak when the temperature is raised and melted again.
- DSC differential scanning calorimeter
- the liquid containing the resin was centrifuged to separate and purify the acid-modified propylene-butene copolymer graft-polymerized with maleic anhydride, the (poly)maleic anhydride and the low molecular weight substances. Then, by drying at 70° C. for 5 hours under reduced pressure, a maleic anhydride-modified propylene-butene copolymer (c1, acid value 338 equivalents/10 6 g, number average molecular weight 25,000, Tm 80° C., ⁇ H 35 J/g ).
- the liquid containing the resin was centrifuged to separate and purify the acid-modified cycloolefin polymer graft-polymerized with maleic anhydride, (poly)maleic anhydride, and low-molecular-weight substances. Then, it was dried at 70° C. under reduced pressure for 5 hours to obtain a maleic anhydride-modified cycloolefin polymer (c5, acid value 339 equivalents/10 6 g, dielectric constant 2.0, dielectric loss tangent 0.0008).
- compound B As compound B, the following was used.
- Tetrad X epoxy resin (manufactured by Mitsubishi Gas Chemical Company, glycidylamine type epoxy)
- Perbutyl P radical generator (manufactured by NOF Corporation, bis(1-t-butylperoxy-1-methylethyl)benzene, 1 minute half-life temperature 175° C.)
- Example 1 The acid-modified polyolefin (c1) obtained in the above synthesis example was dissolved in methylcyclohexane to prepare a methylcyclohexane varnish having a solid content concentration of 20% by mass. To this methylcyclohexane varnish, compound A (a1), compound B (b1), and PERBUTYL P were blended in amounts of 20 parts, 5 parts, and 3 parts, respectively, relative to 100 parts of acid-modified polyolefin (c1). An agent composition (S1) was obtained. The resulting adhesive composition (S1) was evaluated for dielectric constant, dielectric loss tangent, peel strength, solder heat resistance, and adhesive sheet flexibility. The results are listed in Table 1.
- Examples 2 to 9 Comparative Examples 1 to 5> An adhesive composition was prepared in the same manner as in Example 1 except that the type and amount of the curing agent and the like were changed as shown in Tables 1 and 2, and each evaluation was performed. The results are listed in Table 1.
- Example 10 Using an acid-modified polystyrene resin (c2) as an acid-modified resin, (a1) as a compound A, (b1) as a compound B, and 20 parts, 5 parts, and 3 parts of perbutyl P with respect to 100 parts of the acid-modified polystyrene resin (c2). and dissolved in toluene to a solid concentration of 30% by mass to obtain an adhesive composition (S10).
- the resulting adhesive composition (S10) was evaluated for dielectric constant, dielectric loss tangent, peel strength, solder heat resistance and adhesive sheet flexibility. The results are listed in Table 1.
- Adhesive Composition (Relative permittivity ( ⁇ c ) and dielectric loss tangent (tan ⁇ ))
- the adhesive composition was applied to a Teflon (registered trademark) sheet having a thickness of 100 ⁇ m so that the thickness after drying was 25 ⁇ m, and dried at 130° C. for 3 minutes. After curing by heat treatment at 180° C. for 3 hours, the Teflon (registered trademark) sheet was peeled off to obtain an adhesive resin sheet for testing.
- the test adhesive resin sheet thus obtained was cut into strips of 8 cm ⁇ 3 mm to obtain test samples.
- the relative dielectric constant ( ⁇ c ) and dielectric loss tangent (tan ⁇ ) were measured by a cavity resonator perturbation method using a network analyzer (manufactured by Anritsu Corporation) under conditions of a temperature of 23° C. and a frequency of 10 GHz.
- the adhesive composition was applied to a 12.5 ⁇ m thick polyimide film (manufactured by Kaneka Corporation, Apical (registered trademark)) so as to have a thickness of 25 ⁇ m after drying, and dried at 130° C. for 3 minutes.
- the adhesive film (B stage product) thus obtained was laminated to a 18 ⁇ m thick rolled copper foil (manufactured by Nippon Steel Chemical & Materials Co., Ltd., Espanex series). Bonding was performed by pressing the rolled copper foil so that the glossy surface of the rolled copper foil was in contact with the adhesive layer, and pressing for 280 seconds under a pressure of 2 MPa at 170°C.
- the adhesive composition is applied to a Teflon (registered trademark) sheet having a thickness of 100 ⁇ m so that the thickness after drying becomes 25 ⁇ m, and dried at 130° C. for 3 minutes. Next, the state of the coating film was checked when the sheet was folded 180°. ⁇ Evaluation Criteria> ⁇ : No cracks ⁇ : Cracks present
- Examples 1 to 21 are excellent in pot life, dielectric properties, peel strength, solder heat resistance, and adhesive sheet flexibility.
- Comparative Examples 1 and 6 since the compound B did not have an epoxy group, the curing was insufficient and the solder heat resistance was insufficient.
- Comparative Examples 2 and 7 did not contain the compound B and contained an epoxy resin, so the dielectric properties as an adhesive composition were poor.
- Comparative Examples 3 and 8 since Compound A did not have a terminal unsaturated hydrocarbon group, curing was insufficient and solder heat resistance was insufficient. Also, the dielectric loss tangent was high due to the influence of the terminal hydroxyl group.
- Comparative Example 4 since the acid-modified resin was not included, the adhesive sheet was brittle, and the peel strength and solder heat resistance were insufficient. In addition, the relative permittivity and dielectric loss tangent could not be measured because the coating film was fragile. Comparative Examples 5 and 9 were inferior in solder heat resistance because the 5% weight loss temperature of compound A was low.
- the adhesive composition of the present invention is excellent in heat resistance and adhesive strength, has a low dielectric constant and a low dielectric loss tangent, and has good sheet flexibility. Therefore, it is useful as an adhesive or an adhesive sheet for printed wiring boards applied to printed boards (flexible boards, rigid boards, package boards) in a high frequency range.
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Abstract
Description
すなわち、本発明は、以下の構成からなる。
化合物A:末端不飽和炭化水素基を有し、かつ5%重量減少温度が260℃以上である化合物
化合物B:エポキシ基と、末端不飽和炭化水素基とを有する化合物
[2] 酸変性樹脂が酸変性ポリオレフィン、酸変性ポリスチレン樹脂および酸変性シクロオレフィンポリマーから選ばれる少なくとも1種類の樹脂を含有する前記[1]の接着剤組成物。
[3] 前記化合物Aが構造単位として芳香環構造または脂環構造を有する化合物である、前記[1]または[2]の接着剤組成物。
[4] 前記化合物Aが、末端不飽和炭化水素基を有する、ポリフェニレンエーテルまたはフェノール樹脂である、前記[1]または[2]の接着剤組成物。
[5] 前記化合物Bがイソシアヌル環を有する化合物である、前記[1]~[4]の接着剤組成物。
[6] 前記[1]~[5]の接着剤組成物からなる接着剤層を有する接着シート。
[7] 前記[1]~[5]の接着剤組成物からなる接着剤層を有する積層体。
[8] 前記[7]の積層体を構成要素として含むプリント配線板。
本発明で用いる酸変性樹脂は、酸成分を用いて変性が施された樹脂である。酸変性された樹脂を用いることで、銅箔等の金属基材との密着性に優れ、また後記の化合物Bのエポキシ基との架橋反応により、はんだ耐熱性に優れた接着層を形成できる。
本発明では、酸変性樹脂として、酸変性ポリオレフィンを好ましく用いることができる。本発明で用いる酸変性ポリオレフィンは限定的ではないが、ポリオレフィン樹脂にα,β-不飽和カルボン酸及びその酸無水物の少なくとも1種をグラフトすることにより得られるものであることが好ましい。ポリオレフィン樹脂とは、エチレン、プロピレン、ブテン、ブタジエン、イソプレン等に例示されるオレフィンモノマーの単独重合、もしくはその他のモノマーとの共重合、および得られた重合体の水素化物やハロゲン化物など、炭化水素骨格を主体とする重合体を指す。酸変性ポリオレフィンは、ポリエチレン、ポリプロピレン及びプロピレン-α-オレフィン共重合体の少なくとも1種に、α,β-不飽和カルボン酸及びその酸無水物の少なくとも1種をグラフトすることにより得られるものが好ましい。
本発明では、酸変性樹脂として、酸変性ポリスチレン樹脂を好ましく用いることができる。酸変性ポリスチレン樹脂は限定的ではないが、芳香族ビニル化合物単独もしくは、芳香族ビニル化合物と共役ジエン化合物とのブロック及び/又はランダム構造を主体とする共重合体、並びにその水素添加物を、不飽和カルボン酸で変性したものであることが好ましい。芳香族ビニル化合物としては、特に限定されないが、例えばスチレン、t-ブチルスチレン、α-メチルスチレン、p-メチルスチレン、ジビニルベンゼン、1,1-ジフェニルスチレン、N,N-ジエチル-p-アミノエチルスチレン、ビニルトルエン、p-第3ブチルスチレン等が挙げられる。また、共役ジエン化合物としては、例えば、ブタジエン、イソプレン、1,3-ペンタジエン、2,3-ジメチル-1,3-ブタジエン等が挙げられる。これら芳香族ビニル化合物と共役ジエン化合物との共重合体の具体例としては、スチレン-エチレン-ブチレン-スチレンブロック共重合体(SEBS)、スチレン-エチレン-プロピレン-スチレンブロック共重合体(SEPS)、スチレン-エチレン-エチレン・プロピレン-スチレンブロック共重合体(SEEPS)などが挙げられる。
本発明では、酸変性樹脂として、酸変性シクロオレフィンポリマーを使用することも好ましい。酸変性シクロオレフィンポリマーは、シクロオレフィンポリマーに酸変性によってカルボキシ基を導入したものであり、シクロオレフィンポリマーとしては、1種のみのシクロオレフィンモノマーから作製されるホモポリマー(COP)、または1種以上のシクロオレフィンモノマーおよびコモノマーから構成されるコポリマー(COC)のいずれも使用できる。
本発明における化合物Aは、末端不飽和炭化水素基を有し、かつ5%重量減少温度が260℃以上である化合物である。末端不飽和炭化水素基を有することで、後記の化合物Bとの反応により、架橋密度を高め、はんだ耐熱性を向上することができる。また、反応後に誘電特性を悪化させる水酸基を発生させないため、優れた誘電特性を有する接着剤とすることができる。末端不飽和炭化水素基は、1分子中に2個以上有することが、より架橋密度を高められるため好ましい。ここで、末端不飽和炭化水素基とは、例えば、ビニル基、ビニリデン基や、アリル基、アクリル基、メタクリル基、スチレン基など、CH2=Cの構造を有する基をいう。
本発明における化合物Bは、エポキシ基と、末端不飽和炭化水素基とを有する化合物である。エポキシ基を有することで酸変性樹脂や後記のポリカルボジイミドと反応させることができ、末端不飽和炭化水素基を有することで化合物Aと反応させることができるため、これらの化合物間でより架橋密度を高めることによって、優れたはんだ耐熱性を実現できる。ここで、末端不飽和炭化水素基とは、例えば、ビニル基、ビニリデン基や、アリル基、アクリル基、メタクリル基、スチレン基など、CH2=Cの構造を有する基をいう。
本発明の接着剤組成物は酸変性樹脂、化合物Aおよび化合物Bを含んでなる接着剤組成物である。ここで、化合物Aと化合物Bはそれぞれ下記の化合物である。
化合物A:末端不飽和炭化水素基を有し、かつ5%重量減少温度が260℃以上である化合物
化合物B:エポキシ基と、末端不飽和炭化水素基とを有する化合物
化合物Aと化合物Bの末端不飽和炭化水素基同士が反応することで、誘電特性を悪化させる水酸基を発生させることなく硬化できるため、優れたはんだ耐熱性と誘電特性を両立することができる。
本発明の接着剤組成物はラジカル発生剤を含むことも好ましい。本発明の接着剤組成物は加熱によって化合物Aおよび化合物Bを反応させることもできるが、ラジカル発生剤によって発生したラジカルが化合物Aおよび化合物Bの末端不飽和炭化水素基同士を効率的に反応させ、架橋密度を高めることで、はんだ耐熱性や誘電特性を向上させることができる。ラジカル発生剤としては、特に限定されないが、有機過酸化物を使用することが好ましい。有機過酸化物としては、特に限定されないが、ジ-tert-ブチルパーオキシフタレート、tert-ブチルヒドロパーオキサイド、ジクミルパーオキサイド、ベンゾイルパーオキサイド、tert-ブチルパーオキシベンゾエート、tert-ブチルパーオキシ-2-エチルヘキサノエート、tert-ブチルパーオキシピバレート、メチルエチルケトンパーオキサイド、ジ-tert-ブチルパーオキサイド、ラウロイルパーオキサイド、2,5-ジメチル-2,5-ジ(ターシャリブチルパーオキシ)ヘキサン等の過酸化物;アゾビスイソブチロニトリル、アゾビスイソプロピオニトリル等のアゾニトリル類等が挙げられる。
本発明の接着剤組成物はポリカルボジイミドを含有することができる。ポリカルボジイミドとしては、分子内にカルボジイミド結合を2個以上有するものであれば特に限定されない。ポリカルボジイミドを使用することによって、酸変性ポリスチレンエラストマーや化合物Bのエポキシ基とカルボジイミド結合とが反応し、耐熱性や接着性を向上することができる。
本発明の接着剤組成物は、化合物Bとは異なるエポキシ樹脂を含有することができる。本発明で用いるエポキシ樹脂としては、分子中にエポキシ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個以上のエポキシ基を有するものである。具体的には、特に限定されないが、ビフェニル型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ノボラック型エポキシ樹脂、脂環式エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、テトラグリシジルジアミノジフェニルメタン、トリグリシジルパラアミノフェノール、テトラグリシジルビスアミノメチルシクロヘキサノン、N,N,N’,N’-テトラグリシジル-m-キシレンジアミン、およびエポキシ変性ポリブタジエンからなる群から選択される少なくとも1つを用いることができる。好ましくは、N,N,N’,N’-テトラグリシジル-m-キシレンジアミン、ビフェニル型エポキシ樹脂、ノボラック型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂またはエポキシ変性ポリブタジエンである。より好ましくは、N,N,N’,N’-テトラグリシジル-m-キシレンジアミンであり、優れた接着性を発現させることができる。
本発明の接着剤組成物には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、酸変性樹脂、化合物Aおよび化合物Bの合計100質量部に対し、難燃剤を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。前記範囲内とすることで接着性、はんだ耐熱性および電気特性を維持しつつ、難燃性を発現することができる。
本発明の接着剤組成物には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、酸変性樹脂、化合物Aおよび化合物B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。前記範囲内とすることで接着性、はんだ耐熱性および電気特性を維持しつつ、粘着付与剤の効果を発現することができる。
本発明の接着剤組成物には必要に応じてフィラーを配合しても良い。有機フィラーとしては、耐熱性樹脂であるポリイミド、ポリアミドイミド、フッ素樹脂、液晶ポリエステルなどの粉末が挙げられる。また、無機フィラーとしては、例えば、シリカ(SiO2)、アルミナ(Al2O3)、チタニア(TiO2)、酸化タンタル(Ta2O5)、ジルコニア(ZrO2)、窒化硅素(Si3N4)、窒化ホウ素(BN)、炭酸カルシウム(CaCO3)、硫酸カルシウム(CaSO4)、酸化亜鉛(ZnO)、チタン酸マグネシウム(MgO・TiO2)、硫酸バリウム(BaSO4)、有機ベントナイト、クレー、マイカ、水酸化アルミニウム、水酸化マグネシウムなどが挙げられ、この中では分散の容易さや耐熱性向上効果からシリカが好ましい。
本発明の接着剤組成物には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、エポキシ基を有するもの、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エポキシ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配合する場合、その配合量は酸変性樹脂、化合物Aおよび化合物Bの合計100質量部に対して0.5~20質量部の配合量であることが好ましい。前記範囲内とすることではんだ耐熱性や接着性を向上することができる。
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。
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。
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。
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。
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り、例えばフレキシブル基板、リジッド基板、パッケージ基板などがある。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。
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。
ロセスを用いて製造することができる。
(酸価測定)
本発明における酸価(当量/106g)は、酸変性樹脂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。
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。
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。
示差熱・熱重量同時測定装置(株式会社島津製作所、DTG-60)を用いて測定した。アルミニウムパンに入れた5mgの試料を、空気雰囲気下、10℃/分の昇温速度で昇温させ、熱分解によって5%の重量が失われたときの温度を5%重量減少温度(単位:℃)とした。
酸変性樹脂の比誘電率(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10GHzの条件で測定した。
1Lオートクレーブに、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、トルエン150質量部及び無水マレイン酸19質量部、ジ-tert-ブチルパーオキサイド6質量部を加え、140℃まで昇温した後、更に3時間撹拌した。その後、得られた反応液を冷却後、多量のメチルエチルケトンが入った容器に注ぎ、樹脂を析出させた。その後、当該樹脂を含有する液を遠心分離することにより、無水マレイン酸がグラフト重合した酸変性プロピレン-ブテン共重合体と(ポリ)無水マレイン酸および低分子量物とを分離、精製した。その後、減圧下70℃で5時間乾燥させることにより、無水マレイン酸変性プロピレン-ブテン共重合体(c1、酸価338当量/106g、数平均分子量25,000、Tm80℃、△H35J/g)を得た。
(c2):タフテックM1911(旭化成社製)、酸価37当量/106g、比誘電率2.3、誘電正接0.0008
(c3):タフテックM1913(旭化成社製)、酸価185当量/106g、比誘電率2.3、誘電正接0.0008
(c4):タフテックM1943(旭化成社製)、酸価185当量/106g、比誘電率2.3、誘電正接0.0008
1Lオートクレーブに、シクロオレフィンポリマー(日本ゼオン社製「ZEONEX(登録商標)RS420」)100質量部、トルエン150質量部及び無水マレイン酸19質量部、ジ-tert-ブチルパーオキサイド6質量部を加え、140℃まで昇温した後、更に3時間撹拌した。その後、得られた反応液を冷却後、多量のメチルエチルケトンが入った容器に注ぎ、樹脂を析出させた。その後、当該樹脂を含有する液を遠心分離することにより、無水マレイン酸がグラフト重合した酸変性シクロオレフィンポリマーと(ポリ)無水マレイン酸および低分子量物を分離、精製した。その後、減圧下70℃で5時間乾燥させることにより、無水マレイン酸変性シクロオレフィンポリマー(c5、酸価339当量/106g、比誘電率2.0、誘電正接0.0008)を得た。
(a1):SA-9000(SABIC社製、ビニル基を有するポリフェニレンエーテル、数平均分子量1700、5%重量減少温度439℃)
(a2):FTC809AE(群栄化学工業社製、ビニル基を有するフェノール樹脂、数平均分子量1400、5%重量減少温度332℃)
(a3):PEGDA(Sigma-Aldrich社製、ポリエチレングリコールジアクリレート、重量平均分子量700、5%重量減少温度220℃)
(a4):SA-90(SABIC社製、水酸基末端を有するポリフェニレンエーテル(末端不飽和炭化水素基を有さない)、数平均分子量1700、5%重量減少温度430℃。)
(b1):DA-MGIC(四国化成工業社製、ジアリルモノグリシジルイソシアヌレート)
(b2):MA-DGIC(四国化成工業社製、モノアリルジグリシジルイソシアヌレート)
(b3):ジアリルイソシアヌレート(東京化成工業社製)
テトラッドX:エポキシ樹脂(三菱ガス化学社製、グリシジルアミン型エポキシ)
パーブチルP:ラジカル発生剤(日油社製、ビス(1-t-ブチルペルオキシ-1-メチルエチル)ベンゼン、1分間半減期温度175℃)
前記の合成例で得た酸変性ポリオレフィン(c1)をメチルシクロヘキサンで溶解し、固形分濃度20質量%のメチルシクロヘキサンワニスを作成した。このメチルシクロヘキサンワニスに、化合物Aとして(a1)、化合物Bとして(b1)、パーブチルPをそれぞれ酸変性ポリオレフィン(c1)100部に対し20部、5部、3部となるように配合し、接着剤組成物(S1)を得た。
得られた接着剤組成物(S1)について、比誘電率、誘電正接、ピール強度、はんだ耐熱性および接着シート柔軟性の各評価を実施した。結果を表1に記載した。
硬化剤等の種類および配合量を表1および表2に示すように変更した以外は実施例1と同様に接着剤組成物を作成し、各評価を実施した。結果を表1に記載した。
酸変性樹脂として酸変性ポリスチレン樹脂(c2)を用い、化合物Aとして(a1)、化合物Bとして(b1)、パーブチルPをそれぞれ酸変性ポリスチレン樹脂(c2)100部に対し20部、5部、3部となるように配合し、トルエンで固形分濃度30質量%に溶解して接着剤組成物(S10)を得た。
得られた接着剤組成物(S10)について、比誘電率、誘電正接、ピール強度、はんだ耐熱性および接着シート柔軟性の各評価を実施した。結果を表1に記載した。
接着剤組成物の各成分の種類および配合量を表1および表2に示すように変更した以外は実施例10と同様に接着剤組成物を作成し、各評価を実施した。結果を表1および表2に記載した。
(比誘電率(εc)及び誘電正接(tanδ))
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180℃で3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。その後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10GHzの条件で測定した。
<比誘電率の評価基準>
○:2.4以下
×:2.4を超える
<誘電正接の評価基準>
◎:0.0020未満
○:0.0020以上0.0025未満
×:0.0025以上
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))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(日鉄ケミカル&マテリアル株式会社製、エスパネックスシリーズ)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、170℃で2MPaの加圧下に280秒間プレスし、接着した。次いで180℃で3時間熱処理して硬化させ、ピール強度評価用サンプルを得た。ピール強度は、25℃、フィルム引き、引張速度50mm/min、90°剥離の条件で測定した。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
×:1.0N/mm未満
上記のピール強度測定用と同じ方法で評価用サンプルを作製し、2.0cm×2.0cmのサンプル片を288℃で溶融したはんだ浴に浸漬し、膨れなどの外観変化の有無を確認した。
<評価基準>
◎:60秒以上膨れ無し
○:30秒以上60秒未満で膨れ有り
×:10秒未満で膨れ有り
接着剤組成物を厚さ100μmのテフロン(登録商標)シートに、乾燥後の厚みが25μmとなるように塗布し、130℃で3分乾燥する。次いで、そのシートを180°折り曲げた際の塗膜の状態を確認した。
<評価基準>
○:ひび割れ無し
×:ひび割れ有り
Claims (8)
- 酸変性樹脂、化合物Aおよび化合物Bを含んでなる接着剤組成物。
化合物A:末端不飽和炭化水素基を有し、かつ5%重量減少温度が260℃以上である化合物
化合物B:エポキシ基と、末端不飽和炭化水素基とを有する化合物 - 酸変性樹脂が酸変性ポリオレフィン、酸変性ポリスチレン樹脂および酸変性シクロオレフィンポリマーから選ばれる少なくとも1種類の樹脂を含有する請求項1に記載の接着剤組成物。
- 前記化合物Aが構造単位として芳香環構造または脂環構造を有する化合物である、請求項1または2に記載の接着剤組成物。
- 前記化合物Aが、末端不飽和炭化水素基を有する、ポリフェニレンエーテルまたはフェノール樹脂である、請求項1または2に記載の接着剤組成物。
- 前記化合物Bがイソシアヌル環を有する化合物である、請求項1~4のいずれかに記載の接着剤組成物。
- 請求項1~5のいずれかに記載の接着剤組成物からなる接着剤層を有する接着シート。
- 請求項1~5のいずれかに記載の接着剤組成物からなる接着剤層を有する積層体。
- 請求項7に記載の積層体を構成要素として含むプリント配線板。
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CN202280021310.4A CN116997627A (zh) | 2021-03-16 | 2022-03-11 | 粘接剂组合物及含有其的粘接片材、层叠体和印刷线路板 |
JP2022529950A JP7120497B1 (ja) | 2021-03-16 | 2022-03-11 | 接着剤組成物、ならびにこれを含有する接着シート、積層体およびプリント配線板 |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2011011458A (ja) * | 2009-07-02 | 2011-01-20 | Toyobo Co Ltd | 硬化性接着剤層を有する銅張積層体 |
WO2011125778A1 (ja) * | 2010-04-01 | 2011-10-13 | 日立化成工業株式会社 | 接着剤組成物、接着シート及び半導体装置 |
JP2017047686A (ja) * | 2015-09-03 | 2017-03-09 | 株式会社プライマテック | フレキシブル銅張積層板の製造方法とフレキシブル銅張積層板 |
JP2017161837A (ja) * | 2016-03-11 | 2017-09-14 | 日立化成株式会社 | 感光性接着剤組成物、半導体装置の製造方法及び半導体装置 |
WO2020080391A1 (ja) * | 2018-10-17 | 2020-04-23 | ナミックス株式会社 | 樹脂組成物 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011011458A (ja) * | 2009-07-02 | 2011-01-20 | Toyobo Co Ltd | 硬化性接着剤層を有する銅張積層体 |
WO2011125778A1 (ja) * | 2010-04-01 | 2011-10-13 | 日立化成工業株式会社 | 接着剤組成物、接着シート及び半導体装置 |
JP2017047686A (ja) * | 2015-09-03 | 2017-03-09 | 株式会社プライマテック | フレキシブル銅張積層板の製造方法とフレキシブル銅張積層板 |
JP2017161837A (ja) * | 2016-03-11 | 2017-09-14 | 日立化成株式会社 | 感光性接着剤組成物、半導体装置の製造方法及び半導体装置 |
WO2020080391A1 (ja) * | 2018-10-17 | 2020-04-23 | ナミックス株式会社 | 樹脂組成物 |
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