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
• • 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
  • 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
  • C09J123/02—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 not modified by chemical after-treatment
  • C09J123/10—Homopolymers or copolymers of propene
• • 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
• • 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
  • C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
  • C09J125/02—Homopolymers or copolymers of hydrocarbons
  • C09J125/04—Homopolymers or copolymers of styrene
  • C09J125/08—Copolymers of styrene
• • 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
  • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
• • 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
  • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
• • 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
  • C09J7/35—Heat-activated

Definitions

• the present invention relates to an adhesive composition and a laminate with an adhesive layer.
• Flexible printed circuits are flexible printed circuit boards that enable three-dimensional and high-density mounting even in a limited space.
• FPC-related products are diversified and the demand for them is increasing.
• Such related products include flexible copper-clad laminates made by bonding copper foil to polyimide film, flexible printed wiring boards made by forming electronic circuits on flexible copper-clad laminates, and flexible printed wiring boards bonded to stiffeners.
• FFC flexible flat cables
• an adhesive is usually used to bond a polyimide film and a copper foil.
• coverlay film when manufacturing an FPC, a film called a "coverlay film" is usually used to protect the wiring part.
• This coverlay film comprises an insulating resin layer and an adhesive layer formed on the surface thereof, and a polyimide resin composition is widely used for forming the insulating resin layer. Then, for example, using a heat press or the like, the FPC is manufactured by attaching a coverlay film to the surface having the wiring portion via an adhesive layer.
• Patent Document 1 As an adhesive used in such FPC-related products, an epoxy-based adhesive composition containing a thermoplastic resin having high reactivity with epoxy resin has been proposed (for example, Patent Document 1).
• the adhesive composition is usually applied onto a desired substrate film to obtain a laminate with an adhesive layer, and this laminate is bonded to a target adherend via the adhesive layer. If misalignment occurs in this bonding, the laminate is peeled off from the adherend together with the adhesive layer, the position is adjusted again, and the laminate is adhered to the adherend via the adhesive layer. It is necessary to match. Therefore, the adhesive layer is required to have a re-peelability so that it can be easily peeled off even if it is stuck in a so-called B-stage state. In order to achieve this removability, it has been proposed to incorporate a filler into the adhesive composition. For example, Patent Document 2 describes that the anti-blocking property is enhanced by blending a specific amount of hydrophobic silica having an average particle size of 16 nm into an adhesive composition.
• the present inventors have investigated an epoxy-based adhesive composition that is removable in the B-stage state and capable of forming an adhesive layer exhibiting excellent adhesive strength after the curing reaction. .
• an epoxy-based adhesive composition that is removable in the B-stage state and capable of forming an adhesive layer exhibiting excellent adhesive strength after the curing reaction.
• the redispersibility of the filler in the adhesive layer formed using this adhesive composition is poor. If the adhesive composition is stored in a state in which the filler is blended, the filler will sediment over time. When used, it is necessary to redisperse and homogenize the precipitated filler. Constraints may arise in the improvement of uniformity. In other words, improvement of redispersibility is an important factor in improving work efficiency and adhesion reliability.
• the present invention has been made in view of the above circumstances, and an adhesive layer that exhibits excellent filler redispersibility, excellent removability when used for layer formation, and exhibits excellent adhesive strength after a curing reaction.
• An object of the present invention is to provide an epoxy-based adhesive composition capable of forming Moreover, this invention makes it a subject to provide the laminated body with an adhesive bond layer using this adhesive composition.
• [1] containing a graft-modified thermoplastic resin (A) with an ⁇ , ⁇ -unsaturated carboxylic acid compound, an epoxy resin (B), and a filler-like liquid crystal polymer (C),
• the content of the graft-modified thermoplastic resin (A) is 30% by mass or more in the total solid content
• thermoplastic resin constituting the graft-modified thermoplastic resin (A) is at least one of an ethylene-propylene copolymer, a propylene-butene copolymer, an ethylene-propylene-butene copolymer, and a styrene elastomer. , [1] or [2].
• a numerical range represented using “ ⁇ ” means a range including the numerical values described before and after “ ⁇ ” as lower and upper limits. For example, when “A to B" is described, the numerical range is "A or more and B or less”.
• the term "adhesive layer” refers to a state before curing, a state of B stage (that is, a semi-cured state in which a part has begun to be cured, and the adhesive composition is cured by heating or the like. further progresses), or a layer in a state after the curing reaction has progressed to sufficiently form a crosslinked structure.
• the term "cured product” means a product in a state after the adhesive composition has undergone a curing reaction to sufficiently form a crosslinked structure.
• the term "resin” is used in a broader sense than usual. That is, unless otherwise specified, the term “resin” in the present invention includes not only ordinary resins but also elastomers.
• the adhesive composition of the present invention is an epoxy-based adhesive composition, has excellent filler redispersibility, and the adhesive layer formed using this composition has excellent removability and excellent removability after the curing reaction. Exhibits adhesive strength.
• the adhesive layer has excellent removability and exhibits excellent adhesive strength after the curing reaction.
• the adhesive composition of the present invention contains a graft-modified thermoplastic resin (A) with an ⁇ , ⁇ -unsaturated carboxylic acid compound, an epoxy resin (B), and a filler-like liquid crystal polymer (C).
• the content of the graft-modified thermoplastic resin (A) is 30% by mass or more in the total solid content (components excluding the solvent) of the adhesive composition of the present invention.
• the content of the epoxy resin (B) is 1 to 20 parts by mass per 100 parts by mass of the graft-modified thermoplastic resin (A).
• the adhesive composition of the present invention contains one or more of the graft-modified thermoplastic resins (A).
• the graft-modified thermoplastic resin (A) contained in the adhesive composition of the present invention is a resin obtained by graft polymerization of a thermoplastic resin using an ⁇ , ⁇ -unsaturated carboxylic acid compound as a modifier.
• the graft modification (graft polymerization) method itself is known and can be carried out by a conventional method.
• the ⁇ , ⁇ -unsaturated carboxylic acid compound is graft-polymerized to the thermoplastic resin by a radical reaction using a radical initiator (radical generator).
• thermoplastic resin For example, a solution method in which a thermoplastic resin is heated and dissolved in a solvent such as toluene and an ⁇ , ⁇ -unsaturated carboxylic acid compound and a radical initiator are added.
• the desired graft-modified thermoplastic resin (A) can be obtained by a melting method of melt-kneading an ⁇ , ⁇ -unsaturated carboxylic acid compound and a radical initiator.
• the thermoplastic resin, ⁇ , ⁇ -unsaturated carboxylic acid compound and radical initiator may be added all at once or sequentially to the reaction system of the graft polymerization reaction. Modification aids for improving the grafting efficiency of the ⁇ , ⁇ -unsaturated carboxylic acid compound, stabilizers for adjusting the stability of the resin, and the like can also be used.
• thermoplastic resin constituting the graft-modified thermoplastic resin (A) (a thermoplastic resin before graft modification; in the present invention, simply referred to as a "thermoplastic resin” means a thermoplastic resin before graft modification.) It is not particularly limited as long as it is a plastic resin.
• thermoplastic resins include polyolefin resins, polystyrene resins, polyester resins, acrylonitrile-butadiene-styrene copolymers (ABS resins), acrylonitrile-styrene copolymers (AS resins), polyamide resins, styrene elastomers, and the like. , one or more of these can be used.
• At least one of polyolefin resin, polystyrene resin and styrene elastomer is preferable, and at least one of polyolefin resin and styrene elastomer is more preferable.
• Preferred polyolefin resins are homopolymers or copolymers of olefins having 2 to 20 carbon atoms, such as ethylene, propylene, butene, pentene, hexene, heptene, octene, and 4-methyl-1-pentene.
• polyolefin resins are particularly preferably homopolymers or copolymers of olefins having 2 to 6 carbon atoms.
• the content ratio of each structural unit in the polyolefin resin is not particularly limited.
• the polyolefin resin is preferably at least one of an ethylene-propylene copolymer, a propylene-butene copolymer and an ethylene-propylene-butene copolymer.
• the polyolefin resin preferably contains propylene units.
• the polyolefin resin may be a homopolymer consisting of propylene units or a copolymer containing propylene units.
• the content of propylene units in all structural units is preferably 50 mol % or more, more preferably 60 mol % or more.
• the content of propylene units in all structural units is preferably 50 to 98 mol %, more preferably 60 to 98 mol %.
• the styrene-based elastomer is a copolymer mainly composed of a block copolymer structure or a random copolymer structure of a conjugated diene compound and a styrene compound, or a hydrogenated product thereof.
• conjugated diene compounds include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like.
• styrene compounds include styrene, t-butylstyrene, ⁇ -methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N,N-diethyl-p-aminoethylstyrene, and vinyltoluene. , p-tertiary butylstyrene and the like.
• styrene-based elastomers include styrene-butadiene block copolymers, styrene-ethylene-propylene block copolymers, styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, and styrene-ethylenebutylene.
• -styrene block copolymers and styrene-ethylene propylene-styrene block copolymers, and one or more of these can be used.
• at least one of styrene-ethylenebutylene-styrene block copolymer and styrene-ethylenepropylene-styrene block copolymer is preferable.
• the molecular weight of the thermoplastic resin is not particularly limited.
• the weight average molecular weight (Mw) is preferably 30,000 to 250,000, more preferably 50,000 to 200,000.
• the weight average molecular weight can be determined by the method described in Examples below.
• ⁇ , ⁇ -unsaturated carboxylic acid compound is meant to include ⁇ , ⁇ -unsaturated carboxylic acids and compounds derived from ⁇ , ⁇ -unsaturated carboxylic acids.
• Specific examples of ⁇ , ⁇ -unsaturated carboxylic acid compounds include maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, aconitic acid, norbornene dicarboxylic acid, acid anhydrides, acid halides and amides thereof. , imides, esters and the like.
• the ⁇ , ⁇ -unsaturated carboxylic acid compound is preferably at least one of itaconic anhydride, maleic anhydride, aconitic anhydride and citraconic anhydride, from the viewpoint of achieving higher adhesiveness. At least one of is more preferred.
• one or more ⁇ , ⁇ -unsaturated carboxylic acid compounds can be used in the graft polymerization reaction system.
• modifiers in addition to the ⁇ , ⁇ -unsaturated carboxylic acid compound as modifiers.
• Other modifiers include, for example, (meth)acrylic acid ester compounds, (meth)acrylic acid compounds, aromatic vinyl compounds, cycloalkyl vinyl ether compounds, and the like. These other compounds may be used alone or in combination of two or more.
• Examples of the (meth)acrylic acid ester compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, and (meth)acryl hexyl acid, heptyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylic acid Cyclohexyl, benzyl (meth)acrylate, hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, isocyanate-containing (meth)acrylic acid, and the like.
• aromatic vinyl compounds examples include styrene, o-methylstyrene, p-methylstyrene, ⁇ -methylstyrene and the like. These compounds may be used alone or in combination of two or more.
• a modifier other than an ⁇ , ⁇ -unsaturated carboxylic acid compound is used in combination, among the above, octyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate and stearyl (meth)acrylate It is preferable to use at least one of
• the ratio of the ⁇ , ⁇ -unsaturated carboxylic acid compound-derived structural portion (referred to as “graft portion I”) in the graft-modified thermoplastic resin (A) is 0.1 to It is preferably 20% by mass, more preferably 0.2 to 18% by mass. Moreover, the ratio may be 0.2 to 15% by mass, or may be 0.3 to 10% by mass.
• the proportion of the above-mentioned graft portion I in the graft-modified thermoplastic resin (A) can be determined by alkaline titration. Also, when the ⁇ , ⁇ -unsaturated carboxylic acid compound does not have an acid group (for example, in the case of an imide, etc.), it can be determined by, for example, Fourier transform infrared spectroscopy.
• the graft-modified thermoplastic resin (A) contains a structural portion derived from a (meth)acrylic acid ester compound (referred to as “graft portion II”) in the graft portion, the graft portion occupied in the graft-modified thermoplastic resin (A)
• the proportion of II is preferably 30% by mass or less, more preferably 25% by mass or less.
• the ratio may be 15% by mass or less, 10% by mass or less, or 5% by mass or less.
• the lower limit of the ratio is not particularly limited, and for example, it is preferably 0.1% by mass or more, more preferably 0.3 parts by mass or more.
• the solubility in the solvent can be further increased, and when the adhesive composition of the present invention contains a resin or elastomer other than the graft-modified thermoplastic resin (A)
• the compatibility with these can be further improved, and the adhesiveness to the adherend can also be further improved.
• the proportion of the graft portion II in the graft-modified thermoplastic resin (A) can be determined, for example, by Fourier transform infrared spectroscopy.
• the radical initiator used in the graft polymerization reaction for obtaining the graft-modified thermoplastic resin (A) is not particularly limited, and for example, an organic peroxide can be used.
• Organic peroxides such as benzoyl peroxide, dicumyl peroxide, lauroyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, cumene Hydroperoxide etc. are mentioned.
• One or more radical initiators can be used for the graft polymerization reaction.
• modification aid examples include divinylbenzene, hexadiene, and dicyclopentadiene.
• Stabilizers include hydroquinone, benzoquinone, nitrosophenylhydroxy compounds and the like, and one or more of these can be used.
• the weight average molecular weight (Mw) of the graft-modified thermoplastic resin (A) is not particularly limited, it is preferably 30,000 to 250,000, more preferably 50,000 to 200,000. By controlling the molecular weight within such a range, the solubility in the solvent can be sufficiently ensured, the initial adhesiveness to the adherend can be further enhanced, and sufficient solvent resistance can be exhibited after the curing reaction. be able to.
• the weight average molecular weight can be determined by the method described in Examples below.
• the acid value of the graft-modified thermoplastic resin (A) is preferably 0.1-50 mgKOH/g, more preferably 0.5-40 mgKOH/g, even more preferably 1.0-30 mgKOH/g. By controlling the acid value within such a range, the adhesive composition exhibits sufficient curing reactivity.
• the acid value can be determined by the method described in the section [Examples] below.
• the content of the graft-modified thermoplastic resin (A) is 30% by mass or more, preferably 30 to 97% by mass, more preferably 30 to 95% by mass, and 40 to 90% by mass, based on the total solid content of the adhesive composition. % by mass is more preferred, and 50 to 88% by mass is particularly preferred.
• the adhesive composition of the present invention contains one or more of the above epoxy resins (B).
• the epoxy resin (B) is a component that reacts with a reactive group such as a carboxyl group in the graft-modified thermoplastic resin (A) to enhance the adhesiveness to the adherend and further enhance the heat resistance of the adhesive cured product. is.
• the epoxy resin (B) is usually a polyfunctional epoxy having two or more (preferably 2 to 6, more preferably 2 to 4) epoxy groups in one molecule.
• Resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, or hydrogenated products thereof; diglycidyl orthophthalate, diglycidyl isophthalate, diglycidyl terephthalate, p-hydroxybenzoin.
• Glycidyl ester epoxy resins such as acid glycidyl ester, diglycidyl tetrahydrophthalate, diglycidyl succinate, diglycidyl adipate, diglycidyl sebacate, and triglycidyl trimellitate; ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, tetraphenylglycidyl ether ethane, tri Glycidyl ether-based epoxy resins (glycidyl ether compounds) such as phenylglycidyl ether ethane, polyglycidyl ether of sorb
• examples of the epoxy resin (B) include brominated bisphenol A type epoxy resin, phosphorus-containing epoxy resin, dicyclopentadiene skeleton-containing epoxy resin, naphthalene skeleton-containing epoxy resin, anthracene-type epoxy resin, tertiary-butylcatechol-type epoxy resin, A triphenylmethane type epoxy resin, a tetraphenylethane type epoxy resin, a biphenyl type epoxy resin, a bisphenol S type epoxy resin, or the like can be used.
• the epoxy resin (B) is preferably a polyfunctional epoxy resin having an alicyclic skeleton, more preferably a polyfunctional epoxy resin having a dicyclopentadiene skeleton.
• the content of the epoxy resin (B) is 1 to 20 parts by mass, preferably 2 to 18 parts by mass, based on 100 parts by mass of the graft-modified thermoplastic resin (A). 17 parts by mass is more preferable, and 3 to 15 parts by mass is also preferable.
• the adhesive composition of the present invention contains one or more of the filler-like liquid crystal polymer (C).
• the filler-like liquid crystal polymer (C) has excellent redispersibility even after sedimentation during storage of the adhesive composition, and effectively enhances the removability of the adhesive layer formed from the adhesive composition. Adequate adhesion can also be achieved after the curing reaction. That is, the working efficiency and adhesion reliability are improved as compared with the case where the filler-like liquid crystal polymer (C) is not contained.
• the liquid crystal polymer itself is known, and any ordinary liquid crystal polymer processed into a filler (fine particles) can be used as the filler-like liquid crystal polymer (C) in the present invention without any particular limitation.
• a filler-like liquid crystal polymer that can be used in the present invention, for example, a filler composed of a liquid crystal polymer having a structural unit derived from p-hydroxybenzoic acid and a structural unit derived from 6-hydroxy-2-naphthoic acid can be used.
• the liquid crystal polymer preferably further has at least one structural unit derived from an aromatic diol compound and a structural unit derived from an aromatic dicarboxylic acid. It is more preferable to have both structural units that
• the liquid crystal polymer preferably contains 10 to 40 mol%, more preferably 15 to 35 mol%, structural units derived from p-hydroxybenzoic acid, and structural units derived from 6-hydroxy-2-naphthoic acid.
• liquid crystal polymer further contains an aromatic diol compound
• the content thereof is preferably 1 to 20 mol %, more preferably 1 to 15 mol %.
• the liquid crystal polymer further contains an aromatic dicarboxylic acid the content is preferably 1 to 20 mol %, more preferably 1 to 15 mol %.
• the content of the filler-like liquid crystal polymer (C) is 100 mass of the graft-modified thermoplastic resin (A) from the viewpoint of improving the redispersibility and removability of the adhesive composition. It is preferably 1 to 250 parts by mass, more preferably 1 to 200 parts by mass, even more preferably 5 to 100 parts by mass, even more preferably 5 to 80 parts by mass.
• the dielectric constant and dielectric loss tangent of the filler-like liquid crystal polymer (C) can be measured by the split-post dielectric resonator method (SPDR method) using, for example, Agilent Network Analyzer N5247A. Specifically, the filler-like liquid crystal polymer (C) is heated and melted at a temperature between the melting point and the melting point +30° C. and is injection molded to prepare a flat test piece of 30 mm ⁇ 30 mm ⁇ 0.4 mm. Next, the dielectric loss tangent and dielectric constant of this test piece are measured at a frequency of 10 GHz by the split-post dielectric resonator method (SPDR method) using a network analyzer N5247A manufactured by Keysight Technologies.
• SPDR method split-post dielectric resonator method
• the average particle size (d50) of the filler-like liquid crystal polymer (C) is preferably 0.1 to 50 ⁇ m, more preferably 0.1 to 20 ⁇ m, from the viewpoint of further improving the redispersibility and removability of the adhesive composition. More preferably, 1 to 10 ⁇ m is even more preferable.
• the average particle diameter (d50) is the so-called median diameter, and the particle size distribution is measured by a laser diffraction/scattering method, and the particle size when the cumulative distribution is 50% when the total volume of the particles is 100%. means
• the water absorption rate of the filler-like liquid crystal polymer (C) is preferably 0.1% or less, more preferably 0.05% or less, still more preferably 0.03% or less, and particularly preferably 0.02% or less.
• the lower limit of this water absorption is not particularly limited, and is usually 0.002% or more, preferably 0.005% or more. Therefore, the water absorption rate of the filler-like liquid crystal polymer (C) is preferably 0.002 to 0.05%, more preferably 0.005 to 0.03%, and also preferably 0.01 to 0.02%. .
• the melting point of the filler-like liquid crystal polymer (C) is preferably 280 to 350°C, more preferably 300 to 350°C, even more preferably 305 to 335°C. By setting the melting point of the filler-like liquid crystal polymer (C) within the above numerical range, it is possible to impart sufficient heat resistance to the cured product.
• the melting point of the filler-like liquid crystal polymer (C) can be determined according to the test methods of ISO11357 and ASTM D3418. Specifically, the temperature is raised from room temperature to 360 to 380° C. at a temperature elevation rate of 10° C./min to completely melt the polymer, then the temperature is lowered to 30° C. at a rate of 10° C./min, and then further 10° C./min. The apex of the endothermic peak obtained when the temperature is increased to 380°C at a rate of , is defined as the melting point.
• the glass transition temperature of the filler-like liquid crystal polymer (C) is preferably 120 to 150°C. By setting the glass transition temperature of the filler-like liquid crystal polymer (C) within the above numerical range, it is possible to impart sufficient heat resistance to the cured product.
• the glass transition temperature of the filler-like liquid crystalline polymer (C) is measured in accordance with JIS K7244 using a dynamic viscoelasticity measuring device (Hitachi High-Tech Science Co., Ltd., trade name: DMA7100). It can be obtained from the peak top temperature of tan ⁇ obtained by a physical viscoelasticity measurement.
• the adhesive layer formed using the adhesive composition of the present invention has an adhesive strength of 0.7 N/mm or more to the adherend after being adhered to the adherend and subjected to a curing reaction.
• 1.0 N/mm or more is more preferable.
• the upper limit of the adhesive strength is not particularly limited, and is usually 2.0 N/mm or less.
• the adhesive strength can be measured by the following method.
• the curing reaction condition of the adhesive layer for measuring the adhesive strength is 180° C. for 30 minutes. Further, the curing reaction conditions of the adhesive layer for determining each characteristic or physical property other than adhesive strength described in this specification are also set at 180° C. for 30 minutes.
• a release PET film having a thickness of 38 ⁇ m was prepared, and the liquid adhesive composition shown in Table 1 was roll-coated on one surface thereof. Then, this adhesive layer-attached film was placed in an oven and dried at 90° C. for 3 minutes to form a B-stage adhesive layer (thickness: 25 ⁇ m). Next, the adhesive layer surface of the film with an adhesive layer was superimposed on the polyimide surface of a flexible substrate material (manufactured by Panasonic Corporation, product name "FELIOS R-F770”), and the temperature was 120 ° C., the pressure was 0.4 MPa, and the speed was 0. Lamination was carried out under the condition of 0.5 m/min.
• the release PET was peeled off, the adhesive layer and rolled copper foil (thickness: 35 ⁇ m) were overlaid, and lamination was performed under the conditions of a temperature of 120° C., a pressure of 0.4 MPa, and a speed of 0.5 m/min.
• the laminated body flexible substrate material/adhesive layer/copper foil
• Dielectric constant ( ⁇ ) and dielectric loss tangent (tan ⁇ ) are preferably less than 3.0 and less than 0.01, more preferably less than 2.8 and less than 0.01, respectively.
• the dielectric loss tangent is lower than the dielectric loss tangent obtained by measuring at a frequency of 10 GHz a cured product of the adhesive composition having a composition excluding the filler-like liquid crystal polymer (C) from the adhesive composition. is preferred.
• the reduction rate of the dielectric loss tangent (100 ⁇ ⁇ [dielectric loss tangent when the filler-like liquid crystal polymer (C) is not present]-[dielectric loss tangent when the filler-like liquid crystal polymer (C) is present] ⁇ /[filler-like liquid crystal polymer (C) Dielectric loss tangent when nothing]) can be, for example, 5% or more, and the reduction rate is preferably 6 to 100%.
• the dielectric constant ( ⁇ ) and dielectric loss tangent (tan ⁇ ) of the cured adhesive composition can be measured, for example, by the following methods.
• a release polyethylene terephthalate film having a thickness of 38 ⁇ m is prepared, and an adhesive composition is roll-coated on one surface thereof. Then, the coated film is left in an oven and dried at 90° C. for 3 minutes to form a coating (adhesive layer) having a thickness of 50 ⁇ m to obtain a bonding sheet. Next, this bonding sheet is placed in an oven and heat-treated at 180° C. for 30 minutes for curing. After that, the release film is peeled off to prepare a test piece (60 mm x 60 mm x 0.2 mm thickness).
• dielectric constant ( ⁇ ) and dielectric loss tangent (tan ⁇ ) are measured using a network analyzer E5071C (manufactured by Agilent) by the split-post dielectric resonator method (SPDR method) under conditions of a temperature of 23° C. and a frequency of 10 GHz.
• SPDR method split-post dielectric resonator method
• the adhesive composition contains, in addition to the graft-modified thermoplastic resin (A), the epoxy resin (B) and the filler-like liquid crystal polymer (C), a thermoplastic resin different from the graft-modified thermoplastic resin (A) (other thermoplastic resins), tackifiers, flame retardants, curing agents, curing accelerators, coupling agents, thermal anti-aging agents, leveling agents, antifoaming agents, fillers different from the filler-like liquid crystal polymer (C), pigments, and other components such as a solvent can be contained as appropriate within a range that does not impair the effects of the present invention.
• thermoplastic resins examples include phenoxy resins, polyamide resins, polyester resins, polycarbonate resins, polyphenylene oxide resins, polyurethane resins, polyacetal resins, polyethylene resins, polypropylene resins, and polyvinyl resins. These thermoplastic resins may be used alone or in combination of two or more.
• tackifiers examples include coumarone-indene resin, terpene resin, terpene-phenol resin, rosin resin, pt-butylphenol-acetylene resin, phenol-formaldehyde resin, xylene-formaldehyde resin, petroleum-based hydrocarbon resin, Examples include hydrogenated hydrocarbon resins and turpentine resins. These tackifiers may be used alone or in combination of two or more.
• the above flame retardant may be either an organic flame retardant or an inorganic flame retardant.
• organic flame retardants include melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, amide ammonium phosphate, amide ammonium polyphosphate, carbamate phosphate, carbamate polyphosphate, aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, zinc bisdiphenylphosphinate, titanyl bisdiethylphosphinate, titanium tetrakisdiethylphosphinate, Phosphorus flame retardants such as titanyl bismethylethylphosphinate, titanium tetrakismethylethylphosphinate, titanyl bisdiphenylpho
• the curing agent examples include amine-based curing agents (amine compounds) and acid anhydride-based curing agents, but are not limited to these.
• amine curing agents include melamine resins such as methylated melamine resin, butylated melamine resin and benzoguanamine resin, dicyandiamide, 4,4′-diphenyldiaminosulfone and the like.
• Acid anhydrides include aromatic acid anhydrides and aliphatic acid anhydrides. These curing agents may be used alone or in combination of two or more.
• the content of the curing agent is preferably 1 to 100 parts by mass, more preferably 5 to 70 parts by mass, based on 100 parts by mass of the epoxy resin (B).
• the curing accelerator is used for the purpose of promoting the reaction between the graft-modified thermoplastic resin (A) and the epoxy resin (B).
• a tertiary amine salt curing accelerator tertiary amine salt compound
• an imidazole curing accelerator imidazole compound
• Tertiary amine curing accelerators include benzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, tetramethylguanidine, triethanolamine, N,N' -dimethylpiperazine, triethylenediamine, 1,8-diazabicyclo[5.4.0]undecene and the like.
• Tertiary amine salt curing accelerators include 1,8-diazabicyclo[5.4.0]undecene formate, octylate, p-toluenesulfonate, o-phthalate, phenol salt or Phenol novolak resin salts, 1,5-diazabicyclo[4.3.0]nonene formate salts, octylate salts, p-toluenesulfonate salts, o-phthalate salts, phenol salts or phenol novolak resin salts, etc. mentioned.
• imidazole curing accelerators examples include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-methyl-4-ethylimidazole, 2-phenylimidazole, 2-phenyl- 4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2,4-diamino-6-[2′-methylimidazolyl-(1′)]ethyl-s-triazine, 2 ,4-diamino-6-[2′-undecylimidazolyl-(1′)]ethyl-s-triazine, 2,4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′) ] Ethyl-s-triazine, 2,4-diamino-6-[2′-methyl
• the content of the curing accelerator may be appropriately set according to the type of curing accelerator.
• the content of the curing accelerator is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin (B).
• the coupling agent examples include vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, N -2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatopropyltriethoxysilane , silane coupling agents such as imidazole silane; titanate coupling agents; aluminate coupling agents; and zirconium coupling agents. These may be used alone or in combination of two or more.
• thermal anti-aging agents examples include 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionate, Tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenol, triethylene Phenolic antioxidants (phenol compounds) such as glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate; dilauryl-3,3'-thiodipropionate, dimyristyl -Sulfur-based antioxidants (sulfur-containing compounds) such as 3,3'-dithiopropionate; agents (phosphorus-containing compounds), etc. These may be used alone or in combination
• filler examples include powders made of titanium oxide, aluminum oxide, zinc oxide, carbon black, silica, talc, copper, silver, and the like. These may be used alone or in combination of two or more.
• the adhesive composition can be produced by mixing the graft-modified thermoplastic resin (A), the epoxy resin (B), the filler-like liquid crystal polymer (C), and, if necessary, other components.
• the mixing method is not particularly limited as long as the adhesive composition is in a desired uniform state.
• a solvent is also usually used.
• solvents include alcohols such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, isobutyl alcohol, n-butyl alcohol, benzyl alcohol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diacetone alcohol.
• solvents may be used alone or in combination of two or more. By including a solvent in the adhesive composition, coating on the base film and formation of the adhesive layer can be performed smoothly.
• the solid content concentration of the adhesive composition is preferably 3 to 80% by mass, more preferably 10 to 50% by mass, from the viewpoint of workability including formation of the adhesive layer. is in the range of
• the laminate with an adhesive layer of the present invention has an adhesive layer formed from the adhesive composition and a base film in contact with at least one surface of the adhesive layer.
• a coverlay film is one aspect of the laminate with an adhesive layer according to the present invention.
• a coverlay film has an adhesive layer formed on at least one surface of a base film.
• Examples of base films when the laminate with an adhesive layer is a coverlay film include polyimide films, polyetheretherketone films, polyphenylene sulfide films, aramid films, polyethylene naphthalate films, and liquid crystal polymer films.
• polyimide film, polyethylene naphthalate film, and liquid crystal polymer film are preferred from the viewpoint of adhesiveness and electrical properties.
• polyimide films include "Kapton (registered trademark)” manufactured by Toray DuPont Co., Ltd., “Xenomax (registered trademark)” manufactured by Toyobo Co., Ltd., Ube Industries ( “Upilex (registered trademark)-S” manufactured by Co., Ltd., “Apical (registered trademark)” manufactured by Kaneka Corporation, etc. can be used.
• polyethylene naphthalate film “Teonex (registered trademark)” manufactured by Teijin DuPont Films Limited can be used.
• liquid crystal polymer film "Vecstar (registered trademark)” manufactured by Kuraray Co., Ltd., "Biac (registered trademark)” manufactured by Primatec Co., Ltd., and the like can be used.
• the base film can also be used by filming the corresponding resin to a desired thickness.
• the adhesive composition (resin varnish) containing a solvent is applied to the surface of a base film such as a polyimide film to form a coating film, and then this coating film is formed.
• a coverlay film having an adhesive layer formed on the base film can be produced.
• the drying temperature for removing the solvent is preferably 40 to 250°C, more preferably 70 to 170°C. Drying is performed by passing the laminate coated with the adhesive composition through a furnace in which hot air drying, far-infrared heating, high-frequency induction heating, or the like is performed. If necessary, a release film may be laminated on the surface of the adhesive layer for storage or the like.
• Usual release films such as polyethylene terephthalate film, polyethylene film, polypropylene film, silicone release treated paper, polyolefin resin-coated paper, polymethylpentene (TPX) film and fluororesin film are used as the release film.
• the bonding sheet also has the adhesive layer formed on the surface of the substrate film, and the release film is used as the substrate film. Also, the bonding sheet may be in a mode in which an adhesive layer is provided between two release films. When using the bonding sheet, the release film is peeled off before use. A release film similar to that described above can be used.
• Such releasable films are also commercially available, Toray Film Processing Co., Ltd. "Lumirror (registered trademark)", Toyobo Co., Ltd. “Toyobo Ester (registered trademark) Film”, Asahi Glass Co., Ltd. “ Flux (registered trademark)”, Mitsui Chemicals Tohcello Co., Ltd. “Opulant (registered trademark)”, and the like can be used.
• the surface of a release film is coated with the adhesive composition (resin varnish) containing a solvent, and dried in the same manner as in the case of the coverlay film. be.
• the thickness of the base film is preferably 5 to 100 ⁇ m, more preferably 5 to 50 ⁇ m, even more preferably 5 to 30 ⁇ m, in order to make the laminate with the adhesive layer thinner.
• the adhesive layer preferably has a thickness of 5 to 100 ⁇ m, more preferably 10 to 70 ⁇ m, even more preferably 10 to 50 ⁇ m.
• the thicknesses of the base film and the adhesive layer are selected depending on the application, but the base film tends to be thinner in order to improve the electrical properties. In general, when the thickness of the base film is thin and the thickness of the adhesive layer is thick, the laminate with the adhesive layer is likely to warp and the workability is reduced, but the laminate with the adhesive layer of the present invention Even when the thickness of the base film is thin and the thickness of the adhesive layer is thick, the laminate hardly warps.
• the ratio (D1/D2) of the thickness (D1) of the adhesive layer and the thickness (D2) of the base film is preferably 1 to 10, It is more preferably 1 to 5 or less. Furthermore, the thickness of the adhesive layer is preferably thicker than the thickness of the base film.
• a release PET film having a thickness of 38 ⁇ m was prepared, and the liquid adhesive composition shown in Table 1 was roll-coated on one surface thereof. Then, this adhesive layer-attached film was placed in an oven and dried at 90° C. for 3 minutes to form a B-stage adhesive layer (thickness: 25 ⁇ m). Next, the adhesive layer surface of the adhesive layer-attached film was placed on the polyimide surface of a flexible substrate material (manufactured by Panasonic Corporation, product name “FELIOS R-F770”) and heated at 40° C. in an oven. If the film with the adhesive layer can be peeled off as it is even after heating for 60 seconds, " ⁇ " is not applicable. When the film with the adhesive layer adhered to the flexible substrate material when heated for 30 seconds and could not be peeled off as it was, it was evaluated as "x".
• ⁇ Peeling adhesive strength> A release PET film having a thickness of 38 ⁇ m was prepared, and the liquid adhesive composition shown in Table 1 was roll-coated on one surface thereof. Then, this adhesive layer-attached film was placed in an oven and dried at 90° C. for 3 minutes to form a B-stage adhesive layer (thickness: 25 ⁇ m). Next, the adhesive layer surface of the film with an adhesive layer was superimposed on the polyimide surface of a flexible substrate material (manufactured by Panasonic Corporation, product name "FELIOS R-F770”), and the temperature was 120 ° C., the pressure was 0.4 MPa, and the speed was 0. Lamination was carried out under the condition of 0.5 m/min.
• the release PET was peeled off, the adhesive layer and rolled copper foil (thickness: 35 ⁇ m) were overlaid, and lamination was performed under the conditions of a temperature of 120° C., a pressure of 0.4 MPa, and a speed of 0.5 m/min.
• the laminated body flexible substrate material/adhesive layer/copper foil
• the laminated body was heat-pressed for 30 minutes under conditions of a temperature of 180° C. and a pressure of 3 MPa. After thermocompression bonding, the laminate was cut into a size of 10 mm ⁇ 100 mm to obtain an adhesion test piece.
• a filler-like liquid crystal polymer was heat-melted and injection-molded to prepare a flat test piece of a predetermined size. This test piece is immersed in water at room temperature (23° C.) for 24 hours using the test method of ASTM D570, the weight of the test piece before immersion and the weight of the test piece after immersion for 24 hours are measured, and the water absorption rate is calculated. bottom.
• This resin was finely cut and processed into pellets. Next, this pellet-shaped resin was mixed with acetone three times the mass of the resin, and stirred for 1 hour while the temperature was maintained at 50° C. to wash the resin. After recovering the resin, the resin was washed in the same manner to remove free maleic anhydride. The washed resin was dried under reduced pressure in a vacuum dryer to obtain a graft-modified polyolefin resin a1.
• the graft-modified polyolefin resin a1 had a weight average molecular weight of 100,000 and an acid value of 30 mgKOH/g.
• (Graft-modified polyolefin resin a2) 100 parts by mass of a propylene-ethylene random copolymer composed of 97 mol% of propylene units and 3 mol% of ethylene units, produced using a metallocene catalyst as a polymerization catalyst, 0.5 parts by mass of maleic anhydride, and 0.3 parts by mass of lauryl methacrylate and 0.4 parts by mass of di-t-butyl peroxide were kneaded and reacted using a twin-screw extruder in which the maximum temperature of the cylinder section was set to 170°C.
• the graft-modified polyolefin resin a2 had a weight average molecular weight of 180,000 and an acid value of 4 mgKOH/g.
• SEBS styrene-ethylenebutylene-styrene block copolymer
• Tiftec M1913 maleic acid-modified styrene-ethylenebutylene-styrene block copolymer
• This copolymer has an acid value of 10 mgKOH/g, a styrene/ethylene butylene ratio (weight ratio) of 30/70, and a weight average molecular weight of 150,000.
• ADEKA's product name "ADEKA STAB AO-80" was used.
• an adhesive composition of the present invention As shown in the above table, by blending a liquid crystal polymer as a filler to form an adhesive composition of the present invention, it is excellent in redispersibility, and when used for layer formation, it is excellent in removability, and after the curing reaction It can be seen that an adhesive layer exhibiting excellent adhesive strength can be formed.
• the reduction rate of the dielectric loss tangent (tan ⁇ ) obtained by measuring the cured product of the adhesive composition at a frequency of 10 GHz was within the range of 7 to 52%.

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• General Chemical & Material Sciences (AREA)
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• 2022
  • 2022-12-27 JP JP2023571062A patent/JPWO2023127890A1/ja active Pending
  • 2022-12-27 WO PCT/JP2022/048252 patent/WO2023127890A1/ja not_active Ceased
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