JP6074698B1 - Thermosetting adhesive sheet and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To thermally cure excellent in dimensional stability during curing, excellent in adhesion after curing, heat resistance (especially after humidification), flexibility, electrical insulation, low dielectric constant and low dielectric loss tangent. It is providing an adhesive sheet. A resin (A1) containing a total of 0.01 to 9 (mmol / 1 g) of a reactive functional group and a functional group having a hetero atom other than halogen, a specific amount of an organometallic compound (B), and an epoxy group The thermosetting adhesive sheet formed from the thermosetting composition containing a containing compound (C). [Selection figure] None

Description

  The present invention relates to a thermosetting adhesive sheet containing a low polarity resin, an organometallic compound, and an epoxy group-containing compound. The thermosetting adhesive sheet of the present invention is suitably used for protecting the circuit surface of a printed wiring board.

In recent years, there has been a remarkable development in the electronics field, and in particular, electronic devices have become smaller, lighter, and more dense, and electronic materials such as printed wiring boards are increasingly required to be thinner, multilayered, and more precise. It has come to be. In the case of a thick rigid substrate typified by conventional glass epoxy or the like, high flexibility, adhesiveness, high electrical insulation, low dielectric constant, and low dielectric loss tangent associated with a narrow space have not been required.
However, recent printed wiring boards and other electronic materials have not only heat resistance and workability, but also high flexibility, adhesion, high electrical insulation due to narrow space, low dielectric constant, and low dielectric loss tangent. It has been demanded.
Specific examples of adhesives and coating agents used around such electronic materials include the following (1) to (6).

(1) Interlayer adhesive: Used to bond circuit boards together, and is in direct contact with copper or silver circuit. It is used between the layers of a multilayer substrate, and there are liquid and sheet-like ones.

(2) Coverlay film adhesive: used to bond a coverlay film (such as a polyimide film used for the purpose of protecting the outermost surface of a circuit) and an underlying circuit board; In many cases, the adhesive layer is integrated.

(3) Adhesive for copper-clad film (CCL): used to bond polyimide film and copper foil together. Processing such as etching is performed when the copper circuit is formed.

(4) Coverlay: used for the purpose of protecting the outermost surface of the circuit, and is formed by printing a printing ink on the circuit or pasting an adhesive sheet and then curing. Some are photosensitive and thermosetting.

(5) Adhesive for reinforcing plate: For the purpose of complementing the mechanical strength of the wiring board, it is used to fix a part of the wiring board to a reinforcing plate made of metal, glass epoxy, polyimide or the like.

(6) Adhesive for electromagnetic wave shield: Affixed to a flexible printed wiring board for the purpose of shielding electromagnetic noise generated from an electronic circuit.

  As these forms, there are liquid forms (ink-printed for printing), sheet-like forms (film-formed in advance), and the like is appropriately selected according to the application.

Various studies have been made in order to meet such high demands on electronic material peripheral members, but no material that sufficiently satisfies all the characteristics has been obtained.
For example, Patent Document 1 discloses an epoxy resin composition mainly composed of a urethane-modified epoxy resin and an epoxy resin curing agent.

  Patent Documents 2 and 3 disclose curable compositions containing a cyanate ester resin and a monovalent phenol compound.

  Patent Document 4 discloses a curable composition comprising a phenol resin obtained by reacting a phenol, a compound having a triazine ring, and a hydroxyl group-substituted aromatic aldehyde and an epoxy resin.

  Patent Document 5 discloses a curable composition for radical polymerization of polyetheresteramide.

  Patent Document 6 discloses an example in which a liquid crystal polymer is used as a method of forming a laminate circuit using a thermoplastic resin having no cross-linked structure.

  Patent Document 7 discloses a curable composition mainly composed of an oxetane structure and a thermal cation curing catalyst.

  Patent Document 8 discloses a tape with an adhesive for TAB having a flexible organic insulating film, an adhesive layer and a protective film, and the adhesive layer comprises a polyamide resin, an organometallic compound, and an epoxy resin. A tape with an adhesive for TAB is disclosed. Specifically, when a copper foil and a polyimide film are bonded together with an adhesive sheet containing a polyamide resin, an organometallic compound, and a bifunctional epoxy resin, the peel strength (adhesive strength) after plating treatment is It is described that it is excellent and has excellent insulation properties at 150 ° C.

  Patent Document 9 discloses an adhesive composition containing a saturated hydrocarbon polymer, a cyclic aliphatic epoxy resin, and an aluminum chelate compound. It is described that the adhesive composition is liquid in an uncured state and is used for various molding processes and sealing of various electric / electronic components.

  Patent Document 10 discloses a synthetic resin lining adhesive composition for lining (adhering) a chlorine-containing resin to a metal tube. When lining (adhering) a chlorine-containing resin to a metal tube, the adhesive composition for lining is required not to accelerate deterioration (dechlorination reaction and dehydrochlorination reaction) of the chlorine-containing resin accompanying heating. The adhesive composition for synthetic resin lining described in Patent Document 10 comprises a composition A containing a crystalline saturated polyester resin and titanium chelate, and an epoxy group-containing compound B.

  In Patent Document 11, a hydroxyl group-containing polymer compound (A) having a polyester unit or a polyether unit, an epoxy compound (B), an aluminum chelate compound, a titanium chelate compound, and the like that can be used as a resin component of a conductive adhesive. A resin composition containing the chelate compound (D) is disclosed.

  Patent Document 12 discloses a thermally polymerizable and radiation polymerizable adhesive sheet containing a polyimide resin (A), an epoxy resin (B), and an epoxy resin curing agent (C). Furthermore, Patent Document 12 suggests the use of a titanium-based coupling agent and an aluminum-based coupling agent as a means for improving interfacial bonding between different materials.

  Patent Document 13 discloses an adhesive composition containing an acrylic polymer (A), an epoxy thermosetting resin (B), and an organic chelating agent (D). Furthermore, an adhesive sheet is disclosed in which a peelable adhesive layer is formed on the base material from the adhesive composition.

  Patent Document 14 discloses an optical pressure-sensitive adhesive that further contains an acrylic polymer, an isocyanate curing agent, and an epoxy or metal chelate curing agent.

  Patent Document 15 discloses a resin composition containing a polyester resin, a chelate compound (C), and a specific epoxy resin (D). For the body and lid of beverage cans, food cans, etc., a film such as a PET film attached to a metal plate such as aluminum, tin-plated steel plate or tin-free steel is used. Patent Document 15 discloses that the resin composition can be used as an adhesive for attaching the film to the metal plate.

  Patent Documents 16 and 17 disclose an adhesive film containing an epoxy resin, a curing agent, and a polymer compound that is incompatible with the epoxy resin. For the purpose of improving the interfacial bond between different materials, a titanium-based or aluminum-based film is disclosed. The use of coupling agents is suggested.

JP 2011-105916 A JP 2001-214053 A JP 2002-138199 A JP 2006-249178 A JP 2013-45755 A JP 2005-105165 A JP 2007-073330 A JP-A-9-64111 Japanese Patent Laid-Open No. 2000-230091 JP-A-6-313160 Japanese Patent Laid-Open No. 11-80695 JP 2003-41202 A International Publication 2011-125712 JP 2011-37927 A JP 2012-312222 A JP 2008-195943 A JP 2008-112005 A

Although the epoxy resin composition disclosed in Patent Document 1 exhibits adhesiveness derived from urethane and good circuit embedding properties, it has a problem of poor electrical insulation because it contains a large number of highly polar urethane bonds. It was.
Although the curable compositions disclosed in Patent Documents 2 and 3 exhibit good adhesiveness and heat resistance derived from high Tg, there is a problem that a molded product is fragile. Trimerization of cyanate groups forms a symmetric structure, so it exhibits relatively low dielectric properties, but has many polar groups, so the dielectric constant reaches around 3.5, which is the required level in the market. There was a problem that it was not.
Although the curable composition disclosed in Patent Document 4 exhibits high heat resistance and flame retardancy derived from a high aromatic content, there is a problem that flexibility is inferior due to high intermolecular interaction.
Although the curable composition disclosed in Patent Document 5 exhibits high adhesiveness and insulating properties derived from amides and ethers, it has a problem of poor heat resistance after humidification because it has a structure that easily absorbs moisture.
The laminate circuit forming method disclosed in Patent Document 6 can exhibit high adhesiveness by melting a resin at a high temperature, but since the melting temperature is as high as 280 ° C. or higher, it has an adverse effect on other inferior heat resistant members. In addition, there was a problem that it was necessary to introduce equipment corresponding to high temperature melting.
Although the curable composition disclosed in Patent Document 7 exhibits low dielectric constant by suppressing the formation of hydroxyl groups and processing stability derived from low curing shrinkage, which is an advantage of cationic polymerization, it does not cause metal corrosion due to acid generation. There were concerns and problems in stability such as inhibition of curing by moisture. In addition, although the dielectric constant is relatively low at around 3.1, there is a problem that it does not reach the required level in the market.

The tape with an adhesive disclosed in Patent Document 8 has insufficient heat resistance after curing because the epoxy resin used is bifunctional.
Since the adhesive composition disclosed in Patent Document 9 is liquid in an uncured state, it cannot be formed into a sheet.
The adhesive composition disclosed in Patent Document 10 is for attaching a chlorine-containing resin to a metal tube, and Patent Document 10 does not describe application to a printed wiring board.
There is no description that a sheet is obtained using the conductive adhesive disclosed in Patent Document 11.
Patent Document 12 suggests the use of a titanium coupling agent and an aluminum coupling agent. However, its use is only for the purpose of improving the interfacial bond between different materials.
Patent Document 13 discloses the use of an organic chelating agent, but does not describe the use of an organometallic compound.
The pressure-sensitive adhesive sheet disclosed in Patent Document 14 is used by pasting a sheet after aging, that is, after curing, on a glass plate. Patent Document 14 does not disclose that an adhesive sheet before curing is sandwiched between adherends and thermally cured.
The resin composition disclosed in Patent Document 15 is for obtaining a film-coated metal plate for beverage cans and food cans, and Patent Document 15 does not describe application to a printed wiring board.
Patent Documents 16 and 17 suggest the use of a titanium coupling agent and an aluminum coupling agent. However, its use is only for the purpose of improving the interfacial bond between different materials.

  The present invention provides a thermosetting adhesive sheet that is excellent in dimensional stability during curing, and has excellent adhesion after curing, heat resistance (particularly after humidification), flexibility, electrical insulation, low dielectric constant, and low dielectric loss tangent. The purpose is to do. It is difficult to achieve both dimensional stability during curing, heat resistance after curing (particularly after humidification), adhesion and low dielectric loss tangent. Then, this invention aims at providing the thermosetting adhesive sheet which can make these compatible especially.

In order to solve the above problems, the present inventors have conducted intensive studies, and as a result, a reactive functional group capable of reacting with at least one of the organometallic compound (B) or the epoxy group-containing compound (C), and other than halogen. The total amount with functional groups having heteroatoms of 0.01 mmol / g or more,
The present invention has been completed by using a thermosetting composition containing 9 mmol / g or less of resin (A), organometallic compound (B), and trifunctional or higher functional epoxy group-containing compound (C).
That is, the present invention relates to a thermosetting adhesive sheet formed from a thermosetting composition that satisfies all of the following conditions (1) to (9) .
(1) A resin (A1), an organometallic compound (B), and a trifunctional or higher functional epoxy group-containing compound (C) are included.
(2) The resin (A1) does not have an epoxy group and can react with at least one of the organometallic compound (B) and the epoxy group-containing compound (C) (hereinafter simply referred to as “reactive functional group”). (Also abbreviated as a reactive functional group).
(3) The resin (A1) is a functional group other than the reactive functional group and has a hetero atom other than halogen (hereinafter, also abbreviated as other functional group or simply other functional group of the resin (A1)). ).
(4) Resin (A2) which does not have the said reactive functional group and has a functional group which has hetero atoms other than a halogen may be included.
(5) Resin (A3) which does not have any of the said reactive functional group and the functional group which has hetero atoms other than a halogen may be included.
(6) The total amount of the reactive functional group and the functional group having a hetero atom other than the halogen contained in a total of 1 g of the resin (A1), the resin (A2), and the resin (A3) is 0.01 mmol or more, 9 mmol or less.
In addition, the resin (A1), the resin (A2), and the resin (A3) may be collectively referred to as a resin (A) hereinafter.
(7) The organometallic compound (B) includes an aluminum chelate compound, an aluminum alkoxide compound, an aluminum acylate compound, a titanium chelate compound, a titanium alkoxide compound, a titanium acylate compound, a zirconium chelate compound, a zirconium alkoxide compound, and a zirconium acylate compound. It is at least a kind selected from the group consisting of
(8) The metal in the organometallic compound (B) is 0.03 to 3 mol relative to 1 mol of the reactive functional group of the resin (A1).
(9) The resin (A1) comprises an acrylic resin, a polyester resin, a polyurethane resin, a polyurethane polyurea resin, a polyamide resin, a polyimide resin, a polycarbonate resin, a polyphenylene ether resin, a fluororesin, a polyolefin resin, and a styrene maleic anhydride resin. It is at least one selected from the group.

  The reactive functional group is preferably at least one selected from the group consisting of a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group, and an acid anhydride group.

The hetero atom in the polar functional group of the resin (A1) is preferably at least one selected from the group consisting of O, N, S and P.
The polar functional group of the resin (A1) is at least one selected from the group consisting of an ester group, an amide group, an imide group, a urethane group, a urea group, an ether group, a carbonate group, an acryloyl group, and a methacryloyl group. preferable.

The resin (A1) Total reactive functional group value of 1g is preferably 1~80mg with potassium hydroxide terms.

  It is preferable that the epoxy group in the said epoxy-group containing compound (C) is 0.1-12 mol with respect to 1 mol of reactive functional groups of the said resin (A1).

It is a compound other than the organometallic compound (B) and the epoxy group-containing compound (C), and reacts with at least one of the reactive functional group, organometallic compound (B) and epoxy group possessed by the resin (A1). It is preferable that the other hardening | curing agent (D) obtained is further included.
The other curing agent (D) is preferably at least one selected from the group consisting of an isocyanate compound, a carbodiimide compound, and a sulfur element-containing compound.

  In addition, the present invention relates to a thermosetting adhesive sheet with a sheet-like base material, which has the thermosetting adhesive sheet and two sheet-like base materials that cover both surfaces of the thermosetting adhesive sheet.

Furthermore, this invention coats and dries a thermosetting composition satisfying all of the following conditions (1) to (9) on at least one surface of the sheet-like substrate to form a thermosetting adhesive sheet, It is related with the manufacturing method of the thermosetting adhesive sheet with a sheet-like base material which piles up another sheet-like base material on the other side of a curable adhesive sheet.
(1) A resin (A1), an organometallic compound (B), and a trifunctional or higher functional epoxy group-containing compound (C) are included.
(2) The resin (A1) does not have an epoxy group, and has a reactive functional group that can react with at least one of the organometallic compound (B) and the epoxy group-containing compound (C).
(3) The resin (A1) may have a functional group other than the reactive functional group and having a hetero atom other than halogen.
(4) Resin (A2) which does not have the said reactive functional group and has a functional group which has hetero atoms other than a halogen may be included.
(5) Resin (A3) which does not have any of the said reactive functional group and the functional group which has hetero atoms other than a halogen may be included.
(6) The total amount of the reactive functional group and the functional group having a hetero atom other than the halogen contained in a total of 1 g of the resin (A1), the resin (A2), and the resin (A3) is 0.01 mmol or more, 9 mmol or less.
(7) The organometallic compound (B) includes an aluminum chelate compound, an aluminum alkoxide compound, an aluminum acylate compound, a titanium chelate compound, a titanium alkoxide compound, a titanium acylate compound, a zirconium chelate compound, a zirconium alkoxide compound, and a zirconium acylate compound. It is at least a kind selected from the group consisting of
(8) The metal in the organometallic compound (B) is 0.03 to 3 mol relative to 1 mol of the reactive functional group of the resin (A1).
(9) The resin (A1) comprises an acrylic resin, a polyester resin, a polyurethane resin, a polyurethane polyurea resin, a polyamide resin, a polyimide resin, a polycarbonate resin, a polyphenylene ether resin, a fluororesin, a polyolefin resin, and a styrene maleic anhydride resin. It is at least one selected from the group.

  Furthermore, the present invention relates to a sheet-like cured product having a dielectric loss tangent at a frequency of 5 GHz of 0.0001 to 0.01, which is obtained by thermosetting the thermosetting adhesive sheet.

  Furthermore, this invention relates to the printed wiring board with a protective sheet in which the said circuit surface of the printed wiring board which has an electroconductive circuit is protected by the sheet-like base material through the said sheet-like hardened | cured material.

  Further, the present invention provides a protection in which the thermosetting adhesive sheet is sandwiched between the circuit surface of a printed wiring board having a conductive circuit and a sheet-like substrate, and the thermosetting adhesive sheet is thermoset. The present invention relates to a method for manufacturing a printed wiring board with a sheet.

  The thermosetting adhesive sheet of the present invention is excellent in dimensional stability during curing, and is excellent in adhesiveness after curing, heat resistance after humidification, flexibility, electrical insulation, dielectric constant, and dielectric loss tangent. In particular, it has become difficult to achieve both compatibility, dimensional stability during curing, heat resistance after curing (particularly after humidification), adhesion and low dielectric loss tangent.

  As described above, the thermosetting adhesive sheet of the present invention has a total amount of reactive functional groups and other functional groups (hereinafter, both may be abbreviated as polar functional groups or both functional groups). The resin (A) of 0.01 mmol / g or more and 9 mmol / g or less, an organometallic compound (B), and a trifunctional or more functional epoxy group-containing compound (C) are contained. By using the above three components, the conductive circuit surface of a printed wiring board having a conductive circuit is excellent in dimensional stability at the time of hot pressing to paste a protective sheet-like base material, and is represented by copper. Adhesiveness to conductive circuits and polyimide films (substrates for printed wiring boards, protective sheet-like substrates), solder heat resistance after humidification, bendability when folding printed wiring boards, and leak touch for narrow pitch wiring circuits It is possible to remarkably improve the electrical insulating property to prevent and the dielectric constant and dielectric loss tangent which are important as the adhesive and coating agent around the printed wiring board through which the high frequency electrical signal propagates.

  This is because a resin (A) having a total amount of reactive functional groups and other functional groups of 0.01 [mmol / g] or more and 9 [mmol / g] or less is used. That is, since the total amount of the reactive functional group and the other functional group is in the above range, the resin (A) has a lower polarity than the conventional resin. Therefore, the cured product obtained by thermosetting the thermosetting adhesive sheet of the present invention is superior in hydrophobicity as compared with the cured product using a conventional highly polar resin. As a result, the electrical insulation is excellent, the dielectric constant can be lowered, and the low electric tangent can also be lowered. In addition, as a result of excellent hydrophobicity, hygroscopicity is also low, so even if it is placed under high humidity and then brought into contact with a solder bath, it does not swell, etc., has excellent heat resistance, and there are few intermolecular interactions This is because flexibility derived from the above can be imparted.

  Since the organometallic compound (B) is excellent in reactivity, it reacts quickly at the time of curing, can prevent undesired (unplanned) softening, protrusion and misalignment, and is excellent in dimensional stability. In addition, since the organometallic compound (B) forms a hydrophobic skeleton after curing, it is considered that it contributes to an improvement in electrical insulation and a decrease in dielectric constant and dielectric loss tangent.

  Further, the use of the trifunctional or higher functional epoxy group-containing compound (C) makes it possible to form a strong cross-link and remarkably improve heat resistance and insulation. Furthermore, adhesiveness can also be imparted.

  For example, when a resin having a total content of both functional groups of more than 9.0 mmol / g is used instead of the resin (A), generally, a printed wiring that allows high-frequency electrical signals to propagate although adhesion can be obtained. The low dielectric constant required around the plate cannot be satisfied. In order to solve these problems, there may be means such as formation of holes aiming at effective utilization of air having a low dielectric constant, but the flexibility is lowered due to the formation of voids that cause a decrease in strength. Furthermore, since moisture enters the voids, there is a problem that, after placing the cured product under high humidity, contact with the solder bath causes swelling and the like, and the heat resistance is remarkably deteriorated.

  In addition, when a resin having a total content of both functional groups of less than 0.01 mmol / g is used instead of the resin (A), generally a low dielectric constant and a low dielectric loss tangent can be obtained. It cannot be satisfied, and even before the humidification, heat resistance and insulation cannot be satisfied.

  On the other hand, since the present invention uses the resin (A) having a total content of both functional groups of 0.01 [mmol / g] or more and 9 [mmol / g] or less, the polarity that causes deterioration of the dielectric constant in the first place. There are few groups and a low dielectric constant can be satisfied. Furthermore, in addition to characteristics that are important as a thermosetting adhesive sheet for printed wiring boards, such as heat resistance and flexibility, it is possible to impart electrical insulation that prevents leak touch of narrow pitch wiring circuits.

The present invention is also characterized by using an organometallic compound (B). For example, in the case of a photocrosslinking group such as a vinyl group or an allyl group instead of the organometallic compound (B), it is difficult to form a new polar functional group by crosslinking, so that the dielectric constant and dielectric loss tangent derived from the resin tend to be maintained. It is in. However, another problem that the degree of curing changes depending on the irradiation position and thickness occurs.
In addition, in the case of crosslinking using a compound that can be generally used as an adhesive or coating agent for a printed wiring board, such as a phenol compound, instead of the organometallic compound (B), a new polar group such as a hydroxyl group is obtained by curing. Will be formed. Therefore, the advantages of the resin (A) such as low dielectric constant and low dielectric loss tangent cannot be fully utilized, and only a cured product having a high dielectric constant and dielectric loss tangent can be obtained.

  On the other hand, in the present invention, by using the organometallic compound (B), it is possible to suppress the generation of a functional group having a large polarity at the time of curing, and to maintain the characteristics of the resin (A) such as low dielectric constant and low dielectric loss tangent. At the same time, it is possible to impart processability derived from high reactivity and electrical insulation derived from formation of a strong crosslinked structure.

Furthermore, since this invention uses a trifunctional or more than trifunctional epoxy group containing compound (C), heat resistance, insulation, and adhesiveness can be provided to hardened | cured material.
That is, the present invention improves the dimensional stability when curing a thermosetting adhesive sheet with the three components of the resin (A), the organometallic compound (B), and the trifunctional or higher functional epoxy group-containing compound (C). In addition to improving heat resistance after humidification as a cured product, it is possible to solve the trade-off between coexistence of adhesion and low dielectric constant, and compatibility of flexibility and electrical insulation.
This is because a hydroxyl group generated by the reaction between the reactive functional group of the resin (A) and the epoxy group-containing compound (B) is further reacted with the organometallic compound (B) to form a dense cross-linked structure. This is because it is possible to suppress the generation of polar groups that cause deterioration of dielectric constant and dielectric loss tangent.

Hereinafter, the resin (A) will be described in detail.
Resin (A) in this invention makes resin (A1) essential, and can further contain resin (A2) and (A3).
The resin (A1) has two types of reactive functional groups and other functional groups.
Resin (A2) does not have a reactive functional group, but has other functional groups.
Resin (A3) has neither a reactive functional group nor other functional groups.

The reactive functional group possessed by the resin (A1) can be contrary to at least one of the organometallic compound (B) and the epoxy group-containing compound (C). The reactive functional group of the resin (A) is preferably a functional group capable of reacting with the organometallic compound (B) or the epoxy group-containing compound (C), and preferably capable of reacting at 20 to 200 ° C.
Examples of the reactive functional group include a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group, an acid anhydride group and an amino group, a cyanate group, an isocyano group, a cyanato group, an isocyanato group, an imidazole group, a pyrrole group, an acetal group, and an acryloyl group. A methacryloyl group, an aldehyde group, a hydrazide group, a hydrazone group, a phosphoric acid group, etc., and preferably at least one selected from the group consisting of a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group and an acid anhydride group.
The total reactive functional group value of 1 g of the resin (A1) is preferably 1 to 80 mg, more preferably 1 to 50 mg, and further preferably 4 to 30 mg in terms of potassium hydroxide.
Since the reactive functional group contributes to cross-linking formation, the reactive functional group value is preferably 1 mg or more in terms of potassium hydroxide from the viewpoint of heat resistance and insulation of the cured product. Moreover, it is preferable that a reactive functional group value is 80 mg or less in conversion of potassium hydroxide from the point of the adhesiveness of a hardened | cured material, and a flexibility.

The other functional group of the resin (A1) and the resin (A2) is a functional group other than the reactive functional group, which is a functional group having a hetero atom other than halogen, and the hetero atom includes O, At least one selected from the group consisting of N, S and P is preferred.
Such polar functional groups include ester groups, amide groups, imide groups, enone groups, urethane groups, urea groups, ether groups, carbonate groups, ketone groups, acyl groups, imino groups, acid halide groups, maleimide groups, Nitro group, nitrile group, amidine group, phosphine group, acetal group, acryloyl group, methacryloyl group, oxime group, etc.
It is preferably at least one selected from the group consisting of ester groups, amide groups, imide groups, urethane groups, urea groups, ether groups, carbonate groups, acryloyl groups and methacryloyl groups.

The resin (A1) in the present invention is a group consisting of acrylic resin, polyester resin, polyurethane resin, polyurethane polyurea resin, polyamide resin, polyimide resin, polycarbonate resin, polyphenylene ether resin, fluorine resin, polyolefin resin, and styrene maleic anhydride resin. It is at least one kind selected.
The polyolefin resin here is a resin polymerized from a monomer containing an olefin unit such as ethylene, propylene, and butadiene, and may also include a copolymer with a vinyl resin such as styrene. Moreover, what modified | denatured by hydrogenating the C = C part of the obtained polybutadiene component may be included.

As the resin (A1), a plurality of resins having a total content of both functional groups of 0.01 to 9 [mmol / g] can be used. For example, performance can be improved by using a resin excellent in processability as an adhesive sheet and a resin excellent in heat resistance while maintaining the above.
Alternatively, as the resin (A1), a resin having a total content of both functional groups greater than 9 [mmol / g] and a resin having a total content of both functional groups of 0.01 to 9 [mmol / g] are used in combination. Alternatively, a resin having a total content of both functional groups of more than 9 [mmol / g] and a resin having a total content of both functional groups of less than 0.01 [mmol / g] may be used in combination. Since the adhesiveness with the base material interface can be imparted by the high polar component derived from both functional groups, a curable composition having high adhesive strength can be obtained.

Here, how to determine the amount of both functional groups of the resin (A1) will be described in more detail by taking the case of an acrylic resin and a polyester resin as examples.
An acrylate monomer or a methacrylate monomer, which is a raw material for forming an acrylic resin, has an ester bond that is one of other functional groups.
Hereinafter, the case of a monoacrylate monomer or a monomethacrylate monomer will be described as an example. The amount of each monomer subjected to polymerization is W1, W2,... Wn (g), and the molecular weight of each monomer is M1, M2,. The amount (mol) is [(W1 / M1) + (W2 / M2) +... + (Wn / Mn)] / (W1 + W2 +... + Wn).
When an acrylate monomer or a methacrylate monomer has a carboxyl group or a hydroxyl group, it is subjected to polymerization. From the amount of each monomer having a reactive functional group, the molecular weight of each monomer, and the number of functional groups of the reactive functional group, an acrylic resin The amount (mol) of the reactive functional group contained per gram can be determined in the same manner.
Then, the ester bond content (mol) and reactive functional group content (mol) contained per gram of acrylic resin are summed to determine the total content of both functional groups.

  Similarly, in the case where the resin (A1) is a polyester resin, the ester constituting the main chain from the amount (g) of the carboxyl group component (including anhydride) and hydroxyl group component, which are raw materials for forming the polyester resin, and the molecular weight of each component Obtain the amount (mol) of the bond, add the amount (mol) of the polar functional group at the end of the main chain and the amount (mol) of the polar functional group at the end of the side chain, and add the total content of both functional groups per gram of the polyester resin. The amount (mol) is determined. The amount (mol) of the polar functional group at the end of the main chain and the amount (mol) of the polar functional group at the end of the side chain are the difference in the amount (mol) of the functional group between the carboxyl group (including anhydride) and the hydroxyl group. Can be obtained from

As resin (A2) in this invention, the thing similar to resin (A1) can be illustrated. That is, the resin (A2) can be obtained in the same manner as the resin (A1) except that no raw material having a reactive functional group is used. Alternatively, the resin (A2) can also be obtained by obtaining a resin using a raw material having a reactive functional group and then blocking the reactive functional group with an appropriate compound.

  Examples of the resin (A3) in the present invention include polyolefin resins and fluororesins.

The method for obtaining the total content of both functional groups of the resin (A) will be described.
The amounts of reactive functional groups and other functional groups in 1 g of the resin (A1) are determined.
When the resin (A2) is used in combination, the amount of other functional groups in 1 g of the resin (A2) is determined.
Next, from the respective amounts of the resins (A1), (A2) and (A3) to be used, the respective proportions in 1 g of the resin (A) are obtained, and the amounts of reactive functional groups and other functional groups in 1 g of the resin (A1) Is multiplied by the proportion of the resin (A1) in 1 g of the resin (A), and the amount of the other functional group in 1 g of the resin (A2) is multiplied by the proportion of the resin (A2) in 1 g of the resin (A).

Subsequently, the organometallic compound (B) will be described in detail.
The organometallic compound (B) is made of an aluminum chelate compound, an aluminum alkoxide compound, an aluminum acylate compound, a titanium chelate compound, a titanium alkoxide compound, a titanium acylate compound, a zirconium chelate compound, a zirconium alkoxide compound, and a zirconium acylate compound. It is at least one kind selected.

  Typical examples of the aluminum chelate compound used in the present invention include ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetylacetonate bis ( Ethyl acetoacetate), aluminum tris (acetylacetate), aluminum monoacetylacetate bis (ethylacetoacetate), aluminum di-n-butoxide monomethylacetoacetate, aluminum diisobutoxide monomethylacetoacetate, aluminum di-sec-butoxide monomethylacetate Examples include acetate.

  Representative examples of the aluminum alkoxide compound include aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum-sec-butyrate, and aluminum ethylate.

  Typical titanium chelates include titanium acetylacetonate, titanium tetraacetylacetonate, titanium ethylacetoacetate, titanium octylene glycolate, titanium ethylacetoacetate, titanium-1.3-propanedioxybis. (Ethyl acetoacetate), polytitanium acetylacetylacetonate and the like.

  Typical examples of the titanium alkoxide include tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetraoctyl titanate, dark amyl titanate, tetra tertiary butyl titanate, and tetrastearyl titanate. Examples of acylates include titanium isostearate, tri-n-butoxytitanium monostearate, di-i-propoxytitanium distearate, titanium stearate, di-i-propoxytitanium diisostearate, (2-n- Butoxycarbonylbenzoyloxy) tributoxytitanium and the like.

  Representative examples of zirconium chelates include zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, zirconium monobutoxyacetylacetonate bis (ethylacetoacetate), zirconium dibutoxybis (ethylacetoacetate), zirconium Tetraacetylacetonate etc. are mentioned.

  Typical examples of the zirconium alkoxide include normal propyl zirconate and normal butyl zirconate. Examples of the zirconium acylate include zirconium stearate and zirconium octylate.

  As the aluminum chelate compound, titanium chelate compound and zirconium chelate compound, those having an acetylacetonate complex are particularly preferably used from the viewpoint of reactivity.

The organometallic compound (B) used in the present invention contains 0.03 to 3 mol of metal in the organometallic compound (B) with respect to 1 mol of the reactive functional group of the resin (A1). Is important, it is preferable to contain it so that it may become 0.1-1.5 mol, and it is more preferable to contain so that it may become 0.2-1 mol. By setting the amount of metal in the organometallic compound (B)) to 0.03 mol or more, the crosslink density can be increased and the processability as an adhesive sheet can be improved, and the resin (A1) and the epoxy group-containing compound (C) When a new polar group that causes deterioration of the dielectric constant and dielectric loss tangent is generated by the reaction, the organometallic compound (B) reacts with the polar group and suppresses deterioration of the dielectric constant and dielectric loss tangent.
By setting the amount of the metal in the organometallic compound (B) to 3 mol or less, thermally weak bonds are relatively reduced, so that a cured product having excellent heat resistance can be obtained.

<Epoxy group-containing compound (C)>
Subsequently, the epoxy group-containing compound (C) will be described in detail.
The epoxy group-containing compound (C) in the present invention may be a compound having an average of 3 or more epoxy groups in one molecule. As the epoxy group-containing compound, for example, an epoxy resin such as a glycidyl ether type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, or a cyclic aliphatic (alicyclic type) epoxy resin can be used.

  Examples of the glycidyl ether type epoxy resin include a cresol novolak type epoxy resin, a phenol novolak type epoxy resin, an α-naphthol novolak type epoxy resin, a bisphenol A type novolak type epoxy resin, a tetrabromobisphenol A type epoxy resin, and a brominated phenol novolak. Type epoxy resin, tris (glycidyloxyphenyl) methane, tetrakis (glycidyloxyphenyl) ethane and the like.

  Examples of the glycidylamine type epoxy resin include tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, triglycidylmetaaminophenol, and tetraglycidylmetaxylylenediamine. These are excellent in terms of adhesiveness and can be suitably used in the present invention.

  The epoxy group-containing compound (C) used in the present invention is preferably contained in an amount of 0.1 to 12 mol of epoxy group with respect to 1 mol of the reactive functional group in the resin (A1). The content is more preferably 3 to 10 mol, and further preferably 0.5 to 5 mol. By making an epoxy group into 0.1 mol or more with respect to the reactive functional group of resin (A), a crosslinking density can be increased and heat resistance, insulation, and adhesiveness can be improved. By making an epoxy group 20 mol or less, the production | generation of a new polar group can be suppressed and the deterioration of a dielectric loss tangent can be suppressed.

  In the present invention, in addition to the resin (A), the organometallic compound (B), and the epoxy group-containing compound (C), the organometallic compound (B) and the epoxy group-containing compound (C) are within the range not impairing the physical properties. Other curing agents (D) that can react with at least one of the reactive functional group of the resin (A1), the organometallic compound (B), and the epoxy group can be added. . Specific examples of other curing agents (D) include isocyanate group-containing compounds, blocked isocyanate group-containing compounds, oxetane group-containing compounds, aziridine group-containing compounds, carbodiimide group-containing compounds, benzoxazine compounds, and β-hydroxyalkylamide groups. Although a compound, a sulfur containing compound, etc. are mentioned, it is not specifically limited.

  Hereinafter, the isocyanate group-containing compound, the blocked isocyanate group-containing compound, the oxetane group-containing compound, the aziridine group-containing compound, the carbodiimide group-containing compound, the benzoxazine compound, the β-hydroxyalkylamide group-containing compound, and the sulfur-containing compound will be specifically described. To do.

[Isocyanate group-containing compound]
One of the other curing agents (D), the isocyanate compound, is not particularly limited as long as it is a compound having an isocyanate group in the molecule. Specific examples of the isocyanate group-containing compound having one isocyanate group in one molecule include n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, benzyl isocyanate, (meth) acryloyloxyethyl isocyanate, 1,1-bis [ (Meth) acryloyloxymethyl] ethyl isocyanate, vinyl isocyanate, allyl isocyanate, (meth) acryloyl isocyanate, isopropenyl-α, α-dimethylbenzyl isocyanate and the like.
In addition, 1,6-diisocyanatohexane, isophorone diisocyanate, 4,4′-diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, xylylene diisocyanate, tolylene 2,4-diisocyanate, toluene diisocyanate, 2,4-diisocyanic acid Toluene, hexamethylene diisocyanate, 4-methyl-m-phenylene diisocyanate, naphthylene diisocyanate, paraphenylene diisocyanate, tetramethylxylylene diisocyanate, cyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, cyclohexyl diisocyanate, tolidine diisocyanate, 2,2 , 4-Trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate Nitrate, m-tetramethylxylylene diisocyanate, P-tetramethylxylylene diisocyanate, diisocyanate ester compounds such as dimer acid diisocyanate and hydroxyl group, carboxyl group, and amide group-containing vinyl monomers are reacted in equimolar amounts. It can be used as an ester compound.

Specific examples of the isocyanate group-containing compound having two isocyanate groups in one molecule include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, and 4,4′-diphenylmethane. Diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, Aromatic diisocyanates such as 4,4′-diphenyl ether diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate,
Trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene Aliphatic diisocyanates such as diisocyanates,
ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate Araliphatic diisocyanates such as 1,3-tetramethylxylylene diisocyanate,
3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate [alias: isophorone diisocyanate], 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane Alicyclic diisocyanates such as diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,3-bis (isocyanate methyl) cyclohexane, 1,4-bis (isocyanate methyl) cyclohexane Can be mentioned.

  Specific examples of the isocyanate group-containing compound having three isocyanate groups in one molecule include aliphatic polyisocyanates such as aromatic polyisocyanates and lysine triisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates. And the like, and the trimethylolpropane adduct of diisocyanate described above, a burette reacted with water, and a trimer having an isocyanurate ring.

[Blocked isocyanate group-containing compound]
As one of the other curing agents (D), the blocked isocyanate compound may be a blocked isocyanate group-containing compound in which the isocyanate group in the isocyanate group-containing compound is protected with ε-caprolactam, MEK oxime, or the like. There is no particular limitation. Specific examples include those obtained by blocking the isocyanate group of the isocyanate group-containing compound with ε-caprolactam, MEK oxime, cyclohexanone oxime, pyrazole, phenol and the like. In particular, a hexamethylene diisocyanate trimer having an isocyanurate ring and blocked with MEK oxime or pyrazole is very preferable because it has excellent adhesion strength and heat resistance to polyimide and copper.

[Oxetane group-containing compound]
As one of the other curing agents (D), as an oxetane group-containing compound, for example, 1,4-bis {[(3-ethyloxetane-3-yl) methoxy] methyl} benzene, 3-ethyl-3- { [(3-Ethyloxetane-3-yl) methoxy] methyl} oxetane, 1,3-bis [(3-ethyloxetane-3-yl) methoxy] benzene, 4,4′-bis [(3-ethyl-3 -Oxetanyl) methoxymethyl] biphenyl, esterified product of (2-ethyl-2-oxetanyl) ethanol and terephthalic acid, etherified product of (2-ethyl-2-oxetanyl) ethanol and phenol novolac resin, (2-ethyl- 2-oxetanyl) ethanol and an esterified product of a polyvalent carboxylic acid compound. Here, since the reaction rate at the time of hardening improves by using an oxetane group containing compound with an organometallic compound (B), it is used suitably in this invention.

[Aziridine group-containing compound]
One of the other curing agents (D), the aziridine compound, is not particularly limited as long as it is a compound containing an aziridine group in the molecule.
Examples of the aziridine compound include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxite), N, N′-toluene-2,4-bis (1-aziridinecarboxite), bisiso Phthaloyl-1- (2-methylaziridine), tri-1-aziridinylphosphine oxide, N, N′-hexamethylene-1,6-bis (1-aziridinecarboxite), trimethylolpropane-tri-β -Aziridinylpropionate, tetramethylolmethane-tri-β-aziridinylpropionate, tris-2,4,6- (1-aziridinyl) -1,3,5-triazine, trimethylolpropane tris [ 3- (1-aziridinyl) propionate], trimethylolpropane tris [3- (1-aziridinyl) butyrate], Limethylolpropane tris [3- (1- (2-methyl) aziridinyl) propionate], trimethylolpropane tris [3- (1-aziridinyl) -2-methylpropionate], 2,2′-bishydroxymethylbutanol Tris [3- (1-aziridinyl) propionate], pentaerythritol tetra [3- (1-aziridinyl) propionate], diphenylmethane-4,4-bis-N, N′-ethyleneurea, 1,6-hexamethylenebis- N, N′-ethylene urea, 2,4,6- (triethyleneimino) -Syn-triazine, bis [1- (2-ethyl) aziridinyl] benzene-1,3-carboxylic acid amide and the like can be mentioned.

  In particular, 2,2′-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate], when used in the present invention, can suppress protrusion during hot pressing and retain the flexibility of the cured coating film. Since heat resistance can be improved as it is, it is preferably used in the present invention.

[Carbodiimide group-containing compound]
As one of the other curing agents (D), a carbodiimide group-containing compound, a carbodilite series of Nisshinbo Co., Ltd. may be mentioned. Among these, Carbodilite V-01, 03, 05, 07, and 09 are preferable because of excellent compatibility with organic solvents. When used in the present invention, an improvement in adhesiveness can be expected, so that it is preferably used.

[Benzoxazine compounds]
As one of the other curing agents (D), the benzoxazine compound includes “P-a”, “P-alP”, “P-ala”, “B-ala” described in Macromolecules, 36, 6010 (2003). , Macromolecules, 34, 7257 (2001), “P-appe”, “B-appe”, “Ba-type benzoxazine”, “F-a-type benzoxazine”, “B-m” manufactured by Shikoku Kasei Co., Ltd. Type benzoxazine ".

[β-Hydroxyalkylamide group-containing compound]
As one of the other curing agents (D), as a β-hydroxyalkylamide group-containing compound, for example, N, N, N ′, N′-tetrakis (hydroxyethyl) adipamide (Primidi XL-552 manufactured by Ems Chemie) is used. Various compounds including the above can be mentioned.

[Sulfur-containing compounds]
Examples of one of the other curing agents (D) and the sulfur-containing compound include thiol compounds, sulfide compounds, and polysulfide compounds. When used in the present invention, it can be suitably used because it can be expected to improve adhesion and heat resistance.

[Thiol compound]
The thiol compound contains, for example, at least a thiol group and a linear, branched, or cyclic hydrocarbon group. Two or more thiol groups may be contained. The hydrocarbon group may be saturated or unsaturated. Some of the hydrogen atoms of the hydrocarbon group may be substituted with a hydroxyl group, amino group, carboxyl group, halogen atom, alkoxysilyl group, or the like. More specifically, examples of colorless thiols include 1-propanethiol, 3-mercaptopropionic acid, (3-mercaptopropyl) trimethoxysilane, 1-butanethiol, 2-butanethiol, isobutylmercaptan, isoamyl. Mercaptan, cyclopentanethiol, 1-hexanethiol, cyclohexanethiol, 6-hydroxy-1-hexanethiol, 6-amino-1-hexanethiol hydrochloride, 1-heptanethiol, 7-carboxy-1-heptanethiol, 7- Amido-1-heptanethiol, 1-octanethiol, tert-octanethiol, 8-hydroxy-1-octanethiol, 8-amino-1-octanethiol hydrochloride, 1H, 1H, 2H, 2H-perfluorooctanethiol, 1-nonanethiol, 1-decanethiol, 10-carboxy-1-decanethiol, 10-amido-1-decanethiol, 1- Phthalene thiol, 2-naphthalene thiol, 1-undecane thiol, 11-amino-1-undecane thiol hydrochloride, 11-hydroxy-1-undecane thiol, 1-dodecane thiol, 1-tetradecane thiol, 1-hexadecane thiol, 16 -Hydroxy-1-hexadecanethiol, 16-amino-1-hexadecanethiol hydrochloride, 1-octadecanethiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,6-hexanedithiol, 1,2-benzene Examples include dithiol, 1,9-nonanedithiol, 1,10-decanedithiol, 1,3,5-benzenetrithiol, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropyltrimethoxysilane. These thiols can be used alone or in combination of two or more.
[Sulphide compounds]
The sulfide compound contains, for example, at least a sulfide group and a linear, branched, or cyclic hydrocarbon group. Two or more sulfide groups may be contained. Some of the hydrogen atoms of the hydrocarbon group may be substituted with a hydroxyl group, amino group, carboxyl group, halogen atom, alkoxysilyl group, or the like.
More specifically, as the sulfide compound, for example, propyl sulfide, furfuryl sulfide, hexyl sulfide, phenyl sulfide, phenyl trifluoromethyl sulfide, bis (4-hydroxyphenyl) sulfide, heptyl sulfide, octyl sulfide, nonyl sulfide, decyl Examples thereof include sulfide, dodecylmethyl sulfide, dodecyl sulfide, tetradecyl sulfide, hexadecyl sulfide, octadecyl sulfide, bis (triethoxysilylpropyl) tetrasulfide and the like. These sulfides can be used alone or in combination of two or more.
[Polysulfide compound]
Examples of polysulfide compounds include 2-hydroxyethyl disulfide, propyl disulfide, isopropyl disulfide, 3-carboxypropyl disulfide, allyl disulfide, isobutyl disulfide, tert-butyl disulfide, amyl disulfide, isoamyl disulfide, 5-carboxypentyl disulfide, and furfuryl. Disulfide, hexyl disulfide, cyclohexyl disulfide, phenyl disulfide, 4-aminophenyl disulfide, heptyl disulfide, 7-carboxyheptyl disulfide, benzyl disulfide, tert-octyl disulfide, decyl disulfide, 10-carboxydecyl disulfide, hexadecyl disulfide, thiuram disulfide, etc. Can be used.

In the present invention, the use amount of the other curing agent (D) is not particularly limited, but it is preferably 0.01 to 20 mol with respect to 1 mol of the reactive functional group of the resin (A). , 0.5 to 10 mol is more preferable, and 0.1 to 5 mol is more preferable.
Or it is preferable to contain 0.01-20 mol with respect to 1 mol of metals of an organometallic compound (B), it is more preferable to contain 0.5-10 mol, and it is more preferable to contain 0.1-5 mol.
Or it is preferable to contain 0.01-20 mol with respect to 1 mol of epoxy groups in an epoxy-group containing compound (C), It is more preferable to contain 0.5-10 mol, It is preferable to contain 0.1-5 mol. Further preferred.

<Filler>
Next, the filler of the present invention will be described in detail.
The thermosetting adhesive sheet of the present invention can contain a filler for the purpose of imparting flame retardancy, controlling the fluidity of the adhesive, and improving the elastic modulus of the cured product.

Although it does not specifically limit as a filler, As a shape, spherical shape, powder shape, fibrous shape, needle shape, scale shape, etc. are mentioned.
Examples of fillers include polytetrafluoroethylene powder, polyethylene powder, polyacrylic acid ester powder, epoxy resin powder, polyamide powder, polyurethane powder, polysiloxane powder, silicone, acrylic, styrene butadiene rubber, butadiene rubber, etc. Polymer filler such as core shell of multilayer structure used;
(Poly) phosphates such as melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, ammonium amidophosphate, ammonium amidophosphate, carbamate phosphate, carbamate polyphosphate Compounds, organophosphate ester compounds, phosphazene compounds, phosphonic acid compounds, diethyl diethylphosphinate, aluminum methylethylphosphinate, aluminum diphenylphosphinate, aluminum ethylbutylphosphinate, aluminum methylbutylphosphinate, aluminum polyethylenephosphinate, etc. Phosphorus flame retardant fillers such as acid compounds, phosphine oxide compounds, phosphorane compounds, phosphoramide compounds;
Nitrogen-based flame retardant fillers such as benzoguanamine, melamine, melam, melem, melon, melamine cyanurate, cyanuric acid compound, isocyanuric acid compound, triazole compound, tetrazole compound, diazo compound, urea;
Silica, mica, talc, kaolin, clay, hydrotalcite, wollastonite, zonotlite, silicon nitride, boron nitride, aluminum nitride, calcium hydrogen phosphate, calcium phosphate, glass flakes, hydrated glass, calcium titanate, sepiolite, sulfuric acid Magnesium, aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide, calcium hydroxide, titanium oxide, tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, antimony oxide, nickel oxide, carbonic acid Examples include inorganic fillers such as zinc, magnesium carbonate, calcium carbonate, barium carbonate, zinc borate, and aluminum borate.

  Among them, it is desirable to use a non-halogen flame retardant such as a phosphorus flame retardant filler or a nitrogen flame retardant filler, which has been recently taken into consideration as the filler, and in particular, the adhesive of the present invention. It is preferable to use a phosphazene compound, a phosphine compound, a melamine polyphosphate, an ammonium polyphosphate, a melamine cyanurate, or the like that is more effective in flame retardancy when used in combination with the composition. In addition, it is preferable to use polytetrafluoroethylene powder from the viewpoint of further reducing the dielectric constant and dielectric loss tangent, and it has excellent balance not only with dielectric properties but also with adhesion, flexibility, electrical insulation and heat resistance. You can get things. In the present invention, these fillers can be used alone or in combination.

  The average particle size of these fillers is preferably 0.1 μm to 25 μm. When a filler having an average particle diameter close to 0.1 μm is used, a modification effect by the filler is easily obtained, and further, dispersibility and stability of the dispersion liquid are easily improved. Moreover, when the filler which shows the average particle diameter near 25 micrometers is used, the mechanical characteristic of a cured film becomes easy to improve.

  As an addition amount of a filler, it is preferable that it is 0.01-500 mass parts with respect to 100 mass parts of said resin (A). If the amount of filler added is below this range, the modification effect by the filler is difficult to obtain, and if it exceeds this range, the mechanical properties of the cured film may be greatly impaired.

  The method for adding the filler is not particularly limited, and any conventionally known method may be used. Specifically, a method of adding to the polymerization reaction solution before or during the polymerization, using a three roll, etc. Examples thereof include a method of kneading the filler and a method of preparing a dispersion containing the filler and mixing it. Further, in order to disperse the filler satisfactorily and stabilize the dispersion state, a dispersant, a thickener and the like can be used as long as the physical properties of the adhesive sheet are not affected.

<Other additives>
In addition, the thermosetting adhesive sheet of the present invention may further include dyes, pigments, antioxidants, polymerization inhibitors, antifoaming agents, leveling agents, ion scavengers, moisturizing agents as optional components as long as the purpose is not impaired. An agent, a viscosity modifier, an antiseptic, an antibacterial agent, an antistatic agent, an antiblocking agent, an ultraviolet absorber, an infrared absorber, an electromagnetic wave shielding agent, and the like can be added.

[Thermosetting adhesive sheet with sheet-like substrate]
The thermosetting adhesive sheet with a sheet-like substrate of the present invention can be obtained, for example, as follows.
After applying the thermosetting adhesive in a solution or dispersion state to at least one side of the sheet-like substrate, it is usually dried at 40 to 150 ° C., thereby forming a sheet-like base on the so-called B-stage thermosetting adhesive sheet. You can get the one with the material. Next, the other surface of the thermosetting adhesive sheet is covered with another sheet-like base material, whereby the thermosetting adhesive sheet with the sheet-like base material of the present invention can be obtained.
At least one of the sheet-like substrates to be used is preferably a peelable sheet-like substrate. That is, a thermosetting adhesive in a solution or dispersion state is applied to a peelable sheet-like substrate and dried to form a thermosetting adhesive sheet, and the other surface of the thermosetting adhesive sheet is then placed on the other side. It can also be covered with a peelable sheet-like base material, or can be covered with a non-peelable sheet-like base material to be an adherend. Alternatively, a thermosetting adhesive in a solution or dispersion state is applied to a non-peelable sheet-like substrate to be an adherend and dried to form a thermosetting adhesive sheet, and then the thermosetting adhesive sheet The other surface can be covered with another peelable sheet-like substrate.

The dry film thickness of the thermosetting adhesive sheet is preferably 5 to 500 μm, more preferably 10 to 100 μm, from the viewpoint of easy handling and sufficient adhesiveness and solder heat resistance.
Examples of the coating method include comma coating, knife coating, die coating, lip coating, roll coating, curtain coating, bar coating, gravure printing, flexographic printing, dip coating, spray coating, and spin coating.

Examples of the non-peelable sheet-like substrate used include various plastic films, such as polyimide films, polyester films, polyphenylene ether films, polyphenylene sulfide films, polystyrene films, polycarbonate films, polyether ether ketone films. Is mentioned.
Examples of the sheet-like base material that can be peeled include those obtained by subjecting various plastic films to release treatment and those obtained by subjecting paper to release treatment. Examples of the various plastic films to be subjected to the peeling treatment include polyester films and polyolefin films.

[Cured sheet], [Printed wiring board with protective sheet]
The sheet-like cured product of the present invention is obtained by thermosetting the thermosetting adhesive sheet of the present invention, for example, at a temperature of about 40 to 200 ° C.

Use a thermosetting adhesive sheet with a sheet-like substrate in which one side of the thermosetting adhesive sheet is covered with a peelable sheet-like substrate and the other surface is covered with an adherend (for example, a polyimide film or a polyester film). The case will be described.
The peelable sheet-like substrate is peeled off from the thermosetting adhesive sheet with the sheet-like substrate. Another adherend (for example, the circuit surface side of the printed wiring board having a conductive circuit) is overlaid on the exposed thermosetting adhesive sheet. Next, the thermosetting adhesive sheet sandwiched between both adherends is thermoset by heating and pressurizing.
If it does in this way, the printed circuit board with a protection sheet which the said circuit surface of the printed wiring board which has an electroconductive circuit protected by a sheet-like base material can be obtained through a sheet-like hardened | cured material.

Next, the case where the thermosetting adhesive sheet with a sheet-like base material in which two peelable sheet-like base materials respectively cover both surfaces of the thermosetting adhesive sheet is described.
One peelable sheet-like substrate is peeled off from the thermosetting adhesive sheet with the sheet-like substrate. An adherend (for example, a polyimide film or a polyester film) is stacked on the exposed thermosetting adhesive sheet. The other peelable sheet-like substrate that has covered the other surface of the thermosetting adhesive sheet is peeled off. Another adherend (for example, the circuit surface side of the printed wiring board having a conductive circuit) is overlaid on the exposed thermosetting adhesive sheet. Next, the thermosetting adhesive sheet sandwiched between both adherends is thermoset by heating and pressurizing. The circuit surface side of the printed wiring board having a conductive circuit can be overlaid on the surface from which the peelable sheet-like substrate is first peeled off, and a polyimide film or a polyester film can be overlaid on the other surface of the thermosetting adhesive sheet. .

Examples of the printed wiring board having a conductive circuit include a flexible printed wiring board in which a conductive circuit is formed on a plastic film having flexibility and insulation such as polyester and polyimide.
As a method for providing a conductive circuit, for example, a photosensitive etching resist layer is formed on a copper foil of a flexible copper-clad plate in which a copper foil is provided on a base film with or without an adhesive layer. Expose the conductive circuit from the copper foil by exposing it through a mask film with a pattern, curing only the exposed area, then removing the unexposed area of the copper foil by etching, and then peeling off the remaining resist layer. Can be formed.
Or the method of providing only a required circuit by means, such as sputtering and plating, on a base film is also mentioned.
Or the method of forming an electroconductive circuit on a base film with a printing technique using the electroconductive ink containing the particle | grains of silver and copper is also mentioned.

The thermosetting adhesive sheet of the present invention is suitably used for producing a printed wiring board with a protective sheet, and can also be used as follows.
<Multi-layering of multiple flexible printed wiring>
By sandwiching the thermosetting adhesive sheet of the present invention between a plurality of flexible printed wirings and heating and pressing, the thermosetting adhesive sheet can be cured to obtain a multilayer flexible printed wiring board.
<Lamination of base film for flexible printed wiring board and copper foil>
For example, the thermosetting adhesive sheet can be cured by sandwiching the thermosetting adhesive sheet of the present invention between a polyimide film and a copper foil, and heating and pressing.
<Attaching the reinforcing plate>
By sandwiching the thermosetting adhesive sheet of the present invention between a flexible printed wiring board and a reinforcing plate made of glass epoxy, metal, polyimide, etc., the thermosetting adhesive sheet is cured by heating and pressurizing the flexible printed wiring. A reinforcing plate can be attached to the plate.

  The present invention will be described more specifically with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively, and Mw represents a mass average molecular weight.

<Measuring method of hydroxyl value (phenolic and alcoholic)>
The phenolic and alcoholic hydroxyl value is the amount of potassium hydroxide required to neutralize the amount of hydroxyl group contained in 1 g of resin solids to neutralize acetic acid bonded to the hydroxyl group when the hydroxyl group is acetylated (mg ).
The hydroxyl value is measured according to JIS K0070, and is calculated in consideration of the acid value as shown in the following formula.

About 1 g of a sample is accurately weighed in a stoppered Erlenmeyer flask and dissolved by adding 100 ml of cyclohexanone solvent. Further, exactly 5 ml of an acetylating agent (a solution in which 25 g of acetic anhydride was dissolved in pyridine to make a volume of 100 ml) was added and stirred for about 1 hour. To this, phenolphthalein reagent is added as an indicator and lasts for 30 seconds. Thereafter, the solution is titrated with a 0.5N alcoholic potassium hydroxide solution until the solution becomes light red.
The hydroxyl value was determined by the following formula (unit: mgKOH / g).
Hydroxyl value (mgKOH / g) = [{(ba) × F × 28.05} / S] + D
However,
S: Sample collection amount (g)
a: Consumption of 0.5N alcoholic potassium hydroxide solution (ml)
b: Consumption of the 0.5N alcoholic potassium hydroxide solution in the blank experiment (ml)
F: Potency of 0.5N alcoholic potassium hydroxide solution D: Acid value (mgKOH / g)
<Measurement of acid value>
About 1 g of a sample is accurately weighed in a stoppered Erlenmeyer flask and dissolved by adding 100 ml of cyclohexanone solvent. To this is added phenolphthalein reagent as an indicator and held for 30 seconds. Thereafter, the solution is titrated with a 0.1N alcoholic potassium hydroxide solution until the solution becomes light red. The acid value was determined by the following formula (unit: mgKOH / g).
Acid value (mgKOH / g) = (5.611 × a × F) / S
However,
S: Sample collection amount (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution

<Method for measuring acid anhydride value>
About 1 g of a sample was accurately weighed in a stoppered Erlenmeyer flask and dissolved by adding 100 ml of 1,4-dioxane solvent. 10 mL of a mixed solution of octylamine, 1,4-dioxane and water (weight mixing ratio: 1.49 / 800/80) was added thereto, and the mixture was stirred for 15 minutes to complete the reaction. Thereafter, excess octylamine was titrated with a mixed solution of 0.02M perchloric acid and 1,4-dioxane. Moreover, the measurement was carried out using 10 mL of a mixed solution of octylamine, 1,4-dioxane, and water (weight mixing ratio: 1.49 / 800/80), to which no sample was added, as a blank. The acid anhydride value was determined by the following formula (unit: mgKOH / g).
Acid anhydride value (mgKOH / g) = 0.02 × (B−S) × F × 56.11 / W
B: Blank titration (mL)
S: Sample titration (mL)
W: Sample solid content (g)
F: 0.02 mol / L perchloric acid titer

<Measurement method of mass average molecular weight (Mw)>
For measurement of Mw, GPC (gel permeation chromatography) “HPC-8020” manufactured by Tosoh Corporation was used. GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent (THF; tetrahydrofuran) based on the difference in molecular size. For the measurement in the present invention, “LF-604” (manufactured by Showa Denko KK: GPC column for rapid analysis: 6 mm ID × 150 mm size) is connected in series to the column, the flow rate is 0.6 ml / min, and the column temperature. It carried out on the conditions of 40 degreeC, and the determination of the weight average molecular weight (Mw) was performed in polystyrene conversion.

[Synthesis Example 1]
<Synthesis example of acrylic resin>
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet pipe, inlet pipe, thermometer, 300 g of methyl ethyl ketone (hereinafter referred to as MEK) is heated to 80 ° C. while injecting nitrogen gas into the container. At the same temperature, 30 g of butyl methacrylate, 28 g of methyl methacrylate, 3 g of 1: 1 (mass ratio) mixture of lauryl methacrylate and tridecyl methacrylate, 12 g of methacrylic acid, 2,2′-azobisisobutyronitrile 8 g of the mixture was added dropwise over 1 hour to conduct a polymerization reaction. After the completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 1.2 parts of 2,2′-azobisisobutyronitrile dissolved in 50 g of MEK was added, and the mixture was reacted at 80 ° C. for 1 hour. An acrylic resin solution was obtained. The mass average molecular weight was 52,000, and the acid value was 78.2 mgKOH / g.

Here, since 30 g of butyl methacrylate having a molecular weight of 142 is 0.21 mol, 0.21 mol of an ester group is contained in 30 g of butyl methacrylate.
Hereinafter, similarly, 0.28 mol of ester groups are contained in 28 g of methyl methacrylate having a molecular weight of 100,
0.12 mol of ester groups are contained in 30 g of a mixture of lauryl methacrylate having an average molecular weight of 261 and tridecyl methacrylate,
In 12 g of methacrylic acid having a molecular weight of 86, 0.14 mol of an ester group is contained, and further 0.14 mol of a carboxyl group which is a reactive functional group is contained.
Therefore, the number of moles of ester bonds contained in 100 g of resin is 0.74 mol, and the carboxyl group is 0.14 mol. From this, when the functional group in 1 g of resin is calculated, the reactive functional group amount is 1.4 mmol / g, the other functional group amount is 7.4 mmol / g, and the total functional group amount is 8.8 mmol / g.

[Synthesis Examples 2-3], [Comparative Synthesis Examples 1-2]
Synthesis was performed according to the composition shown in Table 1 in the same manner as in Synthesis Example 1 to obtain an acrylic resin.

[Synthesis Example 4]
<Examples of polyester resin synthesis>
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube and thermometer, 57.6 g of sebacic acid, 3.2 g of trimesic acid, 27.5 g of cyclohexanedimethanol, 1.6-hexane Diol 9.7 g and tetrabutyl titanate 0.012 g were charged and stirred until the temperature of the exotherm became constant. When the temperature is stabilized, the temperature is raised to 110 ° C. After confirming that the temperature has stabilized, the temperature is raised to 120 ° C. after 30 minutes, and then the dehydration reaction is performed while raising the temperature by 10 ° C. every 30 minutes. Continued. When the temperature reached 230 ° C., the reaction was continued for 3 hours at the same temperature, and held for 1 hour under a vacuum of about 2 KPa. Thereafter, the temperature was lowered to obtain a polyester resin. The mass average molecular weight was 32,000, and the acid value was 39.8 mgKOH / g.

Here, since 57.6 g of sebacic acid having a bifunctional molecular weight 202 is 0.285 mol, 0.57 mol of a carboxyl group is contained in 57.6 g of sebacic acid.
Hereinafter, similarly, 0.045 mol of a carboxyl group is contained in 3.2 g of trifunctional trimesic acid having a molecular weight of 210,
In 27.5 g of cyclohexanedimethanol having a molecular weight of 144, 0.382 mol of an alcoholic hydroxyl group is contained,
In 9.7 g of 1.6-hexanediol, 0.164 mol of an alcoholic hydroxyl group is contained.
That is, since the monomer containing 0.615 mol of carboxyl group and 0.546 mol of alcoholic hydroxyl group is reacted, the amount of ester groups in the resin is 0.546 mol, and the alcoholic hydroxyl group remaining as the reactive functional group is 0. 0.069 mol.
Since the total amount of charged monomers is 97.9 g, the amount of reactive functional group is (0.069 / 97.9) × 1000 = 0.7 mmol / g when the functional group in 1 g of resin is calculated. The functional group amount is (0.546 / 97.9) × 1000 = 5.6 mmol / g, and the total functional group amount is 6.3 mmol / g.

[Synthesis Examples 5 to 10], [Comparative Synthesis Example 3]
Synthesis was performed in the same manner as in Synthesis Example 4 according to the composition shown in Table 2 to obtain a polyester resin.

[Synthesis Example 11]
<Synthesis example of polyurethane resin>
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, thermometer, 1.6-hexanediol 10.6 g, C36 dimer diol (PRIPOL 2033: CRODA JAPAN, OH value = 207 mgKOH / g) 113.3 g, 44.3 g of tolylene diisocyanate, and 240 g of toluene as a solvent were charged, and the mixture was heated to 60 ° C. with stirring in a nitrogen stream and dissolved uniformly. Subsequently, 0.016 g of dibutyltin dilaurate was added to the flask as a catalyst, and the mixture was stirred at 100 ° C. for 3 hours to carry out a urethanization reaction. Next, 40 g of toluene and 17.6 g of trimellitic anhydride were added, stirred at 90 ° C. for 1 hour, then heated to 135 ° C. and reacted for 4 hours. Cooling to room temperature gave a polyurethane resin. The mass average molecular weight was 11,000, and the acid value was 55.3 mgKOH / g.

Here, 0.16 mol of alcoholic hydroxyl group is contained in 10.6 g of 1.6-hexanediol having a bifunctional molecular weight of 118.
Hereinafter, similarly, 113.3 g of a difunctional molecular weight 540 of 36 dimer diol contains 0.42 mol of an alcoholic hydroxyl group,
In 44.3 g of bifunctional torylene diisocyanate having a molecular weight of 174, 0.508 mol of isocyanate groups are contained.
That is, since the monomer containing 0.6 mol of alcoholic hydroxyl group and 0.508 mol of isocyanate group is reacted, the amount of urethane group in the resin is 0.508 mol, and the alcoholic hydroxyl group remaining as the reactive functional group is 0. 092 mol.
The trimellitic anhydride having a molecular weight of 210 charged continuously has one carboxyl group and one acid anhydride group. Therefore, in 17.6 g of trimellitic anhydride, the acid anhydride group is 0.092 mol, 0.092 mol of carboxyl groups are included. This trimellitic anhydride eliminates the alcoholic hydroxyl group, producing 0.092 mol of ester groups and 0.183 mol of carboxyl groups.
Thus, when the functional group in 1 g of the resin is calculated, the reactive functional group amount is 0.98 mmol / g, the other functional group amount is 3.2 mmol / g, and the total functional group amount is 4.2 mmol / g.

[Synthesis Example 12], [Comparative Synthesis Example 4]
Synthesis was performed according to the composition shown in Table 3 in the same manner as in Synthesis Example 11 to obtain a polyurethane resin.

[Synthesis Example 13]
<Synthesis example of polyurethane urea resin>
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube and thermometer, 28.4 g of 1.6-hexanediol, 8.9 g of dimethylolbutanoic acid, 55.6 g of tolylene diisocyanate, solvent As a solution, 122 g of toluene was charged, and the mixture was heated to 60 ° C. with stirring in a nitrogen stream to be dissolved uniformly. Subsequently, 0.008 g of dibutyltin dilaurate was added to the flask as a catalyst and stirred at 100 ° C. for 3 hours to carry out a urethanization reaction. Next, the temperature was lowered to 80 ° C. and 1.9 g of hexylamine dissolved in 20 g of toluene was dropped over 30 minutes, and then stirred at 100 ° C. for 6 hours. After cooling to room temperature, a polyurethaneurea resin was obtained. The mass average molecular weight was 14,000, and the acid value was 34.8 mgKOH / g.

Here, 0.48 mol of an alcoholic hydroxyl group is contained in the bifunctional molecular weight 118 1.6-hexanediol 28.4.
In 8.9 g of dimethylolbutanoic acid having a bifunctional molecular weight of 148, 0.12 mol of alcoholic hydroxyl group and 0.06 mol of carboxyl group are contained,
0.638 mol of isocyanate groups are contained in 55.6 g of tolylene diisocyanate having a bifunctional molecular weight of 174.
That is, since a monomer containing 0.6 mol of an alcoholic hydroxyl group and 0.638 mol of an isocyanate group is reacted, the amount of urethane groups in the resin is 0.6 mol, and the isocyanate group remaining as a reactive functional group is 0. 038 mol.
0.038 mol of an amino group is contained in 3.9 g of monofunctional molecular weight 101 hexylamine which is continuously added. With this hexylamine, the isocyanate group disappears and 0.038 mol of urea group is formed.
Thus, when the functional group in 1 g of the resin is calculated, the reactive functional group amount is 0.62 mmol / g, the other functional group amount is 6.6 mmol / g, and the total functional group amount is 7.2 mmol / g.

[Synthesis Example 14], [Comparative Synthesis Example 5]
<Synthesis example of polyurethane urea resin>
Synthesis was performed according to the composition shown in Table 4 in the same manner as in Synthesis Example 13 to obtain a polyurethaneurea resin.

[Synthesis Example 15]
<Synthesis example of polyamide resin>
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer, 54.5 g of sebacic acid, 6.4 g of trimesic acid, preamine 1074: C36 dimer diamine (manufactured by Croda Japan Co., Ltd.) (Amine value: 210 mg KOH / g) 148.4 g and 100 g of ion-exchanged water were charged, and the mixture was stirred until the temperature of heat generation became constant. When the temperature was stabilized, the temperature was raised to 110 ° C., and after confirming the outflow of water, the temperature was raised to 120 ° C. after 30 minutes, and then the dehydration reaction was continued while raising the temperature by 10 ° C. every 30 minutes. . When the temperature reached 230 ° C., the reaction was continued for 3 hours at the same temperature, and held for 1 hour under a vacuum of about 2 KPa. Thereafter, the temperature was lowered to obtain a polyamide resin. The mass average molecular weight was 28,000, and the acid value was 20.0 mgKOH / g.

Here, in 202 g of sebacic acid having a bifunctional molecular weight of 202, 0.54 mol of a carboxyl group is contained,
In 6.3 g of trimesic acid having a molecular weight of 210, 0.09 mol of a carboxyl group is contained,
0.556 mol of amino groups are contained in the bifunctional molecular weight 534 of the preamine 1074 and 148.4 g.
That is, since the monomer containing 0.63 mol carboxyl group and 0.556 mol amino group is reacted, the amount of amide group in the resin is 0.556 mol, and the remaining carboxyl group as a reactive functional group is 0.074 mol. It is. Since 10 g of water escapes, when the functional group in 1 g of resin is calculated, the reactive functional group amount is 0.37 mmol / g, the other functional group amount is 2.79 mmol / g, and the total functional group amount is 3.2 mmol / g. g.

[Synthesis Examples 16 to 17], [Comparative Synthesis Example 6]
Synthesis was performed in the same manner as in Synthesis Example 15 in accordance with the composition shown in Table 5 to obtain a polyamide resin.

[Synthesis Example 18]
<Synthesis example of polyimide resin>
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet pipe, inlet pipe, and thermometer, 88.8 g of 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride “6FDA”, dimer isocyanate (BASF) Japan Co., Ltd., NCO% = 13.8%) 110.1 g IPDI nurate (nuphorate of isophorone diisocyanate) 6.06 g was charged and stirred until the temperature of heat generation became constant. When the temperature was stabilized, the temperature was raised to 110 ° C., and after confirming the outflow of water, the temperature was raised to 120 ° C. after 30 minutes, and then the dehydration reaction was continued while raising the temperature by 10 ° C. every 30 minutes. . When the temperature reached 230 ° C., the reaction was continued for 3 hours at the same temperature, and kept under a vacuum of about 2 kPa for 3 hours. Thereafter, the temperature was lowered to obtain a polyimide resin. The mass average molecular weight was 34,000, and the acid anhydride value was 7.5 mgKOH / g.

Here, 0.4 mol of an acid anhydride group is contained in 88.8 g of 6FDA having a bifunctional molecular weight of 444,
In 110.1 g of dimerized isocyanate having a bifunctional molecular weight of 638, 0.345 mol of an isocyanate group is contained,
0.027 mol of an isocyanate group is contained in 6.1 g of a trifunctional molecular weight 667 IPDI nurate.
That is, since the monomer containing 0.4 mol of acid anhydride group and 0.373 mol of isocyanate group is reacted, the amount of imide group in the resin is 1.879 mol, and the acid anhydride group remaining as a reactive functional group Is 0.138 mol. Since 6.7 g of water escapes, the functional group amount in the resin 1 g is calculated to be 0.14 mmol / g, the other functional group amount is 1.88 mmol / g, and the total functional group amount is 2. 0 mmol / g.

[Synthesis Examples 19 to 23], [Comparative Synthesis Example 7]
Synthesis was performed according to the composition shown in Table 6 in the same manner as in Synthesis Example 18 to obtain a polyimide resin.

[Synthesis Example 24]
<Synthesis example of polycarbonate resin>
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, thermometer, ethylene carbonate 25.2 g, 1,4-cyclohexanedimethanol 38.9 g, trimethylolpropane 4.0 g, The transesterification was carried out for 8 hours while adding 0.003 g of tetrabutyl titanate and distilling off a mixture of cyclohexanedimethanol and ethylene carbonate under normal pressure and stirring. During this period, the reaction temperature is gradually raised to 190 ° C. while raising the temperature by 10 ° C. every 30 minutes, so that the composition of the distillate is close to the azeotropic composition of the mixture of cyclohexanedimethanol and ethylene carbonate. Adjusted. The reaction was continued for 3 hours at the same temperature, and was further maintained for 3 hours under a vacuum of about 2 KPa. Thereafter, the temperature was lowered to obtain a polycarbonate resin. The mass average molecular weight was 14,000, and the hydroxyl value was 48.2 mgKOH / g.

Here, 0.54 mol of alcoholic hydroxyl group is contained in 38.9 g of 1,4-cyclohexanedimethanol having a bifunctional molecular weight of 144, and 4.0 g of trimethylolpropane having a trifunctional molecular weight of 134 is alcohol. 0.09 mol of a hydroxyl group is contained,
0.22 mol of carbonate groups are contained in 25.2 g of bifunctional ethylene carbonate having a molecular weight of 88.
That is, since the monomer containing 0.63 mol of alcoholic hydroxyl group and 0.29 mol of carbonate group is reacted, the amount of carbonate group in the resin is 0.29 mol, and the alcoholic hydroxyl group remaining as the reactive functional group is 0. 0.059 mol. Since 17.7 g of ethylene glycol is lost, the functional groups in 1 g of resin are calculated. The amount of reactive functional groups is 1.16 mmol / g, the amount of other functional groups is 5.67 mmol / g, and the total amount of functional groups is 6. 0.8 mmol / g.

[Synthesis Example 25]
<Synthesis example of polycarbonate resin>
A 4-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer was charged with 25.2 g of ethylene carbonate, 35.5 g of 1.6-hexanediol, and 0.003 g of tetrabutyl titanate. The ester exchange reaction was carried out for 8 hours while distilling off a mixture of 1.6 hexanediol and ethylene carbonate under pressure and stirring. During this period, the reaction temperature is gradually raised to 190 ° C. while raising the temperature by 10 ° C. every 30 minutes, and the composition of the distillate is close to the azeotropic composition of the mixture of 1.6-hexanediol and ethylene carbonate. Adjusted as follows. The reaction was continued for 3 hours at the same temperature, and was further maintained for 3 hours under a vacuum of about 2 KPa. Thereafter, the temperature was decreased, 2.2 g of trimellitic anhydride and 30 g of toluene were added and reacted at 110 ° C. for 3 hours, and then the temperature was decreased to obtain a polycarbonate resin. The mass average molecular weight was 13,000, the acid value was 20.4 mgKOH / g, and the hydroxyl value was 15.3 mgKOH / g. The amount of polar functional group calculated from the structure was 7.5 mmol / g.

[Comparative Synthesis Example 8]
Synthesis was performed according to the composition shown in Table 7 in the same manner as in Synthesis Example 24 to obtain a polycarbonate resin.

[Synthesis Example 26]
<Synthesis example of polyphenylene ether resin>
A four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, an inlet tube, and a thermometer was placed in a constant temperature water bath at 30 ° C. 9.9 g of copper (I) chloride was added to 2.0 g of pyridine, stirred while blowing oxygen, and 5.0 g of toluene was added to obtain a copper (II) pyridine complex solution serving as a catalyst solution. In addition, 98.0 g of 2,6-dimethylphenol and 30.0 g of 2.2-bis (4-hydroxy-3,5-dimethylphenyl) propane were dissolved in 3.0 g of toluene to obtain a phenol solution. Thereafter, both the catalyst and phenol solutions were added dropwise and mixed vigorously in a reaction vessel maintained at 30 ° C. and purged with oxygen. 66 minutes after the start of monomer addition, the oxygen was switched to nitrogen to stop the polymerization. The reaction solution was dropped into 110 g of methanol containing 0.3 g of concentrated hydrochloric acid. The precipitated polymer was filtered and washed with 25.0 g methanol, then 25.0 g methanol containing 1.0 g concentrated hydrochloric acid and finally 25.0 g methanol. Polyphenylene which is dried at 120 ° C. for 3 hours, diluted with 50.0 g of toluene and 50.0 g of 2-propanol, and having a total functional group content of 0.01 mmol / g or more and 9.0 mmol / g or less (A) An ether resin was obtained. The mass average molecular weight was 15,000, and the phenolic hydroxyl value was 15.4 mgKOH / g.

In this case, 0.80 mol of phenolic hydroxyl group is contained in 98.0 mg of 2,6-dimethylphenol having a bifunctional molecular weight of 122, and 2,2-bis (4-hydroxy-3,5 having a bifunctional molecular weight of 284 is included. -Dimethylphenyl) propane (30.0 g) contains 0.21 mol of a phenolic hydroxyl group.
The total amount of phenolic hydroxyl groups and ether groups after polymerization is the total amount of initial phenol groups. Since the solid amount is 128 g, the total functional group amount is 7.9 mmol / g according to the calculation formula of 1.01 / 128 × 1000.

[Synthesis Example 27]
<Example of synthesis of olefin resin>
The synthesis was completed in three stages: main chain synthesis, hydrogenation, and acid modification.
<Main chain synthesis>
In a dry nitrogen atmosphere, 330 g of cyclohexane, 576 g of a 25 wt% cyclohexane solution of styrene (144 g as styrene), 9 mmol of n-BuLi, and 45 mmol of THF were added to a stainless steel reactor having a content of 5 liters. For 30 minutes.
Next, 1733 g (306 g as butadiene) of a 17.7% solution of butadiene / cyclohexane was added, and the temperature of the jacket was raised to 75 ° C. to polymerize for 1 hour. Subsequently, 4.05 mmol of dimethyldichlorotin (Me ₂ SnCl ₂ ) was added, and a coupling reaction was performed for 15 minutes to synthesize the main chain.

<Hydrogenation reaction>
Into a reaction vessel purged with nitrogen, 1000 g of dried and purified cyclohexane was added, 100 mmol of biscyclopentadienyltitanium dichloride was added, and an n-hexane solution containing 200 mmol of trimethylaluminum was added with sufficient stirring. The reaction was carried out for 3 days to obtain a hydrogenation catalyst.
To the resin synthesized in the main chain, the above hydrogenation catalyst is added to 100 ppm in terms of titanium per 100 parts by mass of the resin, a hydrogenation reaction is performed at a hydrogen pressure of 0.7 MPa, and a temperature of 75 ° C. Obtained. The resin solution was dried in a vacuum oven at 0.1 Torr for 24 hours for the next step, and a resin with a solid content of 100% was taken out.

<Acid modification>
100 g of the resin obtained above is dry blended with 1 g of maleic anhydride, 0.1 g of benzoyl peroxide, and 0.06 g of Irganox 1010 (manufactured by BASF Japan, antioxidant), 32 mm biaxial extrusion with vent Using a machine, the mixture was further mixed and melt-kneaded to obtain a pellet-like sample. The temperature of the twin screw extruder during mixing and melt-kneading was set to 40 ° C. at the bottom of the hopper, 80 ° C. for the mixing zone, 170 ° C. for the reaction zone, and 180 ° C. for the die.
To 100 parts by weight of the obtained pellet-shaped sample, 85 parts by weight of acetone and 85 parts by weight of heptane were added, and the mixture was heated and stirred at 85 ° C. for 2 hours in a pressure resistant reactor. After completion of the operation, the pellets were collected with a wire mesh and vacuum-dried at 140 ° C. and 0.1 Torr for 20 hours to obtain an olefin resin. The mass average molecular weight was 50,000, and the acid anhydride value was 5.7 mgKOH / g.

  Here, since the resin is modified by adding 1 g of monofunctional maleic acid containing 0.01 mol of acid anhydride group to 100 g of the resin having no functional group, the modified resin is used. When the functional group in 1 g is calculated, the reactive functional group amount is 0.1 mmol / g, the other functional group amount is 0 mmol / g, and the total functional group amount is 0.1 mmol / g.

[Synthesis Examples 28-30]
<Example of synthesis of olefin resin>
Synthesis was performed according to the composition shown in Table 9 in the same manner as in Synthesis Example 27 to obtain an olefin resin.

[Synthesis Example 31]
<Example of synthesis of olefin resin>
After synthesizing according to the composition shown in Table 9 in the same manner as in Synthesis Example 27, 200 g of water was added to open the acid anhydride to obtain an olefin resin.

[Synthesis Examples 32-33]
<Example of synthesis of olefin resin>
Synthesis was performed according to the composition shown in Table 9 in the same manner as in Synthesis Example 27, but an olefin-based resin was obtained without performing the second stage hydrogenation operation.

[Comparative Synthesis Examples 9 to 10]
<Example of synthesis of olefin resin>
Synthesis was performed according to the composition shown in Table 9 in the same manner as in Synthesis Example 27, but an olefin-based resin was obtained without performing the third step of acid modification.

[Synthesis Example 34]
<Synthesis example of fluororesin>
A 1000 mL stainless steel autoclave is charged with 35.2 g of hexafluoropropylene, 46.5 g of vinyl pivalate, 4.93 g of hydroxybutyl vinyl ether, 12.7 g of ethyl vinyl ether, 0.7 g of crotonic acid and 0.8 g of diisopropyl peroxydicarbonate. After cooling to 0 ° C., the mixture was degassed under reduced pressure. Thereafter, the mixture was heated to 40 ° C. with stirring and reacted for 24 hours. The reaction was stopped when the internal pressure of the reactor dropped from 5 kg / cm ² to 2 kg / cm ² to obtain a fluororesin. The mass average molecular weight was 48,000, and the acid value was 4.6 mgKOH / g.

Here, 0.36 mol of ester groups are contained in 46.5 g of vinyl pivalate having a molecular weight of 128, 0.18 mol of ester groups are contained in 12.7 g of ethyl vinyl ether having a molecular weight of 72, and hydroxybutyl vinyl ether having a molecular weight of 116. In 4.93 g, 0.042 mol of alcoholic hydroxyl group and ester group are contained, and in 0.70 g of crotonic acid having a molecular weight of 86, 0.008 mol of carboxyl group is contained.
That is, a monomer containing 0.042 mol of an alcoholic hydroxyl group, 0.008 mol of a carboxyl group and 0.582 mol of an ester group is reacted, and these functional groups remain as they are after the reaction. From this, when the functional group in 1 g of resin is calculated, the reactive functional group amount is 0.5 mmol / g, the other functional group amount is 5.82 mmol / g, and the total functional group amount is 6.3 mmol / g.

[Synthesis Example 35]
<Synthesis example of fluororesin>
Synthesis was performed according to the composition shown in Table 10 in the same manner as in Synthesis Example 34 to obtain a fluororesin.

[Synthesis Example 36]
<Synthesis Example of Styrene Maleic Anhydride Resin>
In a 4-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer, 300 g of MEK was placed, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 516.1 g of styrene at the same temperature. Then, a mixture of 48.4 g of maleic anhydride and 0.2 g of benzoyl peroxide was added dropwise over 1 hour to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 0.2 g of benzoyl peroxide dissolved in 50 g of MEK was added and reacted at 80 ° C. for 1 hour to obtain a styrene maleic anhydride resin solution. It was. The weight average molecular weight was 62,000, and the acid anhydride value was 49.0 mgKOH / g.
Here, 0.49 mol of an acid anhydride group is contained in 48.4 g of maleic anhydride having a monofunctional molecular weight of 98. Since the acid anhydride group remains even after the reaction, calculating the functional group in 1 g of resin, the amount of reactive functional group is 0.9 mmol / g, the amount of other functional groups is 0 mmol / g, the total amount of functional groups is 0.9 mmol / g.

[Synthesis Examples 37 to 38], [Comparative Synthesis Example 11]
<Synthesis Example of Styrene Maleic Anhydride Resin>
Synthesis was performed according to the composition shown in Table 11 in the same manner as in Synthesis Example 36 to obtain a styrene maleic anhydride resin.

Hereinafter, in Tables 1 to 11, common BMA: n-butyl methacrylate MMA: methyl methacrylate LMA: lauryl methacrylate TDMA: tridecyl methacrylate LMA / TDMA = 1/1 mixture tBA: ter-butyl acrylate MAA: methacrylic acid HEMA: 2- Hydroxyethyl methacrylate AIBN: Azobisisobutyronitrile preporal 2033: C36 dimer diol (OH value: 207 mgKOH / g), manufactured by Croda Japan Co., Ltd.
Pripol 1009: C36 dimer acid (acid value: 195.0 mgKOH / g), manufactured by Croda Japan Co., Ltd.
TDI: tolylene diisocyanate TMA: trimellitic anhydride preamine 1074: C36 dimer diamine (amine value: 210 mgKOH / g), manufactured by Croda Japan Co., Ltd.
NBDA: norbornanediamine bisaniline M: manufactured by Mitsui Chemicals Fine Co., Ltd., 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene IPDI nurate: nurate Wandamine HM of isophorone diisocyanate HM: Shin Nippon Rika 4,4'-diaminodicyclohexylmethane KF-8010 manufactured by Shin-Etsu Silicone Co., Ltd., both terminal amino-modified silicone oil (amine value: 430 mgKOH / g)
HAB: 4,4′-diamino-3,3′-dihydroxybiphenyl 1,6-HD: 1,6-hexanediol 2,6-DMP: 2,6-dimethylphenol BXF: 2,2-bis (4-hydroxy -3,5-dimethylphenyl) propane n-BuLi: normal butyl lithium THF: tetrahydrofuran

Example 1
With respect to 100 g of the solid content of the resin (A) having a total functional group amount of 0.01 mmol / g or more and 9.0 mmol / g or less of the polar functional group obtained in Synthesis Example 1, as an organometallic compound (B), When the Al chelate compound “Al chelate A” (manufactured by Kawaken Fine Chemical Co., Ltd.) is used, the metal in the organometallic compound (B) is 0.3 mol with respect to 1 mol of the reactive functional group in the resin (A). The epoxy group-containing compound (C) was added in an amount of jER1031S (manufactured by Mitsubishi Chemical Corporation, tetrafunctional tetrakisphenol type epoxy compound) with respect to 1 mol of the reactive functional group in the resin (A). The thermosetting composition was prepared by adding an amount such that the epoxy group in the containing compound (C) was 2 mol, and dissolving in a cyclohexanone solvent so that the solid content concentration was 25%.
This thermosetting composition was uniformly applied onto a release-treated polyester film so that the film thickness after drying was 30 μm and dried to provide an adhesive sheet. Next, another release-treated polyester film was laminated on the adhesive sheet to obtain an adhesive sheet with a double-sided protective film.

[Examples 2-3]
A double-sided protective film in the same manner as in Example 1 except that the acrylic resin obtained in Synthesis Examples 2 and 3 was used instead of the acrylic resin obtained in Synthesis Example 1 with the composition shown in Table 21. An adhesive sheet with a mark was prepared.

[Comparative Examples 1-2]
Double-sided protective film in the same manner as in Example 1 except that the acrylic resin obtained in Comparative Synthesis Examples 1 and 2 was used instead of the acrylic resin obtained in Synthesis Example 1 with the composition shown in Table 21. An adhesive sheet with a mark was prepared.

[Comparative Example 3]
An adhesive sheet with a double-sided protective film was prepared in the same manner as in Example 1 except that the organometallic compound (B) was not used with the composition shown in Table 21.

[Comparative Example 4]
With the composition shown in Table 21, an adhesive sheet with a double-sided protective film was prepared in the same manner as in Example 1 except that the epoxy group-containing compound (C) was not used.

[Examples 4 to 10], [Comparative Example 5]
Example 1 with the composition shown in Table 22 except that instead of the acrylic resin obtained in Synthesis Example 1, the polyester resins obtained in Synthesis Examples 4 to 10 and Comparative Synthesis Example 3 were used. Similarly, an adhesive sheet with a double-sided protective film was prepared.

[Comparative Example 6], [Comparative Example 7]
The composition shown in Table 22 was the same as Example 4 except that the organometallic compound (B) was not used (Comparative Example 6) and the epoxy group-containing compound (C) was not used (Comparative Example 7). An adhesive sheet with a double-sided protective film was prepared.

[Examples 11 to 12], [Comparative Example 8]
The composition shown in Table 23 was the same as in Example 1 except that instead of the acrylic resin obtained in Synthesis Example 1, the polyurethane resins obtained in Synthesis Examples 11 to 12 and Comparative Synthesis Example 4 were used. Thus, an adhesive sheet with a double-sided protective film was prepared.

[Comparative Example 9], [Comparative Example 10]
The composition shown in Table 23 was the same as Example 11 except that the organometallic compound (B) was not used (Comparative Example 9) or the epoxy group-containing compound (C) was not used (Comparative Example 10). Thus, an adhesive sheet with a double-sided protective film was prepared.

[Examples 13 to 14], [Comparative Example 11]
Example 1 except that the polyurethane urea resin obtained in Synthesis Examples 13 to 14 and Comparative Synthesis Example 5 was used in place of the acrylic resin obtained in Synthesis Example 1 with the composition shown in Table 24. Similarly, an adhesive sheet with a double-sided protective film was prepared.

[Comparative Example 12], [Comparative Example 13]
The composition shown in Table 24 was the same as Example 13 except that the organometallic compound (B) was not used (Comparative Example 12) or the epoxy group-containing compound (C) was not used (Comparative Example 13). Thus, an adhesive sheet with a double-sided protective film was prepared.

[Examples 15 to 17], [Comparative Example 14]
The composition shown in Table 25 was the same as that of Example 1 except that the polyamide resins obtained in Synthesis Examples 15 to 17 and Comparative Synthesis Example 6 were used instead of the acrylic resins obtained in Synthesis Example 1. Thus, an adhesive sheet with a double-sided protective film was prepared.

[Comparative Example 15], [Comparative Example 16]
The composition shown in Table 25 was the same as Example 15 except that the organometallic compound (B) was not used (Comparative Example 15) or the epoxy group-containing compound (C) was not used (Comparative Example 16). Thus, an adhesive sheet with a double-sided protective film was prepared.

[Examples 18 to 23], [Comparative Example 17]
The composition shown in Table 26 was the same as that of Example 1 except that the polyimide resins obtained in Synthesis Examples 18 to 23 and Comparative Synthesis Example 7 were used instead of the acrylic resins obtained in Synthesis Example 1. Thus, an adhesive sheet with a double-sided protective film was prepared.

[Comparative Example 18], [Comparative Example 19]
The composition shown in Table 26 was the same as that of Example 18 except that the organometallic compound (B) was not used (Comparative Example 18) or the epoxy group-containing compound (C) was not used (Comparative Example 19). Thus, an adhesive sheet with a double-sided protective film was prepared.

[Examples 24 to 25], [Comparative Example 20]
The composition shown in Table 27 is the same as that of Example 1 except that instead of the acrylic resin obtained in Synthesis Example 1, the polycarbonate resins obtained in Synthesis Examples 24 to 25 and Comparative Synthesis Example 8 were used. Thus, an adhesive sheet with a double-sided protective film was prepared.

[Comparative Example 21], [Comparative Example 22]
The composition shown in Table 27 was the same as that of Example 24 except that the organometallic compound (B) was not used (Comparative Example 21) or the epoxy group-containing compound (C) was not used (Comparative Example 22). Thus, an adhesive sheet with a double-sided protective film was prepared.

[Example 26]
A double-sided protective film having the composition shown in Table 28 in the same manner as in Example 1 except that the polyphenylene ether resin obtained in Synthesis Example 26 was used instead of the acrylic resin obtained in Synthesis Example 1. An adhesive sheet with a mark was prepared.

[Comparative Example 23], [Comparative Example 24]

The composition shown in Table 28 was the same as that of Example 26 except that the organometallic compound (B) was not used (Comparative Example 23) or the epoxy group-containing compound (C) was not used (Comparative Example 24). Thus, an adhesive sheet with a double-sided protective film was prepared.

[Examples 27 to 33], [Comparative Examples 25 to 26]
Example 1 except that the olefin resins obtained in Synthesis Examples 27 to 33 and Comparative Synthesis Examples 9 and 10 were used in place of the acrylic resin obtained in Synthesis Example 1 with the composition shown in Table 29. In the same manner as above, an adhesive sheet with a double-sided protective film was prepared.

[Comparative Example 27], [Comparative Example 28]
The composition shown in Table 30 was the same as that of Example 27 except that the organometallic compound (B) was not used (Comparative Example 27) and the epoxy group-containing compound (C) was not used (Comparative Example 28). Thus, an adhesive sheet with a double-sided protective film was prepared.

[Examples 34 to 35]
In the composition shown in Table 31, double-sided protection was carried out in the same manner as in Example 1 except that the fluororesins obtained in Synthesis Examples 34 to 35 were used in place of the acrylic resin obtained in Synthesis Example 1. An adhesive sheet with a film was prepared.

[Comparative Example 29], [Comparative Example 30]
The composition shown in Table 31 was the same as that of Example 34 except that the organometallic compound (B) was not used (Comparative Example 27) or the epoxy group-containing compound (C) was not used (Comparative Example 28). Thus, an adhesive sheet with a double-sided protective film was prepared.

[Comparative Example 30]
With the composition shown in Table 31, an adhesive sheet with a double-sided protective film was prepared in the same manner as in Example 1 except that the epoxy group-containing compound (C) was not used.

[Examples 36 to 38], [Comparative Example 31]
In the same manner as in Example 1 except that the styrene maleic anhydride resin obtained in Synthesis Examples 36 to 38 was used in place of the acrylic resin obtained in Synthesis Example 1 with the composition shown in Table 32. An adhesive sheet with a double-sided protective film was prepared.

[Comparative Example 32], [Comparative Example 33]
The composition shown in Table 32 was the same as that of Example 36 except that the organometallic compound (B) was not used (Comparative Example 32) or the epoxy group-containing compound (C) was not used (Comparative Example 33). Thus, an adhesive sheet with a double-sided protective film was prepared.

[Examples 39 to 47], [Examples 48 to 56], [Examples 57 to 65], [Examples 67 to 74]
Double-sided protective film in the same manner as in Examples 15, 18, 26, and 27 except that the types of the organometallic compound (B) and the epoxy group-containing compound (C) were changed in the compositions shown in Tables 33 to 36. An adhesive sheet with a mark was prepared.

[Examples 75 to 80], [Examples 81 to 86], [Examples 87 to 92], [Examples 93 to 98]
Except having changed the compounding quantity of the organometallic compound (B) with the composition shown to Tables 37-40, it carried out similarly to Example 15, 18, 26, and 27, respectively, and created the adhesive sheet with a double-sided protective film. .

[Examples 99 to 104], [Examples 105 to 110], [Examples 111 to 116], [Examples 117 to 122]
Except having changed the compounding quantity of the epoxy-group containing compound (C) with the composition shown in Tables 41-44, it carried out similarly to Example 15, 18, 26, and 27, respectively, and created the adhesive sheet with a double-sided protective film. did.

[Examples 123-127], [Examples 128-132], [Examples 133-137], [Examples 138-142]
Adhesive sheets with double-sided protective films were prepared in the same manner as in Examples 15, 18, 26, and 27 except that the resin (A) was used in combination with the compositions shown in Tables 45 to 48.

[Examples 143 to 151], [Examples 152 to 160], [Examples 161 to 169], [Examples 170 to 178]
Adhesive sheets with double-sided protective films were prepared in the same manner as in Examples 15, 18, 26, and 27 except that the other curing agents (D) were added with the compositions shown in Tables 49 to 52.

Hereinafter, it is common in Tables 21-52.
jER1031S: manufactured by Mitsubishi Chemical Corporation, tetrafunctional tetrakisphenol type epoxy compound jER604: manufactured by Mitsubishi Chemical Corporation, tetrafunctional glycidylamine compound jER630: manufactured by Mitsubishi Chemical Corporation, trifunctional glycidylamine compound TETRAD-C: Mitsubishi Gas TetraAD-X, a tetrafunctional glycidylamine compound manufactured by Kagaku Co., Ltd .: Tetrafunctional glycidylamine compound jER306, manufactured by Mitsubishi Gas Chemical Co., Ltd., bisphenol F type epoxy compound BL3175, manufactured by Mitsubishi Chemical Co., Ltd. ), Isocyanurate type blocked isocyanate V-07: manufactured by Nisshinbo Co., Ltd., polycarbodiimide compound V-03: manufactured by Nisshinbo Co., Ltd., polycarbodiimide compound aluminum chelate A: manufactured by Kawaken Fine Chemical Co., Ltd., Al chelate compound ASBD : Kawaken Fine Chemical ( Co., Ltd., Al alkoxide compound TC401: Matsumoto Fine Chemical Co., Ltd., Ti chelate compound TA-30: Matsumoto Fine Chemical Co., Ltd., Ti alkoxide compound ZC700: Matsumoto Fine Chemical Co., Ltd., Zr chelate compound TC800: Matsumoto Fine Chemical ( Co., Ltd., Ti acylate compound Chemitite PZ: manufactured by Nippon Shokubai Co., Ltd., polyfunctional aziridine compound DICY: dicyandiamide CABRUS 2: manufactured by Daiso Co., Ltd., polysulfide silane coupling agent KBM803: manufactured by Shin-Etsu Silicone Co., Ltd., 3-mercapto Propyltrimethoxysilane noxeller TOT-N: manufactured by Ouchi Shinsei Chemical Co., Ltd., thiuram disulfide compound Noxeller DM: manufactured by Ouchi Shinsei Chemical Co., Ltd., thiazolyl disulfide compound

  For the adhesive sheets obtained in Examples and Comparative Examples, processability, adhesiveness, heat resistance, flexibility, electrical insulation, dielectric constant, and dielectric loss tangent were evaluated by the following methods. The results are shown in Tables 21-52.

<Evaluation>
(1) Dimensional stability A 65 mm × 65 mm adhesive sheet from which the protective film has been removed is sandwiched between polyimide films with a thickness of 75 μm [“Kapton 300H” manufactured by Toray DuPont Co., Ltd.], and 80 ° C. Then, a pressure-bonding process was performed for 30 minutes at 160 ° C. and 1.0 MPa. Furthermore, this test piece was heat-cured at 160 ° C. for 2 hours to prepare an evaluation test piece. About this test piece, the difference of the area of the adhesive bond layer before a press-bonding process and after thermosetting was measured, and processability was evaluated by setting this as the protruding area. This workability is to evaluate the degree to which the adhesive layer is softened by heat during the crimping process and causes the positional deviation of the circuit board and the contact between the wirings, and the result was judged according to the following criteria.
A ... "Projection area ≤ 100mm ² "
B ... “100 mm ² <overhang area ≦ 200 mm ² ”
C: “200 mm ² <overhang area ≦ 350 mm ² ”
D: “350 mm ² <excess area ≦ 500 mm ² ”
E ... "500mm ² <protruding area"

(2) Adhesive The test piece prepared in the evaluation of dimensional stability was cut into a width of 10 mm and a length of 65 mm, and a T peel peel test was conducted at 23 mm relative humidity and 50% relative humidity at a pulling speed of 300 mm / min. The strength (N / cm) was measured. This test evaluates the adhesive strength of the adhesive layer when used at room temperature, and the results were judged according to the following criteria.
A ... "12 (N / cm) <Adhesive strength"
B: “8 (N / cm) <Adhesion strength ≦ 12 (N / cm)”
C: “5 (N / cm) <Adhesion strength ≦ 8 (N / cm)”
D: “3 (N / cm) <Adhesion strength ≦ 5 (N / cm)”
E ... "Adhesive strength ≤ 3 (N / cm)"

(3) Heat resistance As in (2) above, test pieces cut out to a width of 10 mm and a length of 65 mm are stored for 24 hours or more in an atmosphere of 23 ° C. and 50% relative humidity, and then molten solder at various temperatures. The polyimide film surface was brought into contact with and floated for 1 minute. Thereafter, the appearance of the test piece was visually observed to evaluate the presence or absence of adhesion abnormality such as foaming, floating and peeling of the cured adhesive layer. This test evaluates the thermal stability of the cured adhesive layer at the time of solder contact by appearance. Good heat resistance does not change the appearance, while poor heat resistance has no solder. Foaming or peeling occurs after treatment. These evaluation results were judged according to the following criteria.
A ... "No change in appearance even at 300 ° C"
B: “No change in appearance at 280 ° C. Foaming is confirmed at 300 ° C.”
C: "No change in appearance even at 260 ° C. Foaming is confirmed at 280 ° C" D: "No change in appearance at 240 ° C. Foaming is confirmed at 260 ° C" E: "240 Foaming is observed at ℃. ''

(4) Flexibility Uniform coating of the curable resin composition on a polyimide film with a thickness of 75 μm [“Kapton 300H” manufactured by Toray DuPont Co., Ltd.] so that the film thickness after drying becomes 30 μm. Then, this test piece was heat-cured at 160 ° C. for 2 hours to prepare a test piece for evaluation. The evaluation test piece was bent 180 degrees with the cured coating surface facing outward, and the number of times until cracking occurred was evaluated according to the following criteria.
A ... "No cracks are seen even after bending 20 times"
B ... "No cracks are seen even after bending 14 times. Cracks occur up to 20 times"
C ... "No cracks are seen even if bent 8 times. Cracks occur up to 14 times"
D: “No cracks are seen even if bent 3 times. Cracks occur up to 8 times”
E ... "Crack occurs before bending 3 times"

(5) Electrical insulation A 65 mm × 65 mm adhesive sheet from which the protective film has been removed is a 25 μm thick polyimide film [“Kapton 100H” manufactured by Toray DuPont Co., Ltd.] and a copper circuit on the polyimide. It is sandwiched between the formed comb pattern (conductor pattern width / space width = 50 μm / 50 μm) and printed wiring board, laminated at 80 ° C., and then subjected to crimping for 30 minutes at 160 ° C. and 1.0 MPa. It was. Furthermore, this test piece was heat-cured at 160 ° C. for 2 hours to prepare an evaluation test piece. A DC voltage of 50 V was continuously applied to the conductor circuit of this test piece for 100 hours under an atmosphere of a temperature of 130 ° C. and a relative humidity of 85%, and the insulation resistance value between the conductors after 100 hours was measured. The evaluation criteria are as follows.
A: Insulation resistance value 10 ⁹ Ω or more B ... Insulation resistance value 10 ⁸ or more and less than 10 ⁹ Ω C ... Insulation resistance value 10 ⁷ or more and less than 10 ⁸ Ω D ... Insulation resistance value 10 ⁶ or more 10 Less than ⁷ Ω E ・ ・ ・ Insulation resistance less than 10 ⁶

(6) Dielectric constant The protective film on one side of the adhesive sheet with the double-sided protective film prepared in Examples and Comparative Examples is removed, and after heat curing at 160 ° C. and 1.0 MPa for 1 hour, the protective film on both sides is removed. Then, a test piece for evaluation was produced. About this test piece, the dielectric constant and dielectric loss tangent in the measurement temperature of 23 degreeC and the measurement frequency of 5 GHz were calculated | required with the cavity resonator method using the dielectric constant measuring apparatus by an EA Corporation.
A: Dielectric constant is 2.6 or less B: Dielectric constant is more than 2.6 and 2.8 or less C ... Dielectric constant is more than 2.8 and 3.0 or less D ... Dielectric constant is greater than 3.0 and less than or equal to 3.2 E ... Dielectric constant is greater than 3.2

(7) Dielectric loss tangent A: Dielectric tangent is 0.001 or less B: Dielectric tangent is greater than 0.001 and 0.002 or less C: Dielectric tangent is greater than 0.002 D is 01 or less D: Dissipation factor is greater than 0.01 and less than 0.05 E: Dissipation factor is greater than 0.05

As can be seen from the examples and comparative examples shown in Tables 21 to 32, the total content of polar functional groups used in Comparative Examples 1, 2, 5, 8, 11, 14, 17, and 20, that is, reactive functional groups When the adhesive sheet was made using a resin having a total amount of the functional group having a hetero atom other than halogen and more than 9 [mmol / g], the dielectric constant and dielectric loss tangent were significantly deteriorated.
Further, as can be seen from Comparative Examples 25, 26, and 31, when an adhesive sheet is prepared using a resin having a total content of polar functional groups of less than 0.01 [mmol / g], dimensional stability, adhesiveness, and heat resistance. The electrical insulation was significantly deteriorated.
Moreover, as can be seen from Comparative Examples 3, 6, 9, 12, 15, 18, 21, 23, 27, 29, and 32, the epoxy group-containing compound (C) was used without using the organometallic compound (B). As a result, the dimensional stability and dielectric loss tangent deteriorated significantly.
Further, as can be seen from Comparative Examples 4, 7, 10, 13, 16, 19, 22, 24, 28, 30, 33, the organometallic compound (B) was used without using the epoxy group-containing compound (C). As a result, the adhesiveness and heat resistance deteriorated significantly.

  On the other hand, the resin (A) having a total content of polar functional groups used in the examples of 0.01 mmol / g or more and 9 mmol / g or less, a specific amount of the organometallic compound (B), and the epoxy group-containing compound (C) When it contains, good results are obtained in a well-balanced manner in all physical properties, and in particular, it achieves compatibility between adhesiveness and low dielectric loss tangent, which are in a contradictory relationship in the comparative example, and compatibility between dimensional stability and heat resistance. I was able to. This is because the combination of the organometallic compound (B) and the epoxy group-containing compound (C) makes it possible to suppress the generation of polar groups at the time of curing, resulting in a low dielectric constant derived from the resin (A), low This is considered to be because the good adhesiveness with the copper derived from the epoxy group-containing compound (C) was utilized while maintaining the characteristics of the dielectric loss tangent. In addition, since the organometallic compound (B) reacts rapidly with the reactive functional group in the resin (A), the dimensional stability is improved and the robustness by the reaction between the resin (A) and the epoxy group-containing compound (C). This is considered to be because heat resistance can be imparted by forming a proper crosslink.

  The thermosetting composition used for forming the adhesive sheet of the present invention provides a cured product excellent in adhesion, heat resistance after humidification, heat resistance, flexibility, electrical insulation, dielectric constant, and dielectric loss tangent. Suitable for use in coating materials for electronic materials including wiring boards, solder resists for circuit coating, coverlay films, adhesives for electromagnetic wave shielding, plating resists, interlayer electrical insulation materials for printed wiring boards, optical waveguides, etc. it can.

Claims (14)

A thermosetting adhesive sheet formed from a thermosetting composition that satisfies all of the following conditions (1) to (9) .
(1) A resin (A1), an organometallic compound (B), and a trifunctional or higher functional epoxy group-containing compound (C) are included.
(2) The resin (A1) does not have an epoxy group, and has a reactive functional group that can react with at least one of the organometallic compound (B) and the epoxy group-containing compound (C).
(3) The resin (A1) may have a functional group other than the reactive functional group and having a hetero atom other than halogen.
(4) Resin (A2) which does not have the said reactive functional group and has a functional group which has hetero atoms other than a halogen may be included.
(5) Resin (A3) which does not have any of the said reactive functional group and the functional group which has hetero atoms other than a halogen may be included.
(6) The total amount of the reactive functional group and the functional group having a hetero atom other than the halogen contained in a total of 1 g of the resin (A1), the resin (A2), and the resin (A3) is 0.01 mmol or more, 9 mmol or less.
(7) The organometallic compound (B) includes an aluminum chelate compound, an aluminum alkoxide compound, an aluminum acylate compound, a titanium chelate compound, a titanium alkoxide compound, a titanium acylate compound, a zirconium chelate compound, a zirconium alkoxide compound, and a zirconium acylate compound. It is at least a kind selected from the group consisting of
(8) The metal in the organometallic compound (B) is 0.03 to 3 mol relative to 1 mol of the reactive functional group of the resin (A1).
(9) The resin (A1) comprises an acrylic resin, a polyester resin, a polyurethane resin, a polyurethane polyurea resin, a polyamide resin, a polyimide resin, a polycarbonate resin, a polyphenylene ether resin, a fluororesin, a polyolefin resin, and a styrene maleic anhydride resin. It is at least one selected from the group.   The thermosetting adhesive sheet according to claim 1, wherein the reactive functional group is at least one selected from the group consisting of a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group, and an acid anhydride group.   The thermosetting adhesive sheet according to claim 1 or 2, wherein the hetero atom in the functional group having a hetero atom other than halogen is at least one selected from the group consisting of O, N, S and P.   The functional group having a hetero atom other than halogen is at least one selected from the group consisting of an ester group, an amide group, an imide group, a urethane group, a urea group, an ether group, a carbonate group, an acryloyl group, and a methacryloyl group. The thermosetting adhesive sheet according to any one of 1 to 3. The thermosetting adhesive sheet according to any one of claims 1 to 4 , wherein the total reactive functional group value of 1 g of the resin (A1) is 1 to 80 mg in terms of potassium hydroxide. The thermosetting adhesive sheet according to any one of claims 1 to 5 , wherein the epoxy group in the epoxy group-containing compound (C) is 0.1 to 12 mol relative to 1 mol of the reactive functional group of the resin (A1). . It is a compound other than the organometallic compound (B) and the epoxy group-containing compound (C), and reacts with at least one of the reactive functional group, organometallic compound (B) and epoxy group possessed by the resin (A1). The thermosetting adhesive sheet according to any one of claims 1 to 6 , further comprising another curing agent (D) to be obtained. 8. The thermosetting adhesive sheet according to claim 7, wherein the other curing agent (D) is at least one selected from the group consisting of an isocyanate compound, a carbodiimide compound, and a sulfur element-containing compound. The thermosetting adhesive sheet with a sheet-like base material which has the thermosetting adhesive sheet of any one of Claims 1-8, and two sheet-like base materials which cover both surfaces of the said thermosetting adhesive sheet. The thermosetting adhesive sheet with a sheet-like substrate according to claim 9 , wherein at least one of the two sheet-like substrates is a peelable sheet-like substrate. A thermosetting composition satisfying all of the following conditions (1) to (9) is applied to at least one surface of the sheet-like base material, dried to form a thermosetting adhesive sheet, and the thermosetting adhesive sheet A method for producing a thermosetting adhesive sheet with a sheet-like substrate, wherein another sheet-like substrate is stacked on the other surface of the sheet.
(1) A resin (A1), an organometallic compound (B), and a trifunctional or higher functional epoxy group-containing compound (C) are included.
(2) The resin (A1) does not have an epoxy group, and has a reactive functional group that can react with at least one of the organometallic compound (B) and the epoxy group-containing compound (C).
(3) The resin (A1) may have a functional group other than the reactive functional group and having a hetero atom other than halogen.
(4) Resin (A2) which does not have the said reactive functional group and has a functional group which has hetero atoms other than a halogen may be included.
(5) Resin (A3) which does not have any of the said reactive functional group and the functional group which has hetero atoms other than a halogen may be included.
(6) The total amount of the reactive functional group and the functional group having a hetero atom other than the halogen contained in a total of 1 g of the resin (A1), the resin (A2), and the resin (A3) is 0.01 mmol or more, 9 mmol or less.
(7) The organometallic compound (B) includes an aluminum chelate compound, an aluminum alkoxide compound, an aluminum acylate compound, a titanium chelate compound, a titanium alkoxide compound, a titanium acylate compound, a zirconium chelate compound, a zirconium alkoxide compound, and a zirconium acylate compound. It is at least a kind selected from the group consisting of
(8) The metal in the organometallic compound (B) is 0.03 to 3 mol relative to 1 mol of the reactive functional group of the resin (A1).
(9) The resin (A1) comprises an acrylic resin, a polyester resin, a polyurethane resin, a polyurethane polyurea resin, a polyamide resin, a polyimide resin, a polycarbonate resin, a polyphenylene ether resin, a fluororesin, a polyolefin resin, and a styrene maleic anhydride resin. It is at least one selected from the group. A sheet-like cured product having a dielectric loss tangent of 0.0001 to 0.01 at a frequency of 5 GHz, which is obtained by thermosetting the thermosetting adhesive sheet according to any one of claims 1 to 8 . A printed wiring board with a protective sheet, wherein the circuit surface of the printed wiring board having a conductive circuit is protected by a sheet-like substrate through the sheet-like cured product according to claim 12 . The thermosetting adhesive sheet according to any one of claims 1-8, said circuit surface of the printed wiring board having a conductive circuit, sandwiched between the sheet-like substrate, the thermosetting adhesive sheet A method for producing a printed wiring board with a protective sheet, which is thermoset.