WO2010038733A1

WO2010038733A1 - Resin composition for adhesive agent, adhesive agent and adhesive sheet each comprising same, and laminate for print circuit board adhered by using same

Info

Publication number: WO2010038733A1
Application number: PCT/JP2009/066935
Authority: WO
Inventors: 秀樹田中; 武伊藤; 達也粟田; 慎太郎南原; 武久家根; 裕子麻田
Original assignee: 東洋紡績株式会社
Priority date: 2008-09-30
Filing date: 2009-09-29
Publication date: 2010-04-08
Also published as: JP5126239B2; JPWO2010038733A1

Abstract

Disclosed is a resin composition for an adhesive agent, which comprises: (a) a polyester resin containing a radical-polymerizable site; (b) a polymer of a radical-polymerizable monomer; (c) a modified polyester resin modified with a polymer of a radical-polymerizable monomer, in which the resin (a) and the polymer (b) are bound to each other; (d) a polyurethane resin having an acid value of 100 to 1000 equivalents/10⁶ g inclusive; and (e) an epoxy compound having a dicyclopentadiene structure. In the resin composition, maleic anhydride makes up 10 to 60 mass% inclusive of the radical-polymerizable monomer, the resin (c) has a glass transition temperature (Tg(c)) of 0 to 80˚C inclusive, the resin (d) has a glass transition temperature (Tg(d)) of –10 to 60˚C inclusive, Tg(c) and Tg(d) meet the requirement represented by the formula: 50 ≥ Tg(c)–Tg(d) ≥ 5, and the acid value of the resin (c) (AV(c) equivalent/10⁶ g) and the acid value of the resin (d) (AV(d) equivalent/10⁶ g) meet the requirement represented by the formula: 8,000 ≥ AV(c)-AV(d) ≥ 200. Also disclosed are an adhesive agent, an adhesive sheet and a laminate for a print circuit board, each of which comprises the resin composition.

Description

Resin composition for adhesive, adhesive containing the same, adhesive sheet, and laminate for printed wiring board bonded using the same

The present invention provides adhesion to various plastic films, adhesion to metals such as copper, aluminum, and stainless steel, adhesion to glass epoxy, high-temperature heat resistance that can cope with lead-free solder, and FPC for HDD drive. Resin composition that can maintain the adhesive strength under high temperature and high humidity that can be used for various adhesives, secure the sheet life of the B-stage adhesive sheet that can also be used at room temperature, and an adhesive containing the same And a laminated body bonded using the same.

In recent years, adhesives have been used in various fields, but due to the diversification of purpose of use, adhesiveness to various plastic films and adhesives to metals such as copper, aluminum, and stainless steel, compared to conventional adhesives. There are demands for further improvements in performance, such as adhesion, adhesion to glass epoxy, heat resistance, and moisture resistance.

As adhesives for circuit boards including flexible printed wiring boards (hereinafter sometimes abbreviated as FPC), for example, epoxy / acryl butadiene adhesives, epoxy / polyvinyl butyral adhesives, and the like are used. . When used in such applications, solder heat resistance is required, but in recent years, heat resistance at higher temperatures (the adhesive layer does not peel or swell) is required to support lead-free solder. Conventionally used epoxy / acryl butadiene adhesives and epoxy / polyvinyl butyral adhesives cannot satisfy the required performance.

In addition, since the FPC used in a hard disk drive (hereinafter sometimes abbreviated as HDD) is used in a bent state, a strong shearing force is applied to the bonding interface. In particular, with the recent high performance of HDDs, the environment in which adhesives are actually used has become severe, such as the number of motor rotations and the internal temperature of HDDs increasing. Specifically, it is required to maintain stable adhesion performance under high temperature and high humidity conditions such as 60 ° C. and 90% relative humidity. However, conventionally used epoxy / acryl butadiene adhesives and epoxy / polyvinyl butyral adhesives cannot satisfy the required performance.

Also, the adhesive is often stored, distributed, and sold once as a semi-cured (B stage) sheet. Therefore, in the B stage, it is required to ensure the sheet life, and high curing reactivity is required during actual use (when the B stage adhesive sheet and the base material are bonded). Conventionally, FPC adhesive sheets are often refrigerated and the sheet life is secured even with epoxy / acryl butadiene adhesives and epoxy / polyvinyl butyral adhesives. However, in recent years, due to demands for reducing manufacturing costs, it is often required that the products can be stored and distributed at room temperature. The required performance is not satisfied with an epoxy / acryl butadiene adhesive or an epoxy / polyvinyl butyral adhesive (Japanese Patent Laid-Open No. 2001-291964 (Patent Document 1), Japanese Patent Laid-Open No. 2003-313526). Gazette (Patent Document 2), JP-A-2005-139387 (Patent Document 3), JP-A-2005-139391 (Patent Document 4)).

JP 2001-291964 A JP 2003-31526 A JP 2005-139387 A JP 2005-139391 A

The problem of the present invention is to improve each of the problems that these conventional adhesives have, specifically adhesion to various plastic films, adhesion to metals such as copper, aluminum and stainless steel, Adhesiveness to glass epoxy, high-temperature heat resistance that can handle lead-free solder, maintenance of adhesive strength under high-temperature and high-humidity conditions that can also be used for HDD drive FPC adhesives, and B stage that can also be used at room temperature It is in providing the resin composition which can achieve the sheet life ensuring of the adhesive sheet and the above, the adhesive agent containing this, and the laminated body adhere | attached using this.

The present invention includes a resin composition containing the following resin composition, an adhesive containing the resin composition, an adhesive sheet, a laminate for a printed wiring board bonded using the same, and a printed wiring board comprising the laminate as the constituent elements described on the left It is.
(1) a polyester resin (a) containing a radical polymerizable moiety,
A polymer of a radically polymerizable monomer (b),
A modified polyester resin (c) modified with a polymer of a radically polymerizable monomer, in which the resin (a) and the polymer (b) are bonded;
A polyurethane resin (d) having an acid value of 100 equivalents / 10 ⁶ g or more and 1000 equivalents / 10 ⁶ g or less,
An epoxy compound (e) having a dicyclopentadiene structure,
Containing
10 mass% or more and 60 mass% or less of the radical polymerizable monomer is maleic anhydride,
The glass transition temperature Tg (c) of the resin (c) is 0 ° C. or higher and 80 ° C. or lower,
The glass transition temperature Tg (d) of the resin (d) is −10 ° C. or higher and 60 ° C. or lower,
The relationship between Tg (c) and Tg (d) is the following formula (1)
50 ≧ Tg (c) −Tg (d) ≧ 5 (1)
The filling,
An acid value AV (c) equivalents / 10 ⁶ g and the acid value AV (d) eq / 10 ⁶ g relationship formula of the resin (d) of (c) (2)
8,000 ≧ AV (c) −AV (d) ≧ 200 (2)
The resin composition for adhesives satisfy | fills.
(2) The resin composition according to (1), wherein the acid value of the resin (c) is 400 equivalents / 10 ⁶ g or more and 8,500 equivalents / 10 ⁶ g or less.
(3) The resin composition according to (1), wherein the resin (d) has a number average molecular weight of 5,000 or more and 100,000 or less.
(4) The resin composition according to (1), wherein the resin (a) has a number average molecular weight of 5,000 or more and 50,000 or less.
(5) When the total molar amount of all the acid components constituting the resin (a) is 100 mol%, the aromatic acid component is 30 mol% or more, and the acid component and the radical polymerizable site including a radical polymerizable site The resin composition as described in (1) above, wherein the total of glycol components contained is 0.5 mol% or more and 20 mol% or less.
(6) The polymer (b) is composed of a part derived from the monomer constituting the resin (a) with respect to the resin (a), the polymer (b) and the resin (c) as a whole. The resin composition according to (1), wherein the ratio of the monomer-derived portion to the monomer is 10/90 or more and 99/1 or less in terms of mass ratio.
(7) When the total mass of the resin (a), the polymer (b), and the resin (c) is Wc, and the mass of the resin (d) is Wd, Wc / Wd is 1/99 or more and 80/20. The resin composition as described in (1) above, wherein:
(8) An adhesive comprising the resin composition according to (1).
(9) An adhesive sheet comprising the resin composition according to (1).
(10) A laminate in which a plurality of plate-like bodies and / or foil-like bodies are bonded together with an adhesive layer, wherein at least a part of the adhesive layer contains the resin composition described in (1) above. Laminated body for printed wiring board.
(11) The plurality of plate-like bodies and / or foil-like bodies are made of one or more materials selected from the group consisting of polyester resins, polyimide resins, polyamideimide resins, copper, aluminum, glass epoxy, and stainless steel. The laminate for a printed wiring board according to the above (10).
(12) A printed wiring board comprising the laminate according to (10) as a constituent element.

According to the present invention, adhesion to various plastic films, adhesion to metals such as copper, aluminum, and stainless steel, adhesion to glass epoxy, high-temperature heat resistance capable of dealing with lead-free solder, HDD Containing a resin composition capable of maintaining the adhesive strength under high temperature and high humidity that can be used for FPC adhesives for drives, ensuring the sheet life of the B stage adhesive sheet that can also be used at room temperature, and the above. And a laminated body bonded using the adhesive can be obtained.

The resin composition of the present invention mainly comprises a modified polyester resin modified with a polymer of a radical polymerizable monomer (hereinafter referred to as a modified polyester resin), a polyurethane resin, and an epoxy compound, and the radical polymerizable monomer. And a non-modified polyester resin. It is essential that the modified polyester resin and polyurethane resin have an acid value by introducing a carboxyl group, an anhydrous carboxyl group or the like into the resin skeleton. If it does not have an acid value, a crosslinking reaction with the epoxy compound does not occur, so that a tough cured coating film cannot be obtained and a high adhesive force cannot be obtained.

The acid value of the polyurethane resin used in the present invention is 100 equivalents / 10 ⁶ g or more and 1,000 equivalents / 10 ⁶ g or less. When the acid value is less than 100 equivalents / 10 ⁶ g, the adhesion to the metal-based substrate tends to be insufficient. If the acid value exceeds 1,000 equivalents / 10 ⁶ g, the urethane reaction during the production of the polyurethane resin may be slow, and the solution viscosity may be increased, resulting in poor productivity. It is also expected to adversely affect the durability of the ester bond. The lower limit of the acid value is preferably 150 equivalents / 10 ⁶ g, more preferably the lower limit of the acid value is 200 equivalents / 10 ⁶ g, and still more preferably the lower limit of the acid value is 400 equivalents / 10 ⁶ g. A preferred upper limit is 900 equivalents / 10 ⁶ g, a more preferred upper limit is 800 equivalents / 10 ⁶ g, and a more preferred upper limit is 700 equivalents / 10 ⁶ g. In addition, the acid value said here shows the equivalent number of carboxylic acid contained per 10 ⁶ g of resin.

By using dimethylolpropionic acid, dimethylolbutanoic acid, or the like as a chain extender, a carboxyl group can be introduced into the molecular skeleton of the polyurethane resin to give an acid value. In the case of a resin composition consisting only of a polyurethane resin and an epoxy compound (hereinafter referred to as polyurethane resin / epoxy compound), the adhesion to various substrates at normal temperature is good. Moreover, when it is set as the sheet | seat of a semi-hardened state (B stage), even if it bonds together to a base material after storing for 3 months at room temperature, without refrigerated storage, high adhesive performance is shown. However, in the solder reflow process (260 ° C.) when lead-free solder is used, the adhesive layer swells and the heat resistance is insufficient. In particular, after the adhesive is stored at high temperature and high humidity (40 ° C., relative humidity 80%) for 2 days and then undergoes a solder reflow process (260 ° C.), it is sufficient for the stress due to rapid evaporation of water contained in the adhesive. The resin cannot be resisted, and the resin peels off from the substrate. This is presumably due to the low heat resistance derived from the polyurethane resin skeleton and the hygroscopicity derived from the urethane bond. Further, when examined as an FPC adhesive for HDDs (examination of adhesion performance at 90 ° C. and relative humidity of 90%), it was easily peeled off when a shear stress was applied to the adhesion interface. This is also presumed to be due to hygroscopicity derived from urethane bonds. In addition, when the glass transition temperature of the polyurethane resin is designed to be 60 ° C. or higher, peeling of the adhesive interface under the above conditions is not observed, but conversely, the adhesive performance at room temperature is lowered and becomes unpractical. In order to suppress swelling and peeling of the adhesive layer in the solder reflow process (260 ° C.), it is necessary to provide the adhesive layer with further heat resistance and a function to relieve stress generated by rapid evaporation of moisture. There is. In order to be usable in HDD applications, it is necessary to maintain a high bonding ability over a wide range from room temperature to over 60 ° C.

As a result of intensive studies to solve the problems of the polyurethane resin / epoxy compound binary adhesive composition as described above, the resin system is a modified polyester resin / polyurethane resin / epoxy compound ternary system, and the modified polyester resin is used. When the lead-free solder is used while controlling the acid value of the polyurethane resin, the glass transition temperature, and further controlling the skeleton of the epoxy compound to maintain the adhesiveness at room temperature and the B sheet life. It has been found that there is no swelling in the solder reflow process (260 ° C.), and even when examined as an FPC adhesive for HDD (examination of adhesion performance at 90 ° C. relative humidity 90%), peeling of the adhesive interface can be suppressed.

The role of the modified polyester resin is to impart high heat resistance (260 ° C.) and maintain adhesive performance at high temperature and high humidity (60 ° C. relative humidity 90%). First, the modified polyester resin is produced by copolymerizing a monomer containing a radical polymerizable moiety such as a double bond with the polyester resin, and radically reacting the radical polymerizable monomer in the organic solvent solution. Thus, a modified polyester resin graft-modified with a polymer of a radical polymerizable monomer can be easily obtained. At this time, 10 mass% or more and 60 mass% or less of a radically polymerizable monomer is maleic anhydride. Carboxylic anhydride is more reactive with epoxy compounds than carboxyl groups. When this modification method is used, a site having a high acid value and high reactivity with an epoxy compound can be easily introduced into the polyester resin. In the ternary reaction of the modified polyester resin / polyurethane resin / epoxy compound of the present invention, the three parties do not have a completely compatible and uniform structure, but have a non-uniform structure and have such excellent characteristics. Realize. It can be easily confirmed by observation with a phase contrast microscope and an electron microscope that the cured coating film made of the resin composition of the present invention has a non-uniform structure. First, a modified polyester resin having an anhydride carboxyl group with high acid value and high reactivity with an epoxy compound and an epoxy compound produce a crosslinked structure having a high crosslinking density, and then a relatively crosslinking density with a polyurethane resin and an epoxy compound. It is assumed that a small cross-linked structure is generated. A portion having a high crosslinking density composed of a modified polyester resin and an epoxy compound has high heat resistance and can withstand a solder reflow process at 260 ° C. In particular, even when the adhesive is stored for 2 days under high temperature and high humidity (40 ° C. relative humidity 80%) and then undergoes a solder reflow process (260 ° C.), peeling from the substrate does not occur. This is presumed that the part of the cross-linked structure consisting of polyurethane resin and epoxy compound with a relatively low cross-linking density plays the role of a soft segment and can relieve stress due to rapid evaporation of moisture contained in the adhesive. .

In the present invention, the acid value of the modified polyester resin by the polymer of the radical polymerizable monomer is preferably 400 to 8,500 equivalent / 10 ⁶ g. More preferably, it is 650 to 7,000 equivalent / 10 ⁶ g, and still more preferably 900 to 5,500 equivalent / 10 ⁶ g. If the acid value is less than 400 equivalents / 10 ⁶ g, the adhesion to the metal-based substrate tends to be insufficient. Furthermore, since the crosslinking density is small, when blended with a polyurethane resin, the lack of heat resistance of polyurethane may not be compensated. When the acid value exceeds 8,500 equivalents / 10 ⁶ g, the degree of crosslinking of the cured coating film increases, so that the internal stress increases and the adhesive strength tends to decrease. In addition, the reactivity at the B stage tends to increase and the seat life tends to deteriorate.

As described above, 10 mass% or more and 60 mass% or less of the radical polymerizable monomer in the present invention is maleic anhydride. Preferably they are 20 to 55 mass%, More preferably, they are 30 to 50 mass%. By using maleic anhydride, a carboxylic anhydride group highly reactive with an epoxy compound can be easily introduced into the modified polyester resin. When maleic anhydride is 10% by mass or less of the radical polymerizable monomer, the reaction between the modified polyester resin and the epoxy compound does not proceed faster than the reaction between the polyurethane resin and the epoxy compound. In the coating film, the non-uniformity is small and the required performance is not easily expressed. On the other hand, when it is 60% by mass or more, a large amount of unreacted maleic anhydride is present, so that the cured coating film becomes brittle, water resistance is lost, and the adhesive strength is lowered. In particular, the adhesive strength under high humidity decreases. In order to introduce a radical polymerizable moiety into a polyester resin containing a radical polymerizable moiety, it is common to copolymerize unsaturated dicarboxylic acids such as fumaric acid, maleic acid, and itaconic acid. The unsaturated group of dicarboxylic acid and maleic anhydride hardly react by radical reaction. In these radically polymerizable monomers, an electron-withdrawing group is adjacent to the unsaturated bond site, and the charge of the unsaturated group and the radical generated therefrom is biased to be positive. In order to polymerize maleic anhydride efficiently, a radical polymerizable monomer having an electron donating group adjacent to the unsaturated bond site may be used. These radically polymerizable monomers are highly reactive with maleic anhydride, fumaric acid, itaconic acid and the like because the unsaturated groups and the radicals generated therefrom are negatively charged. As radically polymerizable monomers in which an electron donating group is adjacent to the unsaturated bond site, vinyl radical polymerizable monomers such as styrene, α-methylstyrene, t-butylstyrene, and N-vinylpyrrolidone can be used. , Vinyl esters such as vinyl acetate, vinyl ethers such as vinyl butyl ether and vinyl isobutyl ether, allylic radical polymerizable monomers such as allyl alcohol, glycerol monoallyl ether, pentaerythritol monoallyl ether, trimethylolpropane monoallyl ether, Butadiene and the like, and one or a mixture of two or more of these are used. Most preferred is a vinyl radical polymerizable monomer such as styrene. Therefore, in order to suppress the unreacted product of maleic anhydride, it is essential to copolymerize a radical polymerizable monomer such as styrene, and it is not preferable to use 60% by mass or more.

In the present invention, the acid value of the dry coating film of the modified polyester resin by the polymer of the radical polymerizable monomer is AV (c) (equivalent / 10 ⁶ g), and the acid value of the polyurethane resin is AV (d) (equivalent / In the case of 10 ⁶ g), AV (c) -AV (d) is 200 or more and 8,000 or less, preferably 300 or more and 6,500 or less, more preferably 400 or more and 5,000 or less. When AV (c) -AV (d) is 200 equivalents / 10 ⁶ g or less, the difference in crosslink density between the modified polyester / epoxy compound part and the polyurethane part / epoxy compound part is small, and the stress relaxation of the polyurethane resin / epoxy compound part The capacity is small, and the heat resistance in the solder reflow region is insufficient. When AV (c) -AV (d) is 8,000 equivalent / 10 ⁶ g or more, the reactivity of the modified polyester portion is high, the reaction with the epoxy is fast, and the sheet life cannot be maintained. Further, since the cross-linking density of the entire system is increased, the stress relaxation with respect to the peeling stress becomes insufficient, and the peeling strength in a wide range from room temperature to high temperature is reduced.

Also, by controlling the glass transition temperature of the modified polyester resin and polyurethane resin, it is possible to achieve high adhesion performance in a wide temperature range. In particular, in the modified polyester resin of the present invention, a polymer of a radically polymerizable monomer having an anhydrous carboxyl group that is highly reactive with an epoxy compound is chemically bonded to the polyester resin by a graft reaction. When measuring the dynamic viscoelasticity, the loss tangent peak is a broad peak including 130 to 150 ° C, which is the loss tangent peak of the cured film of the epoxy compound alone, and has high adhesive performance in a wide temperature range. Can be shown. In order to achieve stable adhesive performance in a wider range of temperatures using the modified polyester resin / polyurethane resin / epoxy compound ternary system by utilizing the properties of the modified polyester resin, the glass transition temperature of the polyurethane resin is required. A modified polyester resin having a high glass transition temperature may be used.

The glass transition temperature of the polyurethane resin used in the present invention is −10 to 60 ° C. When the glass transition temperature is −10 ° C. or lower, the adhesiveness at high temperatures tends to be insufficient. When the glass transition temperature exceeds 60 ° C., the melt viscosity becomes high, so that the bonding with the base material in the B-stage state becomes insufficient, causing a decrease in peel strength. Moreover, since the elastic modulus at normal temperature is increased, the peel strength at normal temperature is decreased. The lower limit of the preferable glass transition temperature is −5 ° C., the lower limit of the more preferable glass transition temperature is 0 ° C., and the lower limit of the more preferable glass transition temperature is 5 ° C. A preferred upper limit is 55 ° C, a more preferred upper limit is 50 ° C, and a more preferred upper limit is 45 ° C. Methods for controlling the glass transition temperature include a method for controlling the glass transition temperature of the constituent polyester diol and a method for controlling the content of polyisocyanate constituting the polyurethane resin.

In the present invention, the glass transition temperature of the coating film of the modified polyester resin is 0 to 80 ° C., preferably 5 to 75 ° C., more preferably 10 to 70 ° C. Below 0 ° C., the heat resistance of the cured coating film reacted with the curing agent is small, and the adhesiveness at high temperatures is poor. Furthermore, since the reactivity in the B stage state is increased, the seat life is deteriorated. On the other hand, if the temperature exceeds 80 ° C., the melt viscosity of the resin is high even after modification, and the bonding with the base material in the B-stage state becomes insufficient, resulting in a decrease in peel strength. Moreover, since the elastic modulus at normal temperature is increased, the peel strength at normal temperature is decreased.

When the glass transition temperature of the dried coating film of the modified polyester resin is Tg (c) (° C.) and the glass transition temperature of the polyurethane resin is Tg (d) (° C.), Tg (c) −Tg (d) is 5 It is not lower than 50 ° C. and preferably not higher than 7 ° C. and not higher than 45 ° C., more preferably not lower than 10 ° C. and not higher than 40 ° C. When Tg (c) -Tg (d) is 5 ° C. or lower, the adhesiveness in a wide temperature range from room temperature to high temperature cannot be maintained. In particular, the heat resistance in the solder reflow temperature range is insufficient for polyurethane resins / epoxy compounds, and it can be compensated by blending modified polyester. The heat resistance becomes insufficient. In addition, modified polyester is highly reactive with epoxy compound-based curing agents, and the B-stage sheet life is poor with a single resin system. Life can be improved. However, the modified polyester itself modified with a radically polymerizable monomer cannot secure stability unless the glass transition temperature is raised. When Tg (c) -Tg (d) is 5 ° C. or lower, The combined effect of is insufficient. Further, when Tg (c) -Tg (d) is 50 ° C. or higher, an effect of improving the sheet life is seen, but the adhesiveness in a wide temperature range is not obtained.

As shown above, by adding a modified polyester resin to a polyurethane resin / epoxy compound system to form a ternary system, high heat resistance (260 ° C) is imparted and high temperature and high humidity (60 ° C relative humidity 90%) ) Can maintain the adhesion performance. On the other hand, in the modified polyester resin / epoxy compound system, the adhesive performance can be maintained at high heat resistance (260 ° C.) and high temperature and high humidity (60 ° C. relative humidity 90%). It becomes lower than the resin / epoxy compound system and the modified polyester resin / polyurethane resin / epoxy compound system. If the substrate is a material that is difficult to adhere, such as a glossy surface of an aluminum plate or copper foil, it may not be practical.

The resin composition of the present invention contains an epoxy compound having a dicyclopentadiene structure. A cured coating film composed of an epoxy compound having a dicyclopentadiene skeleton is highly hydrophobic and has a very low moisture absorption rate, and is therefore effective in maintaining adhesive performance at high temperature and high humidity (60 ° C. relative humidity 90%). In addition, since the dicyclopentadiene skeleton is bulky, the distance between glycidyl groups in the compound is large, and there is an effect of lowering the crosslinking density of the cured coating film. In particular, the adhesive is subjected to high temperature and high humidity (40 ° C., relative humidity 80%). After two days of storage, when the solder reflow process (260 ° C.) is performed, the ability to relieve stress due to rapid evaporation of moisture contained in the bonded body is great, and the peeling of the adhesive resin from the substrate can be suppressed. it can. Other epoxy can also be used together as an epoxy resin to be blended. For example, glycidyl ether type such as bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, novolak glycidyl ether, brominated bisphenol A diglycidyl ether, glycidyl ester type such as hexahydrophthalic acid glycidyl ester, dimer acid glycidyl ester, triglycidyl Glycidylamine such as isocyanurate, tetraglycidyldiaminodiphenylmethane, or alicyclic or aliphatic epoxide such as 3,4-epoxycyclohexylmethylcarboxylate, epoxidized polybutadiene, epoxidized soybean oil, or tetraglycidyldiaminodiphenylmethane, triglycidylparaamino Phenol, tetraglycidylbisaminomethylcyclohexanone, N, N, ', Glycidyl amine type, such as N'- tetraglycidyl -m- xylene diamine. Glycidylamines such as N, N, N ′, N′-tetraglycidyl-m-xylenediamine have a catalytic amino group in the skeleton, so that the curing speed is high and a stable B-stage state can be obtained. it can. The compounding amount of the epoxy compound is preferably 5 to 30 parts by mass with respect to 100 parts by mass of the polyurethane resin and the modified polyester resin. If it is this range, since the balance of the reaction point of polyester and an epoxy compound suits, strong adhesive performance can be obtained.

In the present invention, the polyester resin containing a radical polymerizable moiety preferably has an aromatic acid content of 30 mol% or more, more preferably 45, when the total amount of all acid components in the polyester resin composition is 100 mol%. It is at least mol%, more preferably at least 60 mol%. When the aromatic acid is 30 mol% or less, the cohesive strength of the coating film made of resin and the coating film made of resin / curing agent is weak, and a decrease in the adhesive strength to various substrates is observed.

Examples of aromatic acids include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, diphenic acid, and 5-hydroxyisophthalic acid. In addition, aromatic compounds having a sulfonic acid group such as sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5- (4-sulfophenoxy) isophthalic acid, sulfoterephthalic acid, etc. Group dicarboxylic acid, metal salt of sulfoterephthalic acid, ammonium salt, metal salt of 5-sulfoisophthalic acid, ammonium salt, metal salt of 4-sulfophthalic acid, ammonium salt, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5 -(4-sulfophenoxy) isophthalic acid metal salt, ammonium salt, sulfoterephthalic acid metal salt, aromatic dicarboxylic acid having a sulfonate group such as ammonium salt, p-hydroxybenzoic acid, p-hydroxyphenylpropionic acid, p-hydroxyphenylacetic acid, 6-hydroxy-2-naphthoic acid And aromatic oxycarboxylic acids such as 4,4-bis (p-hydroxyphenyl) valeric acid. Among these, terephthalic acid, isophthalic acid, and a mixture thereof are particularly preferable in terms of increasing the cohesive strength of the coating film.

Examples of acid components other than aromatic acids include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and alicyclic dicarboxylic acids such as acid anhydrides thereof, and succinic acid. And aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and dimer acid.

On the other hand, the glycol component is preferably composed of an aliphatic glycol, an alicyclic glycol, an aromatic-containing glycol, an ether bond-containing glycol, or the like. Examples of aliphatic glycols include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neo Pentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl-2-butylpropanediol, hydroxypivalic acid neopentyl glycol ester Dimethylol heptane, 2,2,4-trimethyl-1,3-pentanediol, and the like. Examples of alicyclic glycols include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, tricyclodecandiol, tricyclodecane dimethylol, spiroglycol, hydrogenated bisphenol. And ethylene oxide adduct and propylene oxide adduct of hydrogenated bisphenol A. Examples of ether bond-containing glycols include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, neopentyl. Glycol ethylene oxide adducts and neopentyl glycol propylene oxide adducts can also be used if necessary. Examples of aromatic-containing glycols include para-xylene glycol, meta-xylene glycol, ortho-xylene glycol, 1,4-phenylene glycol, 1,4-phenylene glycol ethylene oxide adduct, bisphenol Obtained by adding 1 to several moles of ethylene oxide or propylene oxide to two phenolic hydroxyl groups of bisphenols such as ethylene oxide adduct and propylene oxide adduct of bisphenol A and bisphenol A Examples include glycols.

In addition, an oxycarboxylic acid compound having a hydroxyl group and a carboxyl group in the molecular structure can also be used as a raw material for polyester, such as 5-hydroxyisophthalic acid, p-hydroxybenzoic acid, p-hydroxyphenethyl alcohol, p- Examples thereof include hydroxyphenylpropionic acid, p-hydroxyphenylacetic acid, 6-hydroxy-2-naphthoic acid, 4,4-bis (p-hydroxyphenyl) valeric acid and the like.

In the polyester resin used in the present invention, when the total molar amount of all acid components and all glycol components constituting the polyester resin is 200% for the purpose of introducing a branched skeleton into the polyester resin as necessary, 0% . About 3 to 5 mol% of tri- or higher functional polycarboxylic acids and / or polyols may be copolymerized. In particular, when a cured coating film is obtained by reacting with a curing agent, by introducing a branched skeleton, the terminal group concentration (reaction point) of the resin is increased, and a strong coating film having a high crosslinking density can be obtained. Examples of tri- or higher functional polycarboxylic acids are trimellitic acid, trimesic acid, ethylene glycol bis (anhydro trimellitate), glycerol tris (anhydro trimellitate), trimellitic anhydride, pyromellitic anhydride Acid (PMDA), oxydiphthalic dianhydride (ODPA), 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride (BTDA), 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride Anhydride (BPDA), 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4 ′-(hexafluoroisopropylidene) diphthalic dianhydride (6FDA), 2, Compounds such as 2′-bis [(dicarboxyphenoxy) phenyl] propane dianhydride (BSAA) can be used. Trifunctional or higher polyol - glycerin Examples Le, trimethylol - Ruetan, trimethylol - trimethylolpropane, pentaerythritol - Le like. When using a tri- or higher functional polycarboxylic acid and / or polyol, the total acid component or the total glycol component is 0.1 to 5 mol%, preferably 0.5 to 3 mol%. Copolymerization is good, and if it exceeds 5 mol%, mechanical properties such as elongation at break of the coating film may be lowered, and gelation may occur during polymerization.

In the polyester resin used in the present invention, when the total molar amount of all acid components and all glycol components constituting the polyester resin is set to 200% for the purpose of introducing a carboxyl group at the end of the polyester resin as necessary, it is 0. An acid addition of about 1 to 10 mol% can be performed. When a monocarboxylic acid, a dicarboxylic acid, or a polyfunctional carboxylic acid compound is used for the acid addition, the molecular weight is reduced by transesterification. Therefore, it is preferable to use an acid anhydride. Acid anhydrides include succinic anhydride, maleic anhydride, orthophthalic acid, 2,5-norbornene dicarboxylic acid anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride (PMDA), oxydiphthalic dianhydride (ODPA), 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride (BTDA), 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride (BPDA), 3,3 ′ , 4,4′-Diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4 ′-(hexafluoroisopropylidene) diphthalic dianhydride (6FDA), 2,2′-bis [(dicarboxyphenoxy) Compounds such as phenyl] propane dianhydride (BSAA) can be used. When the acid addition is carried out at 10 mol% or more, gelation may occur, and polyester depolymerization may occur and the resin molecular weight may be lowered. The acid addition includes a method of directly performing in a bulk state after the polyester polycondensation and a method of adding the polyester in a solution. The reaction in the bulk state is fast, but if it is added in a large amount, gelation may occur, and since it becomes a reaction at a high temperature, care must be taken such as blocking oxygen gas to prevent oxidation. On the other hand, the addition in the solution state is slow, but a large amount of carboxyl groups can be stably introduced. In particular, pyromellitic anhydride (PMDA), oxydiphthalic dianhydride (ODPA), 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA), 3,3 ′, 4,4′- Diphenyltetracarboxylic dianhydride (BPDA), 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4 ′-(hexafluoroisopropylidene) diphthalic dianhydride ( The use of acid dianhydrides such as 6FDA), 2,2′-bis [(dicarboxyphenoxy) phenyl] propane dianhydride (BSAA) can increase the molecular weight due to chain extension effect. In the present invention, in order to obtain a high weight average molecular weight as a polyester resin after modification with a polymer of a radical polymerizable monomer, in particular, pyromellitic anhydride (PMDA), 3,3 ′, 4,4′- Use of benzophenone tetracarboxylic dianhydride (BTDA) or 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride (BPDA) is effective.

In the present invention, examples of the radical polymerizable moiety include an unsaturated bond and a tertiary carbon that easily generates a radical by hydrogen abstraction. However, the radical polymerizable moiety is efficiently modified with a polymer of a radical polymerizable monomer. For this purpose, it is effective to introduce a polymerizable unsaturated bond into the resin constituting the main chain and to carry out a graft reaction with a radically polymerizable monomer. The introduction of an unsaturated bond can be achieved by copolymerizing an acid component and / or a glycol component having an unsaturated bond. Examples of dicarboxylic acids containing polymerizable unsaturated bonds include α, β-unsaturated dicarboxylic acids such as fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, etc. containing unsaturated double bonds Examples of the alicyclic dicarboxylic acid include 2,5-norbornene dicarboxylic acid anhydride and tetrahydrophthalic anhydride. Of these, fumaric acid and itaconic acid are particularly preferable in terms of high thermal stability at the time of polyester polymerization and high activity for radical polymerization reaction.

Examples of glycols containing a polymerizable unsaturated bond include glycerin monoallyl ether, trimethylolpropane monoallyl ether, pentaerythritol monoallyl ether, and the like.

The copolymerization amount of the monomer containing a polymerizable unsaturated double bond is preferably 0.5 to 20 mol% when the total molar amount of all acid components and all glycol components constituting the polyester resin is 200%, More preferably, it is 1.5 to 15 mol%, further preferably 2.5 to 10 mol%, and most preferably 3 to 7 mol%. When the monomer containing a polymerizable unsaturated double bond exceeds 20 mol%, a gelation reaction tends to occur in the graft reaction step, the insoluble matter content increases, and the production stability and workability deteriorate. In addition, when the amount is 0.5 mol% or less, the graft reaction is insufficient, unreacted polyester exists, and the molecular weight of the resin after radical reaction does not increase. Therefore, it does not have high heat resistance and adhesiveness under high temperature and high humidity. .

The amount of the titanium compound as a polymerization catalyst contained in the polyester resin used in the present invention is preferably 10 to 200 ppm, more preferably 15 to 100 ppm, still more preferably 20 to 80 ppm as titanium atoms in the polyester resin. is there. If it is 10 ppm or less, the activity is extremely lowered when used as a catalyst, which is not preferable. If it is 200 ppm or more, the water resistance, heat resistance, and color tone of the coating film tend to decrease, such being undesirable.

Titanium compounds used as a polymerization catalyst when polymerizing the polyester resin used in the present invention include tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate, Examples include tetracyclohexyl titanate, tetraphenyl titanate, tetrabenzyl titanate and the like, and the use of tetra-n-butyl titanate is particularly preferable.

On the other hand, the polyester resin used in the present invention is a polymerization catalyst such as an antimony compound, germanium compound, tin compound, aluminum compound, and the addition of these components causes problems in the water resistance, heat resistance, color tone, etc. of the coating film. When these are used together as a polymerization catalyst, it is effective in improving the productivity by shortening the polymerization time, and is preferable.

It is preferable that a radical polymerization inhibitor is allowed to coexist when the polyester resin used in the present invention is polymerized and in the resin composition of the present invention. The amount thereof is 10 to 800 ppm, more preferably 100 to 400 ppm as a radical polymerization inhibitor molecule in the polyester resin. If it is 10 ppm or less, the possibility of gelation by double bond cleavage increases, and it may be difficult to produce a high molecular weight polyester resin. If it is 800 ppm or more, the polyester resin may be colored, the color tone of the coating film may be lowered and the appearance may be impaired, and the radical reactivity may be lowered.

The radical polymerization inhibitor used in the present invention is mainly used to prevent gelation by double bond cleavage when polymerizing a polyester resin, and further to improve the curability of the paint. In order to enhance the properties, it may be added after polymerization. Examples of radical polymerization inhibitors include known antioxidants such as phenolic antioxidants, phosphorus antioxidants, amine antioxidants, sulfur antioxidants, and inorganic compound antioxidants.

Examples of phenolic antioxidants include 2,5-di-t-butylhydroquinone, 4,4′-butyldenbis (3-methyl-6-t-butylphenol), 1,1,3-tris (2-methyl-4 -Hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris-methyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3 , 5-di-t-butyl-4-hydroxyphenyl) isocyanurate, or derivatives thereof.

Phosphorus antioxidants include tri (nonylphenyl) phosphite, triphenyl phosphite, diphenylisodecyl phosphite, trioctadecyl phosphite, tridecyl phosphite, diphenyldecyl phosphite, 4,4'-butylidene-bis (3-methyl-6-t-butylphenyl ditridecyl phosphite), distearyl-pentaerythritol diphosphite, trilauryl trithiophosphite, etc., or derivatives thereof.

Amine-based antioxidants include phenyl-β-naphthylamine, phenothiazine, N, N′- diphenyl-p-phenylenediamine, N, N′-di-β-naphthyl-p-phenylenediamine, N-cyclohexyl-N ′. -Phenyl-p-phenylenediamine, aldol-α-naphthylamine, 2,2,4-trimethyl-1,2-dihydroquinoline, etc., or derivatives thereof.

Examples of sulfur-based antioxidants include thiobis (N-phenyl-β-naphthylamine, 2-mercaptobenchazole, 2-mercaptobenzimidazole, tetramethylthiuram disulfide, nickel isopropyl xanthate, and derivatives thereof.

Nitro compound antioxidants include 1,3,5-trinitrobenzene, p-nitrosodiphenylamine, p-nitrosodimethylaniline, 1-chloro-3- クロロ nitrobenzene, o-dinitrobenzene, m-dinitrobenzene, p-di Examples thereof include nitrobenzene, p-nitrobenzoic acid, nitrobenzene, 2-nitro-5-cyanothiophene, and derivatives thereof.

Examples of the inorganic compound antioxidant include FeCl ₃ , Fe (CN) ₃ , CuCl ₂ , CoCl ₃ , Co (ClO ₄ ) ₃ , Co (NO ₃ ) ₃ , and Co ₂ (SO ₄ ) ₃ .

As the radical polymerization inhibitor used in the present invention, among the above-mentioned antioxidants, phenol-based antioxidants and amine-based antioxidants are preferable in terms of thermal stability, and the melting point is 120 ° C. or higher and the molecular weight is 200 or higher. More preferred are those having a melting point of 170 ° C. or higher. Specific examples include phenothiazine and 4,4'-butyldenbis (3-methyl-6-t-butylphenol).

The polyester resin used in the present invention can be produced by a known method, but is preferably produced at a reaction temperature of 180 ° C. to 270 ° C. When the reaction temperature is 180 ° C. or lower, the resin molecular weight does not increase, the adhesiveness and workability tend to decrease, and the properties as an adhesive tend not to exist. On the other hand, when the reaction temperature is 270 ° C. or higher, even when the polymerization inhibitor is added, the unsaturated group is thermally cleaved to generate a gel-like product, which tends to be difficult to produce stably.

The polyester resin used in the present invention has a number average molecular weight in the range of 5,000 to 50,000, preferably a number average molecular weight in the range of 7,000 to 40,000, and more preferably 9,000. It is in the range of ~ 30,000. When the number average molecular weight is less than 5,000, the cohesive force as a resin is small, and therefore the adhesiveness, particularly the adhesiveness under high temperature and high humidity is lowered. On the other hand, if the number average molecular weight exceeds 100,000, the viscosity is increased during the grafting reaction, the uniform progress of the reaction is hindered, a gel is generated, and the production stability and workability deteriorate.

In addition to maleic anhydride, (meth) acrylic acid, (meth) acrylic acid ester as the radical polymerizable monomer constituting the side chain of the modified polyester resin by the polymer of the radical polymerizable monomer in the present invention A compound, a radical polymerizable monomer containing a nitrogen atom, a dicarboxylic acid type radical polymerizable monomer, a vinyl radical polymerizable monomer, an allyl radical polymerizable monomer, and the like are preferable. Examples of ester compounds of (meth) acrylic acid include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isopropyl (meth) acrylate, ethylhexyl (meth) acrylate, (meth ) Isobornyl acrylate, hydroxyethyl (meth) acrylate, hydroxyisopropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, 2- (meth) acryloyloxy Phthalic acid derivatives such as ethyl hydrogen phthalate and esters of hydroxyethyl (meth) acrylate, as well as a reaction product of acrylic acid, methacrylic acid and phenyl glycidyl ether, ie, 2-hydroxy-3-phenoxypropyl (meth) acrylate Relates can be mentioned. Examples of the radically polymerizable monomer containing a nitrogen atom include (meth) acrylamide, dimethylacrylamide, N-methylolacrylamide, acrylamide-2-methylpropanesulfonic acid, acrylonitrile, methacrylonitrile and the like. Dicarboxylic acid type radical polymerizable monomers include fumaric acid, monoethyl fumarate, diethyl fumarate, fumaric acid monoesters such as dibutyl fumarate and fumaric acid diesters, maleic acid, monoethyl maleate, diethyl maleate, maleate Mention may be made of maleic acid monoesters and maleic acid diesters such as dibutyl acid, itaconic acid and its anhydride, itaconic acid monoesters and itaconic acid diesters, and maleimides such as phenylmaleimide. Examples of vinyl radical polymerizable monomers include styrene derivatives such as styrene, α-methyl styrene, t-butyl styrene, chloromethyl styrene, N-vinyl pyrrolidone, vinyl acetate such as vinyl acetate, vinyl butyl ether, vinyl isobutyl ether. And allyl radical polymerizable monomers such as vinyl ether, allyl alcohol, glycerin monoallyl ether, pentaerythritol monoallyl ether, and trimethylolpropane monoallyl ether.

The reaction product after completion of the grafting reaction consists of 1) a graft polymer, 2) a non-graft base resin that has not undergone grafting, and 3) a non-graft radical polymer that has not been grafted with the base resin. It is normal. In general, when the ratio of the graft polymer in the reaction product is low and the ratio of the non-graft base resin and the non-graft radical polymer is high, not only the effect of modification is low, but the coating is whitened by the non-graft radical polymer. Adverse effects such as doing are observed. Therefore, it is important to select reaction conditions with a high graft polymer production ratio. It is possible to remove the non-graft base resin that has not been grafted and the non-graft radical polymer that has not been grafted with the base resin by the reprecipitation method, but considering the production efficiency, as described above, the reaction A method of selecting a radical polymerizable monomer in consideration of the properties is desirable. It is preferable to increase the graft efficiency and suppress the amount of the non-graft base resin that has not been grafted and the amount of the non-graft radical polymer that has not been grafted with the base resin. Hereinafter, a coating film of a modified polyester resin by a polymer of a radical polymerizable monomer is a coating film including a non-graft base resin and a non-graft radical polymer that has not been grafted with the base resin.

In carrying out the grafting reaction of the radical polymerizable monomer to the base resin, the radical polymerizable monomer mixture and the radical initiator may be added to the base resin at a time, or separately for a certain period of time. Then, the reaction may be continued by further heating with stirring for a certain period of time. The grafting reaction temperature is desirably in the range of 50 to 120 ° C. Below 50 ° C., the reaction activity of the radical initiator is low and the radical reaction is difficult to proceed, and when it is 120 ° C. or more, the generated radicals are rapidly deactivated by heat and the sufficient radical reaction is difficult to proceed, and the modification effect is difficult to obtain.

The mass ratio of the part derived from the monomer constituting the base resin and the part derived from the radical polymerizable monomer in the graft reaction product suitable for the purpose of the present invention is the part / radical polymerization derived from the monomer constituting the base resin. The portion derived from the functional monomer is preferably in the range of 10/90 to 99/1 by mass ratio, more preferably 25/75 to 95/5, still more preferably 40/60 to 90/10, particularly The range is preferably 60/40 to 85/15. When the mass ratio of the portion derived from the monomer constituting the base resin is less than 10% by mass, it tends to be difficult to sufficiently exhibit the excellent performance of the base resin, that is, the adhesiveness. When the mass ratio of the portion derived from the monomer constituting the base resin exceeds 99 mass%, the ratio of the ungrafted base resin in the graft product becomes almost all, and the effect of introducing functional groups due to modification is small, and curing There exists a tendency for the toughness of a coating film to be inferior.

As the radical polymerization initiator used in the present invention, known organic peroxides and organic azo compounds can be used. That is, benzoyl peroxide, t-butylperoxypivalate as organic peroxides, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) as organic azo compounds, etc. Can be illustrated. The amount of the radical initiator used for carrying out the grafting reaction is required to be at least 0.2% by mass relative to the radical polymerizable monomer, and preferably 0.5% by mass or more is used. In the case of 0.2% by mass or less, modification of the radical polymerizable monomer by the polymer is insufficient and the performance is insufficient. On the other hand, when the content is 0.2% by mass or less, the graft reaction becomes insufficient.

Chain transfer agents such as octyl mercaptan, dodecyl mercaptan, mercaptoethanol, β-mercaptopropionic acid, β-mercaptopropionic acid methyl ester, β-mercaptopropionic acid ethyl ester, β-mercaptopropionic acid 2-ethylhexyl ester, β-mercapto Propionic acid n-octyl ester, β-mercaptopropionic acid methoxybutyl ester, β-mercaptopropionic acid stearyl ester, β-mercaptopropionic acid isononyl ester, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis ( 3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tris [(3-mercaptopropionyloxy) -ethyl] isocyanurate Addition of bets like are also used as needed for the graft chain length adjustment. In that case, it is preferably added in the range of 0 to 20% by mass relative to the radical polymerizable monomer.

As the reaction solvent for the grafting reaction, a solvent having high solubility for polyester and polyester polyurethane can be used. Applicable solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclic ethers such as tetrahydrofuran, dioxane, glycol ethers such as propylene glycol methyl ether, propylene glycol propyl ether, ethylene glycol. Ethyl ether, ethylene glycol butyl ether, carbitols such as methyl carbitol, ethyl carbitol, butyl carbitol, glycols or lower esters of glycol ether such as ethylene glycol diacetate, ethylene glycol Ethyl ether acetate, ketone alcohols such as diacetone alcohol, and N-substituted amides such as dimethylformamide, dimethylacetamide, N-methylpi Pyrrolidone, toluene, aromatic solvents such as xylene, can be exemplified, and the like. Moreover, even if it is a poor solvent which does not melt | dissolve polyester and polyester polyurethane independently, when it is set as a mixed solvent with a good solvent, if it can melt | dissolve resin, it can be used. Examples of the poor solvent for polyester and polyester polyurethane include lower alcohols, lower carboxylic acids, lower amines, and water. As a combination of a good solvent and a poor solvent, one or a combination of two or more of the above solvents can be mentioned.

When the boiling point of the grafting reaction solvent for carrying out the present invention exceeds 250 ° C., the evaporation rate is slow, and it is not preferable because it cannot be sufficiently removed even by drying at a high temperature. On the other hand, when the boiling point is 50 ° C. or lower, when the grafting reaction is carried out using the solvent as a solvent, an initiator that cleaves into radicals at a temperature of 50 ° C. or lower must be used.

The number average molecular weight of the polyurethane resin used in the present invention is preferably 5,000 to 100,000. If the molecular weight is less than 5,000, the adhesion immediately after coating is insufficient and the workability is poor, and if the molecular weight exceeds 100,000, the solution viscosity at the time of coating is too high and a uniform coating film may not be obtained. is there. The lower limit molecular weight is preferably 8,000, more preferably the lower limit molecular weight is 10,000, preferably the upper limit molecular weight is 50,000, and more preferably the upper limit molecular weight is 35,000.

As the polyester polyol, those described as the polyester resin (base resin) used in the present invention can be used.

The polyisocyanate used in the production of the polyurethane resin used in the present invention is one kind of diisocyanate, its dimer (uretdione), its trimer (isocyanurate, triol adduct, burette), or two or more kinds thereof. It may be a mixture. For example, the diisocyanate component includes 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, 3,3′-dimethoxy. -4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 4,4'-diisocyanate diphenyl ether, 1,5-xylylene diisocyanate, 1,3-diisocyanate methylcyclohexane, 1,4 -Diisocyanate methylcyclohexane, 4,4'-diisocyanate cyclohexane, 4,4'-diisocyanate cyclohexyl methane, Isophorone diisocyanate, dimer acid diisocyanate, although norbornene diisocyanate, and the like, since the application of the the transparent vapor deposited film is often yellowing becomes a problem, diisocyanates aliphatic alicyclic is preferable. Further, hexamethylene diisocyanate and isophorone diisocyanate are particularly preferable for easy availability and economical reasons.

In producing the polyurethane resin used in the present invention, a chain extender may be used if necessary. Examples of the chain extender include a low molecular weight diol as a glycol component when synthesizing a polyester polyol, and a carboxyl group-containing low molecular weight diol such as dimethylolpropionic acid and dimethylolbutanoic acid. Among them, dimethylolbutanoic acid is preferable because of easy introduction of an acid value and solubility in a general-purpose solvent. Also, the use of trimethylolpropane is preferred because of the ease of introduction of hydroxyl groups.

As a reaction method of the polyurethane resin used in the present invention, the polyester polyol, the polyisocyanate, and, if necessary, a chain extender may be charged all at once into the reaction vessel, or may be charged separately. In any case, the total of the hydroxyl groups of the polyester polyol and chain extender in the system and the total of the isocyanate groups of the polyisocyanate are reacted at an isocyanate group / hydroxyl group functional group ratio of 1 or less. In addition, this reaction can be produced by reacting in the presence or absence of a solvent inert to isocyanate groups. The solvents include ester solvents (ethyl acetate, butyl acetate, ethyl butyrate, etc.), ether solvents (dioxane, tetrahydrofuran, diethyl ether, etc.), ketone solvents (cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, etc.), aromatic carbonization. Examples thereof include hydrogen-based solvents (benzene, toluene, xylene, etc.) and mixed solvents thereof, and ethyl acetate and methyl ethyl ketone are preferable from the viewpoint of reducing environmental burden. As the reaction apparatus, not only a reaction can equipped with a stirring apparatus but also a mixing and kneading apparatus such as a kneader or a twin screw extruder can be used.

Catalysts used in ordinary urethane reactions to promote urethane reactions, such as tin catalysts (trimethyltin laurate, dimethyltin dilaurate, trimethyltin hydroxide, dimethyltin dihydroxide, stannous octoate, etc.), lead catalysts (Red oleate, red-2-ethylhexoate, etc.), amine catalysts (triethylamine, tributylamine, morpholine, diazabicyclooctane, etc.) and the like can be used.

A curing catalyst can be used for the curing reaction of the epoxy compound used in the present invention. For example, imidazole compounds such as 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, and triethylamine , Triethylenediamine, N'-methyl-N- (2-dimethylaminoethyl) piperazine, 1,8-diazabicyclo (5,4,0) -undecene-7 and 1,5-diazabicyclo (4,3,0)- Tertiary amines such as nonene-5 and 6-dibutylamino-1,8-diazabicyclo (5,4,0) -undecene-7, and tertiary amines such as phenol, octylic acid and quaternized tetraphenylborate Compounds converted to amine salts with salts, triallylsulfonium hexafluoroantimonate and dia Le iodonium hexafluoroantimonate Mona bets and cationic catalysts include triphenylphosphine and the like. Among these, 1,8-diazabicyclo (5,4,0) -undecene-7, 1,5-diazabicyclo (4,3,0) -nonene-5 and 6-dibutylamino-1,8-diazabicyclo (5 , 4,0) -undecene-7 and the like, and compounds obtained by converting these tertiary amines into amine salts with phenol, octylic acid or the like or quaternized tetraphenylborate salts are thermosetting and heat resistant. It is preferable in terms of adhesion to metal and storage stability after blending. The blending amount at that time is preferably 0.01 to 1.0 part by mass with respect to 100 parts by mass of the polyester. If it is this range, the effect with respect to reaction of polyester and an epoxy compound will increase further, and the firm adhesive performance can be acquired.

In the present invention, when the mass of the modified polyester resin by the polymer of the radical polymerizable monomer is Wc (g) and the mass of the polyurethane resin is Wd (g), Wc / Wd is 1/99 to 80/20. It is preferable that When Wc is 1% or less, the low heat resistance of polyurethane cannot be covered, and the adhesiveness at high temperature is lowered. On the other hand, if it is 80% or more, the adhesiveness at room temperature is lowered.

Various adhesives and additives can be blended with the resin composition of the present invention to form an adhesive composition. Examples of the curable resin include silicone resin, melamine resin, phenol-formalin resin, and isocyanate resin.

Examples of the phenol resin include formaldehyde condensates of alkylated phenols and cresols. Specifically alkylated (methyl, ethyl, propyl, isopropyl, butyl) phenol, p-tert-
Amylphenol, 4,4'-sec-butylidenephenol, p-tert-butylphenol, o-, m-, p-cresol, p-cyclohexylphenol, 4,4'-
Examples include formaldehyde condensates such as isopropylidenephenol, p-nonylphenol, p-octylphenol, 3-pentadecylphenol, phenol, phenyl-o-cresol, p-phenylphenol, and xylenol.

Examples of amino resins include formaldehyde adducts such as urea, melamine, and benzoguanamine, and alkyl ether compounds of these alcohols having 1 to 6 carbon atoms. Specific examples include methoxylated methylol urea, methoxylated methylol N, N-ethyleneurea, methoxylated methylol dicyandiamide, methoxylated methylol melamine, methoxylated methylol benzoguanamine, butoxylated methylol melamine, butoxylated methylol benzoguanamine, etc. They are methoxylated methylol melamine, butoxylated methylol melamine, and methylolated benzoguanamine, each of which can be used alone or in combination.

Isocyanate compounds include aromatic and aliphatic diisocyanates, and tri- or higher polyisocyanates, which may be either low molecular compounds or high molecular compounds. For example, tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as HDI), toluene diisocyanate, diphenylmethane diisocyanate (hereinafter abbreviated as MDI), hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene Diisocyanate, isophorone diisocyanate or trimers of these isocyanate compounds, and excess amounts of these isocyanate compounds, such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanol Low molecular active hydrogen compounds such as amines or various polyester polyols Polyether polyols include terminal isocyanate group-containing compounds obtained by reacting with such polymer active hydrogen compound polyamides.

The isocyanate compound may be a blocked isocyanate. Examples of the isocyanate blocking agent include phenols such as phenol, thiophenol, methylthiophenol, cresol, xylenol, resorcinol, nitrophenol, and chlorophenol, oximes such as acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime, methanol, ethanol, propanol, Alcohols such as butanol, halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol, tertiary alcohols such as t-butanol and t-pentanol, ε-caprolactam, δ-valerolactam, Examples include lactams such as γ-butyrolactam and β-propyllactam. In addition, aromatic amines, imides, acetylacetone, acetoacetate ester, ethyl malonate Active methylene compounds such as Le, mercaptans, imines, ureas, and also such as diaryl compounds sodium bisulfite. The blocked isocyanate is obtained by subjecting the above isocyanate compound, isocyanate compound and isocyanate blocking agent to an addition reaction by a conventionally known appropriate method.

In the adhesive composition of the present invention, silica may be blended as necessary. It is very preferable to add silica because heat resistance is improved. Hydrophobic silica and hydrophilic silica are generally known as silica, but here, hydrophobic silica treated with dimethyldichlorosilane, hexamethyldisilazane, octylsilane, etc. in order to impart moisture absorption resistance. Is good. The average particle diameter of silica is preferably 3 μm or less. More preferably, it is 50 nm or less. If the average particle size is larger than 3 μm, poor dispersion or poor adhesion may occur, and heat resistance and adhesion may be reduced. The compounding amount of silica is preferably 0.05 to 30 parts by mass with respect to 100 parts by mass of the polyester. If it is less than 0.05 parts by mass, the effect of improving the heat resistance may not be exhibited. On the other hand, if it exceeds 30 parts by mass, there may be a case where poor dispersion of silica occurs or the solution viscosity becomes too high, resulting in a malfunction in workability or a decrease in adhesiveness.

A silane coupling agent may be blended in the adhesive composition of the present invention as necessary. It is very preferable to add a silane coupling agent because adhesion to metal and heat resistance are improved. Although it does not specifically limit as a silane coupling agent, What has an unsaturated group, What has a glycidyl group, What has an amino group, etc. are mentioned. Examples of the silane coupling agent having an unsaturated group include vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, and vinyltrimethoxysilane. Examples of silane coupling agents having a glycidyl group include γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane. Etc. Examples of the silane coupling agent having an amino group include N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-phenyl-γ. -Aminopropyltrimethoxysilane and the like. Of these, from the viewpoint of heat resistance, glycidyl groups such as γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltriethoxysilane More preferred is a silane coupling agent having The compounding amount of the silane coupling agent is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the polyester. If it is less than 0.5 parts by mass, heat resistance may be deteriorated. On the other hand, if it exceeds 20 parts by mass, heat resistance failure or adhesion failure may occur.

In the adhesive composition of the present invention, flame retardants such as bromine-based, phosphorus-based, nitrogen-based, and metal hydroxide compounds, leveling agents, pigments, dyes, and other additives can be appropriately blended as necessary.

In the present invention, the adhesive sheet is composed of a base material and the adhesive composition of the present invention, or a base material, the adhesive composition of the present invention and a release base material. The adhesive sheet has a function of bonding the substrate to the adherend with the adhesive composition. The base material of the adhesive sheet functions as a protective layer for the adherend after adhesion. Moreover, when a releasable base material is used as the base material of the adhesive sheet, the releasable base material can be released and the adhesive layer can be transferred to another material to be adhered.

The adhesive sheet of the present invention can be obtained by applying and drying the adhesive composition of the present invention on various substrates according to a conventional method. In addition, after drying, pasting the release substrate to the adhesive layer makes it possible to scrape off without causing the substrate to be transferred to the substrate, which improves operability and protects the adhesive layer. Excellent storage and easy to use. Moreover, after applying and drying to a mold release base material, if another mold release base material is stuck as needed, it will also become possible to transfer the adhesive layer itself to another base material.

Here, the substrate to which the composition of the present invention is applied is not particularly limited, and examples thereof include a film-like resin, a metal plate, a metal foil, and papers. Examples of the film-like resin include polyester resin, polyamide resin, polyimide resin, polyamideimide resin, and olefin resin. Examples of metal plate and metal foil materials include various metals such as SUS, copper, aluminum, iron, and zinc, and alloys and plated products thereof. Glassine paper etc. can be illustrated. Moreover, glass epoxy etc. can be illustrated as a composite material. From the viewpoint of adhesive strength and durability with the adhesive composition, the base material to which the composition of the present invention is applied is polyester resin, polyamide resin, polyimide resin, polyamideimide resin, SUS steel plate, copper foil, aluminum foil, glass epoxy. Is preferred.

Further, the release substrate to which the composition of the present invention is applied is not particularly limited. For example, clay, polyethylene, and polypropylene are provided on both surfaces of paper such as fine paper, kraft paper, roll paper, and glassine paper. In addition, a coating layer of a sealing agent such as a silicone, fluorine-based, or alkyd-based release agent is coated on each coating layer, and polyethylene, polypropylene, ethylene-α-olefin copolymer Examples include various olefin films such as a polymer, propylene-α-olefin copolymer, and those obtained by applying the release agent on a film such as polyethylene terephthalate, but the release force with the applied adhesive layer, Due to reasons such as the adverse effect of silicone on electrical properties, polypropylene seals are treated on both sides of high-quality paper and alkyd release agents are used on top of that. Those using an alkyd release agent on polyethylene terephthalate are preferred.

In the present invention, the method of coating the adhesive composition on the substrate is not particularly limited, and examples thereof include a comma coater and a reverse roll coater. Or as needed, an adhesive film layer can also be provided in the rolled copper foil which is a printed wiring board constituent material, or a polyimide film directly or by the transfer method. The thickness of the adhesive film after drying is appropriately changed as necessary, but is preferably in the range of 5 to 200 μm. When the adhesive film thickness is less than 5 μm, the adhesive strength is insufficient. When the thickness is 200 μm or more, there is a problem that drying is insufficient, a residual solvent increases, and bulge is generated at the time of printed circuit board production. The drying conditions are not particularly limited, but the residual solvent ratio after drying is preferably 1% or less. If it is 1% or more, there is a problem that the residual solvent is foamed during press-pressing of the printed wiring board to cause swelling.

The “printed wiring board” in the present invention includes a laminate formed from a metal foil and a resin layer forming a conductor circuit as constituent elements. A printed wiring board is manufactured by conventionally well-known methods, such as a subtractive method, using a metal-clad laminated body, for example. If necessary, a so-called flexible circuit board (FPC), flat cable, tape automated bonding (covered by using a cover film or screen printing ink, etc., partially or entirely covered with a conductor circuit formed of metal foil (tape automated bonding) TAB) circuit board and the like.

The printed wiring board of the present invention can have any laminated structure that can be employed as a printed wiring board. For example, it can be set as the printed wiring board comprised from four layers, a base film layer, a metal foil layer, an adhesive bond layer, and a cover film layer. For example, it can be set as the printed wiring board comprised from five layers, a base film layer, an adhesive bond layer, a metal foil layer, an adhesive bond layer, and a cover film layer. The printed wiring board may be reinforced with a reinforcing material as necessary. In that case, the reinforcing material and the adhesive layer are provided under the base film layer.

Furthermore, if necessary, a configuration in which two or three or more of the above-described printed wiring boards are laminated may be employed.

The resin composition of the present invention can be suitably used for each adhesive layer of a printed wiring board. In particular, when the resin composition of the present invention is used as an adhesive, it has high adhesiveness to the base material constituting the printed wiring board, has high heat resistance that can be used for lead-free solder, and has a high temperature. It is possible to maintain high adhesion even under high humidity. Especially in the high temperature range where solder resistance is evaluated, a high crosslink density can be obtained while maintaining a low storage modulus, so the impact due to evaporation of moisture in the solder resistance test in a humidified state must be sufficiently mitigated. It is suitable for bonding between the metal foil layer and the cover film layer and between the base film layer and the reinforcing material layer. In particular, when a rigid reinforcing material such as a SUS plate is used, the impact on the adhesive layer between the base film layer and the reinforcing material layer when soldering in a humidified state is strong. It is suitable as a resin composition used for adhesion.

In the printed wiring board of the present invention, any resin film conventionally used as a substrate for printed wiring boards can be used as the substrate film. As the resin for the base film, a resin containing halogen may be used, or a resin not containing halogen may be used. From the viewpoint of environmental problems, a resin containing no halogen is preferable. However, from the viewpoint of flame retardancy, a resin containing halogen can also be used. The base film is preferably a polyimide film or a polyamideimide film.

As the metal foil used in the present invention, any conventionally known conductive material that can be used for a circuit board can be used. As the material, for example, copper foil, aluminum foil, steel foil, nickel foil and the like can be used, and composite metal foil obtained by combining these and metal foil treated with other metals such as zinc and chromium compounds are also used. be able to. Preferably, it is a copper foil.

The thickness of the metal foil is not particularly limited, but is preferably 1 μm or more, more preferably 3 μm or more, and further preferably 10 μm or more. Moreover, it is preferably 50 μm or less, more preferably 30 μm or less, and still more preferably 20 μm or less. If the thickness is too thin, it may be difficult to obtain sufficient electrical performance of the circuit. On the other hand, if the thickness is too thick, the processing efficiency at the time of circuit fabrication may be reduced.

Metal foil is usually provided in the form of a roll. The form of the metal foil used when manufacturing the printed wiring board of this invention is not specifically limited. When a roll-shaped metal foil is used, its length is not particularly limited. The width is not particularly limited, but is preferably about 250 to 500 mm.

As the cover film, any conventionally known insulating film can be used as an insulating film for a printed wiring board. For example, films produced from various polymers such as polyimide, polyester, polyphenylene sulfide, polyethersulfone, polyetheretherketone, aramid, polycarbonate, polyarylate, polyimide, and polyamideimide can be used. More preferably, it is a polyimide film or a polyamidoimide film, More preferably, it is a polyimide film.

The polyimide film has a polyimide resin as a main component as its resin component. Of the resin components, 90% by mass or more is preferably polyimide, more preferably 95% by mass or more is polyimide, more preferably 98% by mass or more is polyimide, and 99% by mass or more is polyimide. It is particularly preferred. Any conventionally known resin can be used as the polyimide resin.

As the material resin for the cover film, a resin containing halogen may be used, or a resin not containing halogen may be used. From the viewpoint of environmental problems, a resin containing no halogen is preferable. However, from the viewpoint of flame retardancy, a resin containing halogen can also be used.

As the reinforcing material, a metal plate such as a SUS plate or an aluminum plate, a polyimide film, a plate obtained by curing glass fiber with an epoxy compound, or the like is used.

The printed wiring board of the present invention can be manufactured using any conventionally known process except that the material of each layer described above is used.

In a preferred embodiment, a semi-finished product in which an adhesive layer is laminated on a cover film layer (hereinafter referred to as “cover film-side semi-finished product”) is manufactured. On the other hand, an adhesive layer is laminated on a semi-finished product (hereinafter referred to as “base film side two-layer semi-product”) or a base film layer in which a desired circuit pattern is formed by laminating a metal foil layer on the base film layer. And a semi-finished product (hereinafter referred to as “base film side three-layer semi-product”) having a desired circuit pattern formed by laminating a metal foil layer thereon (hereinafter referred to as base film side two-layer semi-product) The base film side three-layer semi-finished product is collectively referred to as “base film side semi-finished product”). A four-layer or five-layer printed wiring board can be obtained by laminating the cover film side semi-finished product and the base film side semi-finished product thus obtained. Furthermore, a semi-finished product in which an adhesive layer is laminated on a reinforcing material layer (hereinafter referred to as “reinforcing material-side semi-finished product”) can be manufactured and bonded to a substrate film layer of a printed wiring board and reinforced as necessary. . Moreover, the adhesive agent used between a reinforcing material and a base film can be apply | coated to a mold release base material, it can transcribe | transfer to the base film back surface of a printed wiring board, and can also be bonded together with a reinforcing material.

The base film side semi-finished product is, for example,
(A) The process of apply | coating the resin solution used as a base film to the said metal foil, and initial-drying a coating film,
(B) A step of heat-treating and drying the laminate of the metal foil obtained in (A) and the initial dry coating film (hereinafter referred to as “heat treatment / solvent removal step”),
It is obtained by the manufacturing method containing.

A conventionally known method can be used to form a circuit in the metal foil layer. An active method may be used and a subtractive method may be used. The subtractive method is preferable.

The obtained base film side semi-finished product may be used as it is for pasting with the cover film side semi-finished product. May be used.

The cover film side semi-finished product is manufactured, for example, by applying an adhesive to the cover film. If necessary, a crosslinking reaction in the applied adhesive can be performed. In a preferred embodiment, the adhesive layer is semi-cured.

The obtained cover film-side semi-finished product may be used as it is for pasting with the base-side-side semi-finished product. May be used.

The base film side semi-finished product and the cover film side semi-finished product are each stored, for example, in the form of a roll, and then bonded together to produce a printed wiring board. Arbitrary methods can be used as the method of bonding, for example, it can bond using a press or a roll. Further, the two can be bonded together while heating by a method such as using a heating press or a heating roll device.

For example, in the case of a reinforcing material that can be rolled up softly, such as a polyimide film, the reinforcing material-side semi-finished product is preferably manufactured by applying an adhesive to the reinforcing material. Also, for example, in the case of a reinforcing plate that cannot be rolled up hard, such as a metal plate such as SUS or aluminum, or a plate obtained by curing glass fibers with an epoxy compound, by transferring and applying an adhesive previously applied to a release substrate. It is preferred to be manufactured. Moreover, the crosslinking reaction in the apply | coated adhesive agent can be performed as needed. In a preferred embodiment, the adhesive layer is semi-cured.

The obtained reinforcing material-side semi-finished product may be used as it is for pasting with the back side of the printed wiring board, and after being used for pasting with the base film-side semi-finished product after storing the release film. May be.

The base film side semi-finished product, the cover film side semi-finished product, and the reinforcing agent side semi-finished product are all laminated bodies for printed wiring boards in the present invention.

<Example>
Hereinafter, the present invention will be specifically illustrated by examples. In the examples, “parts” means “parts by mass”.

(Physical property evaluation method)
(1) Composition of Resin such as Polyester Resin Resin such as polyester resin was dissolved in deuterated chloroform, and the molar ratio of acid component to glycol component was determined by ¹ H-NMR analysis. When the resin did not dissolve in deuterated chloroform, another soluble D solvent was used.

(2) Number average molecular weight Mn
The sample was dissolved and / or diluted with tetrahydrofuran so that the resin concentration was about 0.5%, and filtered through a polytetrafluoroethylene membrane filter with a pore size of 0.5 μm. The molecular weight was measured by gel permeation chromatography using a differential refractometer as the phase detector. The flow rate was 1 mL / min and the column temperature was 30 ° C. KF-802, 804L and 806L manufactured by Showa Denko were used for the column. Monodisperse polystyrene was used as the molecular weight standard.

(3) Glass transition temperature It measured with the temperature increase rate of 20 degree-C / min using the differential scanning calorimeter (DSC).

(4) Acid value 0.2 g of a sample was dissolved in 20 ml of chloroform and titrated with a 0.1N potassium hydroxide ethanol solution using an indicator phenolphthalein and calculated (mg KOH / g).

(Characteristic evaluation method)
(1) Solder resistance, peel strength An adhesive composition to be described later was applied to a 25 μm-thick polyimide film (manufactured by Kaneka Corporation, Apical) so that the thickness after drying would be 30 μm, and at 130 ° C. for 3 minutes. Dried. When the adhesive film (B stage product) obtained in this way is bonded to a 30 μm rolled copper foil, 35 kgf / cm ² is applied at 160 ° C. so that the glossy surface of the rolled copper foil is in contact with the adhesive. It was pressed and pressed for 30 seconds under pressure. Subsequently, it was cured by heat treatment at 140 ° C. for 4 hours to obtain a solder resistance and peel strength evaluation sample (for initial evaluation).

The adhesive film (B stage product) was allowed to stand at 40 ° C. and 80% humidification for 14 days, and then cured by pressing with a rolled copper foil and heat treatment under the above conditions to obtain a sample for evaluation over time.
Each characteristic was evaluated by the following method;
Solder resistance (humidification): The sample was allowed to stand at 40 ° C. and 80% humidification for 2 days, then floated in a heated solder bath for 1 minute, and the upper limit temperature at which swelling did not occur was measured at a pitch of 10 ° C. Also in this test, it shows that the higher the measured value has better heat resistance, but it is necessary to suppress the impact caused by evaporation of water vapor contained in each base material and adhesive layer. More severe heat resistance is required. In consideration of practical performance, 260 ° C. or higher is favorable.

Peel strength: At 25 ° C., a 90 ° peel test was conducted at a tensile speed of 50 mm / min, and the peel strength was measured. This test shows the adhesive strength at room temperature. Considering from practical performance, 15 N / cm or more is good.
(2) Creep properties An adhesive composition described below was applied to a 125 μm-thick polyimide film (manufactured by Toray DuPont, Kapton) so that the thickness after drying was 30 μm, and dried at 130 ° C. for 3 minutes. . The adhesive film (B stage product) obtained in this way was cut to a width of 5 mm, and pressed with a 500 μm SUS304 plate at 160 ° C. under a pressure of 5 kgf / cm ² for 30 seconds and adhered. Subsequently, it was cured by heat treatment at 140 ° C. for 4 hours to obtain a sample for creep property evaluation (initial sample). Further, the adhesive film (B stage product) was allowed to stand for 14 days at 40 ° C. and 80% humidification, and then cured by press and heat treatment with a SUS plate under the above conditions to obtain a sample for evaluation over time. A 200 g weight was hung from the obtained sample in an atmosphere of 60 ° C. × 90%, and the distance peeled off in 30 minutes was measured. Note that the weight was hung so that the peeling form was 180 ° peeling. This test shows the adhesive strength under high temperature and high humidity, and preferably has no peeling. The longer the peeling distance, the lower the adhesive strength. Considering practical performance, 4 mm or less is good.

Example of Polymerization of Polyester Resin A Containing Radical Polymerizable Site A reaction vessel equipped with a thermometer, stirrer, reflux condenser and distillation tube was charged with 236.6 parts of terephthalic acid, 236.6 parts of isophthalic acid, and 17.4 of fumaric acid. Water, 266.6 parts of ethylene glycol, 240.2 parts of neopentyl glycol, and 0.13 part of phenothiazine, and gradually heated to 230 ° C. over 4 hours in a nitrogen atmosphere and 2 atm. The esterification reaction was carried out while removing from the system. Subsequently, after returning to normal pressure, 0.11 part of titanium tetrabutoxide was added, and after stirring for 5 minutes, initial polymerization was performed under reduced pressure to 10 mmHg over 30 minutes and the temperature was raised to 250 ° C., and further 1 mmHg or less The late polymerization was carried out for 60 minutes. Thereafter, the pressure was returned to normal pressure with nitrogen to obtain polyester resin A. The composition and characteristic values of the polyester thus obtained are shown in Table 1. Each measurement evaluation item followed the above-mentioned method.

Polymerization Examples of Polyester Resins C, F, G, I, J, L, and N Containing Radical Polymerizable Sites In the same manner as the polymerized examples of polyester resin A, the raw materials shown in Table 1 are used to include radical polymerizable sites. Polyester resins C, F, G, I, J, L and N were obtained. However, the late polymerization time of 1 mmgHg or less was 42 minutes for G, 32 minutes for H, 16 minutes for L, and 60 minutes for the others. The composition and characteristic values of these resins are shown in Table 1.

Polymerization Example of Polyester Resin B Containing Radical Polymerizable Site A reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and a distillation tube was charged with 80.5 parts terephthalic acid, 24.9 parts isophthalic acid, and 60.6 sebacic acid. Part, 5.8 parts of fumaric acid, 74.4 parts of ethylene glycol, 83.2 parts of neopentyl glycol and 0.1 part of phenothiazine were gradually added to 230 ° C. over 4 hours in a nitrogen atmosphere and 2 atm. The esterification reaction was performed while warming and removing the distilled water out of the system. Subsequently, after returning to normal pressure, 0.11 part of titanium tetrabutoxide was added, and after stirring for 5 minutes, initial polymerization was performed under reduced pressure to 10 mmHg over 30 minutes and the temperature was raised to 250 ° C., and further 1 mmHg or less The late polymerization was carried out for 60 minutes. Thereafter, the pressure is returned to normal pressure with nitrogen, the temperature is lowered to 80 ° C., 430 parts of 2-butanone (MEK) is added and dissolved, and 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride (BTDA) 32 2 parts were added and the mixture was stirred for 2 hours to perform acid addition to obtain a polyester resin B solution. MEK is adjusted so that the resin content in the solution is 30%. Furthermore, the polyester resin A solution was heated at 80 ° C. for 3 hours under a vacuum condition (5 mmHg or less) to evaporate the solvent, and the resin composition and characteristics were evaluated. The results are shown in Table 1. In addition, each measurement evaluation item followed the above-mentioned method.

Polymerization examples of polyester resins D and K containing radical polymerizable sites Polyester resins D and K containing radical polymerizable sites were obtained using the raw materials shown in Table 1 in the same manner as the polymerization examples of polyester resin B. . The composition and characteristic values of this resin are shown in Table 1.

Polymerization Example of Polyester Resin E Containing Radical Polymerizable Site In a reaction vessel equipped with a thermometer, stirrer, reflux condenser and distillation tube, 78.0 parts of terephthalic acid, 81.3 parts of isophthalic acid, 2.3 of fumaric acid Of water, 135.0 parts of 2-methyl-1,3-propanediol and 0.1 part of phenothiazine, and gradually heated to 230 ° C. over 4 hours in a nitrogen atmosphere and 2 atm. The esterification reaction was carried out while removing from the system. Subsequently, after returning to normal pressure, 0.11 part of titanium tetrabutoxide was added, and after stirring for 5 minutes, initial polymerization was performed under reduced pressure to 10 mmHg over 30 minutes and the temperature was raised to 250 ° C., and further 1 mmHg or less The late polymerization was carried out for 60 minutes. Thereafter, the pressure was returned to normal pressure with nitrogen, the temperature was lowered to 220 ° C., 3.8 parts of trimellitic anhydride was added, the mixture was stirred for 30 minutes, and acid addition was performed to obtain polyester resin E. The composition and characteristic values of the polyester thus obtained are shown in Table 1. Each measurement evaluation item followed the above-mentioned method.

Polymerization Example of Polyester Resins H and M Containing Radical Polymerizable Sites Polyester resins H and M containing radical polymerizable sites were obtained using the raw materials shown in Table 1 in the same manner as in the polymerization example of polyester resin E. . The composition and characteristic values of this resin are shown in Table 1.

Polymerization Example of Modified Polyester Resin 1 Modified with Polymer of Radical Polymerizable Monomer 30% by Mass MEK Solution of Polyester Resin A (Polyester A) in a reactor equipped with a stirrer, thermometer, reflux device and quantitative dropping device Resin content 75 parts) was prepared and heated and stirred at 75 ° C. On the other hand, 25 parts of radically polymerizable monomer (12 parts of maleic anhydride, 13 parts of styrene) and 2,2′-azobisisobutyronitrile as a polymerization initiator were 6% by mass of the total amount of radically polymerizable monomers. As a chain transfer agent, octyl mercaptan was dissolved in 10% by mass of the total mass of radical polymerizable monomers and 60.3 parts of methyl ethyl ketone (hereinafter sometimes abbreviated as MEK) to obtain 30% of the radical polymerizable monomer. A% MEK solution was prepared. Solution 1 was added dropwise to the polyester resin A solution over 1.5 hours, and further reacted for 4 hours to obtain a modified polyester resin solution using a polymer of a radical polymerizable monomer. During this time, the solution was kept at 75 ° C. The acid value of the modified polyester resin composition by the polymer of the obtained radical polymerizable monomer was 2454 equivalent / 10 < ⁶ > g, and the glass transition temperature was 72 degreeC.

Example of Polymerization of Modified Polyester Resin 2-16 Modified with Polymer of Radical Polymerizable Monomer Similar to the example of polymerization of modified polyester resin 1, using the raw materials shown in Table 2, the modified polyester resins 2-16 were prepared. Obtained. As an example of the modified polyester resin 2, 80 parts of a radical polymerizable monomer (38 parts of maleic anhydride, 37 parts of styrene, acrylic resin) with respect to a 30% by mass MEK solution of polyester resin B (containing 20 parts of polyester resin B). Acid 2-ethylhexyl 5 parts), polymerization initiator 2,2′-azobisisobutyronitrile 4.8 parts (6% of the total mass of radical polymerizable monomers), octyl mercaptan 8 parts (radical) as chain transfer agent 10% of the total polymerizable monomer mass) is dissolved in 186.7 parts of MEK (solution 2), and the solution 2 is added dropwise over 1.5 hours, followed by further reaction for 4 hours. A modified polyester resin solution 2 was obtained.

Example of polymerization of polyester polyols O, P, R, S, T used for polyurethane resin In the same manner as polymerization example of polyester resin E, using the raw materials shown in Table 3, polyester polyols O, P, R, S, T were obtained. The composition and characteristic values of this resin are shown in Table 3.

Polymerization Example of Polyester Polyol Q Used for Polyurethane Resin Polyester resin Q containing a radical polymerizable moiety was obtained using the raw materials shown in Table 3 in the same manner as in the polymerization example of polyester resin A. The composition and characteristic values of this resin are shown in Table 3.

Polymerization Example of Polyurethane Resin I A reactor equipped with a thermometer, stirrer, reflux condenser and distillation tube was charged with 100 parts of polyester polyol (O) listed in Table 3 and 70 parts of toluene. The reaction system was dehydrated by azeotropic distillation with toluene / water. After cooling to 60 ° C., 9 parts of 2,2-dimethylolbutanoic acid (DMBA) and 50 parts of methyl ethyl ketone were added. After DMBA is dissolved, add 8 parts of hexamethylene diisocyanate and 0.4 parts of dibutyltin dilaurate as a reaction catalyst, react at 80 ° C. for 3 hours, and then add a mixed solution of methyl ethyl ketone and toluene in the same mass to obtain a solid content concentration. Was adjusted to 30% by mass to obtain a polyurethane resin (I) solution. Table 4 shows the characteristics of the polyurethane resin. The acid value was determined with an ethanol solution of potassium hydroxide in chloroform using a film from which the solvent was removed by drying the polyurethane resin (I) solution at 120 ° C. for 1 hour. In Table 4, the number average molecular weight was measured by gel permeation chromatography using tetrahydrofuran as a solvent, and the glass transition temperature was measured by a differential scanning calorimeter at a temperature rising rate of 20 ° C./min.

Polymerization examples of polyurethane resins II to XI Polyurethane resins II to XI were obtained using the raw materials shown in Table 4 in the same manner as the polymerization examples of polyurethane resin I. The characteristic values are shown in Table 4.

<Example 1>
75 parts of polyurethane resin I (mass only of solid content, does not include solvent; the same applies hereinafter), modified polyester resin 525 parts, epoxy compound [manufactured by Dainippon Ink Industries, Ltd. HP7200-H (dicyclopentanediene type epoxy) Compound)] 38 parts was blended to obtain a desired adhesive composition. The epoxy compound was blended as a MEK 70% solution. The compounding amount of the epoxy compound was determined by calculating so as to include 1.05 times the total amount of acid values of the polyurethane and the modified polyester resin. In this case, Tg (c) -Tg (d) is 8 ° C. and AV (c) -AV (d) is 1841 equivalent / 10 ⁶ g, which falls within the scope of the claims of the present invention. Table 5 shows the evaluation results of the adhesion evaluation samples prepared by the above-described methods. Both the initial evaluation and the time evaluation showed good results.

<Examples 2 to 6>
As in Example 1, samples were prepared with the resin types and blending amounts shown in Table 5, and the resin characteristics were evaluated. The epoxy compound I is TETRAD-X (N, N, N ′, N′-tetraglycidyl-m-xylenediamine) manufactured by Mitsubishi Gas Chemical Co., Ltd., and the epoxy compound C is YDCN703 (o -Cresol novolac-type epoxy compounds), all formulated as MEK 70% solution. The compounding amount of the epoxy compound was determined by calculating so as to include 1.05 times the total amount of acid values of the polyurethane and the modified polyester resin. Table 5 shows the evaluation results. Both the initial evaluation and the time evaluation showed good results.

<Comparative Examples 1 to 14>
In the same manner as in Examples 1 to 6, samples were prepared with the resin types and blending amounts shown in Tables 6 and 7, and the resin characteristics were evaluated. The evaluation results are shown in Tables 6 and 7.

In Comparative Example 1, the glass transition temperature, Tg (c) -Tg (d), AV (c) -AV (d) of the modified polyester resin (7) is outside the scope of the present invention. The proportion of maleic anhydride in the radical polymerizable monomer is also 65% by mass, which is outside the scope of the present invention. The excellent adhesiveness of polyester resin is impaired, and Tg (c) -Tg (d) is large, so the peel strength at room temperature is low, and the creep properties and solder reflow are indicators of adhesiveness at high temperature and high humidity. Solder resistance that is an index of high heat resistance in the region (260 ° C.) is also poor. Furthermore, since AV (c) -AV (d) is also large, the reaction rate at the B stage is high, and the performance after aging is further deteriorated.

In Comparative Example 2, since the modified polyester resin (8) is blended with the polyurethane resin (III) having a low acid value and a high glass transition temperature, Tg (c) -Tg (d), AV (c)- Both AV (d) are outside the scope of the present invention. This is because the mass ratio of the monomer constituting the polyester resin component (a) containing the radical polymerizable moiety of the modified polyester (8) and the monomer constituting the polymer component (b) of the radical polymerizable monomer is 99.99. This is because the acid value of the modified polyester resin is small because the polyester resin component is large at 5 / 0.5. Polyurethane resin with a high concentration in the coating film has a high glass transition temperature (52 ° C.), so the creep characteristics as evaluated at 60 ° C. are good, but the heat resistance of the solder reflow region due to the increased cross-link density of the modified polyester resin The improvement effect is small, and the solder resistance performance is insufficient. Further, Tg (c) -Tg (d) is small, the reaction of the modified polyester resin (8) at the B stage is fast, and the characteristics after aging are greatly deteriorated.

In Comparative Example 3, the glass transition temperature of the modified polyester resin (7) is as high as 129 ° C., and the proportion of maleic anhydride in the radical polymerizable monomer is 65% by mass, which is out of the scope of the present invention. Yes. The acid value of polyurethane resin (VII) is as small as 90 equivalent / 10 ⁶ g, and Tg (c) -Tg (d) and AV (c) -AV (d) are both outside the scope of the present invention. This is because the mass ratio of the monomer constituting the polyester resin component (a) containing the radical polymerizable moiety of the modified polyester (8) and the monomer constituting the polymer component (b) of the radical polymerizable monomer is 99.99. This is due to the fact that the polyurethane resin (VII) does not use DMBA as a chain extender and has an acid value of 90 equivalents / 10 ⁶ g, which is out of the present invention. Since the curability of the polyurethane resin corresponding to 30% of the mass in the coating film is low, the heat resistance as an adhesive is low, and the solder resistance is extremely poor. Further, since Tg (c) -Tg (d) is large, the peel strength is also poor, and since AV (c) -AV (d) is large, the performance failure with time is also remarkable.

In Comparative Example 4, a modified polyester resin (10) having a glass transition temperature lower than that of the polyurethane resin (VIII) is blended, and Tg (c) -Tg (d) is −13 ° C., which is outside the scope of the present invention. . The polyurethane resin (VIII) has an acid value of 1150 equivalents / 10 ⁶ g, which is outside the scope of the present invention. Since Tg (c) -Tg (d) is outside the scope of the present invention, a wide range of well-balanced thermal properties is insufficient, and the mass of the component consisting of (a), (b), (c) Wc / Wd is 90/10 when the mass of Wc and polyurethane resin (d) is Wd, and the peel strength is low because the concentration of polyurethane resin is low. Furthermore, since the acid value of the polyurethane resin is high and the crosslink density is increased, the stress relaxation ability generated in the coating film in the solder resistance test in the solder reflow region is lowered, and the modified polyester (10) is used. Since the polyester resin H has no unsaturated groups and the modified polyester H is not grafted, it has no effect of supporting heat resistance and has no solder resistance. Since the polymer (homopolymer) of the radical polymerizable monomer which is not grafted reacts very quickly, the adhesiveness deterioration with time is also great.

In Comparative Example 5, the modified polyester resin (11) having a glass transition temperature lower than that of the polyurethane resin (IV) is blended, and Tg (c) -Tg (d) is -14 ° C., which is outside the scope of the present invention. . Further, maleic anhydride is not used as the radical polymerizable monomer, which is outside the scope of the present invention. Since Tg (c) -Tg (d) is out of the scope of the present invention, a wide range of well-balanced thermal characteristics are insufficient, and adhesion at high temperatures (solder resistance, creep characteristics) is particularly poor. ing. Furthermore, since the polyester resin (I) containing a radically polymerizable site used in the modified polyester (11) has a high acid component (itaconic acid) containing a radically polymerizable site of 22 mol%, it is gelled during the grafting process. Samples were prepared by removing them with a 100 mesh nylon filter cloth, but it was confirmed that fine gels were scattered on the entire surface with an optical microscope. confirmed. In actual adhesive property evaluation, peeling occurs from the existing portion of the gel-like material, and the performance is greatly reduced as a whole.

In Comparative Example 6, since the glass transition temperature of the modified polyester resin (14) is as low as −5 ° C. and the glass transition temperature of the blended polyurethane resin (IX) is higher, Tg (c) −Tg (d ) Is −14 ° C., which is outside the scope of the present invention. Since Tg (c) -Tg (d) is out of the scope of the present invention, a wide range of well-balanced thermal characteristics are insufficient, and adhesion at high temperatures (solder resistance, creep characteristics) is particularly poor. ing. Furthermore, the number average molecular weight of the polyurethane resin (IX) is 4,500, and the number average molecular weight of the modified polyester (14) is as small as 4,500, and the cohesive strength of the resin is small, so that the peel strength at room temperature is also small. It has become.

In Comparative Example 7, the polyurethane resin (X) is blended with a modified polyester resin (12) having a glass transition temperature as high as 83 ° C. and a glass transition temperature lower than that of the polyurethane resin, and Tg (c) −Tg (d ) Is −23 ° C., which is outside the scope of the present invention. Since Tg (c) -Tg (d) is outside the scope of the present invention, a wide range of well-balanced thermal properties are insufficient, and in particular, since the glass transition temperature of polyurethane resin (X) is low, peeling at room temperature Insufficient strength. On the contrary, the adhesiveness (solder resistance, creep characteristics) at high temperature is good both in the initial stage and after aging. Further, the number average molecular weight of the polyester resin (J) containing a radical polymerizable moiety used in the modified polyester (12) is as low as 4,000, and the number average molecular weight of the modified polyester (12) itself is as low as 4,500. Therefore, it is estimated that the adhesiveness at room temperature is further lowered.

Comparative Example 8 has a Tg (c) -Tg (d) of 55 ° C., which is outside the scope of the present invention. Polyurethane resin (XI) has a low glass transition temperature of −19 ° C., which is outside the scope of the present invention. Since Tg (c) -Tg (d) is out of the scope of the present invention, a wide range of well-balanced thermal properties are insufficient, and particularly the polyurethane resin has a low glass transition temperature, so that the peel strength at normal temperature is good. However, it has poor adhesion at high temperatures (solder resistance, creep properties). The polyester resin (G) containing a radical polymerizable moiety used in the modified polyester resin (9) has an aromatic acid content (terephthalate) when the total molar amount of all acid components constituting the resin is 100%. Acid) is as low as 20%, and the content of the modified polyester is as low as Wc / Wd of 0.5 / 99.5 when the mass of the modified polyester resin is Wc and the mass of the polyurethane resin is Wd. Since the concentration of the modified polyester is low and the aromatic component is small and the cohesive force is small, the function of covering the heat resistance is also deteriorated.

In Comparative Example 9, the modified polyester resin (13) having a glass transition temperature lower than that of the polyurethane resin (III) is blended, and Tg (c) -Tg (d) is -21 ° C., which is outside the scope of the present invention. . Furthermore, the ratio of the modified polyester (13) to the radical polymerizable monomer of maleic anhydride is as low as 8% by mass, which is out of the scope of the present invention. The number average molecular weight of the polyester resin (K) containing the radical polymerizable moiety used is as large as 53,000, which is outside the scope of the present invention. Further, Tg (c) -Tg (d) is out of the scope of the present invention, and the proportion of maleic anhydride in the radical polymerizable monomer is as low as 8% by mass, and the coating film becomes more uneven. Because it is difficult, it lacks a wide range of well-balanced thermal properties. Furthermore, since the polyester resin (K) containing a radical polymerizable site has many branched components and has a high molecular weight, the modified polyester resin (13) has a gel-like substance, and is made of 100 mesh nylon filter cloth. The sample was prepared by filtering and removing, but it was confirmed with an optical microscope that fine gels were scattered on the entire surface of the sample. In actual adhesive property evaluation, peeling occurs from the existing portion of the gel-like material, and the performance is greatly reduced as a whole.

In Comparative Example 10, since the modified polyester resin (14) has a low glass transition temperature of −5 ° C. and a polyurethane resin (II) having a higher glass transition temperature than that, Tg (c) −Tg ( d) is -44 ° C, outside the scope of the present invention. Furthermore, since Tg (c) -Tg (d) is outside the scope of the present invention, a wide range of well-balanced thermal characteristics are insufficient, and particularly, adhesiveness (solder resistance) at high temperatures is poor. . In addition, since the glass transition temperature of the modified polyester is low, the reactivity of the B stage state with time is large, and the adhesive properties after the time are greatly reduced. Furthermore, in the modified polyester (14), the number average molecular weight of the polyester resin (L) containing the radical polymerizable moiety used is as low as 2500, the cohesive strength of the resin is small, and the peel strength at room temperature is also small. Yes.

In Comparative Example 11, the modified polyester resin (15) having a glass transition temperature lower than that of the polyurethane resin (II) is blended, and Tg (c) -Tg (d) is −26 ° C., which is outside the scope of the present invention. . Furthermore, the epoxy compound does not include those having a dicyclopentadiene skeleton, which is outside the scope of the present invention. Since Tg (c) -Tg (d) is outside the scope of the present invention and it does not contain maleic anhydride, it is difficult to make the coating non-uniform. In combination with the absence of an epoxy compound having a dicyclopentadiene skeleton, the adhesiveness (solder resistance) particularly at high temperatures is poor.

In Comparative Example 12, the glass transition temperature of the modified polyester resin (16) is as high as 84 ° C., the glass transition temperature of the polyurethane resin (XI) is as low as −19 ° C., and Tg (c) -Tg (d) is 103 ° C. High and outside the scope of the present invention. Furthermore, the epoxy compound does not include those having a dicyclopentadiene skeleton, which is outside the scope of the present invention. Since Tg (c) -Tg (d) is outside the scope of the present invention, a wide range of well-balanced thermal characteristics is insufficient. In combination with the absence of an epoxy compound having a dicyclopentadiene skeleton, adhesion at high temperatures (solder resistance, creep properties) is particularly poor. Since the glass transition temperature of the modified polyester resin is high, the peel strength at normal temperature is also poor.

Comparative Example 13 does not contain a modified polyester resin and is outside the scope of the present invention. There is no heat resistance in the solder reflow area, and solder resistance is poor. Furthermore, the adhesive performance cannot be maintained even in the temperature range used for HDD applications, and the creep characteristics are poor.

Comparative Example 14 does not contain a polyurethane resin and is outside the scope of the present invention. The initial performance is good, but the B stage is not stable and the performance over time is poor.

Claims

A polyester resin (a) containing a radically polymerizable moiety,
A polymer of a radically polymerizable monomer (b),
A modified polyester resin (c) modified with a polymer of a radically polymerizable monomer, in which the resin (a) and the polymer (b) are bonded;
A polyurethane resin (d) having an acid value of 100 equivalents / 10 6 g or more and 1000 equivalents / 10 6 g or less,
An epoxy compound (e) having a dicyclopentadiene structure,
Containing
10 mass% or more and 60 mass% or less of the radical polymerizable monomer is maleic anhydride,
The glass transition temperature Tg (c) of the resin (c) is 0 ° C. or higher and 80 ° C. or lower,
The glass transition temperature Tg (d) of the resin (d) is −10 ° C. or higher and 60 ° C. or lower,
The relationship between Tg (c) and Tg (d) is the following formula (1)
50 ≧ Tg (c) −Tg (d) ≧ 5 (1)
The filling,
An acid value AV (c) equivalents / 10 6 g and the acid value AV (d) eq / 10 6 g relationship formula of the resin (d) of (c) (2)
8,000 ≧ AV (c) −AV (d) ≧ 200 (2)
The resin composition for adhesives satisfy | fills.
The resin composition according to claim 1, wherein the acid value of the resin (c) is 400 equivalent / 10 6 g or more and 8,500 equivalent / 10 6 g or less.
The resin composition according to claim 1, wherein the resin (d) has a number average molecular weight of 5,000 or more and 100,000 or less.
The resin composition according to claim 1, wherein the resin (a) has a number average molecular weight of 5,000 or more and 50,000 or less.
When the total molar amount of all the acid components constituting the resin (a) is 100 mol%, the aromatic acid component is 30 mol% or more, the acid component containing a radical polymerizable moiety and the glycol component containing a radical polymerizable moiety 2. The resin composition according to claim 1, wherein the total is from 0.5 mol% to 20 mol%.
From the resin (a), the polymer (b) and the resin (c) as a whole, derived from the monomer constituting the resin (a) and the monomer constituting the polymer (b) 2. The resin composition according to claim 1, wherein the ratio to the portion to be processed is 10/90 or more and 99/1 or less by mass ratio.
When the total mass of the resin (a), the polymer (b), and the resin (c) is Wc, and the mass of the resin (d) is Wd, Wc / Wd is 1/99 or more and 80/20 or less. The resin composition according to claim 1, wherein:
An adhesive comprising the resin composition according to claim 1.
An adhesive sheet comprising the resin composition according to claim 1.
A laminate comprising a plurality of plate-like bodies and / or foil-like bodies bonded together with an adhesive layer, wherein at least a part of the adhesive layer contains the resin composition according to claim 1 Laminate for board.
The plurality of plate-like bodies and / or foil-like bodies are made of at least one material selected from the group consisting of polyester resin, polyimide resin, polyamideimide resin, copper, aluminum, glass epoxy, and stainless steel. The laminate for a printed wiring board according to claim 10.
A printed wiring board comprising the laminate according to claim 10 as a constituent element.