JP2019119886A - Radical polymerizable polyamide, resin composition, and insulation member - Google Patents

Abstract

To provide a radical polymerizable polyamide good in heat resistance and flexure stress tolerance, and capable of forming a resin layer good in adhesiveness to a metal, and a resin composition.SOLUTION: There is provided radical polymerizable polyamide, which is a reaction product of polyamide having a hydroxyl group in a side chain and radical polymerizable epoxy, in which the polyamide having the hydroxyl group in the side chain has a dimer structure consisting of dimer acid or dimer diamine, and a phenolic hydroxyl group unit.SELECTED DRAWING: None

Description

The present invention relates to a radically polymerizable polyamide, and a resin composition thereof.

  Integrated circuits (ICs) using semiconductors are mounted on various electronic devices such as a computer, a smartphone, and a flat panel display as microphone processors, transistors, memories and the like as essential members of electronic components. Furthermore, these electronic components and devices are widely used in automobiles, industrial machines, ships, aircrafts, etc.

  Flat panel displays (FPDs) represented by liquid crystal displays and organic EL displays have touch panel functions and are used in smartphones and tablet terminals. However, FPDs equipped with touch panels are increasingly required to have high image quality and multiple functions, and inevitably IC requires high-speed processing of information, for example, when it is mounted on a smartphone, physically on the IC. Rather than increasing the size, thinner and smaller directions have been sought. As described above, since an IC or the like is subjected to a higher thermal load than before, the epoxy resin used for sealing a semiconductor or insulating an IC has a problem that it can not cope with the thinning of the insulating layer. .

  Therefore, Patent Document 1 discloses an example in which a polyamide such as polyamide 6 and polyamide 66 is used as a sealing resin. Patent Document 2 discloses an example in which polyimide is used as a sealing resin.

JP-T 2017-531919 gazette International Publication 2015/098508

  In recent years, with the development of a flexible display (FPD) that can be bent, in addition to high heat load, bending stress such as bending has come to be applied to mounted ICs and semiconductors. However, since the polyamide of Patent Document 1 has a linear structure, it is easy to cope with bending stress but high. It was difficult to simultaneously satisfy the heat load, and although the polyimide of Patent Document 2 has both excellent heat resistance and bending stress resistance, the heat treatment process until completion of crosslinking is complicated and expensive, and the semiconductor and IC There is a problem that the adhesion to the metal substrate is bad.

  An object of the present invention is to provide a radically polymerizable polyamide and a resin composition capable of forming a resin layer having good heat resistance and bending stress resistance and good adhesion to metal.

The radically polymerizable polyamide of the present invention is a reaction product of a polyamide having a hydroxyl group in a side chain and a radically polymerizable epoxy,
The polyamide having a hydroxyl group in the side chain has a dimer structure consisting of a dimer acid or dimer diamine, and a phenolic hydroxyl group unit.

  According to the above-mentioned present invention, it is possible to provide a radically polymerizable polyamide and a resin composition capable of forming a resin layer having good heat resistance and bending stress resistance and good adhesion to metal.

  The terms in the present specification are defined. The radically polymerizable functional group is, for example, a vinyl group, a (meth) acryloyl group or the like. The (meth) acryloyl group includes an acryloyl group and a methacryloyl group. (Meth) acrylates include acrylates and methacrylates. The monomer is an ethylenically unsaturated group-containing monomer.

The radically polymerizable polyamide in the present specification is a reaction product of a polyamide having a hydroxyl group in a side chain and a radically polymerizable epoxy,
The polyamide having a hydroxyl group in the side chain has a dimer acid unit or dimer diamine unit, and a phenolic hydroxyl unit.

  The radically polymerizable polyamide has, in the side chain, radical polymerizability in which a hydroxyl group in a side chain derived from a phenolic hydroxyl group and a radically polymerizable epoxy are reacted. Therefore, the radically polymerizable polyamide is polymerized by active energy rays. The radical polymerizable polyamide can be polymerized (crosslinked) without a photopolymerization initiator when the active energy ray is an eletron beam (EB), and when it is light including ultraviolet light, the photopolymerization initiation It polymerizes by the agent.

  Since the main chain terminal of the radically polymerizable polyamide has a carboxyl group and / or an amino group, it is preferable to prepare a resin composition by blending a curing agent and a photopolymerization initiator. When the resin composition is heated, a curing agent reacts with a carboxyl group or an amino group to form a crosslinked structure, and then, when light is irradiated, the radical polymerization functional group of the side chain is crosslinked (hereinafter referred to as radical crosslinking). The order of heating and light may be reversed. Further, a layer formed (cured) from the resin composition is referred to as a resin layer.

  Since the radically polymerizable polyamide has a unit consisting of a dimer acid unit or a dimer diamine unit in the molecule (hereinafter sometimes referred to as dimer structure or dimer unit), the resin layer after radical crosslinking is crosslinked The toughness derived from the high density improves the heat resistance. Furthermore, the resin layer has a plurality of hydrocarbon chain units derived from the dimer structure, and in addition to the fact that good adhesion to metal is obtained, the resin layer also has flexibility and excellent bending stress is obtained. The dimer unit refers to a structure having a ring structure and a plurality of hydrocarbon chains. The hydrocarbon chain may also have a reactive functional group (amino group, carboxyl group, etc.) at the end. Also, the dimer unit may have a dimer acid unit and a dimer diamine unit.

<Polyamide having hydroxyl group in side chain>

  One of the raw materials of radically polymerizable polyamide, the polyamide having a hydroxyl group in the side chain is synthesized by the polymerization reaction of a polybasic acid and a polyamine. Among the above compounds, for example, when the carboxyl group is excessive, the carboxyl group is easily generated at the end of the main chain, and when the amino group is excessive, the amino group is easily generated at the end of the main chain. The functional group at the end of the main chain can be appropriately selected depending on the application and use conditions of the radically polymerizable polyamide. The radically polymerizable polyamide may have an amide group and a carboxyl group at the end of the main chain.

  The polyamide having a hydroxyl group in the side chain has a hydroxyl group as a crosslinking point capable of reacting with the radically polymerizable epoxy. The said hydroxyl group is obtained by using the compound which has a phenolic hydroxyl group unit. By containing a phenolic hydroxyl group, a polyamide having a hydroxyl group in the side chain can be obtained.

The polyamide having a hydroxyl group in the side chain is preferably, for example, any of the following (1) to (3) as a reactant. It goes without saying that the polyamide having a hydroxyl group in the side chain is not limited to the following reaction products.
(1) Reactant of polybasic acid phenol, dimer acid and polyamine (2) Reactant of polybasic acid phenol and dimer diamine (3) Reactant of polyamine phenol and dimer acid

  (1) A polyamide having a hydroxyl group in a side chain which is a reaction product of a polybasic acid phenol, a dimer acid and a polyamine is described.

  A polybasic acid phenol is a compound having a hydroxyl group (also referred to as a phenolic hydroxyl group) directly bonded to an aromatic ring, similarly to phenol, and having two or more acidic functional groups. The acidic functional group includes, for example, a carboxyl group.

Examples of polybasic acid phenols include 2-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 5-hydroxyisophthalic acid and the like as monohydroxyisophthalic acid. Examples of dihydroxyisophthalic acid include 2,5-dihydroxyisophthalic acid, 2,4-dihydroxyisophthalic acid and 4,6-dihydroxyisophthalic acid. Examples of monohydroxyphthalic acid include dihydroxyterephthalic acid such as 2-hydroxyterephthalic acid, 2,3-dihydroxyterephthalic acid and 2,6-dihydroxyterephthalic acid; 4-hydroxyphthalic acid and 3-hydroxyphthalic acid. Examples of dihydroxyphthalic acid include 3,4-dihydroxyphthalic acid, 3,5-dihydroxyphthalic acid, 4,5-dihydroxyphthalic acid and 3,6-dihydroxyphthalic acid. In the polybasic acid phenol, the carboxyl group of the compound exemplified in the upper part may form an acid anhydride group, and the carboxyl group may form an ester.
Among these, polybasic acid phenol is preferably 5-hydroxyisophthalic acid in view of copolymerizability, availability, and the like.
Polybasic acid phenol can be used individually or in combination of 2 or more types.

In the present specification, in addition to the polybasic acid phenol, a polybasic acid can be used in combination as needed. This makes it easy to adjust the number of hydroxyl groups of the polyamide having hydroxyl groups in the side chain.
A polybasic acid is a compound other than a dimer acid and has no phenolic hydroxyl group. Examples of polybasic acids include dibasic acids and trifunctional or higher functional polybasic acids. The polybasic acid may be an acid anhydride.

Examples of dibasic acids include phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, benzophenone-4,4'-dicarboxylic acid and 4,4'-biphenyldicarboxylic acid Aromatic dibasic acids such as oxalic acid, malonic acid, methylmalonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, malic acid, tartaric acid, thiomalic acid, pimelic acid, suberic acid, azelaic acid Aliphatic dibasic acids such as sebacic acid, dodecanedioic acid, hexadecanedioic acid and diglycolic acid, and oils such as 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 1,3-cyclopentanedicarboxylic acid A ring dibasic acid etc. are mentioned.
Examples of trifunctional or higher polybasic acid compounds include trimellitic acid, hydrogenated trimellitic acid, pyromellitic acid, hydrogenated pyromellitic acid, trimesic acid, 1,4,5,8-naphthalenetetracarboxylic acid, etc. Be
Among these, polybasic acids are preferably isophthalic acid and 1,4-cyclohexanedicarboxylic acid in terms of further improving bending stress resistance and heat resistance. In addition, when a trifunctional or higher functional polybasic acid compound is used, a branched structure can be introduced into the radically polymerizable polyamide, so the cohesion of the resin layer is improved, and the heat resistance and the dimensional stability are further improved.
The polybasic acids can be used alone or in combination of two or more.

Dimer acids are dimers of fatty acids (hereinafter referred to as fatty acid dimers).
The fatty acid dimer is preferably a compound having 20 to 60 carbon atoms, more preferably a compound having 24 to 56 carbon atoms, still more preferably a compound having 28 to 48 carbon atoms, and still more preferably a compound having 36 to 44 carbon atoms. The fatty acid dimer is preferably a dicarboxylic acid having a branched structure obtained by Diels-Alder reaction of a fatty acid. The branched structure is preferably a fatty chain and a ring structure, more preferably a ring structure. The ring structure is preferably one or more aromatic rings or alicyclic structures, and more preferably alicyclic structures. The alicyclic structure may have no double bond if it has one double bond in the ring.

  Examples of the dimer acid include structures represented by the following chemical formulas (1) to (4). Needless to say, the dimer acid is not limited to the following structure.

The fatty acid is preferably, for example, an unsaturated fatty acid having 10 to 30 carbon atoms, and more preferably an unsaturated fatty acid having 10 to 24 carbon atoms. The unsaturated fatty acid has one or more carbon-carbon double bonds or carbon-carbon triple bonds.
Examples of the fatty acid include natural fatty acids such as soybean oil fatty acid, tall oil fatty acid and rapeseed oil fatty acid, and oleic acid, linoleic acid, linolenic acid, erucic acid etc. obtained by purifying them.
When the fatty acid dimer is synthesized, in addition to the fatty acid dimer, a trimer of fatty acid and optionally a tetramer are formed. Therefore, the dimer acid is not only the fatty acid dimer of the main component, but also a trimer of fatty acid and the like, and in some cases, a mixture containing the fatty acid of the raw material.
70 mass% or more is preferable in 100 mass% of dimer acids, and 95 mass% or more of a fatty acid dimer is more preferable.

Since the dimer acid uses unsaturated fatty acid as a raw material, unsaturated bond may remain. In such a case, the number of unsaturated bonds can be suppressed by hydrogenation (also referred to as hydrogenation reaction). Thereby, the reaction stability at the time of synthesizing a radically polymerizable polyamide is improved, and further, the high temperature resistance of the resin layer in which the radically polymerizable polyamide is reacted is improved.
A dimer acid can be used individually or in combination of 2 or more types.

  Examples of commercially available dimer acids include "Pripol 1004", "Pripol 1006", "Pripol 1009", "Pripol 1013", "Pripol 1015", "Pripol 1017", "Pripol 1022" manufactured by Croda Japan. “Pripole 1025”, “Pripole 1040”; “Empol 1008”, “Empol 1012”, “Empol 1016”, “Empol 1026”, “Empol 1028”, “Empol 1043”, “Empol 1061”, manufactured by BASF Japan Ltd. , "Empol 1062" and the like. Among these, “Pripol 1009” having a carbon number of 36 is easy to obtain a radically polymerizable polyamide having good heat resistance while maintaining adhesion to metal. In addition, “Pripol 1004” having 44 carbon atoms is easy to obtain a radically polymerizable polyamide having good flexibility.

Polyamines include, for example, diamines, polyamine phenols, and other polyamines.
Examples of diamines include 1,4-diaminobenzene, 1,3-diaminobenzene, 1,2-diaminobenzene, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene, 2,6. -Diaminotoluene, 2,4-diaminotoluene, 3,4-diaminotoluene, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylether, 4,4'-diaminodiphenylether, 4,4'-diamino-1,4 2-diphenylethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 3,3 ' -Aromatic diamines such as diaminodiphenyl sulfone; ethylene diamine, 1,3-propane Aliphatic diamines such as lopane diamine, 1,4-butanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,9-nonanediamine, 1,12-dodecamethylenediamine, meta-xylene diamine; isophorone diamine, norbornane Examples thereof include diamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4′-diaminodicyclohexylmethane, and alicyclic diamines such as piperazine.

  Polyamine phenol is phenol having a plurality of amino groups. Examples of polyamine phenols include polyamines represented by the following general formula (1).

In the formula, R ₁ represents a direct bond or a group containing carbon, hydrogen, oxygen, nitrogen, sulfur or halogen. The group is, for example, a divalent hydrocarbon group having 1 to 30 carbon atoms or a divalent hydrocarbon group having 1 to 30 carbon atoms in which a part or all of hydrogen is substituted by a halogen atom,-(C = _{O) -, - SO 2 -} , - O -, - S -, - NH- (C = O) -, - (C = O) -O-, group and the following represented by the following general formula (2) The group shown by General formula (3) is mentioned. In the formula, r and s each independently represent an integer of 1 to 20, and R ₂ represents a hydrogen atom or a methyl group.

  The polyamine represented by the general formula (1) is, for example, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 9,9-bis (3-amino-4-hydroxyphenyl) fluorene, 2,2-bis Examples include (3-amino-4-hydroxyphenyl) hexafluoropropane and the like.

  Other polyamines are amines having three or more amino groups and having no phenolic hydroxyl group. Other polyamines include, for example, 1,2,4-triaminobenzene, 3,4,4'-triaminodiphenyl ether and the like. Polyamines are classified into aliphatic amines when they have an aromatic ring and the aromatic ring and the amino group are not directly bonded.

Among these, isophorone diamine and norbornane diamine are preferable in terms of further improving bending stress and heat resistance. Moreover, since a polyamine can introduce | transduce branch structure to radically polymerizable polyamide if other polyamines are used, the cohesion force of a resin layer improves and heat resistance and bending stress tolerance improve more.
The polyamine can be used alone or in combination of two or more.

  In the present specification, in addition to the polyamine, a monoamine can be used in combination. Since monoamine acts as a reaction terminator, it is easy to adjust the molecular weight of the polyamide having a hydroxyl group in the side chain. In addition, since a part of the main chain terminal of the radically polymerizable polyamide is not a reactive functional group, the temporal stability is improved.

  Examples of monoamines include aniline, 4-aminophenol, 2-ethylhexylamine and the like.

  The synthesis of the polyamide having a hydroxyl group in a side chain is preferably solution polymerization, for example, since it can be synthesized by melt polymerization, interfacial polymerization, solution polymerization, bulk polymerization, solid phase polymerization, and a combination thereof. The synthesis can be performed by reaction of polybasic acid phenol, dimer acid and polyamine in the presence or absence of a catalyst at 150 to 300 ° C. for about 1 to 24 hours. It is preferable to conduct dehydration or dealcoholization reaction to accelerate the synthesis reaction, and it is preferable to carry out the reaction at 180 to 270 ° C. under reduced pressure to avoid coloration and decomposition reaction at high temperature.

  The conditions for the synthesis of the polyamide having a hydroxyl group in the side chain are, for example, charging a predetermined amount of a polybasic acid phenol, a dimer acid, a polyamine and ion exchange water into a nitrogen-filled flask and heating and stirring at 20 to 100 ° C. It dissolves uniformly or disperses uniformly. Thereafter, the temperature is gradually raised to 230 ° C. while removing the ion-exchanged water and the water generated by the reaction, the pressure is reduced to about 15 mmHg as soon as it reaches 230 ° C., and the state is maintained for about 1 hour. You can get

  The polyamide having a hydroxyl group in the side chain is preferably a hydroxyl value of 1 to 80 mg KOH / g, more preferably 5 to 60 mg KOH / g, and still more preferably 5 to 30 mg KOH / g. Since it is easy to introduce a radically polymerizable functional group if it has a hydroxyl value in an appropriate amount, an appropriate crosslinking density is obtained in the resin layer, and heat resistance, bending stress resistance, and adhesion to metal are further improved.

  The weight average molecular weight of the polyamide having a hydroxyl group in the side chain is preferably 3,000 to 1,000,000, more preferably 5,000 to 550,000, and 10,000 to 300,000. Is more preferred.

  -40 degreeC-120 degreeC is preferable, and, as for the glass transition temperature (Tg) of the polyamide which has a hydroxyl group in a side chain, -30 degreeC-80 degreeC is more preferable. In addition, Tg is the numerical value measured by the temperature increase rate of 10 degree-C / min using DSC-1 made from Mettler-Toledo company.

(2) Polybasic acid phenol and polyamide which has a hydroxyl group in the side chain which is a reaction product of dimer diamine are explained.
The polybasic acid phenol is identical to the polybasic acid phenol described above. In addition to the polybasic acid phenol, polybasic acids and dimer acids can be used in combination as needed.

  Examples of the dimer diamine include compounds in which the carboxyl group of the dimer acid is converted to an amino group. Examples of the conversion method include a method of amidating a carboxylic acid, amination by Hofmann rearrangement, and further distillation and purification.

Examples of commercially available dimer diamines include "Priamine 1071", "Priamine 1073", "Priamine 1074" and "Priamine 1075" manufactured by Croda Japan, and "Varsamine 551" manufactured by BASF Japan.
Dimer diamine can be used individually or in combination of 2 or more types.

  Moreover, the polyamide which has a hydroxyl group in a side chain can be used in addition to a dimer diamine and a polyamine. This allows the balance between toughness and flexibility to be adjusted appropriately. As the polyamine, the compounds described above can be used.

The polyamide having a hydroxyl group in the side chain of (2) can be synthesized in the same direction as the polyamide having a hydroxyl group in the side chain of (1) above. The hydroxyl value, weight average molecular weight and Tg of the polyamide having a hydroxyl group in the side chain are the same as (1).

(3) Polyamine phenol, and the polyamide which has a hydroxyl group in the side chain which is a reaction product of dimer acid is explained.
The polyamide having a hydroxyl group in the side chain of (3) introduces a phenolic hydroxyl group using the polyamine phenol already described. In addition, polybasic acid phenol can be used together with polyamine phenol.

  Examples of polyamine phenols include 3,3'-dihydroxybenzidine.

  Moreover, a polybasic acid can also be used together with a dimer acid. Other polyamines can also be used in combination with the polyamine phenol. The polyamide having a hydroxyl group in the side chain of (3) can be synthesized in the same manner as the polyamide having a hydroxyl group in the side chain of (1). The hydroxyl value, weight average molecular weight and Tg of the polyamide having a hydroxyl group in the side chain of (3) are the same as in (1) and (2).

  The polyamide having a hydroxyl group in the side chain of (1) to (3) preferably contains 10 to 95% by mole, and 14 to 92% by mole of a dimer structure consisting of dimer diamine units and dimer acid units in all constituent units. It is more preferable that 18-88 mol% is included. When the dimer structure is in the above range, heat resistance and bending stress resistance are further improved, and adhesion to metal is further improved.

<Radically polymerizable epoxy>
Radically polymerizable epoxy is an epoxy having a radically reactive functional group. The radically polymerizable epoxy reacts with the epoxy group and the hydroxyl group of the polyamide having a hydroxyl group at the side chain to synthesize a radically polymerizable polyamide in which the radical reactive functional group is grafted to the side chain.
Since a radically polymerizable polyamide has a radical reactive functional group in the side chain, when forming a resin layer, it can be cured (crosslinked) by means of heat curing, light curing, heat curing and light curing combined use; Both heat resistance and bending stress resistance can be achieved at a high level.

The radically polymerizable epoxy includes, for example, glycidyl (meth) acrylate and alicyclic epoxy (meth) acrylate.
Commercially available products of radically polymerizable epoxy include, for example, 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei Co., Ltd.), Cyclomer M100 manufactured by Daicel Co., Ltd., Celoxide 2000 (manufactured by Daicel Co., Ltd.), Brimmer G (glycidyl methacrylate) , NOF Corporation), glycidyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), and the like.

  The reaction between the polyamide having a hydroxyl group in the side chain and the radically polymerizable epoxy is that the epoxy group of the radically polymerizable epoxy has an equivalent ratio of more than 0.1 and 3 or less with respect to the hydroxyl group of the hydroxyl group-containing polyamide. It is preferable to react in the range, 0.2 to 2.5 is more preferable, 0.3 to 2 is more preferable. When the reaction is carried out at a suitable equivalent ratio, the reaction rate of esterification is further improved, and it becomes easy to synthesize a radically polymerizable epoxy.

A catalyst can be used for the reaction of the said epoxy group and a hydroxyl group.
Examples of the catalyst include amine catalysts, phosphorus catalysts, and halogen catalysts. Examples of amine catalysts include N, N-dimethylalkylamine, N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, N, N-diethylalkylamine, N, N-dipropylbutylamine and the like. . The phosphorus-based catalyst includes, for example, triphenyl phosphine, triparatolyl phosphine, diphenylcyclohexyl phosphine, tricyclohexyl phosphine and the like.

A polymerization inhibitor can be used in combination with the reaction of the epoxy group and the hydroxyl group in order to suppress the thermal polymerization of the radically polymerizable functional group.
Examples of the polymerization inhibitor include methoquinone, hydroquinone, 1,4-benzoquinone, phenothiazine and the like.

  A polymerization inhibitor can be mix | blended 0.001-0.1 mass part with respect to 100 mass parts of polyamide which has a hydroxyl group in a side chain.

  40% or more is preferable, 50% or more of the reaction rate (henceforth a hydroxyl group reaction rate) of the hydroxyl group of the polyamide which has a hydroxyl group in a side chain and radically polymerizable epoxy is more preferable, and 60% or more is more preferable. When the hydroxyl group reaction rate is 40% or more, when radically polymerizing polyamide is radically polymerized, it is easy to obtain a high crosslinking density. The upper limit of the hydroxyl group reaction rate is 100%.

The hydroxyl group reaction rate can be calculated by the following formula. Although the carboxyl group or amino group of the polyamide having a hydroxyl group in the side chain may react with the radically polymerizable epoxy in some cases, it is not considered in the reaction rate in this specification.
[Hydroxyl conversion rate] (%) = (hydroxyl value of polyamide having hydroxyl group in side chain) / (hydroxyl value of radically polymerizable polyamide) × 100

  3,000-1,000,000 are preferable, as for the weight average molecular weight (Mw) of radically polymerizable polyamide, 5,000-550,000 are more preferable, and 10,000-300,000 are more preferable. When it has a predetermined Mw, the heat resistance and the bending stress resistance are further improved, and the adhesion to metal is further improved. In the present specification, a radically polymerizable polyamide is referred to as a resin.

  -40 degreeC-120 degreeC is preferable, and, as for Tg of radically polymerizable polyamide, -30 degreeC-80 degreeC is more preferable. By adjusting the glass transition temperature of the radically polymerizable polyamide to a range of −40 ° C. to 120 ° C., the embeddability and adhesion to the substrate can be further improved.

  The adjustment of the glass transition temperature includes, for example, adjusting the ratio of the dimer structure. When the blend ratio of the dimer structure is increased, the Tg may be lowered.

  The resin composition of the present specification preferably comprises a radically polymerizable polyamide and a radical polymerization initiator, and more preferably further comprises a polyfunctional radically polymerizable compound. In addition, the resin composition of the present specification can use a monofunctional radically polymerizable monomer in combination with or instead of the polyfunctional radically polymerizable compound. Thereby, the crosslink density of the resin layer can be appropriately adjusted. The resin composition can form a resin layer only by reacting a radically polymerizable polyamide and a radical polymerization initiator, but when it is further reacted with a polyfunctional radically polymerizable compound, the toughness of the resin layer is increased, and the heat resistance and bending are obtained. Stress resistance can be compatible at a higher level.

  The radically polymerizable polyamide is preferably contained in an amount of 1 to 95% by mass, more preferably 5 to 90% by mass, and still more preferably 10 to 85% by mass in 100% by mass of the nonvolatile components of the resin composition. By being in the said range, adhesiveness, a flexibility, and heat resistance improve more.

  When the radical polymerization initiator is a peroxide, an azo compound or the like, the resin composition is thermally polymerized. When the radical polymerization initiator is a photopolymerization initiator, the resin composition photopolymerizes.

Examples of the peroxide include benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, di-tert-butyl peroxide, tert-butyl hydroperoxide and the like.
The azo compound is, for example, 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), etc. Can be mentioned.

  Examples of the photopolymerization initiator include oxime ester photopolymerization initiator, thioxanthone photopolymerization initiator, acetophenone photopolymerization initiator, benzoin photopolymerization initiator, benzophenone photopolymerization initiator, and triazine photopolymerization initiator And borate type photopolymerization initiators, carbazole type photopolymerization initiators, imidazole type photopolymerization initiators and the like.

  The photopolymerization initiator is a triphenylsulfonium photopolymerization initiator, an alkylphenone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, an oxime ester photopolymerization from the viewpoint of reactivity and resolution after development. Initiators are preferred.

  0.01-10 mass parts is preferable with respect to 100 mass parts of compounds containing a radically polymerizable functional group, and, as for a radical polymerization initiator, 0.1-5 mass parts is more preferable. In addition, the compound containing a radically polymerizable functional group contains radically polymerizable polyamide, a polyfunctional radically polymerizable compound, and a monofunctional radically polymerizable monomer.

  The polyfunctional radically polymerizable compound is, for example, a monomer having a radically polymerizable functional group having two or more functionalities (hereinafter referred to as a polyfunctional monomer), an oligomer having a radically polymerizable functional group having two or more functionalities (hereinafter referred to as a polyfunctional oligomer Can be mentioned. The polyfunctional monomer is a compound having a molecular weight of less than 800. The polyfunctional oligomer is a compound having a molecular weight of 800 or more. In addition, monofunctional radically polymerizable monomers can be used in combination with or instead of the polyfunctional radically polymerizable compound. As a result, the viscosity of the resin composition can be easily adjusted to be lower, and the crosslink density of the resin layer can be easily adjusted.

  Examples of polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. Ethoxylated isocyanurate tri (meth) acrylate, ε-caprolactone modified tris- (2-acryloxyethyl) isocyanurate and the like.

  Examples of polyfunctional oligomers include urethane (meth) acrylates, acrylic oligomers grafted with (meth) acryloyl groups, and epoxy (meth) acrylates.

  A polyfunctional radically polymerizable compound can be used individually or in combination of 2 or more types.

  The polyfunctional radically polymerizable compound is preferably contained in an amount of 1 to 90% by mass, more preferably 5 to 80% by mass, and still more preferably 10 to 70% by mass in 100% by mass of the nonvolatile matter of the resin composition. .

  The monofunctional radically polymerizable monomer is, for example, a (meth) acrylic acid alkyl ester; a monomer having one selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and an amide group; a heterocycle containing monomer, other vinyl monomers Can be mentioned.

  Radically polymerizable polyamide is, for example, radically polymerized at the main chain terminal by reacting an amino group or carboxyl group at the main chain terminal with a (meth) acryloyl group-containing isocyanate, epoxy (meth) acrylate, or hydroxy (meth) acrylate. It is also possible to use radically polymerizable polyamides having functional groups.

  The resin composition of the present specification can contain a thermosetting resin such as an epoxy resin and a phenol resin. A thermosetting resin can be used individually or in combination of 2 or more types.

The epoxy resin is a resin having no radical reactive functional group and having an epoxy group.
Examples of the epoxy resin include triphenylmethane epoxy resin, cresol novolac epoxy resin, biphenyl epoxy resin, modified bisphenol A epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, modified bisphenol F epoxy resin, Dicyclopentadiene type epoxy resin, phenol novolak type epoxy resin, phenoxy resin etc. are mentioned.
Among these, phenol novolac type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol methane type epoxy resin, biphenyl type epoxy resin, bisphenol F type epoxy resin, in terms of further improving insulation reliability Glycidyl amine type epoxy resins are preferred.

  The epoxy resin has an epoxy equivalent of 150 to 250 g / eq. Is preferred. In addition, it is preferable that the epoxy resin be rigid in view of heat resistance. A rigid epoxy resin refers to an epoxy resin having a softening point or melting point of 50 to 130 ° C. When the softening point or the melting point is 50 ° C. or more, the heat resistance at the time of curing can be secured, and when the softening point or the melting point is 130 ° C. or less, the resin fluidity at the time of molding and curing such as extrusion can be secured.

  The phenolic resin is a resin having a phenolic unit and no epoxy group. Examples of the phenol resin include phenol novolac resin, phenol aralkyl resin, biphenyl aralkyl resin, dicyclopentadiene type phenol resin, cresol novolac resin, resol resin and the like. Among these, phenol novolak resins are preferable in terms of high reactivity. In addition, a phenol aralkyl resin and a biphenyl aralkyl resin are preferable in terms of further improving the insulation reliability.

  The hydroxyl equivalent of the phenol resin is 70 to 250 g / eq. Is preferred. The reactivity is further improved by appropriately having a hydroxyl group. Moreover, as for the softening point of a phenol resin, 50-110 degreeC is preferable.

  The thermosetting resin is preferably contained in an amount of 5% by weight or more and 40% by weight or less in 100% by mass of the nonvolatile content of the resin composition. When it is 5% by weight or more, for example, the adhesion to the substrate is further improved. When the content is 40% by weight or less, the flexibility of the resin layer is further improved. The content is more preferably 20% by weight or less

  The ratio in the case of using the epoxy resin and the phenol resin in combination may be such that the total of hydroxyl groups in the phenol resin is 0.7 to 1.5 equivalents with respect to 1 equivalent of the epoxy group in the epoxy resin. Preferably, 0.9 to 1.2 equivalents are more preferred. By combining the two appropriately, the reactivity is further improved.

  The resin composition of the present specification can contain a curing accelerator. As the curing accelerator, the catalyst described above can be used.

The resin composition of the present specification can contain a solvent. Examples of the solvent include hydrocarbon solvents, alcohol solvents, ketone solvents and ester solvents, and other solvents.
Examples of hydrocarbon solvents include benzene, toluene, ethylbenzene, xylene, cyclohexane, hexane and the like. Examples of alcohol solvents include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol and the like. Examples of the ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like. Examples of ester solvents include methyl acetate, ethyl acetate, propyl acetate, butyl acetate and the like. Other solvents include, for example, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, tetrahydrofuran, oxolane and the like.

  The resin composition of the present specification can contain an inorganic filler. When the inorganic filler is included, the heat resistance of the resin layer is further improved. Examples of the inorganic filler include quartz glass, talc, silica (such as fused silica and crystalline silica), alumina, aluminum nitride, silicon nitride, boron nitride and the like. Among these, silica and alumina are preferable in terms of further reducing the thermal expansion coefficient of the resin layer, and silica is more preferable. Silica is preferably fused silica from the viewpoint of excellent fluidity, and spherical fused silica is more preferred.

  1-50 micrometers is preferable and, as for the average particle diameter of an inorganic filler, 5-30 micrometers is more preferable. When the average particle diameter is 1 μm or more, the flexibility and flexibility of the resin layer are further improved. When the average particle size is 50 μm or less, the resin layer is easily highly filled. In addition, an average particle diameter is D50 average particle diameter, for example, it measures using a laser diffraction scattering type particle size distribution measuring apparatus using the sample arbitrarily extracted from a population.

  The inorganic filler is preferably used after being treated (pretreated) with a silane coupling agent. By this, the affinity with other materials is further improved, and the dispersibility of the inorganic filler is further improved.

The silane coupling agent is a compound having a hydrolyzable group and a reactive functional group.
Examples of the hydrolyzable group include an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; an acetoxy group; a 2-methoxyethoxy group and the like. Among these, a methoxy group is preferable in terms of easy removal of volatile components such as alcohol generated by hydrolysis.

  The reactive functional group may, for example, be a vinyl group, an epoxy group, a styryl group, a methacryl group, an acryl group, an amino group, a ureido group, a mercapto group, a sulfide group or an isocyanate group.

  The silane coupling agent is, for example, a vinyl group-containing silane coupling agent such as vinyltrimethoxysilane and vinyltriethoxysilane; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxyme Epoxy group-containing silane coupling agents such as silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; p-styryltrimethoxysilane etc. Styryl group-containing silane coupling agent; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane Methacryl group-containing silane coupling agent; acrylic group-containing silane coupling agent such as 3-acryloxypropyltrimethoxysilane; N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (amino Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl Amino group-containing silane coupling agents such as -3-aminopropyltrimethoxysilane and N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane; ureido group-containing such as 3-ureidopropyltriethoxysilane Silane coupling agent; 3-mercap Mercapto-containing silane coupling agents such as propylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; sulfide-containing silane coupling agents such as bis (triethoxysilylpropyl) tetrasulfide; 3-isocyanate propyltriethoxysilane and the like An isocyanate group containing silane coupling agent is mentioned.

  Examples of the method for treating the inorganic filler with the silane coupling agent include a wet method in which the inorganic filler and the silane coupling agent are mixed in a solvent, and a dry method in which the inorganic filler and the silane coupling agent are treated in the gas phase. Be

  The processing amount of the silane coupling agent is preferably about 0.1 to 1 part by weight of the silane coupling agent with respect to 100 parts by weight of the untreated inorganic filler.

  The inorganic filler is preferably contained in an amount of 40% by mass or more, more preferably 60% by mass or more, and still more preferably 80% by mass or more in 100% by mass of nonvolatile components of the resin composition. When the content is 40% by mass or more, the heat resistance of the resin layer is further improved. The upper limit of the content is 95% by mass.

  The resin composition of the present specification also preferably contains a radically polymerizable polyamide, a curing agent, a photopolymerization initiator, and a polyfunctional radically polymerizable compound. Thus, for example, after first reacting the carboxyl group or amide group of the radically polymerizable polyamide with the curing agent, the radically polymerizable functional group of the radically polymerizable polyamide and the polyfunctional radically polymerizable compound can be polymerized by light irradiation.

  The resin composition can include an additive. Additives include, for example, thermoplastic resins (elastomers), dyes, pigments (for example, carbon black), flame retardants, antioxidants, polymerization inhibitors, antifoaming agents, antifoaming agents, leveling agents, ion collectors, humectants, viscosity A modifier, an antiseptic, an antibacterial agent, an antistatic agent, an antiblocking agent, an ultraviolet absorber, an infrared absorber, an electromagnetic wave shielding agent, a filler, etc. are mentioned.

The resin composition forms a resin layer by curing.
5-500 micrometers is preferable and, as for the thickness of a resin layer, 10-100 micrometers is more preferable. The film of the resin layer can be formed by, for example, spin coating, spray coating, inkjet method, dipping method, roll coating, screen printing, gravure printing, or the like. After the film formation, drying to curing may be performed. Examples of the drying device include a hot air dryer, an infrared heater, and the like. The drying temperature is about 50 to 200 ° C. As for thermosetting, 60-230 degreeC is preferable.

Among the curing described above, it is preferable that the light curing be performed at an irradiation intensity of 10 to 1000 mW / cm ² and an integrated illuminance of about 100 to 5000 mJ / cm ² . The light has a wavelength of about 150 to 550 nm, and is preferably a wavelength at which the photopolymerization initiator has sensitivity. Examples of light sources include low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, chemical lamps, black light lamps, microwave excited mercury lamps, LED lamps, xenon lamps, metal halide lamps and the like.

  Since the resin composition has an insulating property, in addition to sealing applications for semiconductors, for example, sealing materials for printed wiring boards, sealing materials for solar cell materials, adhesion between sealing materials substrates for electric wires and cables, and semiconductor chips It is preferable to use for an agent, an interlayer insulation film, a bonding sheet, a spacer, a cover coat solder resist film of a flexible base, etc.

The insulating member of the present specification comprises a substrate, and a resin layer containing the resin composition of the present specification. The base material may be either conductive, semiconductor or insulating, but is an insulating member since the resin layer is insulating.
The substrate is preferably a plate or a film. Examples of the material of the substrate include silicon, ceramic, aluminum, other metals, plastics and the like. 1-500 micrometers is preferable and, as for the thickness of a base material, 5-300 micrometers is more preferable.

  The sealing application of a semiconductor element will be described as an example of the application of the insulating member. The semiconductor element is provided with a silicon wafer and a resin layer which is a cured product of a resin composition. In the production of the semiconductor device, for example, in the production of the semiconductor package, the resin composition is spin-coated on a silicon wafer, and a film is formed so that the thickness after curing becomes about 0.1 to 30 μm. Next, the film is prebaked at about 60 to 130 ° C. to dry the film. Next, in the case of forming a relief pattern on the film, light irradiation is performed by applying a photomask. Then, a relief pattern is obtained by dissolving and removing the uncured portion with a developer.

  The thickness of the silicon wafer is about 100 to 5000 μm.

The developer includes an alkali developer and a solvent developer.
The alkaline developer includes, for example, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and aqueous ammonia; primary amines such as ethylamine and n-propylamine; diethylamine, di-n- Secondary amines such as propylamine, tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; An aqueous solution is mentioned.

  An alcohol and a surfactant can be appropriately blended in the alkali developer.

Examples of the solvent developer include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone and 3-methyl-2-pentanone. , 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, pyruvine And ethyl acetate, ethyl acetate, butyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.
Examples of the development method include spray, paddle, immersion, ultrasonic waves and the like.

The relief pattern formed by development is preferably rinsed. The rinse solution may, for example, be distilled water. Next, heat treatment (curing) of the rinsed relief pattern is performed to obtain a resin layer (cured film). The heat treatment can be performed at high temperature or low temperature, and the heat treatment temperature at high temperature is preferably 280 ° C. to 380 ° C., and more preferably 290 ° C. to 350 ° C. 150 degreeC-280 degreeC are preferable and, as for the heat processing temperature in low temperature, 180 degreeC-260 degreeC are more preferable.
The heat treatment may, for example, be a heating oven, a hot plate, an electric furnace, an infrared ray, a microwave or the like.

  A temporary fixing film is laminated on a glass substrate, and a semiconductor element is disposed thereon. A cured film cut into a predetermined size is placed on a semiconductor element, and pressed at 185 ° C. for 1 hour using a vacuum laminator to produce a laminate. The temporary fixing film is peeled off from the laminate to obtain a semiconductor package.

  Applications other than sealing of the semiconductor element of the insulating member include, for example, semiconductor device application, spacer application of semiconductor element, display device application such as TFT type liquid crystal and organic EL, interlayer insulating film of multilayer circuit, flexible copper clad plate , A solder resist film, a liquid crystal alignment film, and the like.

  The semiconductor device uses, for example, a passivation film on a semiconductor element, a protective film such as a buffer coat film formed on the passivation film, an insulating film constituting a semiconductor chip, an alpha ray blocking film, a planarization film, and a protrusion (Resin post), a partition, etc. are mentioned.

  The present invention will be more specifically described, but the following examples do not in any way limit the scope of the present invention. In the examples, “parts” is “parts by mass” and “%” is “mass%”. The compounding amounts in the table are parts by mass.

<Method of measuring hydroxyl value>
The hydroxyl value is the amount of hydroxyl group contained in 1 g of hydroxyl group-containing polyamide, expressed by the amount (mg) of potassium hydroxide necessary to neutralize the acetic acid bonded to the hydroxyl group when acetylating the hydroxyl group It is. The hydroxyl value was measured according to JIS K 0070.
In the present invention, when the hydroxyl value of the hydroxyl group-containing polyamide of the terminal carboxylic acid is calculated, the acid value is taken into consideration as shown in the following formula.
<Measurement of hydroxyl value>
Accurately measure about 1 g of the sample in a stoppered Erlenmeyer flask, 100 mL of cyclohexanone solvent
Add and dissolve. Furthermore, an acetylating agent (25 g of acetic anhydride is dissolved in pyridine and the volume is 100
Exactly 5 mL of the solution (in mL) was added and stirred for about 1 hour. To this, add phenolphthalein test solution as an indicator and hold for 30 seconds. Then, until the solution becomes pinkish 0.
Titrate with 5N alcoholic potassium hydroxide solution.
The hydroxyl value was determined by the following formula (unit: mg KOH / g).
Hydroxyl value (mg KOH / g)
= [{(B-a) x F x 28.05} / S] + D
However,
S: Amount of sample collected (g)
a: Consumption of 0.5 N alcoholic potassium hydroxide solution (mL)
b: Consumption of empty 0.5N alcoholic potassium hydroxide solution (mL)
F: Titer of 0.5 N alcoholic potassium hydroxide solution D: Acid value (mg KOH / g)

<Measurement of acid number>
Accurately measure about 1 g of the sample in a stoppered Erlenmeyer flask, 100 mL of cyclohexanone solvent
Add and dissolve. To this, add phenolphthalein TS as an indicator and hold for 30 seconds. It is then titrated with 0.1 N alcoholic potassium hydroxide solution until the solution is pinkish. The acid value was determined by the following formula (unit: mg KOH / g).
Acid value (mg KOH / g) = (5.611 x a x F) / S
However,
S: Amount of sample collected (g)
a: Consumption of 0.1 N alcoholic potassium hydroxide solution (mL)
F: titer of 0.1 N alcoholic potassium hydroxide solution

<Amine number measurement>
Accurately measure about 1 g of the sample in a stoppered Erlenmeyer flask, 100 mL of cyclohexanone solvent
Add and dissolve. Add a few drops of an indicator prepared by mixing 0.20 g of MethylOrange in 50 mL of distilled water and another solution of 0.28 g of Xylene Cyanol FF in 50 mL of methanol. . It is then titrated with 0.1 N alcoholic hydrochloric acid solution until the solution appears bluish gray. The amine titer was determined by the following formula (unit: mg KOH / g).
Acid value (mg KOH / g) = (5.611 x a x F) / S
However,
S: Amount of sample collected (g)
a: Consumption of 0.1 N alcoholic hydrochloric acid solution (mL)
F: titer of 0.1 N alcoholic hydrochloric acid solution

<Measuring method of mass average molecular weight (Mw)>
The measurement of Mw used GPC (gel permeation chromatography) "GPC-101" by Showa Denko. GPC is a liquid chromatography that separates and quantifies a substance dissolved in a solvent (THF; tetrahydrofuran) by the difference in molecular size. In the measurement in the present invention, two “KF-805L” (manufactured by Showa Denko: GPC column: 8 mm ID × 300 mm size) are connected in series to the column, and the sample concentration is 1 wt%, flow rate 1.0 ml / min, pressure The measurement was performed under the conditions of 3.8 MPa and a column temperature of 40 ° C., and the weight average molecular weight (Mw) was determined in terms of polystyrene. For data analysis, a calibration curve, a molecular weight, and a peak area were calculated using manufacturer's built-in software, and a mass average molecular weight was determined using a range of retention time of 17.9 to 30.0 minutes as an analysis target.

<Method of measuring glass transition temperature>
About the polyamide which removed the solvent by drying, using METTLER TOLEDO “DSC-1”, the sample amount of about 5 mg is weighed in a standard container made of aluminum, temperature modulation amplitude ± 1 ° C, temperature modulation cycle 60 seconds, temperature rise It measured to -80-200 degreeC on conditions of speed | rate 2 degrees C / min, and calculated | required the glass transition temperature from the differential thermal curve of a reversible component.

<Synthesis of polyamide having hydroxyl group in side chain>
Synthesis Example 1-1
In a four-necked flask equipped with a stirrer, a reflux condenser equipped with a Dean-Stark tube, a nitrogen inlet tube, an inlet tube, and a thermometer, 202.9 g of Pripol 1009 as a dimer acid of carbon number 36 (0 in dibasic acid conversion) .5 mol), 25.7 g (0.2 mol) of 5-hydroxyisophthalic acid as polybasic acid phenol, 35.1 g (0.3 mol) of terephthalic acid as other polybasic acid, norbornane diamine as polyamine (0 as a diamine conversion) 98.9 g of .91 mol) and 100 g of ion exchange water were charged, and the mixture was stirred until the temperature of heat generation became constant. When the exotherm subsided, the temperature was raised to 110 ° C. After confirming the outflow of water, the temperature was raised to 120 ° C. after 30 minutes, and then the dehydration reaction was continued while raising the temperature by 10 ° C. every 30 minutes. When the temperature reached 230 ° C., the temperature was maintained and the reaction was continued for 3 hours. Then, the pressure was reduced and maintained at about 2 kPa for 1 hour to complete the reaction and start cooling. Then, an antioxidant is added, and a polyamide having a hydroxyl group at a side chain having a weight average molecular weight of 9800, an acid value of 19.8 mg KOH / g, an amine value of 0.3 mg KOH / g, a hydroxyl group of 13.7 mg KOH / g, and a glass transition temperature of 21 ° C. I got
In addition, the compound which has a dimer unit is 26.2 mol% in a total of 100 mol% of the polybasic acid and polyamine of the raw material which were provided to reaction.

Synthesis Example 1-2 to Synthesis Example 1-13
The synthesis was performed according to the composition and the preparation mass parts in Table 1 in the same manner as in Synthesis Example 1-1 to obtain a polyamide having a hydroxyl group. The characteristic values are shown in Table 1.

[Comparative Synthesis Example 1-1] to [Comparative Synthesis Example 1-2]
Synthesis was carried out in the same manner as in Synthesis Example 1 according to the composition and parts by mass as listed in Table 1. Comparative Synthesis Example 1-1 is a polyamide having no hydroxyl group, and Comparative Synthesis Example 1-2 is a polyamide having a hydroxyl group and having no dimer skeleton. The characteristic values are shown in Table 1.

Comparative Synthesis Example 1-3
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, thermometer, 25.7 g of 5-hydroxyisophthalic acid as a polybasic acid having a phenolic hydroxyl group and adipic acid as another polybasic acid Were charged with 332.4 g of pripol 2033 as a C36 polyol, and 139.3 g of toluene, and the temperature was raised to 60 ° C. while stirring under a nitrogen stream to dissolve uniformly. Subsequently, 0.77 g of tetrabutyl orthotitanate as a catalyst was added thereto, and reacted at 110 ° C. for 3 hours. Then, the temperature is raised to 230 ° C., held for 1 hour under a vacuum of about 2 kPa, and allowed to react for 2-3 hours under a vacuum of about 1 kPa, finally, an antioxidant is added, weight average molecular weight 9600, A phenolic hydroxyl group-containing polyester having an acid value of 23.4 mg KOH / g, a phenolic hydroxyl group value of 18.0 mg KOH / g, and a glass transition temperature of 34 ° C. was obtained.

The contents of the abbreviations in Table 1 are shown below.
Pripol 1009: manufactured by Croda Japan, C36 dimer acid having a C6 ring structure (dimer structure ratio: 95% or more, acid value: 195 mg KOH / g)
Pripol 1004: Croda Japan Ltd., C6-C4 dimer acid having a C6-C6 ring structure (dimer structure ratio: 95% or more, acid value: 164 mg KOH / g)

1,4-CHDA: 1,4-cyclohexanedicarboxylic acid 5-HIPA: 5-hydroxyisophthalic acid TMBDPA; α, α, α ', α'-tetramethyl-1,3-benzenedipropionic acid

MXDA: metaxylene diamine NBDA: norbornane diamine wandamine HM: Shin Nippon Rika Co., Ltd., 4,4′-diaminodicyclohexylmethane

PRIAMIN 1074: manufactured by Croda Japan, C36 dimer diamine having a C6 ring structure (dimer structure ratio: 95% or more, amine value: 210 mg KOH / g)
PRIAMIN 1071: A mixture containing a C36 dimer diamine having a C6 ring structure and a C54 trimer triamine having a C6 ring structure in a mass ratio of 80:20 (manufactured by Croda Japan Co., Ltd.) : 198 mg KOH / g)
HAB: 4,4'-diamino-3,3'-dihydroxybiphenyl

<Synthesis of Radically Polymerizable Polyamide>
Synthesis Example 2-1
100 g of the polyamide having a hydroxyl group obtained in Synthesis Example 1-1 and 165.9 g of cyclohexanone were added to a four-necked flask equipped with a stirrer, a reflux condenser, an oxygen inlet, an inlet, and a thermometer, and dissolved. Next, 10.6 g of glycidyl methacrylate, 0.05 g of methoquinone, and 1 g of triphenylphosphine as radically polymerizable epoxy are added, and the mixture is reacted at 100 ° C. for 5 hours while bubbling oxygen, and a radically polymerizable polyamide having a hydroxyl conversion of 55%. I got

[Synthesis Example 2-2] to [Synthesis Example 2-15], [Comparative Synthesis Example 2-1 to 2-3]
Synthesis was carried out according to the compositions and amounts used in Tables 2 and 3 in the same manner as in Synthesis Example 2-1.

[Comparative Example of Synthesis 2-4]
In a 4-neck flask equipped with a stirrer, a reflux condenser, an oxygen inlet tube, an inlet tube, and a thermometer, 100 g of the hydroxyl group-containing polyamide obtained in Synthesis Example 1-1 and 150 g of cyclohexanone are added and dissolved to obtain radical polymerization. It did not have and obtained the polyamide which has a hydroxyl group.

The contents of the abbreviations in Table 2 and Table 3 are shown below.
GMA; glycidyl methacrylate GAc; glycidyl acrylate 4HBAGE; 4-hydroxybutyl acrylate glycidyl ether celloxide 2000; 1,2-epoxy-4-vinylcyclohexane TPP; triphenylphosphine DMBA; dimethylbenzylamine TPP-EB; ethyltriphenylphosphonium bromide

Example 1
To 50 parts of radically polymerizable polyamide solution of the radically polymerizable polyamide solution obtained in Synthesis Example 2-1, 0.5 part of IRGACURE 184, which is a kind of photopolymerization initiator, is added as a radical polymerization initiator, followed by epoxy 250 parts of resin (EPICLON HP-6000 DIC), 166 parts of phenol resin (MEHC-7841-4S, Meiwa Kasei Co., Ltd.) and 1.3 parts of carbon black (Mitsubishi Chemical Co., Ltd.) are added and solid with cyclohexanone The content was adjusted to 40% and uniformly stirred to obtain a resin composition.

[Example 2] to [Example 37], [Comparative Example 1] to [Comparative Example 4]
Resin compositions were obtained in the same manner as in Example 1.

  For the resin composition obtained in each example and each comparative example, the residual film ratio of the coating on the silicon wafer, the adhesion of the coating to the silicon wafer, the reflow resistance on the silicon wafer, and the coating on the copper plate according to the following method The adhesion of the film and the flexibility of the coating on a polyethylene terephthalate (hereinafter, PET) film were evaluated.

Residual film rate
After applying the obtained resin composition on a silicon wafer, it was dried on a hot plate at 120 ° C. for 5 minutes to obtain a 10 μm thick film. Subsequently, 300 mJ / cm ² of ultraviolet light was irradiated.
Next, development was performed using a 2.38% aqueous solution of γ-butyrolactone or tetramethylammonium hydroxide, and the film thickness after development was divided by the film thickness (10 μm) before development to obtain a residual film ratio.
In Tables 2 and 3, when the sum of the acid value and the phenolic hydroxyl value was less than 30, the developability with an aqueous solution of tetramethyl ammonium hydroxide was not performed.
The residual film rate was evaluated as follows.
95% or more of residual film rate ... excellent (aa)
Residual film rate is 90% or more and less than 95% ... good (a)
Residual film rate 80% or more and less than 90% ... OK (b)
Residual film rate less than 80% ... defect (c)

[Resolution]
After applying the obtained resin composition on a silicon wafer, it was dried on a hot plate at 120 ° C. for 5 minutes to obtain a 10 μm thick film. This film was exposed at 300 mJ / cm 2 through a photomask using an i-line stepper exposure apparatus NSR-4425i (manufactured by Nikon Corporation). Thereafter, development was performed using a 2.38% aqueous solution of tetramethylammonium hydroxide, and the coating was dried to form a film of a stripe pattern. Thereafter, the film was cured by heating at 160 ° C. for 60 minutes. The obtained stripe pattern was observed by an optical microscope, and the line and space (L / S) minimum size of the pattern was evaluated as the resolution. Evaluation criteria are as follows.
In addition, evaluation of resolution was implemented only about [Example 33]-[Example 37]-to which the photoinitiator was changed.
Pattern line L / S = 100/100 μm or less ... excellent (aa)
Pattern line L / S = 150/150 μm or less ... good (a)
Pattern line L / S = 200/200 μm or less ... Yes (b)
There is no pattern left, an abnormality is seen ... Defect (c)

  Next, the following evaluation was performed about the case where the residual film rate by (gamma) -butyrolactone image development is aa, a, b.

[Adhesion of coating to silicon wafer]
In the same manner as described above, a 10 μm thick film was irradiated with 300 mJ / cm ² of ultraviolet light. Then, the film was cured by heating at 160 ° C. for 60 minutes.
A cutter was used to insert each of the 11 cuts so as to form a grid pattern longitudinally and transversely at intervals of 1 mm in the cured coating film so as to reach the silicon wafer, to create 100 independent films.
Then, the peeling test was done with cellophane tape. The adhesion was evaluated as follows by the number of peeling.
Peeling not seen ... excellent (aa)
The number of peeled pieces is 1 or more and 5 or less ... good (a)
The number of peeled pieces is 6 or more and 10 or less ... Allowed (b)
The number of peeled pieces is 11 or more ... Defect (c)

[Reflow resistance]
The same sample as the sample for the adhesion test was prepared, and flux BF-30 (manufactured by Tamura Kaken Co., Ltd.) was coated on the cured coating film with a spin coater under conditions of 500 rpm / 30 seconds + 1000 rpm / 30 seconds.
The sample for a test was obtained by 140-160 degreeC / 100 second (preheating) with a reflow oven.
Next, the obtained test sample was aged at 260 ° C. for 30 seconds, left at 25 ° C. for 10 minutes, and again aged at 260 ° C. for 30 seconds and left at 25 ° C. After cooling, the test sample was washed with xylene for 10 minutes, rinsed with isopropyl alcohol and dried. The surface of the resin layer from which the flux was removed was observed with a microscope, and it was confirmed whether or not floating, cracks, wrinkles and the like occurred.
Separately, the same procedure was followed except that the reflow temperature of the test sample was changed to 280 ° C., 300 ° C. and 320 ° C. respectively, and it was confirmed whether there was floating, cracks or wrinkles on the surface of the resin layer.
In the evaluation, the reflow resistance was evaluated at the time-lapse temperature at which the surface of the test sample floated, cracked and wrinkled.
No floats, cracks, wrinkles, etc. observed above 300 ° C ... excellent (aa)
Lifting at 280 ° C or more and less than 300 ° C, cracks, wrinkles, etc. are not found ... Good (a)
It floats at 260 ° C or more and less than 280 ° C, and cracks, wrinkles, etc. are not seen ... Yes (b)
It floats at less than 260 ° C, and cracks, wrinkles, etc. are seen ... Defect (c)

[Adhesion of coating to copper plate]
A cured coating was similarly formed on a copper plate except that a copper plate having a thickness of 500 μm was used as a substrate in place of a silicon wafer, and adhesion was evaluated. The evaluation method and the evaluation criteria are the same as in the case of the silicon wafer.
[Flexibility]
A cured coating was formed on a PET film in the same manner as in Example 1 except that a PET film having a thickness of 38 μm was used instead of the silicon wafer, and the flexibility of the cured coating was evaluated according to the following method.
Based on JIS K 5600-5-1, a PET film is wound around the outer circumference of a 10, 20, and 32 mm mandrel so that the cured coating is on the outside, and flexibility is achieved according to the smallest mandrel diameter without cracking in the cured coating. Was evaluated. Evaluation criteria are as follows.
In the case of less than 10 mm in diameter ... excellent (aa)
In the case of diameter 10 mm or more and less than 20 mm ... good (a)
In the case of a diameter of 20 mm or more and less than 32 mm: Allowed (b)
In the case of 32 mm or more in diameter: Defect (c)

The contents of the abbreviations in Tables 4 to 8 are shown below.
HP-6000; EPICLON HP-6000 rigid epoxy resin (softening point 80 degrees epoxy equivalent 250 g / eq. DIC)
jER 825; liquid epoxy resin (epoxy equivalent 175 g / eq. manufactured by Mitsubishi Chemical Corporation)
HP-7200HHH; EPICLON HP-7200HHH Rigid epoxy resin (softening point 115 degrees epoxy equivalent 286 g / eq DIC).
NC-7000L; rigid epoxy resin (softening point 88 degrees epoxy equivalent 231 g / eq. Manufactured by Nippon Kayaku Co., Ltd.)

MEHC-7841-4S; phenol resin (hydroxy group equivalent 166 g / eq. Manufactured by Meiwa Kasei Co., Ltd.)
MEH-7000; phenol resin (hydroxy group equivalent 143 g / eq. Manufactured by Meiwa Kasei Co., Ltd.)
TD-2093; phenol novolak resin (hydroxy group equivalent 104 g / eq. DIC)

Irgacure TPO; acyl phosphine oxide photopolymerization initiator (IGM Resins B. V.)
Irgacure 907; alkylphenone photopolymerization initiator (IGM Resins B.V.)
OXE-01; oxime ester photopolymerization initiator (manufactured by BASF Japan Ltd.)
OXE-02; oxime ester photopolymerization initiator (manufactured by BASF Japan Ltd.)

FB-350FD; spherical silica (average particle size 12 μm, manufactured by Denka)
SO-E6; Adoma fine SO-E6 (spherical silica average particle diameter 2 μm, manufactured by Admatex Co.)
MUF-3V; (Spherical fused silica, average particle diameter 3.5 μm, manufactured by Ryumori Corporation)
MA-100; (Carbon black made by Mitsubishi Chemical Corporation)
KBM-403; 3-glycidoxypropyl trimethoxysilane (silane coupling agent, Shin-Etsu Chemical Co., Ltd.)

A-DCP; tricyclodecane dimethanol diacrylate A-TMPA; trimethylolpropane triacrylate
A-DPH; dipentaerythritol hexaacrylate

  From the results in Tables 4 to 8, the radically polymerizable polyamides of Examples 1 to 37 have good heat resistance and bending stress resistance, and can form a resin layer having good adhesion to metals.

Claims (10)

A reaction product of a polyamide having a hydroxyl group in a side chain and a radically polymerizable epoxy,
The radically polymerizable polyamide in which the polyamide which has a hydroxyl group in the said side chain has a dimer structure which consists of dimer acid or dimer diamine, and a phenolic hydroxyl group unit. The radically polymerizable polyamide according to claim 1, wherein the polyamide having a hydroxyl group in the side chain is any one of the following (1) to (3).
(1) Reactant of polybasic acid phenol, dimer acid and polyamine.
(2) Reactant of polybasic acid phenol and dimer diamine.
(3) Reactant of polyamine phenol and dimer acid.   The radically polymerizable polyamide according to claim 1 or 2, wherein the equivalent ratio of the epoxy group of the radically polymerizable epoxy to the hydroxyl group of the polyamide having a hydroxyl group is more than 0.1 and not more than 3.   The radically polymerizable polyamide according to any one of claims 1 to 3, wherein the polyamide having a hydroxyl group in the side chain has a hydroxyl value of 1 to 80 mg KOH / g.   The radically polymerizable polyamide according to any one of claims 1 to 4, wherein the polyamide having a hydroxyl group in the side chain contains a total of 10 to 95 mole% of a dimer structure derived from a dimer diamine and a dimer acid in all constituent units. .   The resin composition containing the radically polymerizable polyamide of any one of Claims 1-5, and a radical polymerization initiator.   The resin composition according to claim 6, further comprising a polyfunctional radically polymerizable compound.   Furthermore, the resin composition of Claim 6 or 7 containing a thermosetting resin.   The resin composition according to claim 8, wherein the thermosetting resin comprises an epoxy resin.   An insulating member, comprising: a base material; and a resin layer containing the resin composition according to any one of claims 6 to 9.