JP2006111817A - Interlayer insulator material comprising aryl ester oligomer and cured product of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an interlayer insulating material consisting of an allyl ester oligomer, which has excellent characteristics for processing and excellent storage stability, and also to provide an allyl ester resin prepared by curing the allyl ester oligomer for an interlayer insulating material, which has excellent electric characteristics, thermal resistance and mechanical strength. <P>SOLUTION: The interlayer insulating material comprises an allyl oligomer having a group represented by formula (1), a group represented by formula (2) in the figure and/or a group represented by formula (3). In formula (1), R<SB>1</SB>represents an allyl group or a methallyl group and when there are more than one group in one oligomer molecule, they can be either the same or different. In formulae (2) and (3), X<SB>1</SB>, X<SB>2</SB>and X<SB>3</SB>are each independently a 1-10C organic group, X<SB>2</SB>and X<SB>3</SB>are bonded through a chain having above formula (1) and an ester bond. R<SB>2</SB>represents H atom or a 1-10C organic group. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an interlayer insulating material composed of an allyl ester oligomer applied to an interlayer insulating film such as a printed wiring board, a manufacturing method thereof, and a cured product of the interlayer insulating material composed of this allyl ester oligomer. More specifically, the present invention relates to an interlayer insulating material composed of an allyl ester oligomer excellent in storage stability and processability, and a cured product of the interlayer insulating material composed of an allyl ester oligomer excellent in heat resistance, electrical characteristics, and mechanical strength.

  Heat resistant polymer materials in the field of electronic materials are required to improve various properties such as heat resistance, electrical properties, workability, and mechanical strength. Among these, improvement in heat resistance is required mainly due to an increase in the melting temperature of solder accompanying the progress of lead-free soldering. In addition, with respect to electrical characteristics, with the improvement of signal propagation speed in the element and on the substrate due to the downsizing and speeding up of electronic components, low dielectric materials and the like with low dielectric loss are required. Although the processability differs between thermoplastic resins and thermosetting resins, the present situation is that they are properly used according to the required heat resistance. Furthermore, thermosetting resin materials used for electronic components tend to be hard and brittle as heat resistance increases, and further improvement in mechanical strength is required.

  As heat-resistant thermoplastic resins having excellent electrical properties, for example, polyimide, polyamide, polyphenylene ether, and the like are known. However, these resins are solid at room temperature and are heated to a melting point or higher when molding. It must be melted or dissolved in a solvent to provide fluidity. When molding by heating and melting, it must be melted at a temperature much higher than the heat-resistant temperature required for electronic materials. In addition, a thermoplastic resin that can be dissolved in a solvent is easy to mold, but has a problem of low solvent resistance.

  In contrast, in a thermosetting resin, a monomer or oligomer (a compound having at least one repeating unit) before being cured can be liquid at room temperature or melted or dissolved in a solvent at a relatively low temperature, and is required for electronic materials. Since it can be processed at a temperature lower than the heat-resistant temperature that can be obtained, it is characterized by good workability. Many thermosetting resins are excellent in solvent resistance and chemical resistance.

  However, monomers or oligomers that are precursors of thermosetting resins are generally not good in storage stability. For example, in a radical curable resin, it is essential to add a polymerization inhibitor to the monomer or oligomer. Furthermore, the monomer or oligomer and the curing agent are often stored separately and mixed immediately before use. For example, since radically curable styrene, (meth) acrylic acid ester monomer or (meth) acrylic acid ester oligomer may be radically cured even at room temperature, at least 100 ppm of polymerization inhibitor is added, or at low temperature It must be preserved and a curing agent must be added just before use. For high-viscosity or solid monomers and oligomers, in order to improve the coatability, after heating to such an extent that radical curing does not proceed before starting use, the viscosity is lowered, and then a curing agent is added, and sufficient in a short time. There is a problem that the mixture must be mixed by stirring.

  Epoxy resin is mentioned as typical thermosetting resin other than radical curable resin. Similarly to the radical curable resin, the epoxy resin before curing needs to store the epoxy resin and the curing agent separately. In addition, in the case of storing in a mixture with a curing agent, if it is left at room temperature after mixing with a curing agent, there is a possibility that viscosity increase or curing may occur, so it is often necessary to store in a cool and dark place.

  On the other hand, allyl ester resin (cured product) is known as a thermosetting resin used as a crack preventing material for optical materials, artificial marble, decorative plates, and unsaturated polyester resins. The allyl ester resin is obtained by radical curing an allyl ester oligomer obtained using allyl alcohol or methallyl alcohol, polybasic acid ester, and polyhydric alcohol as a raw material with a radical curing agent. Unlike other radical curable monomers and oligomers, allyl ester oligomers have a slow curing rate, and therefore have few cracks during molding and excellent storage stability. Specifically, it is described in page 17 of Non-Patent Document 1 (thermosetting resin, Vol. 15, No. 1, (1994), Synthetic Resin Industry Association).

  In this way, allyl ester oligomers are excellent in storage stability and processability, but allyl ester resins excellent in both electrical properties represented by dielectric constant, heat resistance, and mechanical strength are not so much. unknown. As an allyl ester oligomer for an allyl ester resin excellent in heat resistance and mechanical strength, an allyl ester obtained by polycondensation of a nitrogen atom-containing polyol and a dicarboxylic acid ester described in Patent Document 1 (Japanese Patent Laid-Open No. 4-272922) Oligomers are known. However, for example, a polycondensate of diallyl terephthalate (hereinafter abbreviated as DATP) and tris (2-hydroxyethyl) isocyanurate (hereinafter abbreviated as THEIC) described in Example 4 of Patent Document 1 has a high glass transition. Although it has a point (hereinafter abbreviated as Tg), further improvement in bending strength is required. Further, the polycondensation product of diallyl isophthalate (hereinafter abbreviated as DAIP) described in Example 2 of Patent Document 1 with THEIC and propylene glycol has high bending strength, but further improvement is required for Tg. ing. On the other hand, as allyl ester resins having excellent electrical properties, commercially available allyl ester resins described on page 23 of Non-Patent Document 1 are known, but these resins have either low mechanical strength or Tg. .

Thus, an allyl ester resin excellent in any of electric characteristics, heat resistance and mechanical strength has not been known yet.
JP-A-4-272921 Thermosetting resin, Volume 15, No. 1, 17 (1994), Japan Plastics Industry Association

  INDUSTRIAL APPLICABILITY The present invention can be suitably used for an interlayer insulating film or a solder resist of a printed wiring board, and is an interlayer insulating material composed of an allyl ester oligomer excellent in storage stability and processability, and excellent in heat resistance, electrical characteristics, and mechanical strength. Another object of the present invention is to provide a cured product of an interlayer insulating material comprising an allyl ester oligomer.

  In order to solve the above problems, the present inventors have conducted intensive research. As a result, in addition to the characteristics of conventional allyl ester oligomers, the cured product of allyl ester oligomers containing isophthalic acid residues and isocyanuric rings instead of terephthalic acid has excellent processability and storage stability, The present inventors have found that it is excellent in both electrical characteristics and mechanical strength, and have completed the present invention.

That is, the present invention relates to the following items [1] to [18].
[1] An interlayer insulating material comprising an allyl ester oligomer having a group represented by the following formula (1), a group represented by the following formula (2) and / or a group represented by the following formula (3).

(In the formula, R ₁ represents an allyl group or a methallyl group, and when there are a plurality of these groups in one molecule of the oligomer, they may be the same or different from each other.)

(In the formula, X ₁ , X ₂ and X ₃ each independently represent an organic group having 1 to 10 carbon atoms, and X ₂ and X ₃ are a chain having an ester group and an ester bond having the group represented by (1) above) R ₂ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms).
[2] The interlayer according to the above [1], wherein the repeating unit in the allyl ester oligomer consists only of a group represented by the above formula (2) and / or a group represented by the above formula (3) Insulating material.
[3] The interlayer insulating material according to the above [1], wherein X _{1 to} X ₃ described in the formulas (2) and (3) are substituted or unsubstituted alkylene groups.
[4] A substituted or unsubstituted alkylene group is selected from ethylene, 2-methylethylene, 2-ethylethylene, 2-chloromethylethylene, 2-bromomethylethylene, 2-allyloxymethylethylene, 2-phenoxymethylethylene, and cyclohexene. The interlayer insulating material according to [3] above, which is one or more alkylene groups selected from the group consisting of silene, 2-phenylethylene, 2-methacryloxymethylethylene, and 2-acryloxymethylethylene.
[5] The interlayer insulating material according to the above [1], wherein X _{1 to} X ₃ described in the formulas (2) and (3) are an ethylene group and / or a 2-methylethylene group.
[6] An interlayer insulating material comprising an allyl ester oligomer obtained by a transesterification polycondensation reaction between di (meth) allyl isophthalate and a compound having an isocyanuric ring and two or more hydroxyl groups.
[7] The interlayer insulating material as described in [6] above, wherein the compound having an isocyanuric ring and two or more hydroxyl groups is a compound obtained by reacting isocyanuric acid and an alkylene monoepoxide.
[8] The alkylene monoepoxide is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epibromohydrin, allyl glycidyl ether, phenyl glycidyl ether, cyclohexene oxide, styrene oxide, and glycidyl (meth) acrylate. The interlayer insulating material according to [7], wherein the interlayer insulating material is at least one kind of alkylene monoepoxide.
[9] The compound having an isocyanuric ring and two or more hydroxyl groups is selected from the group consisting of bis (2-hydroxyethyl) isocyanurate, tris (2-hydroxyethyl) isocyanurate and tris (2-hydroxypropyl) isocyanurate. The interlayer insulating material as described in [6] above, which is at least one kind of isocyanurate.
[10] An interlayer insulating material comprising an allyl ester oligomer having a structure in which isophthalic acid, an isocyanuric ring and a compound having two or more hydroxyl groups are ester-bonded, and an allyl group and / or a methallyl group at the terminal.
[11] The interlayer insulating material according to the above [10], wherein the compound having an isocyanuric ring and two or more hydroxyl groups is a compound obtained by reacting isocyanuric acid and an alkylene monoepoxide.
[12] The alkylene monoepoxide is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epibromohydrin, allyl glycidyl ether, phenyl glycidyl ether, cyclohexene oxide, styrene oxide, and glycidyl (meth) acrylate. The interlayer insulating material as described in [11] above, which is an alkylene monoepoxide of a kind or more.
[13] The compound having an isocyanuric ring and two or more hydroxyl groups is selected from the group consisting of bis (2-hydroxyethyl) isocyanurate, tris (2-hydroxyethyl) isocyanurate and tris (2-hydroxypropyl) isocyanurate. The interlayer insulating material according to [10], wherein the interlayer insulating material is one or more isocyanurates.
[14] The transesterification polycondensation reaction of di (meth) allylisophthalate with a compound having an isocyanuric ring and two or more hydroxyl groups is carried out as described in any one of [1] to [5] above A method for producing an interlayer insulating material comprising an allyl ester oligomer.
[15] An interlayer insulating material composition comprising the interlayer insulating material according to any one of [1] to [13] and a curing agent.
[16] A cured product of the interlayer insulating material composition according to [15].
[17] An interlayer insulating film obtained by curing the interlayer insulating material composition according to [15].
[18] A printed wiring board using the interlayer insulating material according to any one of [1] to [13].

  According to the present invention, compared to a conventional interlayer insulating material made of diallyl terephthalate oligomer, an interlayer insulating material made of an allyl ester oligomer having excellent processability and storage stability, and excellent heat resistance, electrical properties and mechanical strength. Further, an allyl ester resin (cured product) for an interlayer insulating material can be obtained.

Hereinafter, the present invention will be described in more detail.
The interlayer insulating material according to the present invention is an allyl ester oligomer having a group represented by the following formula (1), a group represented by the following formula (2) and / or a group represented by the following formula (3). Become.

(In the formula, R ₁ represents an allyl group or a methallyl group, and when there are a plurality of these groups in one molecule of the oligomer, they may be the same or different from each other.)

(In the formula, X ₁ , X ₂ and X ₃ each independently represent an organic group having 1 to 10 carbon atoms, and X ₂ and X ₃ are a chain having an ester group and an ester bond having the group represented by (1) above) R ₂ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms.)
As such an allyl ester oligomer, for example, a structure in which an isophthalic acid and an isocyanuric ring represented by the following formula (4) and a compound having two or more hydroxyl groups are ester-bonded, an allyl group and / or methallyl at the terminal And allyl ester oligomers having a group.

In the allyl ester oligomer, a hydroxyl group is eliminated from a saturated glycol such as a divalent saturated alcohol composed only of carbon such as ethylene glycol or propylene glycol, or a divalent saturated alcohol containing an ether group such as diethylene glycol or dipropylene glycol. It does not contain an organic residue, and it is particularly preferred that the repeating unit consists only of a group represented by the above formula (2) and / or a group represented by the above formula (3).

In the above formula (1), R ₁ represents an allyl group or a methallyl group. The group represented by the above formula (1) is a molecular end group of the allyl ester oligomer, and a plurality of groups are usually present in one molecule of the allyl ester oligomer. In this case, a plurality of R ₁ present in the allyl ester oligomer in a molecule, each independently represents an allyl group or methallyl group.

  The allyl ester oligomer may have a group represented by the following formula (5) as a terminal group in addition to the group represented by the above formula (1).

In the above formula (5), R ₃ represents a non-polymerizable group such as a methyl group or an ethyl group.
The ratio of the group represented by the above formula (1) to all terminal groups in the allyl ester oligomer molecule is preferably 60 to 100 mol%, more preferably from the viewpoint of obtaining a cured product having excellent mechanical strength. Is desirably 80 to 100 mol%, most preferably 90 to 100 mol%. When the ratio of the group represented by the above formula (1) is less than 60 mol%, the mechanical strength of the cured product of the obtained allyl ester oligomer may be lowered, which is not preferable.

In the above formulas (2) and (3), X _{1 to} X ₃ each independently represents an organic group having 1 to 10 carbon atoms. However, X _{1 to} X ₃ are usually the same group in many cases. Examples of the organic group having 1 to 10 carbon atoms include ethylene, propylene, 2-methylethylene, butylene, 2-ethylethylene, 2-chloromethylethylene, 2-bromomethylethylene, 2-allyloxymethylethylene, and 2-phenoxymethyl. Examples include substituted or unsubstituted alkylene groups such as ethylene, hexylene, cyclohexylene, 2-phenylethylene, 2-methacryloxymethylethylene and 2-acryloxymethylethylene. Of these, an ethylene group and a 2-methylethylene group are preferable.

In the above formula (2), R ₂ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms. Examples of the organic group having 1 to 10 carbon atoms include alkyl groups such as methyl, ethyl, propyl, and butyl; and hydroxyalkyl groups such as hydroxyethyl, hydroxypropyl, and hydroxybutyl.

  The compound having an isocyanuric ring and two or more hydroxyl groups is preferably a compound having an isocyanuric ring and two or more hydrogen-containing groups, and examples thereof include compounds represented by the following formula (6) or (7).

(Wherein, X ₁ to X ₃ and R _2, respectively, the same meanings as X ₁ to X ₃ and R ₂ in the formula (2) and (3).)
Such a compound can be obtained, for example, by reacting isocyanuric acid with an alkylene monoepoxide. This reaction can be performed using a catalyst and a solvent, if necessary.

  The charging ratio of isocyanuric acid and alkylene monoepoxide is such that the molar ratio of alkylene monoepoxide residue to 1 mol of isocyanuric ring formed is preferably 1 to 10, more preferably 1.5 to 8, and most preferably 2 to 6. Set to be. If this ratio is less than 1, the possibility that unreacted isocyanuric acid remains in the reaction mixture increases, which is not preferable. When it is 10 or more, for example, when the purpose is to synthesize tris (hydroxyalkyl) isocyanurate, the selectivity may be low, which is not preferable. That is, it is not preferable because the amount of the compound in which an alkylene monoepoxide is further added to the hydroxyalkyl group is increased, and the heat resistance of the obtained allyl ester resin may be lowered.

  Although reaction temperature is not specifically limited, From a viewpoint that reaction advances appropriately, Preferably it is 0 to 130 degreeC, More preferably, 10 to 100 degreeC is desirable. Below 0 ° C., the progress of the reaction may be remarkably slow. On the other hand, if the temperature exceeds 130 ° C., there is a risk that the reaction may run away.

  The above synthesis can be carried out in the absence of a catalyst or in the presence of an acid catalyst. The solvent is not particularly limited. For example, a solvent having low reactivity and high solubility such as dimethylformamide is preferable.

  The resulting reaction mixture may be subjected to the next transesterification reaction as it is, but if necessary, the unreacted alkylene monoepoxide, solvent and catalyst may be removed and further the esterification may be carried out after further purification. preferable.

As the alkylene monoepoxide in the above synthesis, for example, ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epibromohydrin, allyl glycidyl ether, phenyl glycidyl ether, cyclohexene oxide,
Examples thereof include styrene oxide and glycidyl (meth) acrylate.

  Examples of the compound having an isocyanuric ring and two or more hydroxyl groups synthesized in this way include bis (2-hydroxyethyl) isocyanurate, tris (2-hydroxyethyl) isocyanurate and tris (2-hydroxypropyl). Poly (hydroxyalkyl) isocyanurates such as isocyanurates are mentioned.

In the above formulas (2) and (3), X ₂ and X ₃ are bonded to the chain having the group represented by the above (1) through an ester bond. Thereby, in particular, the group represented by the above formula (3) can form a branched structure. According to the method for producing an allyl ester oligomer described later, when the number of hydroxyl groups of the compound having an isocyanuric ring and two or more hydroxyl groups is 3 or more, the oligomer chain extends in three directions by polycondensation by transesterification, and the allyl ester The oligomer forms a branched structure. This branched structure is also formed in the branched chain, and may eventually form a network structure. However, in the case of the allyl ester oligomer used in the present invention, a network structure, a high degree of branching, and an extremely high molecular weight are not preferable from the viewpoints of application properties to a printed board or the like as an interlayer insulating material. Therefore, it is necessary to control the branching degree, molecular weight, viscosity, etc. of the allyl ester oligomer by adjusting the charging ratio of the reaction raw materials and the reaction time.

  The method for producing the allyl ester oligomer used in the present invention is not particularly limited. However, from the viewpoint of ease of synthesis, allyl group-containing isophthalate and / or methallyl group-containing isophthalate (hereinafter referred to as allyl isolate) in the presence of a catalyst for transesterification. A synthetic method by transesterification of a compound having an isocyanuric ring and two or more hydroxyl groups is preferably applied. Examples of the transesterification catalyst include dibutyltin oxide, dioctyltin oxide, tetraisopropyl titanate, tetrabutyl titanate, and zirconium acetylacetonate. In this synthesis method, for example, the reaction proceeds as follows.

The charged molar ratio of allyl isophthalate to the compound having an isocyanuric ring and two or more hydroxyl groups is allyl to one mole of the compound having an isocyanuric ring and two or more hydroxyl groups from the viewpoint of moldability and mechanical strength. Isophthalate is preferably 1.0 mol-1
A range of 0.0 mol, more preferably 1.2 mol to 5 mol, and most preferably 2 mol to 4 mol is desirable. If the molar ratio of allyl isophthalate is lower than 1.0 mol, the resulting allyl ester oligomer may have a high viscosity and the moldability may be deteriorated. On the other hand, when the amount is larger than 5 mol, the mechanical strength of the resulting cured product of allyl ester oligomer may be lowered, which is not preferable.

  The reaction temperature is preferably in the range of 100 ° C to 250 ° C, more preferably in the range of 130 ° C to 220 ° C, and most preferably in the range of 150 to 200 ° C. If the reaction temperature is less than 100 ° C., the reaction rate may be remarkably slow, which is not preferable. If it exceeds 250 ° C., the allyl group may cause a thermal polymerization reaction and run away, which is not preferable.

  The reaction atmosphere is preferably an inert gas atmosphere such as helium, nitrogen, or argon. The replacement from the air atmosphere to the inert gas atmosphere can be performed by a conventionally known method such as pressure replacement, reduced pressure replacement, or bubbling. In particular, in the present invention, the oxygen concentration in the reaction atmosphere is preferably 1% by volume or less, more preferably 1000 volume ppm or less, and most preferably 100 volume ppm or less. If the oxygen concentration is higher than 1% by volume, side reactions such as coloring and polymerization reaction may proceed, which is not preferable.

  The reaction pressure is preferably in the range of 0.1 Pa to 0.2 MPa, more preferably in the range of 0.5 Pa to 1.0 MPa, and most preferably in the range of 1 Pa to 0.1 MPa. If it is less than 0.1 Pa, the raw material allyl ester monomer may be distilled from the reaction system, which is not preferable. If it is higher than 0.2 MPa, the reaction rate may be extremely slow, which is not preferable.

Although a solvent may be used as needed, it is preferable to carry out without a solvent in consideration of the solvent separation after the reaction.
The allyl ester oligomer used in the present invention can have, for example, the following structures, but is not limited thereto.

In the formula, m and n are each independently an integer of 0 to 20. However, m and n are not 0 at the same time.
The weight average molecular weight of the allyl ester oligomer used in the present invention is 300 to 10,000, preferably 500 to 9000, and more preferably 800 to 8000. An allyl ester oligomer having a weight average molecular weight of less than 300 often contains a large amount of allyl isophthalate, and the allyl ester resin as a cured product may become brittle, which is not preferable. On the other hand, if it exceeds 10,000, the allyl ester oligomer has a high viscosity, which may deteriorate the moldability. The molecular weight is determined by gel permeation chromatography (column: manufactured by Showa Denko KK, Shodex KG, K801, K802 and K802.
. It is a value obtained by measuring 5 with 4 in series, solvent: chloroform) and converting to standard polystyrene.

  The viscosity of the allyl ester oligomer used in the present invention is not particularly limited. In addition, the viscosity can be adjusted in consideration of workability. For example, you may use as a varnish obtained by melt | dissolving an allyl ester oligomer in various solvents. From the viewpoint of processability, the viscosity of the varnish containing the allyl ester oligomer or the allyl ester oligomer is preferably 0.1 to 2000 Pa · s, more preferably 1 to 1000 Pa · s, and most preferably 5 to 500 Ps · s. It is desirable to be. If the viscosity of the allyl ester oligomer is less than 0.1 Pa · s, the weight average molecular weight of the allyl ester oligomer is low, and the cured allyl ester resin may become brittle, which is not preferable. In addition, if the viscosity of the varnish containing the allyl ester oligomer is less than 0.1 Pa · s, it often contains a large amount of solvent, and a large amount of solvent must be removed before curing, which is not economically preferable. . If the viscosity of the allyl ester oligomer or its varnish exceeds 2000 (Pa · s), the fluidity is remarkably lowered, and the workability may be deteriorated. In addition, the measuring method of the viscosity of an allyl ester oligomer and its varnish is measured with a B-type viscometer at 25 ° C. according to JIS K6901.

  Next, the interlayer insulating material composition according to the present invention will be described. The interlayer insulating material composition according to the present invention contains an interlayer insulating material comprising the allyl ester oligomer or its varnish. This interlayer insulating material composition further includes a curing agent, a reactive monomer, and a phenol resin, an unsaturated polyester resin, an epoxy resin, a vinyl ester resin, an alkyd resin, an acrylic resin, a melamine resin, a xylene resin, if necessary. A thermosetting resin such as a guanamine resin, a furan resin, an imide resin, a urethane resin, or a urea resin may be included. These components are added for the purpose of controlling the reaction rate, adjusting the viscosity, improving the crosslinking density, adding functions, and the like.

  The reactive monomer is preferably used also as a diluent solvent for increasing the crosslink density of the allyl ester oligomer or adjusting the viscosity of the interlayer insulating material composition. In this case, there is an advantage that a viscosity adjusting solvent is not necessary, and the step of removing the solvent by volatilization or the like can be omitted. Examples of such reactive monomers include radical reactive monofunctional or crosslinkable polyfunctional monomers containing a carbon-carbon unsaturated double bond such as a vinyl group or an allyl group.

  Examples of the monofunctional monomer include unsaturated fatty acid esters, aromatic vinyl compounds, vinyl esters of saturated fatty acids or aromatic carboxylic acids, and derivatives thereof, and more specifically methyl (meth) acrylate, ethyl (meth) acrylate. , Propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, octyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) ) Acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) Acrylate, vinyl acetate, acrylonitrile, allyl acetate, allyl acetoacetate, allyl benzoate, cyclohexanecarboxylic acid allyl, styrene, vinyl toluene, and the like.

Examples of the crosslinkable polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and tripropylene glycol di (meth). ) Acrylate, 1,3-butylene glycol di (meth) acrylate,
1,4-butanediol di (meth) acrylate, 1,5-pentadiol di (meth) acrylate, 1,6-hexadiol di (meth) acrylate, neopentyl glycol di (meth) acrylate, oligoester di (meth) ) Acrylate, polybutadiene di (meth) acrylate, 2,2-bis (4- (meth) acryloyloxyphenyl) propane, 2,2-bis (4-ω- (meth) acryloyloxypyriethoxy) phenyl) propane, etc. Di (meth) acrylates: diallyl phthalate, diallyl isophthalate, dimethallyl isophthalate, triallyl trimellitic acid, diallyl 2,6-naphthalenedicarboxylate, diallyl 1,5-naphthalenedicarboxylate, 1,4-xylenedicarboxylic acid Allyl, 4,4'-diphenyldicarbo Aromatic carboxylic acid diallyls such as diallyl acid; bifunctional crosslinkable monomers such as diallyl cyclohexanedicarboxylate and divinylbenzene; trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri Trifunctional crosslinkable monomers such as (meth) acrylate, tri (meth) allyl isocyanurate, tri (meth) allyl cyanurate, triallyl trimellitate, diallyl chlorendate; pentaerythritol tetra (meth) acrylate, etc. And tetrafunctional crosslinkable monomers.

Specific examples of the phenol resin include a resol type phenol resin and a novolac type phenol resin.
Unsaturated polyester resin can be obtained by converting a condensation product obtained by esterification reaction of polyhydric alcohol, unsaturated polybasic acid and, if necessary, saturated polybasic acid into a polymerizable unsaturated compound such as styrene. Dissolved and described in, for example, “Polyester resin handbook (Nikkan Kogyo Shimbun, published in 1988)”, “painting glossary (edited by Color Material Association, published in 1993)”, etc., and its production is publicly known It is done by the method.

  Specific examples of the epoxy resin include bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin and the like.

  The vinyl ester resin is also called an epoxy (meth) acrylate resin, and is generally an open group between an epoxy group of an epoxy compound represented by an epoxy resin and a carboxyl group of a carboxyl compound having a polymerizable unsaturated group such as (meth) acrylic acid. An ester resin having a polymerizable unsaturated group produced by a ring reaction, or a compound having a carboxyl group, and an epoxy group of a compound having a polymerizable unsaturated group and an epoxy group in the molecule such as glycidyl (meth) acrylate An ester resin having a polymerizable unsaturated group produced by the ring-opening reaction of, for example, “Polyester Resin Handbook (Nikkan Kogyo Shimbun, published in 1988)”, “Paint Glossary of Terms (Color Material Association, published in 1993) And the like, and the production thereof is carried out by a known method.

  The epoxy resin used as the raw material for the vinyl ester resin includes bisphenol A diglycidyl ether and its high molecular weight homologue, glycidyl ether of bisphenol A alkylene oxide adduct, bisphenol F diglycidyl ether and its high molecular weight homologue, bisphenol F alkylene oxide. Examples include adduct glycidyl ethers and novolac-type polyglycidyl ethers.

  Heat of these reactive monomers, phenol resins, unsaturated polyester resins, epoxy resins, vinyl ester resins, alkyd resins, acrylic resins, melamine resins, xylene resins, guanamine resins, furan resins, imide resins, urethane resins, urea resins, etc. A curable resin can be used individually by 1 type or in mixture of 2 or more types.

The amount of these used is not particularly limited, but is 1 to 150 parts by mass with respect to 100 parts by mass of the allyl ester oligomer in that the effects of controlling the reaction rate, adjusting the viscosity, improving the crosslinking density, and adding functions are exhibited. It is preferable that it is preferably 2 to 120 parts by mass, and more preferably 3 to 100 parts by mass. When the use amount of the thermosetting resin or the like is less than 1 part by mass, the effect of addition is small with respect to reaction rate, viscosity, crosslinking density, function addition, etc., and when it exceeds 150% by mass, the interlayer according to the present invention The effect of using an insulating material may not appear, which is not preferable.

  As a hardening | curing agent, if the interlayer insulation material composition which concerns on this invention can be hardened | cured, there will be no restriction | limiting in particular and it can use. Among these, radical polymerization initiators are desirable. Examples of the radical polymerization initiator include organic peroxides, photopolymerization initiators, azo compounds, and the like, but organic peroxides are more preferable.

  As the organic peroxide, known organic peroxides such as dialkyl peroxide, acyl peroxide, hydroperoxide, ketone peroxide, and peroxyester can be used. More specifically, benzoyl peroxide, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-dibutylperoxycyclohexyl) propane, t-butylperoxy-2-ethylhexanate 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl2,5-di (benzoylperoxy) hexane, t-butylperoxybenzoate, t-butylcumyl peroxide , P-methane pydroperoxide, t-butyl hydroperoxide, cumene hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-dibutylperoxyhexyne- 3 etc. are mentioned.

  Moreover, when using the interlayer insulation material composition which concerns on this invention for the interlayer insulation film for buildup wiring boards, a photoinitiator can also be used as a hardening | curing agent. Examples of the photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, benzophenone, and 2-methyl-1- (4-methylthiophenyl) -2. -Monfolinopropane-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-hydroxy-2-methyl-1-phenylpropan-1-one, 2, Examples include 4,6-trimethylbenzoyldiphenylphosphine oxide.

These curing agents may be used alone or in combination of two or more.
The blending amount of the curing agent is not particularly limited, but is 0.1 to 10 parts by mass with respect to 100 parts by mass of the total of allyl ester oligomer and reactive monomer (monofunctional and crosslinkable polyfunctional monomer). It is preferably 0.5 to 5 parts by mass. If the blending amount is less than 0.1 parts by mass, a sufficient curing rate cannot be obtained, and if it exceeds 10 parts by mass, the electrical characteristics may be deteriorated.

  Furthermore, the interlayer insulating material composition according to the present invention includes an ultraviolet absorber, an antioxidant, an antifoaming agent, a leveling agent, and a release agent for the purpose of improving hardness, strength, moldability, durability, and water resistance. Additives such as lubricants, water repellents, flame retardants, low shrinkage agents, and crosslinking aids can be added as necessary.

  There is no restriction | limiting in particular as antioxidant, A conventionally well-known thing can be used. Among these, phenolic antioxidants and amine antioxidants that are radical chain inhibitors are preferred. Examples of phenolic antioxidants include 2,6-t-butyl-p-cresol, 2,6-t-butyl-4-ethylphenol, and 2,2′-methylenebis (4-methyl-6-t-butylphenol). 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane and the like.

The cured product (allyl ester resin) of the interlayer insulating material composition according to the present invention can be produced by thermosetting or photocuring the interlayer insulating material composition.
The film made of the cured product and the interlayer insulating film according to the present invention can be produced by film-forming the above-mentioned interlayer insulating material composition by, for example, extrusion molding, calendar molding method or solvent casting method. When the film is cured by heating, the heating temperature is preferably in the range of 50 ° C to 300 ° C. When heated at 50 ° C. or lower, the curing rate may be remarkably slow, and when heated at a temperature higher than 300 ° C., the cured product may be deteriorated. Further, when curing, it is preferable to cure at two or more stages of a temperature in the range of 50 ° C. to 150 ° C. and a temperature in the range of 151 ° C. to 300 ° C., rather than maintaining at a constant temperature. When it hardens | cures by hold | maintaining at a fixed temperature, possibility that it will not fully harden | cure becomes high. The curing time is preferably 0.1 hours to 4 hours, more preferably 0.2 hours to 3 hours, and most preferably 0.3 hours to 4 hours. If the curing time is less than 0.1 hour, it may not be sufficiently cured, which is not preferable. Moreover, when it becomes 4 hours or more, it is economically unpreferable.

  The heat resistance, electrical properties, and mechanical strength of the cured product (allyl ester resin) obtained from the interlayer insulating material composition according to the present invention are the glass transition point (Tg), dielectric constant (hereinafter abbreviated as ε), and The tensile strength and tensile elongation in the tensile test can be evaluated. Tg is measured by a method according to JIS K7197, ε is measured by JIS K6911, and tensile strength and tensile elongation are measured by a method according to JIS K7113.

  Tg is preferably 130 ° C. or higher, more preferably 140 ° C. or higher, and most preferably 150 ° C. or higher. If Tg is less than 130 ° C., it may be greatly deformed during heating such as soldering, which is not preferable.

ε is preferably 3.5 or less, more preferably 3.4 or less, and most preferably 3.3 or less. If ε is greater than 3.5, the dielectric loss may increase, which is not preferable.
The tensile strength is preferably 50 MPa or more, more preferably 70 MPa or more, and most preferably 80 MPa or more. The tensile elongation is preferably 0.5% or more, more preferably 1.5% or more, and most preferably 2.0% or more. When the tensile strength is less than 50 MPa and the tensile elongation is less than 0.5%, the cured product may become brittle, which is not preferable.

Such an interlayer insulating material having excellent heat resistance, electrical characteristics, and mechanical strength is suitably used for a printed wiring board and a sealant.
[Example]
EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention does not receive any limitation by these description. Each physical property was measured by the following methods.

1. Measurement of viscosity The viscosity of the allyl ester oligomer and the interlayer insulating material composition was measured according to JIS K 6901 (1999). Using a B-type viscometer (model B8U type) manufactured by Tokyo Keiki Co., Ltd., using an HH-4 rotor, 10.3 ml of a sample was placed in a specified container and measured at a measurement temperature of 25 ° C. and a rotation speed of 20 rpm.

2. Measurement of flexural strength and flexural modulus The flexural strength and flexural modulus of the obtained cured product were measured by a method based on JIS K7171. A test piece of 65 mm × 25 mm × 3 mm was measured under the conditions of a test speed of 1.5 mm / min, a fulcrum distance of 48 mm, an indenter radius of 5 mm, a support base radius of 2 mm, and n = 5.

3. Measurement of Tensile Strength, Tensile Elastic Modulus, and Tensile Elongation Tensile strength, tensile elastic modulus, and tensile elongation of the obtained cured product were measured by a method based on JIS K7113. No. 1 dumbbell was used as a test piece, the test temperature was 23 ° C., the distance between the chucks was 115 mm, the distance between the marked lines was 25 mm, the test speed was 1 mm / min when measuring the elastic modulus, 5 mm / min when measuring the strength and elongation, and n = Measurement was performed under the conditions of 5.

4). Measurement of dielectric constant and dielectric loss tangent The dielectric constant and dielectric loss tangent of the obtained cured product were measured by a method based on JIS K6911 (1995). Under the conditions of a measurement temperature of 23 ° C. and a humidity of 65 RH%, a value of 1 MHz was measured by an automatic equilibrium bridge method using a high-precision impedance / LCR meter 6440A manufactured by Weinker.

5. Measurement of Tg and Linear Expansion Coefficient Tg and linear expansion coefficient of the obtained cured product were measured by a method based on JIS K 7197 (1991). Using a thermoanalyzer (TMA-50) manufactured by Shimadzu Corporation, about a test piece of 3 mm × 3 mm × 5 mm, nitrogen 50 mL / min. Temperature increase rate of 5 ° C./min. The linear expansion coefficient from 30 ° C. to 300 ° C. was measured and Tg was determined from the discontinuity point. The linear expansion coefficient of the cured product was evaluated by an average value between 30 ° C. and Tg.

  In a 2 liter three-necked flask equipped with a stirrer and a distillation apparatus equipped with a rectifier, 1478 g (6.0 mol) of diallyl isophthalate (manufactured by Showa Denko KK), tris (2-hydroxyethyl) isocyanurate (Wako Pure) After charging 392 g (1.5 mol) manufactured by Yakuhin Kogyo Co., Ltd. and 1.50 g (6.0 mmol) of dibutyltin oxide, nitrogen substitution was performed. This flask was immersed in a silicon oil bath equipped with a stirrer and a temperature controller, and the pressure in the flask was reduced to about 10 kPa from the distillation apparatus side. About 20 ° C. water was passed through the cooling water channel of the distillation apparatus. The above silicon oil was heated to 180 ° C. at a temperature rising rate of about 3 to 5 ° C./min to carry out the reaction. Distillation of allyl alcohol started from the middle of the temperature increase. The distillation temperature was about 64 ° C. When the distillate reached about 250 g, nitrogen was introduced to return the inside of the flask to atmospheric pressure. The distillation apparatus was switched to a reflux tube with a rectifier, and water at about 20 ° C. was passed through the cooling water channel of the reflux tube. The inside of the flask was gradually depressurized to about 100 Pa so as not to bump, and the reaction was further performed for 1 hour, followed by cooling immediately after the reaction to obtain an allyl ester oligomer. The distillate gas that passed through the reflux tube was collected by a trap cooled with methanol containing dry ice. The total amount of distillate collected in the distillation apparatus and trap was 263 g. The viscosity and weight average molecular weight of the obtained allyl ester oligomer were measured.

  2 parts by mass of dicumyl peroxide (manufactured by Nippon Oil & Fats Co., Ltd., trade name: Park Mill D) was added to 100 parts by mass of this allyl ester oligomer and sufficiently stirred to prepare an interlayer insulating material composition. The viscosity of this composition was measured. Thereafter, the composition was heated to about 80 ° C., then cast into a predetermined size, and cured by heating at 130 ° C. for 1 hour and further at 160 ° C. for 1 hour. The obtained cured product was cooled to room temperature, and the electrical properties, mechanical strength and heat resistance were measured.

Further, the allyl ester oligomer was put in a sealed container, stored in an oven at 40 ° C., the viscosity was measured at regular time intervals, the change in viscosity with time was examined, and the viscosity after storage for 1 month was evaluated.
The above measurement results are shown in Table 1.

[Comparative Example 1]
In a 2 liter three-necked flask equipped with a stirrer and a distillation apparatus equipped with a rectifier, 1478 g (6.0 mol) of diallyl terephthalate (manufactured by Showa Denko KK), tris (2-hydroxyethyl) isocyanurate (Wako Pure Chemical Industries, Ltd.) An allyl ester oligomer was synthesized in the same manner as in Example 1 except that 392 g (1.5 mol) manufactured by Kogyo Co., Ltd. and 1.50 g (6.0 mmol) of dibutyltin oxide were charged.

  The viscosity of the allyl ester oligomer obtained, its change with time, and the weight average molecular weight were measured. Further, a cured product was produced in the same manner as in Example 1, and the electrical characteristics, mechanical strength, and heat resistance were measured. The measurement results are shown in Table 1.

Claims (18)

An interlayer insulating material comprising an allyl ester oligomer having a group represented by the following formula (1), a group represented by the following formula (2) and / or a group represented by the following formula (3).

(In the formula, R ₁ represents an allyl group or a methallyl group, and when there are a plurality of these groups in one molecule of the oligomer, they may be the same or different from each other.)

(In the formula, X ₁ , X ₂ and X ₃ each independently represent an organic group having 1 to 10 carbon atoms, and X ₂ and X ₃ are a chain having an ester group and an ester bond having the group represented by (1) above) R ₂ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms.)   2. The interlayer insulating material according to claim 1, wherein the repeating unit in the allyl ester oligomer consists only of the group represented by the formula (2) and / or the group represented by the formula (3). 2. The interlayer insulating material according to claim 1, wherein X _{1 to} X _{3 in the} formulas (2) and (3) are substituted or unsubstituted alkylene groups.   A substituted or unsubstituted alkylene group is selected from ethylene, 2-methylethylene, 2-ethylethylene, 2-chloromethylethylene, 2-bromomethylethylene, 2-allyloxymethylethylene, 2-phenoxymethylethylene, cyclohexylene, 2 The interlayer insulating material according to claim 3, wherein the interlayer insulating material is one or more alkylene groups selected from the group consisting of -phenylethylene, 2-methacryloxymethylethylene, and 2-acryloxymethylethylene. The interlayer insulating material according to claim 1, wherein X _{1 to} X ₃ described in the formulas (2) and (3) are an ethylene group and / or a 2-methylethylene group.   An interlayer insulating material comprising an allyl ester oligomer obtained by a transesterification polycondensation reaction between di (meth) allyl isophthalate and a compound having an isocyanuric ring and two or more hydroxyl groups.   The interlayer insulating material according to claim 6, wherein the compound having an isocyanuric ring and two or more hydroxyl groups is a compound obtained by reacting isocyanuric acid with an alkylene monoepoxide.   The alkylene monoepoxide is at least one selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epibromohydrin, allyl glycidyl ether, phenyl glycidyl ether, cyclohexene oxide, styrene oxide, and glycidyl (meth) acrylate. The interlayer insulating material according to claim 7, which is an alkylene monoepoxide.   The compound having an isocyanuric ring and two or more hydroxyl groups is selected from the group consisting of bis (2-hydroxyethyl) isocyanurate, tris (2-hydroxyethyl) isocyanurate and tris (2-hydroxypropyl) isocyanurate The interlayer insulating material according to claim 6, which is the above isocyanurate.   An interlayer insulating material comprising an allyl ester oligomer having an ester-bonded structure of isophthalic acid, an isocyanuric ring and a compound having two or more hydroxyl groups, and an allyl group and / or a methallyl group at the terminal.   The interlayer insulating material according to claim 10, wherein the compound having an isocyanuric ring and two or more hydroxyl groups is a compound obtained by reacting isocyanuric acid and an alkylene monoepoxide.   The alkylene monoepoxide is at least one selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epibromohydrin, allyl glycidyl ether, phenyl glycidyl ether, cyclohexene oxide, styrene oxide, and glycidyl (meth) acrylate. The interlayer insulating material according to claim 11, which is an alkylene monoepoxide.   The compound having an isocyanuric ring and two or more hydroxyl groups is selected from the group consisting of bis (2-hydroxyethyl) isocyanurate, tris (2-hydroxyethyl) isocyanurate and tris (2-hydroxypropyl) isocyanurate It is the above isocyanurate, The interlayer insulation material of Claim 10 characterized by the above-mentioned.   6. An interlayer comprising an allyl ester oligomer according to claim 1, wherein di (meth) allyl isophthalate is subjected to an ester exchange polycondensation reaction between a compound having an isocyanuric ring and two or more hydroxyl groups. Insulating material manufacturing method.   An interlayer insulating material composition comprising the interlayer insulating material according to claim 1 and a curing agent.   Hardened | cured material of the interlayer insulation material composition of Claim 15.   An interlayer insulating film obtained by curing the interlayer insulating material composition according to claim 15.   The printed wiring board using the interlayer insulation material in any one of Claims 1-13.