JP2008069205A - New thermosetting polymerization liquid and thermosetting resin using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new thermosetting polymerization liquid and a thermosetting resin using the same. <P>SOLUTION: The thermosetting polymerization liquid is obtained by polymerizing a compound group consisting essentially of a compound (a) containing one (meth)acrylic group and one alicyclic epoxy group and has a viscosity of 10 mPa s to 2,000,000 mPa s at 25°C. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention provides electrical insulating materials such as liquid underfill materials and interlayer insulating films, electrical insulating properties that are expected to be used in fields such as IC and VLSI sealing materials, LED sealing materials, and laminates. The present invention relates to a novel liquid thermosetting resin having excellent characteristics and a method for producing the same.

  In recent years, with the remarkable development of the polymer industry, a wide variety of polymer materials have been widely used. In particular, in recent years, development of more excellent polymer materials has been promoted along with higher functionality and higher performance of industrial products.

Among such materials, epoxy resins have a wide range of industrial uses as thermosetting resins and other reactive resins, and have been studied and developed from various fields.
The most widely used epoxy resin in the industry is bisphenol A type epoxy resin produced by the reaction of bisphenol A and epichlorohydrin.
This resin has a wide range of products from liquid to solid, and is excellent in reactivity, chemical resistance, toughness, adhesiveness, heat resistance, etc., and is widely used in civil engineering, architecture, paints, adhesives and so on.
However, since the bisphenol A type epoxy resin is reacted with bisphenol A and epichlorohydrin, the resin contains several tens of ppm to 100 ppm of chlorine, which deteriorates the electrical characteristics of the electrical components. The dielectric constant of bisphenol A type epoxy resin is also high, and an alicyclic epoxy resin that does not contain chlorine and has excellent electrical characteristics and heat resistance is used as a semiconductor sealing material.
As the alicyclic epoxy resin, those having the following structure are industrially produced and used.

In addition, as other epoxy resin with reduced residual halogen, for example, epoxy resin in which vinyl group is epoxidized after ring-opening polymerization of 4-vinyl-epoxycyclohexane (see Patent Document 1 below), A resin obtained by epoxidizing a compound obtained by alternating copolymerization of 4-vinyl-epoxycyclohexane and an acid anhydride (see Patent Document 2 below), and a methacrylic ester of epoxycyclohexanemethanol with other methacrylic or An epoxy resin composition obtained by polymerizing with an acrylate ester (see the following Patent Document 3) has also been proposed.
JP-A-60-166675 Japanese Patent Laid-Open No. 06-41275 Japanese Patent Laid-Open No. 08-291214

Each of the above conventional techniques has achieved a certain result, but there are still a number of aspects that are still insufficient. For example, the compound represented by (c) has a problem that it is highly toxic and the operator's skin is significantly irritated, and the compounds represented by (c) and (d) are both low-viscosity epoxy resins. Therefore, a molding system of solid epoxy resin such as transfer molding cannot be applied.
Moreover, in the case of patent document 1 and patent document 2, the epoxy group of 4-vinyl-epoxycyclohexane is polymerized by ring-opening polymerization, and is converted to an epoxy resin using a peracid in the next step. Epoxidation is industrially difficult to convert all double bonds to epoxy groups in high yield. Further, in Patent Document 3, it is difficult to control the molecular weight of an epoxycyclohexane acrylic acid ester or methacrylic acid ester radical polymerized polymer, and if the molecular weight is too large, there may be a problem in compatibility and solubility.

  As a result of intensive studies on the above problems, the inventors of the present invention are based on a compound having both a (meth) allyl group and an alicyclic epoxy group, so that a specific viscosity can be obtained by radical polymerization of a (meth) allyl group. It was found that a polyfunctional epoxy group-containing compound having a low halogen concentration was obtained by controlling the temperature to be high, and that the curing rate was high even though it was liquid while having high electrical insulation. In addition, by controlling the epoxy value by copolymerization with vinyl polymerizable compounds (other compounds having an ethylenically unsaturated bond), in recent years excellent novel epoxy-containing compounds that can meet physical properties in various applications Has been achieved, leading to the present invention.

  That is, the present invention relates to the following [1] to [11].

  [1] By polymerizing a compound group mainly composed of the compound (a) having one (meth) allyl group and one alicyclic epoxy group, the viscosity at 25 ° C. is changed from 10 mPa · s to 2,000,000 mPa · s. A liquid curable polymerization liquid characterized by the above.

｛式中、R1〜R41は水素または炭素数１〜８までのアルキルまたはアリール基を表す。｝で表されることを特徴とする、前記［１］に記載の液状硬化性重合液。 [2] A compound having one (meth) allyl group and one alicyclic epoxy group has the following structural formula:

{Wherein R1 to R41 represent hydrogen or an alkyl or aryl group having 1 to 8 carbon atoms. } The liquid curable polymerization liquid as described in [1] above, wherein

[3] The liquid curable polymerization according to [1] or [2], further comprising polymerizing a compound group including the (meth) allyl compound (b) and / or the monovinyl polymerizable compound (c). liquid.

[4] The liquid curable polymerization solution according to any one of [1] to [3], wherein an epoxy equivalent is 150 to 2,000.

[5] A compound group mainly composed of the compound (a) having one (meth) allyl group and one alicyclic epoxy group is used, and the 10-hour half-life temperature of the radical polymerization initiator used is −10 to + 50 ° C. A method for producing a liquid curable polymerization liquid, wherein the polymerization is performed in a temperature range of

[6] The liquid curability according to the above [5], wherein the radical polymerization initiator is at least one selected from peroxydicarbonate, peroxymonocarbonate, peroxyketal, and dialkyl peroxide. A method for producing a polymerization solution.

[7] A compound group mainly composed of the compound (a) having one (meth) allyl group and one alicyclic epoxy group is obtained at 100 ° C. or higher and 300 ° C. under a gas stream having an oxygen concentration of 5% or higher. A method for producing a liquid curable polymerization liquid, wherein the polymerization is carried out at a temperature of ℃ or less.

[8] The method according to any one of [5] to [7], further comprising polymerizing a compound group including the (meth) allyl compound (b) and / or the monofunctional vinyl polymerizable compound (c). A method for producing a liquid curable polymerization liquid.

[9] A thermosetting resin composition comprising 0 to 100 parts by mass of a liquid epoxy resin with respect to 100 parts by mass of the liquid curable polymerization liquid according to any one of [1] to [4]. object.

  The cationic curing agent is 0.01 to 3 parts by mass and the radical initiator is 0 to 4 with respect to 100 parts by mass in total of the liquid curable polymerization liquid according to any one of [1] to [4] and the liquid epoxy resin. The thermosetting resin composition according to [9], wherein the thermosetting resin composition is contained in parts by mass.

[11] The acid anhydride is added to 1 mol of epoxy groups in the liquid curable polymerization liquid with respect to 100 parts by mass in total of the liquid curable polymerization liquid and liquid epoxy resin of any one of [1] to [4]. The thermosetting according to [9] above, wherein 0.7 to 1.5 molar equivalents are used, and further containing 0 to 6 parts by mass of a curing accelerator and 0 to 4 parts by mass of a radical initiator. Resin composition.

  According to the present invention, electrical insulating materials expected to be used in the fields of electrical insulating materials such as liquid underfill materials and interlayer insulating films, IC and VLSI sealing materials, LED sealing materials, laminates, etc. It is possible to provide a novel epoxy group-containing compound having excellent optical properties and a method for producing the compound.

｛式中、R1〜R41は水素または炭素数１〜８までのアルキルまたはアリール基を表す。｝で表される。 The present invention will be specifically described below.
First, a compound having one (meth) allyl functional group and one epoxy functional group as a raw material of the present invention has the following structural formula:

{Wherein R1 to R41 represent hydrogen or an alkyl or aryl group having 1 to 8 carbon atoms. }.

  These compounds with one (meth) allyl functional group and one epoxy functional group are either non-catalyzed or suitable by using a peroxide such as hydrogen peroxide or peracetic acid. It can be obtained by reacting in the presence of a catalyst to convert the double bond of the cyclohexene ring to an epoxy group.

  Among these, particularly from the viewpoint of the reactivity of the epoxy group and the availability of raw materials, 3,4-epoxycyclohexane-1-carboxylic acid allyl ester, 3,4-epoxycyclohexane-1-methyl- Examples include 1-carboxylic acid allyl ester, 3,4-epoxycyclohexane-6-methyl-1-carboxylic acid allyl ester, and N-allyl perhydroepoxyphthalimide. In these, the carbon of the epoxy group is tertiary, and is highly reactive such as cationic polymerization. Also, industrially, by esterifying or imidizing a compound obtained by a Diels-Alder reaction with inexpensive acrylic acid, methacrylic acid, crotonic acid, maleic acid, or butadiene using allyl alcohol or allylamine. A compound having a cyclohexene ring and an allyl group, which is a precursor of an epoxy compound, can be obtained.

  These compounds have a (meth) allyl group. In general, a (meth) allyl group has a very slow polymerization rate and does not increase the degree of polymerization, so that it is difficult to obtain a high molecular weight polymer. However, from the viewpoint of obtaining a thermosetting oligomer before curing, runaway polymerization is difficult even if radical polymerization is performed, and polymerization control is easy, and polymerization is stopped at an appropriate molecular weight without the presence of a chain transfer agent. Is possible. Therefore, it is possible to perform cast polymerization without solvent without sacrificing physical properties by controlling the monomer conversion rate and molecular weight without performing an operation such as diluting the low molecular weight monomer in a large excess after polymerization. It can be a composition.

  Surprisingly, when radical polymerization is attempted in a short period of time, usually without solvent, the type and amount of initiator can be combined with (meth) acrylic compounds that are extremely runaway and difficult to control. By controlling the polymerization temperature and the like, a liquid composition can be obtained even when polymerization is carried out without solvent. The obtained (meth) acrylic acid is said to have poor copolymerizability with allyl groups, but in these copolymers, (meth) allyl compounds partially having epoxy groups are present. Since it is incorporated, a clear transparent cured product can be obtained even if a subsequent cationic polymerization or curing reaction with an acid anhydride is performed.

  Here, as a method for obtaining a liquid curable polymerization liquid, polymerization is generally carried out without a solvent, but in the case of a raw material having a high melting point such as N-allylperhydroepoxyphthalimide, other monomers are used. It is desirable to perform the polymerization without solvent, but if this is not possible, it is possible to use a low boiling point solvent. However, since it is necessary to finally distill off the solvent, the boiling point of the solvent is desirably at least 200 ° C., more preferably 150 ° C. or less. Of course, it is necessary to have no functional group such as an alcoholic hydroxyl group, a carboxyl group or an amine group that reacts with an epoxy group.

  Examples of such solvents include aromatic hydrocarbons such as benzene, toluene, and xylene, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ethers such as diethyl ether, dibutyl ether, and t-butyl methyl ether, THF, Cyclic ethers such as dioxane, esters such as ethyl acetate, acetic acid-n-propyl, acetic acid-n-butyl, and isobutyl acetate, (di) ethylene glycol dialkyl ethers, (di) propylene glycol dialkyl ethers, ethylene glycol mono Alkyl ether acetates, propylene glycol monoalkyl ether acetates, halogenated hydrocarbons such as carbon tetrachloride, chloroform, and methylene chloride can be used. However, it is safer to avoid the use of ketone solvents and halogenated hydrocarbon solvents because of their high radical chain transfer ability. Among these, considering the boiling point, benzene, toluene, ethyl acetate, ethylene glycol dimethyl ether and the like are desirable solvents.

  In the present invention, other copolymerizable monovinyl polymerizable compounds other than the epoxy compound may be used. As the copolymerizable compound, in addition to the mono (meth) allyl compound, other radical polymerizable monomers such as a mono (meth) acrylic compound can be used.

  Examples include (meth) acrylic acid esters and derivatives thereof, styrene and derivatives thereof, vinyl acetate and derivatives thereof, (meth) acrylonitrile and derivatives thereof, vinyl esters of organic carboxylic acids and derivatives thereof, and dialkyls of fumaric acid. Examples include esters and derivatives thereof, dialkyl esters of maleic acid and derivatives thereof, dialkyl esters of itaconic acid and derivatives thereof, N-vinylamide derivatives of organic carboxylic acids, maleimides and derivatives thereof, terminal unsaturated hydrocarbons and derivatives thereof, and the like.

  First, as allyl compounds, allyl acetate, allyl propionate, allyl n-hexanoate, allyl cyclohexanecarboxylate, allyl cyclohexylpropionate, allyl benzoate, allyl phenylacetate, allyl phenoxyacetate, allyl trifluoroacetate, allyl methyl carbonate , Ethyl allyl carbonate, allyl methyl ether, allyl glycidyl ether, allyl benzyl ether, allyloxytrimethylsilane, and the like. There are also restrictions on the amount used, but there are also compounds with multiple allyl groups such as diallyl terephthalate, diallyl isophthalate, diallyl phthalate, diallyl adipate, triallyl trimellitic acid, triallyl isocyanurate, triallyl cyanurate, etc. Can be used. In the case of using such an allyl compound, in the case of a compound having two allyl groups, it is 30 parts by weight or less, more preferably 15 parts by weight or less, and in the case of a compound having three allyl groups, 20 parts by weight. More preferably, it is suppressed to 10 parts by weight or less, and it is desirable that the gelation is not excessively increased even if the conversion rate is increased.

  As the (meth) acrylic acid esters and derivatives thereof, monovinyl compounds or (meth) acrylates having a plurality of vinyl groups can be used, although the amount of use is limited, methyl (meth) acrylate, ) Ethyl acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid-sec-butyl, ( Hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate , Benzyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl ( ) Acrylate, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-3-hydroxypropyl, (meth) acrylic acid-2-hydroxybutyl, (meth) ) -2-hydroxyphenylethyl acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di ( (Meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol penta (meth) acrylate, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) Acrylamide, N-acryloylmorpholine and the like.

  Examples of styrene and derivatives thereof include styrene, 2,4-dimethyl-α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 2 , 6-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, 2,4,5-trimethylstyrene, pentamethylstyrene, o-ethylstyrene, m-ethyl Styrene, p-ethylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxy Styrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxys Len, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-vinyl-p-terphenyl, 1-vinylanthracene, α-methylstyrene, o-isopropenyl Toluene, m-isopropenyltoluene, p-isopropenyltoluene, 2,4-dimethyl-α-methylstyrene, 2,3-dimethyl-α-methylstyrene, 3,5-dimethyl-α-methylstyrene, p-isopropyl -Α-methylstyrene, α-ethylstyrene, α-chlorostyrene, divinylbenzene, divinylbiphenyl, diisopropylbenzene and the like.

  Examples of (meth) acrylonitrile and derivatives thereof include acrylonitrile and methacrylonitrile.

  Examples of vinyl esters of organic carboxylic acids and derivatives thereof include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, and divinyl adipate.

  Dialkyl esters of fumaric acid and derivatives thereof include dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, di-sec-butyl fumarate, diisobutyl fumarate, di-n-butyl fumarate, di-2-ethylhexyl fumarate And dibenzyl fumarate.

  Dialkyl esters of maleic acid and derivatives thereof include dimethyl maleate, diethyl maleate, diisopropyl maleate, di-sec-butyl maleate, diisobutyl maleate, di-n-butyl maleate, di-2-ethylhexyl maleate And dibenzyl maleate.

  Dialkyl esters of itaconic acid and derivatives thereof include dimethyl itaconate, diethyl itaconate, diisopropyl itaconate, di-sec-butyl itaconate, diisobutyl itaconate, di-n-butyl itaconate, di-2-ethylhexyl itaconate And dibenzyl itaconate.

  Examples of N-vinylamide derivatives of organic carboxylic acids include N-methyl-N-vinylacetamide.

  Examples of maleimide and derivatives thereof include N-phenylmaleimide and N-cyclohexylmaleimide.

  Examples of terminal unsaturated hydrocarbons and derivatives thereof include 1-butene, 1-pentene, 1-hexene, 1-octene, vinylcyclohexane, vinyl chloride, and allyl alcohol.

    In this case, when a compound having two or more double bonds is used in combination, there are many radically polymerizable compounds such as (meth) acrylic acid derivatives and styrene derivatives, so the amount of use is more restrictive than allyl compounds. It is desirable to keep it to 10 parts by weight, more preferably 5 parts by weight.

  Among monofunctional vinyl polymerizable compounds other than allyl, a (meth) acrylic acid derivative is particularly preferable because the obtained polymerization solution is low in color and gives a transparent cured product even after curing.

Since these compounds can be arbitrarily selected, various performances can be imparted to the resin containing these compounds as a component, and are determined in consideration of the performance desired to be imparted to the finally obtained epoxy resin composition. It is desirable. However, with respect to the amount of the epoxy compound used, if the amount is too small, the epoxy equivalent of the resulting compound increases, and the heat resistance and solvent resistance deteriorate. Therefore, it is desirable to use at least 20 parts by weight or more, more desirably 50 parts by weight or more. In addition, regarding the epoxy equivalent of the resulting polymerization solution, the epoxy group may be somewhat ring-opened during the polymerization, so that the epoxy equivalent is in the range of 150 to 2,000, more preferably 150 to 1,000 in consideration of them. In addition, it is desirable to determine the composition and polymerization conditions.
When the epoxy equivalent is lower than 150, the heat resistance increases, but it becomes very brittle. On the other hand, if it exceeds 2000, the cationic polymerization rate and the curing rate with an acid anhydride are slow, which is not preferable.

The epoxy equivalent of the epoxy group-containing compound is measured by the following method. A sample of 2 to 4 mg equivalent is put into a 200 ml stoppered Erlenmeyer flask and precisely weighed with a precision balance. In this container, 25 mL of 0.2 M hydrochloric acid-dioxane solution is added and dissolved using a whole pipette and left at room temperature for 30 minutes. Next, add 10 ml of methyl cellosolve while washing the stopper and inner wall of the Erlenmeyer flask, add 4 to 6 drops of 0.1% cresol red-ethanol solution as an indicator, and stir well until the sample is uniform. This is titrated with a 0.1 M potassium hydroxide-ethanol solution, and the end point of neutralization is taken when the blue-violet indicator continues for 30 seconds. The result is calculated as follows:
Epoxy equivalent (g / eq) = 10000 × S / [(BA) × f]
S: Sample collection amount (g)
A: Amount of 0.1M potassium hydroxide-ethanol solution used
B: Amount of 0.1 M potassium hydroxide-ethanol solution used in the blank test (ml)
f: The value obtained using a factor of 0.1 M potassium hydroxide-ethanol solution is defined as the epoxy equivalent of the resin.

  As the polymerization initiator, a normal radical polymerization initiator can be used. For example, azo series such as 2,2′-azobisisobutyronitrile and 2,2′-azobis- (2,4-dimethylvaleronitrile) , Lauroyl peroxide, di-t-butyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxy (2-ethylhexanoate), 1,1 di (t-hexylperoxide) Oxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-butylperoxy) cyclohexane, t-butylperoxyisopropyl monocarbonate, methyl ethyl ketone peroxide, benzoyl peroxide, t-butylperoxybenzoate, Peroxides such as cumene hydroperoxide, or molecular oxygen Are used alone or in combination. The initiator is blended in the range of 0.1 wt% to 10 wt% with respect to the raw material of the polymerization liquid except for oxygen on the molecule. When oxygen on the molecule is used, the reaction is carried out by diluting air with nitrogen as necessary and blowing it directly into the heated polymerization solution.

  Among these polymerization initiators, in the case of an initiator that decomposes and generates an acid like a perester, the generated acid reacts with the epoxy group, so the epoxy equivalent increases. Caution must be taken. In the case of an azo-based initiator, in particular, when the polymerization is attempted only with an allyl group, the initiator efficiency is remarkably deteriorated.

  Therefore, there are peroxydicarbonate, peroxymonocarbonate, peroxyketal, and dialkyl peroxide as initiators with few such problems, and it is desirable to select from these initiators as initiators.

  The polymerization temperature depends on the type of the polymerization initiator, but can be appropriately selected between 10 and 250 ° C., and is preferably 50 to 180 ° C. from the viewpoint of the stability of the epoxy group and the ease of handling. Within this range, it is desirable to further select from the temperature range of −10 to + 50 ° C. of the ten-hour half-life temperature of the polymerization initiator. In the case of oxygen, it is desirable to carry out at a polymerization temperature of 100 ° C. or higher.

The half-life is the time required for the active organic content to be halved by decomposition of the original organic peroxide, and the 10-hour half-life is measured as follows.
First, using a solvent inert to the radical initiator, for example, benzene, an organic peroxide solution of 0.1 mol / L is prepared and sealed in a glass tube subjected to nitrogen substitution. This is immersed in a thermostat set at a predetermined temperature and thermally decomposed.
Decomposition of organic peroxides can generally be handled by a primary reaction, so measure the thermal decomposition rate after a certain period of time, plot the relationship with time using the following formula, and determine the decomposition rate from the slope of the obtained straight line. A constant is obtained, and then the half-life time at that temperature is obtained.
ln (a / (ax)) = kt (1)
Where a: initial concentration of organic peroxide
x: Decomposed concentration of organic peroxide
k: Decomposition rate constant
t: The decomposition rate constant is obtained at a plurality of temperatures for a time, and the activation energy is obtained by the following Arrhenius plot.
lnk = lnA−ΔE / RT (2)
A: Frequency factor
ΔE: Activation energy
R: Gas constant
T: The rate constant required to halve in 10 hours is obtained from the absolute temperature (1) equation, and the 10-hour half-life temperature is obtained from the equation (2) using the obtained activation energy.

  The monomer conversion rate and molecular weight of the produced polymerization liquid can be adjusted by the amount of initiator used, the polymerization temperature, and the type of monomer. Here, when used as an underfill material or LED encapsulant, if the viscosity is too low, the liquid will flow too much during casting curing, and if it is too high, the casting operation It becomes impossible to do itself. Therefore, it is desirable to control the viscosity at 25 ° C. from 50 mPa · s to 2,000,000 mPa · s, more preferably 300 mPa · s to 500,000 mPa · s by controlling the parameters during polymerization.

  As a viscosity control method, if a large amount of polymerization initiator is used, the monomer conversion rate increases and the viscosity increases, and even if the amount of the (meth) acrylic monomer is increased, the molecular weight increases and the degree of polymerization increases. The optimum condition is usually determined by trial and error experiments.

  In particular, in the case of a monomer having a high melting point, such as N-allylperhydroepoxyphthalic acid, it may become a solid after polymerization. It is necessary to devise so as not to precipitate.

  For the purpose of finely adjusting the viscosity, other epoxy monomers can be further added. Examples of such an epoxy resin include bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, alicyclic epoxy resin, aliphatic polyalcohol polyglycidyl ether, and the like.

  Here, as a compounding quantity of the epoxy resin to mix, it is preferable to restrain to 5 mass parts-100 mass parts of the whole liquid hardened | cured material, More preferably, it is 5 mass parts-80 mass parts or less. If it is 5 parts by mass or less, there is almost no effect such as viscosity adjustment when blended. On the other hand, when the amount exceeds 100 parts by mass, the balance of cationic curability, heat resistance and toughness, which are goodness of the composition of the present invention, may be lost, which is not desirable.

  The viscosity is measured by the single rotational viscometer method in JIS-K7233. When the amount is small, it may be measured with a cone plate viscometer instead of a single rotational viscometer on the assumption that the test is performed with a viscosity standard solution.

  Since the liquid polymer thus obtained has a cyclohexene oxide skeleton in the polymer, it is possible to carry out a curing reaction with an epoxy in the presence of a curing reaction with a cationic curing agent or an acid anhydride. . In particular, since a plurality of cyclohexene oxides are incorporated in the polymer, a very high curing rate can be achieved.

  As such a curing system, a cationic curing agent can be used for a Lewis acid and a Bronsted acid that are used as a curing agent for an epoxy resin.

  As a thermosetting catalyst, for example, Lewis acid such as BF3 is used as a cationic curing catalyst, but by itself, the pot life is extremely short, and is used as an amine complex for practical use. BF3-amine complexes include BF3-amine complexes such as monoethylamine, triethylamine, piperidine, ethanolamine and the like. Also known are sulfonium salt type, ammonium salt type, pyridinium salt type compounds, α-substituted benzylammonium salts and heterocyclic ammonium salts having a benzyl group.

  Also known are phosphonium salt and iodonium salt cation curing catalysts. These are generally onium salts of nitrogen, sulfur, phosphorus or iodine which are anionic components such as SbF6-, BF4-, AsF6-, PF6-. Typical examples of these are given below.

1) Quaternary ammonium salt type compound:
N, N-dimethyl-N-benzylanilinium hexafluoroantimony N, N-diethyl-N-benzylanilinium tetrafluoride N, N-dimethyl-N-benzylpyridinium hexafluoroantimony N, N-dimethyl- N- (4-Chlorobenzyl) anilinium hexafluoroantimony N, N-diethyl-N-benzylpyridinium trifluoromethanesulfonic acid N, N-dimethyl-N- (4-methoxybenzyl) pyridinium hexafluoroantimony N, N- Diethyl-N- (4-methoxybenzyl) pyridinium hexafluoromonium N, N-dimethyl-N- (4-methoxybenzyl) toluidinium hexafluoride antimony N, N-diethyl-N- (4-methoxybenzyl) toluidinium 6 Antimony fluoride

2) Sulfonium salt type:
Triphenylsulfonium tetrafluoride Triphenylsulfonium hexafluoroantimony Triphenylsulfonium hexafluoride Arsenic tri (4-methoxyphenyl) sulfonium hexafluoride Arsenic diphenyl (4-phenylthiophenyl) sulfonium hexafluoride p -T-Butylbenzyltetrahydrothiophenium antimony hexafluoride

3) Phosphonium salt type compounds:
Ethyltriphenylphosphonium antimony hexafluoride Tetrabutylphosphonium antimony hexafluoride

4) Iodonium salt type compound:
Diphenyliodonium hexafluoride arsenic di-4-chlorophenyliodonium hexafluoride arsenic di-4-bromophenyliodonium hexafluoride arsenic di-p-tolyliodonium hexafluoride arsenic phenyl (4-methoxyphenyl) Iodonium hexafluoride

  Examples of cationic photopolymerization initiators include Lewis acid diazonium salts, Lewis acid iodonium salts, Lewis acid sulfonium salts, Lewis acid phosphonium salts, and the like. Specific examples include triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroantimonate, N, N-diethylaminophenyldiazonium hexafluorophosphonate, p-methoxyphenyldiazonium fluoro A phosphonate etc. are mentioned.

  The compounding amount of the cationic curing agent is 0.01 to 3 parts by weight, more preferably 0.05 to 2 parts by weight. When the amount of the cationic curing agent is larger than this, the generated cations adversely affect the physical properties of the cured product. However, if it is less than this, the curing rate is undesirably low.

  Further, as a curing system other than a cation, there is a system that uses an acid anhydride in combination, but such a carboxylic acid anhydride is not particularly limited. For example, the following formulas (5) to (8) A compound represented by: hexahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 3-methyl-1,2,3,6-tetrahydro Phthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride , Norbornane-2,3-dicarboxylic anhydride, methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride, methyl-3,6-endomethylenehexahydrophthalic anhydride, dodecenyl In addition to succinic anhydride, it has conjugated double bonds such as α-terpinene and alloocimene. Alicyclic compounds and Diels-Alder reaction product of maleic anhydride and alicyclic carboxylic acid anhydride curing agents such as hydrogenated products thereof are preferred that. In addition, arbitrary structural isomers and arbitrary geometrical isomers can be used as the Diels-Alder reaction product and hydrogenated products thereof.

  Aromatic acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, polyadipic acid anhydride, polyazeline acid anhydride, polysebacic acid anhydride, etc. is there.

  These acid anhydrides can be appropriately chemically modified as long as they do not substantially interfere with the curing reaction.

  From the viewpoint of fluidity and transparency of the composition, 3-methyl-1,2,3,6-tetrahydrophthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, 3-methyl- Hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride, methyl-3,6-endomethylenehexahydrophthalic anhydride preferable.

  These alicyclic carboxylic anhydride-based curing agents can be used alone or in admixture of two or more.

  Further, the aliphatic carboxylic acid anhydride and the aromatic carboxylic acid anhydride can be appropriately chemically modified as long as they do not substantially interfere with the curing reaction.

  The total use ratio of the aliphatic carboxylic acid anhydride and the aromatic carboxylic acid anhydride is preferably 50% by weight or less, based on the total amount with the alicyclic carboxylic acid anhydride, so that the liquid state can be maintained. More preferably, it is 30 weight% or less.

  In the present invention, the amount of carboxylic acid anhydride used is preferably from the viewpoint of reduction in glass transition point (Tg), coloring, etc. as an equivalent ratio of carboxylic acid anhydride groups to 1 mol of epoxy groups in the epoxy compound. It is 7-1.5, More preferably, it is 0.8-1.3.

  Furthermore, in the present invention, in addition to the carboxylic acid anhydride, components that are known as curing agents for epoxy compounds and epoxy resins, such as phenols, dicyandiamides, and adipic acid, within a range that does not impair the intended effect of the present invention. One or more organic hydrazides such as hydrazide and phthalic acid hydrazide may be used in combination.

  The use ratio of the other curing agent is usually 50% by weight or less, preferably 30% by weight or less, based on the carboxylic acid anhydride.

  In particular, when curing an acid anhydride and an epoxy resin, it is desirable to use a curing accelerator in order to accelerate the curing reaction. Such a curing accelerator is a component that accelerates the curing reaction between the alicyclic epoxy compound and the carboxylic acid anhydride. Such a curing accelerator is not particularly limited. For example, tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, dimethylcyclohexylamine; 1-cyanoethyl Imidazoles such as 2-ethyl-4-methylimidazole and 2-ethyl-4-methylimidazole; organophosphorus compounds such as triphenylphosphine and triphenyl phosphite; tetraphenylphosphonium bromide, tetra-n -Quaternary phosphonium salts such as butylphosphonium bromide; diazabicycloalkenes such as 1,8-diazabicyclo [5,4,0] undecene-7 and organic acid salts thereof; zinc octylate, tin actinate , Organometallic compounds such as aluminum acetylacetone complex; Quaternary ammonium salts such as ruammonium bromide and tetra-n-butylammonium bromide; Boron compounds such as boron trifluoride and triphenyl borate; Metal halides such as zinc chloride and stannic chloride, dicyandiamide and amines High melting point dispersion type latent curing accelerators such as amine addition type accelerators such as adducts of epoxy resin and epoxy resins; microcapsule type latent coatings with the surface of curing accelerators such as imidazole, phosphorus and phosphine coated with polymer Curable curing accelerators; amine salt type latent curing accelerators; latent curing accelerators such as high temperature dissociation type thermal cationic polymerization type latent curing accelerators such as Lewis acid salts and Bronsted acid salts it can.

  Among these curing accelerators, quaternary phosphonium salts, diazabicycloalkenes, organometallic compounds and quaternary ammonium salts are colorless and transparent, and a cured product that is difficult to discolor even when heated for a long time can be obtained. preferable.

The said hardening accelerator can be used individually or in mixture of 2 or more types.
In this invention, the usage-amount in the case of using a hardening accelerator becomes like this. Preferably it is 0.1-6 weight part with respect to 100 weight part of epoxy compounds, More preferably, it is 0.3-4 weight part. In this case, if the amount of the curing accelerator used is less than 0.1 parts by weight, the curing rate tends to decrease. On the other hand, if it exceeds 6 parts by weight, there are disadvantages such as Tg reduction and coloring of the resulting cured product. May occur.

  The thermosetting resin composition can be cured by heat or light irradiation as it is, but if necessary, a radical polymerization initiator is added for the purpose of reacting the remaining double bonds. Inorganic and / or organic fine particles and an antifoaming agent can be blended.

  As the radical polymerization initiator, any radical polymerization initiator can be used, and as such, azo-based and organic peroxides can be raised as in the first polymerization. preferable.

  For example, ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, acetylacetone peroxide, isobutyryl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, o-methylbenzoyl peroxide , Diacyl peroxides such as lauroyl peroxide, p-chlorobenzoyl peroxide, 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene peroxide, cumene hydroperoxide, t-butyl peroxide, etc. Diperoxides such as hydroperoxides, dicumyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide, tris (t-butylperoxy) triazine, 1,1-di-t-butylperoxide Peroxyketals such as oxycyclohexane and 2,2-di (t-butylperoxy) butane, t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyiso Butyrate, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyacetate, t- Alkyl peresters such as butyl peroxybenzoate and di-t-butylperoxytrimethyladipate, diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate, t-butylperoxyisopropylcarbonate And other Parkerbonates.

  In the case of using such a radical polymerization initiator, it should preferably be suppressed to 0.2 to 4 parts by mass, more preferably 3 parts by mass or less with respect to the epoxy compound in consideration of coloring of the cured product. When the amount used is large, not only the use effect is not obtained, but also coloring is caused, which is not preferable. If the amount is less than 0.1 parts by mass, the added effect is small, and the adverse effect such as coloring is more significant.

  Known inorganic or organic fillers can be used. The blending ratio varies depending on the selection of the heat-resistant thermosetting resin, and when added, it is preferably in the range of 5 to 40 wt% with respect to the entire resin composition. Examples of organic fillers include epoxy resin powder, melamine resin powder, urea resin powder, guanamine resin powder, polyester resin powder, and silicone powder.Inorganic fillers include silica, alumina, titanium oxide, barium sulfate, talc, calcium carbonate, Examples thereof include inorganic fillers such as glass powder and quartz powder.

  As the antifoaming agent, a silicone-based antifoaming agent or a non-silicone-based antifoaming agent is used, and in particular, it is used in consideration of bubble entrainment properties and bubble removal properties during screen printing. Several of these may be used in combination, and the blending amount and blending ratio are not particularly limited, and can be changed in a timely manner in consideration of the bubble entrainment property and bubble removal property during screen printing. For example, as a silicone type antifoaming agent, KS-602A (made by Shin-Etsu Chemical Co., Ltd .: trade name), KS-603 (made by Shin-Etsu Chemical Co., Ltd .: trade name), KS-608 (made by Shin-Etsu Chemical Co., Ltd.) : Trade name), FA600 (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name), BYK-A506 (manufactured by BYK Japan, Inc .: trade name), BYK-A525 (manufactured by BYK Japan, Inc .: trade name), BYK- A530 (BIC Chemie Japan Co., Ltd .: trade name), as non-silicone antifoaming agents, BYK-A500 (BIC Chemie Japan Co., Ltd .: trade name), BYK-A500 (BIC Chemie Japan Co., Ltd .: trade name) ), BYK-A501 (BIC Chemie Japan Co., Ltd .: trade name), BYK-A515 (BIC Chemie JA Made emissions Co., Ltd. trade name), BYK-A555 (BYK Chemie Japan Co., Ltd .: trade name), etc., are preferably used. There is no restriction | limiting in particular also about the compounding quantity and compounding ratio.

  Further, various known additives according to the use, for example, fiber reinforcing materials such as glass fiber, carbon fiber and boron nitride fiber, antioxidants such as hindered phenol compounds, phosphorus compounds and hindered amine compounds, benzotriazole UV absorbers such as UV-based compounds and benzophenone compounds, viscosity modifiers, flame retardants, antibacterial agents, antifungal agents, anti-aging agents, antistatic agents, plasticizers, lubricants, foaming agents, etc. may be added and mixed it can.

  Examples The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

In this specification, unless otherwise specified, the GPC measurement conditions are as follows.
Device name: JASCO Corporation HPLC unit HSS-2000
Column: Shodex column LF-804
Mobile phase: Tetrahydrofuran Flow rate: 1.0 mL / min
Detector: RI-2031Plus manufactured by JASCO Corporation
Temperature: 40.0 ° C
Sample volume: 100 μl of sample loop Sample concentration: prepared around 0.1 wt%

Synthesis Example 1
In a 50 ml flask, 20.02 g of 3,4-epoxycyclohexane-1-carboxylic acid allyl ester (CEA), 1,1-di- (t-hexoxyperoxytrimethylcyclohexane) (Perhexa TMH manufactured by NOF Corporation) 0.639 g was charged, immersed in an oil bath at 120 ° C., and heated for 2 hours under a nitrogen stream.
Two hours later, the number average molecular weight by GPC of the polymerization solution was 1410 (excluding CEA), the viscosity was 91 mPa · s, and the epoxy equivalent was 199.

Synthesis Example 2
A 50 ml flask is charged with CEA 20.06 g and t-butyl peroxyisopropyl monocarbonate (Nippon Yushi Co., Ltd., Perbutyl I) 0.67 g, soaked in an oil bath at 130 ° C., and heated under a nitrogen stream for 6 hours. Continued.
After 6 hours, the number average molecular weight by GPC of the polymerization solution was 1410 (excluding CEA), the viscosity was 2360 mPa · s, and the epoxy equivalent was 237.

Synthesis Example 3
A 100 ml flask is charged with 50.07 g of CEA and 3.03 g of di-t-butyl peroxide (Perbutyl D manufactured by NOF Corporation), immersed in an oil bath at 130 ° C., and heated for 8 hours under a nitrogen stream. It was.
After 8 hours, the number average molecular weight by GPC of the polymerization solution was 1790 (excluding CEA), the viscosity was 618000 mPa · s, and the epoxy equivalent was 184.

Synthesis Example 4
A 200 ml flask is charged with 80.21 g of CEA, 20.15 g of methyl methacrylate (MMA; manufactured by Mitsubishi Rayon Co., Ltd.) and 4.03 g of Perhexa TMH, immersed in an oil bath at 100 ° C., and heated under a nitrogen stream for 2 hours. Continued.
Two hours later, the number average molecular weight by GPC of the polymerization solution was 1150 (excluding CEA), and the epoxy equivalent was 234.

Synthesis Example 5
A 200 ml flask was charged with 60.09 g of CEA, 40.10 g of methyl methacrylate (MMA; manufactured by Mitsubishi Rayon Co., Ltd.), and 3.02 g of Perhexa TMH, immersed in an oil bath at 100 ° C., and 2.5 under a nitrogen stream. Heating was continued for hours.
After 2.5 hours, the number average molecular weight by GPC of the polymerization solution was 2430 (excluding CEA), the viscosity was 118000 mPa · s, and the epoxy equivalent was 293.

Synthesis Example 6
A 100 ml flask was charged with 30.06 g of CEA, 20.30 g of butyl acrylate and 1.50 g of Perhexa TMH, immersed in an oil bath at 100 ° C., and heated for 6 hours under a nitrogen stream.
After 6 hours, the number average molecular weight of the polymerization solution by GPC was 1470 (excluding CEA), and the epoxy equivalent was 293.

Synthesis Example 7
A 100 ml flask was charged with 30.05 g of CEA, 7.54 g of glycidyl methacrylate and 0.77 g of Perhexa TMH, immersed in an oil bath at 100 ° C., and heated for 2 hours under a nitrogen stream.
After 2 hours, the number average molecular weight by GPC (excluding CEA) was 2370, the viscosity was 87600 mPa · s, and the epoxy equivalent was 176.

Synthesis Example 8
A 100 ml flask was charged with 30.01 g of CEA, 8.01 g of vinyl benzoate and 0.78 g of Perhexa TMH, immersed in an oil bath at 100 ° C., and heated under a nitrogen stream for 2.5 hours.
After 2.5 hours, the number average molecular weight by GPC was 3000 (excluding CEA), the viscosity was 14600 mPa · s, and the epoxy equivalent was 241.

Synthesis Comparative Example 1
A 100 ml flask was charged with 40.31 g of allyl benzoate, 10.21 g of MMA, and 2.04 g of Perhexa TMH, immersed in an oil bath at 100 ° C., and heated under a nitrogen stream for 2.5 hours.
After 2.5 hours, the number average molecular weight by GPC was 3000 (excluding CEA), the viscosity was 1430 mPa · s, and the epoxy equivalent was 0.5.

Curing Test as Epoxy Resin A liquid curable polymerization solution was prepared with the formulation shown in Table 1 below, heat-cured, and measured for physical properties.

  As described above, according to the present invention, a liquid and excellent curable composition is provided. Therefore, an electrical insulating material such as an underfill material or an interlayer insulating film, an IC or VLSI sealing material, an LED sealing material. And can be used in fields such as laminates.

Claims (11)

  Viscosity at 25 ° C was changed from 10 mPa · s to 2,000,000 mPa · s by polymerizing a compound group consisting mainly of compound (a) having one (meth) allyl group and one alicyclic epoxy group. A liquid curable polymerization liquid characterized by A compound having one (meth) allyl group and one alicyclic epoxy group has the following structural formula:

{Wherein R1 to R41 represent hydrogen or an alkyl or aryl group having 1 to 8 carbon atoms. } The liquid curable polymerization liquid of Claim 1 characterized by the above-mentioned.   Furthermore, the compound group containing the (meth) allyl compound (b) and / or the monovinyl polymerizable compound (c) is polymerized, The liquid curable polymerization liquid according to claim 1 or 2 characterized by things.   The liquid curable polymerization solution according to any one of claims 1 to 3, wherein an epoxy equivalent is 150 to 2,000.   A compound group consisting mainly of the compound (a) having one (meth) allyl group and one alicyclic epoxy group, a temperature range of −10 to + 50 ° C. of the 10-hour half-life temperature of the radical polymerization initiator used. A method for producing a liquid curable polymerization liquid, characterized in that polymerization is carried out in   6. The liquid curable polymerization liquid according to claim 5, wherein the radical polymerization initiator is at least one selected from peroxydicarbonate, peroxymonocarbonate, peroxyketal and dialkyl peroxide. Method.   A compound group mainly composed of a compound (a) having one (meth) allyl group and one alicyclic epoxy group, and having an oxygen concentration of 5% or more in a gas stream of 100 ° C. or more and 300 ° C. or less A method for producing a liquid curable polymerization liquid, characterized by performing polymerization at a temperature.   The liquid curable composition according to any one of claims 5 to 7, further comprising polymerizing a compound group including the (meth) allyl compound (b) and / or the monofunctional vinyl polymerizable compound (c). A method for producing a polymerization solution.   The thermosetting resin composition characterized by containing 0-100 mass parts of liquid epoxy resins with respect to 100 mass parts of liquid curable polymerization liquids in any one of Claims 1-4.   Containing 0.01 to 3 parts by mass of a cationic curing agent and 0 to 4 parts by mass of a radical initiator for a total of 100 parts by mass of the liquid curable polymerization solution according to any one of claims 1 to 4 and the liquid epoxy resin The thermosetting resin composition according to claim 9, wherein:   The acid anhydride is added in an amount of 0.7 to 1 mol of the epoxy group in the liquid curable polymerization liquid with respect to 100 parts by mass in total of the liquid curable polymerization liquid and the liquid epoxy resin according to claim 1. The thermosetting resin composition according to claim 9, wherein 1.5 thermoequivalents are used, and further 0 to 6 parts by mass of a curing accelerator and 0 to 4 parts by mass of a radical initiator are contained.