JP6332614B2 - Curable resin composition - Google Patents

Description

The present invention relates to a curable resin composition capable of achieving both a high glass transition temperature (Tg) of a cured product and storage stability when uncured.

Conventionally, various curable resin compositions having high heat resistance have been used in applications such as mounting of electronic materials, sealing of internal combustion engines, and adhesion, coating, filling, and the like to members having a large heat load. As the curable resin composition, an epoxy resin composition is most commonly used, but in order to increase the heat resistance of the epoxy resin composition, a method of increasing the glass transition temperature (Tg) of the cured product. In that case, it is essential to formulate a filler in the composition, and as a result, the workability is lowered due to the increase in viscosity, or the transparency is impaired, so that it is applied to applications where transparency is required. The evil that it was not possible occurred.

In order to solve such a problem, Patent Document 1 proposes a curable resin composition comprising a cyanate ester compound, an epoxy resin, a metal complex catalyst, and the like as a material used for fixing in the electric / electronic field. The curable resin composition containing the cyanate ester compound is liquid at normal temperature, and the Tg of the cured product is a good value. However, in the composition, there is no mention of storage stability due to the reactivity of cyanate ester.

On the other hand, Patent Document 2 attempts to improve stability by using a composition comprising a triazine ring-containing compound and an epoxy resin, which are compounds obtained by reacting a cyanate ester in advance. . However, in the composition, the use of the triazine ring-containing compound makes the viscosity very high, so that the handleability is lowered and Tg cannot be sufficiently increased.

Patent Document 3 discloses a curable resin composition used for insulation of a circuit board and the like, which is composed of an epoxy resin such as a cyanate ester compound and an alicyclic epoxy, a metal compound catalyst, and the like. However, the composition contains the above components for the purpose of improving electrical characteristics such as dielectric constant and dielectric loss tangent, and there is no mention of Tg or storage stability.

Patent Document 4 discloses an insulating composition comprising a cyanate ester compound such as a novolak type, an epoxy resin, a metal catalyst, and the like. However, the purpose of including the above components in the composition is to increase Tg and improve heat resistance, and there is no mention of storage stability.

Patent Document 5 discloses a fluxing composition containing a cyanate ester and an epoxy resin as a thermosetting resin and further containing a compound selected from various metal acetoacetonates (including titanium acetoacetonate) as a transition metal catalyst. ing. However, the use of the cyanate ester in the composition is only for the purpose of being sensitive to acidic conditions, and the addition amount aims at a secondary action less than the epoxy resin. Moreover, although titanium acetoacetonate is mentioned as an example as a metal catalyst, there is no mention of showing a special effect as compared with other metal acetoacetonates arranged in the same row.

JP 2010-254838 A JP 2001-206931 A JP 2003-138133 A JP 2002-338786 A JP 2006-334669 A

As described above, when a curable resin composition containing a cyanate ester compound is used for the purpose of improving Tg, there is a possibility that there is a problem in terms of storage stability.

Accordingly, the present invention has been made in order to solve the above-mentioned problems, and is a curable resin composition having a low viscosity characteristic in an uncured state, a good storage stability, and a high Tg characteristic of a cured product. It came to complete the invention regarding a thing.

The gist of the present invention will be described in detail below.
The first embodiment of the present invention is a curable resin composition comprising the following components (A) to (C).
(A) Cyanate ester compound having two or more cyanate ester groups in the molecule
(B) Epoxy resin 25 to 75 parts by mass with respect to 100 parts by mass of component (A)
(C) Titanium complex compound 0.01 to 10 parts by mass with respect to 100 parts by mass in total of the components (A) and (B)

The second embodiment relates to a curable resin composition in which the component (A) is a mixture of two and three cyanate ester groups in the molecule.

The third embodiment relates to a curable resin composition in which the component (B) is an alicyclic epoxy resin.

The fourth embodiment relates to a curable resin composition in which the component (C) is a titanium complex compound containing an acetylacetone derivative as a ligand.

The fifth embodiment relates to a curable resin composition in which the component (C) is ethoxyisopropoxybis (ethylacetoacetate) titanate.

The sixth embodiment relates to a curable resin composition for mounting an electronic component, which is used for mounting the electronic component by the curable resin composition.

INDUSTRIAL APPLICATION This invention can implement | achieve the curable resin composition which has the characteristic of the low viscosity characteristic in the uncured state and favorable storage stability, and the characteristic of high Tg of hardened | cured material.

The constituent requirements of the present invention will be described in detail below.
Component (A) used in the present invention: Any cyanate ester compound having two or more cyanate ester groups in the molecule can be appropriately selected and used. Especially in this invention, the mixture of what has two cyanate ester groups and what has three in a molecule | numerator can be used suitably. In the present invention, as the component (A), a liquid at room temperature (about 25 ° C.) can be particularly preferably used. When a liquid that is not liquid at room temperature is used, the viscosity of the composition increases, so that the workability in the coating process is reduced. Solvents may volatilize, contaminating the work environment, and traces of solvent volatilization may become blisters and pinholes, and residual stress due to shrinkage during curing may lead to reduced reliability of the cured product. There is.

Commercially available industrial products include 2,2-bis (4-cyanatophenyl) ethane (trade name: Primaset LECY) and 2,2-bis (4-cyanatophenyl) propane (trade name: Primaset) manufactured by LONZA. BADCY), 2,2-bis (4-cyanato-3,5-methylphenyl) methane (trade name: Primaset METYLCY), phenol novolac type polyfunctional cyanate ester resin (trade name: PT30), part of bisphenol A dicyanate Alternatively, a prepolymer (trade name: BA230) in which all of the triazine is converted into a trimer, 2,2-bis (4-cyanatophenyl) propane (trade name: Skylex CA200), manufactured by Mitsubishi Gas Chemical Company, Inc., 2 , 2-bis (4-cyanatophenyl) propane partially crosslinked product (trade name: 216 RX), a cyanate ester of phenol dicyclopentadiene copolymer (trade name: XU-71787-02) manufactured by Huntsman, and 10% rubber fine particles added thereto (trade name: XU-71787-07), Vantico 4,4'-ethylidenebisphenylene cyanate (trade name: AroCy L-10), hexafluorobisphenol A dicyanate (trade name: Arocy-40S), bisphenol M dicyanate (trade name: RTX-366), novolak resin Modified multifunctional cyanate ester (XU366), 2-wood phenol cyanate ester, 4-methoxyphenol cyanate ester, bisphenol A cyanate ester, 4-phenylpheno from Oakwood Products Cyanate ester, 4-cumylphenol cyanate ester, 4,4′-bisphenol cyanate ester, 2,2-bis (4-cyanatophenol) -1,1,1,3,3,3-hexafluoropropane, diallyl Bisphenol A cyanate ester, 1,1,1-tris (4-cyanatophenyl) ethane, 1,1-bis (4-cyanatophenyl) ethane, 2,2,3,4,4,5,5,6 , 6,7,7-dodecafluorooctanediol dicyanate ester and the like.

The role of the component (A) in the present invention is as a base resin for the purpose of increasing the Tg of the curable composition without adding a filler component. The cyanate ester group, which is a reactive group of the component (A), forms a triazine ring by associating three molecules intermolecularly and possibly within the molecule. Therefore, a network polymer through a triazine ring is formed by the reaction of a cyanate ester compound having two or more cyanate ester groups in the molecule. By using this component as a thermosetting resin, a cured product having a high Tg is obtained. Is known to be obtained.

(B) component used by this invention: As an epoxy resin, if it is a well-known material, ie, the compound which has an epoxy group in a molecule | numerator, it can use suitably, but it is especially fat from a viewpoint of the external appearance and storage stability of hardened | cured material. A cyclic epoxy resin can be suitably used. The alicyclic epoxy referred to in the present invention has one or more aliphatic cyclic structures in the molecule, and two carbon atoms and oxygen atoms in the aliphatic ring form a ring to form an epoxy group. If the epoxy group is contained in the molecule, it does not prevent the epoxy group having other structure from being contained in the same molecule. The number of the epoxy groups present in the molecule is not limited as long as it is 1 or more, but preferably 2 or more. Specific examples of the component (B) include 3,4-epoxycyclohexenylmethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide, bis (3,4-epoxycyclohexylmethyl) ether, 2- (3 , 4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate, allylcyclohexene dioxide, 3,4-epoxy-4-methylcyclohexyl Examples include 2-propylene oxide, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexyl) diethylsiloxane, and the like.

The purpose of adding the component (B) in the present invention is to add properties such as adhesion to the substrate, toughness of the cured product, and chemical resistance. The preferred composition amount in the present invention is preferably 25 to 75 parts by mass, more preferably 30 to 70 parts by mass, and even more preferably 35 to 60 parts by mass with respect to 100 parts by mass of the component (A). Part. If it is less than 25 parts by mass, the curable resin composition of the present invention cannot give sufficient strength to the cured product, and cannot ensure reliability by breaking due to external force. On the other hand, if it exceeds 75 parts by mass, Tg cannot be sufficiently increased, and the object of the present invention cannot be achieved. It is known that an epoxy group contained in an epoxy resin reacts with a cyanate ester group contained in the component (A) to form an oxazoline structure or an oxazolidine structure. Therefore, the increase in the composition amount of component (B) inhibits the reaction between the cyanate ester groups of component (A), resulting in the formation of a number of structures with low crosslink density, leading to a decrease in Tg. It is done.

(C) component used by this invention: As a titanium complex compound, the well-known complex compound which the ligand coordinated to titanium can be used. Specifically, diisopropoxy bis (acetyl acetate) titanate, diisopropoxy bis (methyl acetyl acetate) titanate, diisopropoxy bis (ethyl acetyl acetate) titanate, diethoxy bis (acetyl acetate) titanate, diethoxy bis (methyl acetyl acetate) Titanate, diethoxybis (ethylacetylacetate) titanate, di-n-butoxybis (acetylacetate) titanate, di-n-butoxybis (methylacetylacetate) titanate, di-n-butoxybis (ethylacetylacetate) titanate, ethoxyisopropoxybis ( Acetoacetate) titanate, ethoxyisopropoxybis (methylacetoacetate) titanate, ethoxyisopropoxybis (ethyl Cetoacetate) titanate, di-n-butoxybis (triethanolamine) titanate, dihydroxybis (lactideside) titanate, tetraoctylene glycol titanate, diisopropoxybis (ethyl acetoacetate) titanate, ethyl acetoacetate aluminum diisopropylate And aluminum tris (ethyl acetoacetate). In the present invention, a titanium complex compound containing an acetylacetone derivative as a ligand can be preferably used, and ethoxyisopropoxybis (ethylacetoacetate) titanate can be particularly preferably used.

The purpose of the addition of the component (C) in the present invention is a curing catalyst for the components (A) and (B) of the present invention, and particularly for improving the storage stability of the composition in an uncured state. . Although it has been conventionally known that a metal complex compound can be used as a curing catalyst for both the components (A) and (B), particularly by selecting titanium as a complex metal, the storage stability is remarkably improved. It was the greatest feature of the present invention that it could be achieved. Although the detailed mechanism of the storage stability by the component is not clear, when a metal complex compound outside the scope of the present invention is used as a curing agent for a composition containing both the components (A) and (B), Immediately after production or during storage for 1 week to 1 month at room temperature, the stability is impaired, but this is dramatically improved by using the titanium complex compound (C) of the present invention. It is. The storage stability as referred to in the present invention means the presence or absence of occurrence of precipitation, gelation or significant discoloration when an uncured composition is stored for 1 week to 1 month in a room temperature environment.

The preferred composition amount of the component (C) in the present invention is desirably 0.01 to 10 parts by mass with respect to a total of 100 parts by mass of the components (A) and (B), more preferably It is 0.03-5 mass parts, More preferably, it is 0.05-3 mass parts. If it is less than 0.01 part by mass, the composition of the present invention cannot be sufficiently cured, and if it is 10 parts by mass or more, the reactivity is too high and the object of the present invention cannot be achieved. .

Furthermore, in the present invention, in addition to the components (A) to (C), a component for imparting appropriate characteristics to the composition may be further added within a range not impairing the effects of the present invention. For example, reactive or non-reactive diluents, anti-aging agents, thickeners, surfactants, tackifiers, flame retardants, stabilizers, pigments, dyes and other colorants, metal powder, calcium carbonate, talc, Additives such as inorganic fillers such as silica, alumina and aluminum hydroxide, organic fillers, flame retardants, plasticizers, antifoaming agents, leveling agents, rheology control agents and coupling agents can be selected.

EXAMPLES Hereinafter, although this invention is further explained in full detail based on an Example, this invention is not limited to these Examples at all.

[Evaluation method]
The characteristics of the curable resin compositions used in the examples were evaluated by the following methods.

[Viscosity characteristics]
The viscosity characteristics of the composition were evaluated under the following conditions in an environment of 25 ° C.
・ Measuring device: VISCOMETER TV-33 manufactured by Toki Sangyo Co., Ltd.
・ Cone: 1 ° 34 '× R24
・ Rotation speed: 20rpm / 3min
The measured value under the above conditions was rounded to one digit and used as an evaluation value in units of 100 mPa · s.

[Glass-transition temperature]
The glass transition temperature of the composition was evaluated under the following conditions in an environment of 25 ° C.
-Measuring device: Thermo Plus TMA8310, manufactured by Rigaku Corporation
・ Temperature range: -50 ~ 300 ℃
・ Temperature setting: 10 ° C / min
The composition was poured into a cylindrical shape having a diameter of 5 mm and heated at 120 ° C. × 15 min + 150 ° C. × 30 min as curing conditions to prepare a cured product. Under the above conditions, the measurement was performed twice in the tension mode, and the glass transition temperature (° C.) was calculated from the point where the slope of the dimensional change signal in the second measurement changed. Based on the measured value in Example 1, which is 212 ° C., a measured value that is equal to or higher than this value is indicated as “good”, and a measured value that is less than this value is indicated as “failed”. did.

[Storage stability]
The viscosity of the composition was evaluated under the following conditions.
The prepared composition was sealed in a transparent glass bottle and allowed to stand in a 25 ° C. environment. 30 minutes after standing, “30 min” for 1 week, “1 week” for 1 week, and “1 month” for 1 month. Visually check each sample and check for the presence of precipitates, gels, significant discoloration, etc. in the liquid. Is indicated by x as defective.

[Preparation of curable resin composition]
Each composition used in the examples is prepared by the following materials, and the components (A) and (B) are uniformly mixed and stirred in advance, and then the component (C) is added, mixed and stirred. did. The formulation of each composition evaluated in Examples and Comparative Examples is shown in Table 1 on a mass basis.

(A) Component · LECY: 1,1-bis (4- cyanatophenyl ) ethane, product name Primaset LECY, product of LONZA · PT-30: phenol novolac-type cyanate ester resin, hydroxyl group of novolac resin with cyanate ester group , Product name Primaset PT-30, product (B) component of LONZA Corporation, OC1005: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trade name OMNI LANE OC1005 , I.C. G. M.M. Resins product (C) component AA-105: bis (acetylacetonato) (ethoxyisopropoxy) titanium , trade name Tyzor AA-105, Dupont product comparison (C) component Indicated as (C ') in the table V -acac: vanadium acetylacetonate, reagents · Cu-AcAc: acetylacetonate copper reagent _{· Ni-AcAc · 2H 2 O} : acetylacetone nickel dihydrate, reagent · Co-AcAc: acetylacetonate cobalt reagent · Zr-AcAc: acetylacetone zirconium, reagent

In the examples included in the technical scope of the present invention, it was confirmed that the storage stability at normal temperature was good and the storage stability was not impaired during one month. On the other hand, when a complex compound other than titanium is used as the component (C) outside the technical scope of the present invention, a failure occurs at the time of “30 min” at an early stage, and at least at the time of “1 week”. It was confirmed that defects occurred. In Example 2, since the composition amount of the component (B) was small and the dilution action was small, the viscosity value was slightly increased. In Example 3, the composition amount of the component (B) was large, and a decrease in the Tg value that was attributed to a decrease in the degree of crosslinking of the cured product was observed.

The curable resin composition of the present invention is capable of realizing a high glass transition temperature without containing a filler, and has good storage stability of the composition in an uncured state at room temperature, and excellent handleability. is there. Therefore, as a material suitable for mounting, adhesion, filling, coating, etc. of highly exothermic members such as electric elements, it is difficult to realize with conventional cyanate ester compositions as curable resin compositions. It is a useful thing that can be expanded.

Claims (5)

A curable resin composition comprising the following components (A) to (C):
(A) Cyanate ester compound (B) epoxy resin having two or more cyanate ester groups in the molecule 25 to 75 parts by mass of (C) acetylacetone derivative as a ligand with respect to 100 parts by mass of component (A) Titanium complex compound 0.01 to 10 parts by mass with respect to 100 parts by mass in total of the components (A) and (B). A curable resin composition comprising the following components (A) to (C):
(A) Cyanate ester compound (B) epoxy resin having two or more cyanate ester groups in the molecule 25 to 75 parts by mass (C) bis (acetylacetonate) (ethoxy ) per 100 parts by mass of component (A) Isopropoxy) titanium 0.01 to 10 parts by mass with respect to 100 parts by mass in total of the components (A) and (B). The curable resin composition according to claim 1 or 2, wherein the component (A) is a mixture of two and three cyanate ester groups in the molecule. The curable resin composition according to any one of claims 1 to 3, wherein the component (B) is an alicyclic epoxy resin. The curable resin composition according to any one of claims 1 to 4, wherein the curable resin composition is used for electronic component mounting .