JP2015117375A - Allylphenol novolac resin composition, cured product obtained by curing the same, method for producing cured product, and fiber-reinforced resin molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an improved easily-handleable allyl phenol novolak resin composition having a low viscosity, curable at a low temperature, and excellent in a mechanical characteristic of a cured product thereof, heat resistance and low expansion property; and to provide a cured product obtained by curing the same, a production method of a cured product, and a fiber-reinforced resin molding.SOLUTION: An allyl phenol novolak resin composition contains an allyl phenol novolak resin and a bismaleimide compound. In the allyl phenol novolak resin composition, the allyl phenol novolak resin is a liquid having a viscosity of 10 Pa s or lower at 25°C, and the ratio between an allyl group equivalent number of the allyl phenol novolak resin and a maleimide group equivalent number of the bismaleimide compound [maleimide group equivalent number/allyl group equivalent number] is in the range of 0.85-1.30.

Description

  The present invention relates to an improved allylphenol novolac resin composition containing an allylphenol novolac resin and a bismaleimide compound as a curing agent thereof. In particular, the present invention is an improved allylphenol novolak resin composition that has low viscosity, is easy to handle, can be cured at low temperatures, and has excellent mechanical properties, heat resistance, low expansion properties, etc. , A cured product obtained by curing the cured product, a method for producing the cured product, and a fiber-reinforced resin molded body.

As a heat-resistant matrix resin of a fiber reinforced composite material, a resin using a bismaleimide compound as a main ingredient is known. However, the bismaleimide compound alone has poor curability and the molded product becomes brittle.
For this reason, for example, Kelimide resin (Rhône-Poulenc, France) uses 4,4′-diphenylmethane bismaleimide with a chain extender such as methylene dianiline to reduce the crosslinking density due to polymerization of maleimide. Yes. Since this resin is generally solid, it is difficult to impregnate fibers. Matrimid resin (Ciba-Geigy) is a resin obtained by heating, melting and mixing 4,4′-diphenylmethane bismaleimide and o, o′-diallylbisphenol A. This resin has a problem that a maleimide component precipitates at room temperature, and mechanical properties and heat resistance are not sufficient.

Patent Document 1 discloses a method for producing a crosslinked polymer containing an imide group by reacting a bismaleimide compound with an alkenylphenol such as o, o′-diallylbisphenol A.
In Patent Document 2, in order to improve toughness and workability, bismaleimide or a bisphenol obtained by adding allylphenol novolac as a reactive diluent to bismaleimide and a chain extender such as methylenedianiline or aminophenol. Maleimide-containing thermosetting compositions have been proposed. However, here, allylphenol novolak was used as a reaction diluent, and as a specific example, an example in which bismaleimide and allylphenol novolak were used at 50:50 (weight: weight) (Example 2). ) Is only disclosed.

  Phenol novolac resins are usually cured using a curing agent such as hexamethylenetetramine. Phenol novolac resins are also suitably used as curing agents for epoxy resins. However, detailed studies have not been made on curing phenol novolac resins using bismaleimide compounds as curing agents.

JP-A-52-994 JP-A-2-110158

  The present invention is an improved allylphenol novolac resin composition that has low viscosity, is easy to handle, can be cured at low temperatures, and is excellent in mechanical properties, heat resistance, low expansion, etc. of the cured product, It is to propose a cured product obtained by curing the cured product, a method for producing the cured product, and a fiber-reinforced resin molded product.

The present invention relates to the following matters.
1. An allylphenol novolak resin composition comprising an allylphenol novolak resin and a bismaleimide compound, wherein the allylphenol novolac resin is a liquid having a viscosity of 10 Pa · s or less at 25 ° C., and the number of allyl group equivalents of the allylphenol novolak resin. The allylphenol novolak resin composition, wherein the ratio of the number of maleimide group equivalents of the bismaleimide compound [number of maleimide group equivalents / allyl group equivalent number] is in the range of 0.85 to 1.30.
2. 2. The allylphenol novolak resin composition according to item 1, wherein the allylphenol novolak resin is represented by the following chemical formula (1).

（式中、ｎは０〜２０の整数である。）
３． ビスマレイミド化合物が脂肪族環状構造及び／又は芳香族環状構造を有するビスマレイミド化合物であることを特徴とする前記項１又は２に記載のアリルフェノールノボラック樹脂組成物。
４． アリルフェノールノボラック樹脂とビスマレイミド化合物とが３０〜１５０℃の温度で均一に溶融混合されたものであることを特徴とする前記項１〜３のいずれかに記載のアリルフェノールノボラック樹脂組成物。
５． さらに、ラジカル開始剤を含有することを特徴とする前記項１〜４のいずれかに記載のアリルフェノールノボラック樹脂組成物。

(In the formula, n is an integer of 0 to 20.)
3. Item 3. The allylphenol novolak resin composition according to Item 1 or 2, wherein the bismaleimide compound is a bismaleimide compound having an aliphatic cyclic structure and / or an aromatic cyclic structure.
4). Item 4. The allylphenol novolac resin composition according to any one of Items 1 to 3, wherein the allylphenol novolac resin and the bismaleimide compound are uniformly melt-mixed at a temperature of 30 to 150 ° C.
5. The allylphenol novolak resin composition according to any one of Items 1 to 4, further comprising a radical initiator.

6). Hardened | cured material obtained by heat-processing the allyl phenol novolak resin composition in any one of said items 1-5.
7). 6. A fiber reinforced resin molded article, wherein the matrix resin comprises the allylphenol novolac resin composition according to any one of Items 1 to 5.
8). Item 6. A method for producing a cured product, wherein the allylphenol novolak resin composition according to any one of Items 1 to 5 is heat-treated at a temperature of 150 to 280 ° C to obtain a cured product.

According to the present invention, it is easy to handle with low viscosity and can be cured at a low temperature. The cured product has mechanical properties, heat resistance (for example, glass transition temperature of 255 ° C. or higher), low expansion (low expansion). An improved allylphenol novolak resin composition, a cured product obtained by curing it, a method for producing the cured product, and a fiber-reinforced resin molded product can be obtained.
In other words, the allylphenol novolak resin composition of the present invention can be made highly fluidized simply by heating to a relatively low temperature of about 30 to 110 ° C., so that handling such as impregnation into fibers is extremely easy. Curing at about 150 to 280 ° C. is also possible, and the cured product is excellent in mechanical properties, heat resistance, low expansibility and the like. Therefore, the allylphenol novolac resin composition of the present invention can be used very suitably as a matrix resin for obtaining a fiber-reinforced resin molded article.

2 is a chart obtained by measuring the fluidity of the allylphenol novolac resin composition obtained in Example 1. FIG. 10 is a chart obtained by measuring dynamic viscoelasticity of a laminate obtained in Example 9.

The allylphenol novolak resin used in the allylphenol novolak resin composition of the present invention is not particularly limited as long as it is a phenol novolak resin containing an allyl group as a substituent, but preferably phenols containing allylphenol and formaldehyde (formaldehyde) An allylphenol novolac resin obtained by reacting a chemical substance as a source) in the presence of an acidic catalyst. In addition, as allylphenol, o-allylphenol is particularly used because the fluidity and reactivity of the resulting allylphenol resin composition are excellent, such as mechanical properties, heat resistance, and low expansibility of the resulting cured product. Is preferred.
That is, the allylphenol novolak resin of the present invention is preferably an allylphenol novolak resin represented by the chemical formula (1) prepared using o-allylphenol and formaldehyde.

In the allylphenol novolak resin composition of the present invention, a liquid allylphenol novolak resin having a viscosity of 10 Pa · s or less at 25 ° C. is used. When an allylphenol novolak resin that is solid at 25 ° C. is used, melt mixing is physically difficult when preparing a composition by melt mixing with a bismaleimide compound. If it is heated too much to reduce the viscosity, the curing reaction may proceed. Even if a composition is obtained, such a composition cannot be fluidized unless heated to a relatively high temperature. For example, when impregnating fibers, unimpregnated parts are formed or bubbles are involved. Easy to handle.
The allylphenol novolak resin used in the allylphenol novolak resin composition of the present invention is a liquid having a viscosity of 10 Pa · s or less at 25 ° C., preferably 5.0 Pa · s or less, more preferably 3.0 Pa at 25 ° C.・ Liquid in a liquid state of s or less, more preferably 2.0 Pa · s or less. By using such a low-viscosity allylphenol novolac resin, the allylphenol novolak resin composition of the present invention can be easily prepared by melt mixing, and is, for example, 110 ° C. or less, preferably 100 ° C. or less, More preferably, the fluidity can be increased simply by heating to a relatively low temperature such as 90 ° C. or less, more preferably 80 ° C. or less, and particularly preferably 70 ° C. or less.
The allyl group equivalent of the allylphenol novolak resin of the present invention is not particularly limited, but is preferably in the range of 100 to 300 g / eq.

The bismaleimide compound used in the allylphenol novolak resin composition of the present invention is not particularly limited as long as it is a compound containing two maleimide groups in the molecule. For example, 1,6-bismaleimide- (2,2,4-trimethyl) hexane, 1,6-bismaleimide- (2,4,4-trimethyl) hexane, N, N′-decamethylene bismaleimide, The skeleton of the compound is aliphatic (non-N, N′-octamethylene bismaleimide, N, N′-hexamethylene bismaleimide, N, N′-trimethylene bismaleimide, N, N′-ethylene bismaleimide, etc. Cyclic) structure, but bis [(2,5-dioxo-2,5-dihydropyrrol-1-yl) methyl] bicyclo [2.2.1] heptane, N, N′-m-phenylene Bismaleimide, 4,4′-diphenylmethane bismaleimide, 4,4′-diphenyl ether bismaleimide, 4,4′-diphenylsulfone bismaleimide, 4,4′-diphenylsulfate Fido bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,3-phenylene bismaleimide, 2,2'-bis [4- (4-maleimidophenoxy) phenyl] propane, 3,3'-dimethyl- 5,5′-diethyl-4,4′-diphenylmethane bismaleimide, 3,3′-dimethyl-4,4′-diphenylmethane bismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, 1,3-bis The skeleton of the compound such as (4-maleimidophenoxy) benzene or 1,3-bis (3-maleimidophenoxy) benzene may have an aliphatic cyclic structure or an aromatic cyclic structure.
Among them, bis [(2,5-dioxo-2,5-dihydropyrrol-1-yl) methyl] bicyclo [2.2.1] heptane, 1,6-bismaleimide- (2,2,4-trimethyl) A compound selected from the group consisting of hexane and N, N′-hexamethylene bismaleimide, preferably having a skeleton of an aliphatic (non-cyclic) structure, or 4,4′-diphenylmethane bismaleimide, 4,4 ′ -Diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 4,4'-diphenyl sulfide bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,3-phenylene bismaleimide, 2,2'- Bis [4- (4-maleimidophenoxy) phenyl] propane, 1,3-bis (4-maleimidophenoxy) benzene, 1, - selected from the group consisting of bis (3-maleimido phenoxy) benzene, the skeleton of the compound is preferably those having an aliphatic cyclic structure or aromatic ring structure.
In the present invention, one type of bismaleimide compound may be used alone, but two or more types of bismaleimide compounds may be mixed and used. From the viewpoint of improving heat resistance, a bismaleimide compound in which the skeleton of the compound has an aliphatic cyclic structure or an aromatic cyclic structure is preferable.

In the allylphenol novolak resin composition of the present invention, the ratio of the number of allyl group equivalents of the allylphenol novolak resin and the number of maleimide group equivalents of the bismaleimide compound [maleimide group equivalent number / allyl group equivalent number] is 0.85. The range is 1.30, preferably 0.85 to 1.20, more preferably 0.85 to 1.15.
When this ratio is smaller than the above range, the heat resistance (glass transition temperature) and expandability (linear expansion coefficient) of the cured product are not sufficient. On the other hand, if this ratio is larger than the above range, it is a problem of conventionally known bismaleimide compounds, the fluidity is poor and the handling becomes difficult, the curing at low temperature is not easy, and the cured product obtained The toughness and the like are lowered and become brittle. For example, it becomes difficult to use as a matrix resin of a fiber reinforced resin molded product.

  In addition, the number of functional group equivalents such as the number of maleimide group equivalents and the number of allyl group equivalents is B / A (in the case where the functional group equivalent of the compound is A (g / eq) and the charge amount is B (g). When the purity of the compound is C%, it can be obtained by [B × C / 100] / A). That is, functional group equivalents such as maleimide group equivalent and allyl group equivalent represent the molecular weight of the compound per functional group, and the number of functional group equivalents refers to the number of functional groups per equivalent (preparation amount) of compound (equivalent weight). Number).

The allylphenol novolak resin composition of the present invention can obtain a cured product suitably by heat treatment without using a radical initiator or a curing accelerator, but contains a radical initiator as necessary. Also good. The radical initiator makes it possible to stably obtain a cured product having excellent characteristics by heat treatment at a relatively low temperature. The radical initiator may be a conventionally known one, such as acyl peroxide, hydroperoxide, ketone peroxide, organic peroxide having t-butyl group, peroxide having cumyl group, etc. An organic peroxide etc. can be mentioned. Specific examples include, but are not limited to, benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, lauroyl peroxide, di-t-butyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, cumene hydroperoxide. Preferable examples include oxide and dicumyl peroxide.
Although the usage-amount of a radical initiator is not specifically limited, It is 0.1-8 mass parts with respect to 100 mass parts of allyl phenol novolak resins, Preferably it is 1-6 mass parts.

The allylphenol novolak resin composition of the present invention can further use a curing accelerator. Examples of the curing accelerator include 2-ethyl-4-methylimidazole, 2-n-undecylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-methyl-2-methylimidazole. Preferred examples include imidazoles such as 1-isobutyl-2-methylimidazole.
Although the usage-amount of a hardening accelerator is not specifically limited, It is 0.01-5 mass parts with respect to 100 mass parts of allyl phenol novolak resins, Preferably it is 0.1-2 mass parts.

  In the allylphenol novolak resin composition of the present invention, additives such as inorganic or organic fillers, coupling agents, pigments, and dyes can be suitably used as necessary. An organic solvent can also be used.

The allylphenol novolak resin composition of the present invention comprises a liquid allylphenol novolak resin and a normally bismaleimide compound, a ratio of the number of allyl group equivalents of the allylphenol novolak resin and the number of maleimide group equivalents of the bismaleimide compound. [Maleimide group equivalent number / allyl group equivalent number] is blended so as to be in the range of 0.85 to 1.30, and the curing reaction does not substantially proceed at 30 to 150 ° C, preferably 50 to 140 ° C, more preferably. Can be suitably obtained by relatively melt-mixing with stirring at a relatively low temperature of 70 to 130 ° C. Although mixing time is not specifically limited, Preferably it is 0.1 to 5 hours, More preferably, it is about 0.2 to 2 hours. The allylphenol novolak resin composition of the present invention obtained by melt mixing usually solidifies when cooled to room temperature, but the bismaleimide compound does not precipitate.
Even when the allylphenol novolak resin composition of the present invention is solidified by cooling to room temperature after melt mixing, it is 30 ° C or higher, preferably 40 ° C or higher, more preferably 50 ° C or higher, and 110 ° C or lower, preferably It is easily fluidized at a relatively low temperature of 100 ° C. or less, more preferably 90 ° C. or less, still more preferably 80 ° C. or less, and particularly preferably 70 ° C. or less. For this reason, handling is very easy.
In addition, when melt mixing, a radical initiator, a curing accelerator, a filler, an additive, and the like can be blended together as necessary.

  The allylphenol novolak resin composition of the present invention can be suitably obtained as a cured product by heat treatment. The heat treatment is affected by the presence or absence of a radical initiator or a curing accelerator, but is preferably 150 to 280 ° C, more preferably 150 to 250 ° C, preferably 1 to 24 hours, more preferably 1 to 12 hours, It is good to carry out under normal pressure or under pressure using an autoclave. In particular, it is preferable that the temperature conditions include post-cure while raising the temperature stepwise. The maximum temperature of the heat treatment is preferably 150 to 200 ° C. when it contains a radical initiator or a curing accelerator, more preferably 150 to 180 ° C., and no radical initiator or curing accelerator is contained. 200-250 degreeC is preferable and the range of 200-240 degreeC is more suitable.

By using the allylphenol novolac resin composition of the present invention as a matrix resin, it is possible to suitably obtain a fiber-reinforced resin molded body by combining with a reinforcing fiber such as carbon fiber, glass fiber, alumina fiber, boron fiber, or aramid fiber. it can.
The compounding means may be a conventionally known method. The method for impregnating the reinforcing fiber with the allylphenol novolak resin composition of the present invention is not particularly limited, but a method that does not use a solvent is preferable, and the allylphenol novolak resin composition of the present invention is preferably 30 to 110 ° C., preferably 40 It is suitable to impregnate in a state of high fluidization by heating to a relatively low temperature of -100 ° C, more preferably 50-90 ° C, further preferably 50-80 ° C, particularly preferably 50-70 ° C. .
The prepreg obtained by impregnating the reinforcing fiber with the allylphenol novolak resin composition of the present invention is usually 20 to 80% by mass, preferably 25 to 65% by mass, more preferably 30 to 50% by mass of allylphenol novolak resin. Contains the composition.
The prepreg can be cured by a known method to obtain a fiber reinforced resin molded product. For example, a fiber reinforced resin molded article can be suitably obtained by laminating a predetermined number of prepregs, pressurizing for 15 minutes with a hot press machine heated to 170 ° C., and then heat-treating at 200 ° C. for 90 minutes under normal pressure. it can. Also, for example, a predetermined number of prepregs are laminated, pressurized to ² to 10 kg / cm ² in an autoclave, 150 ° C. for 2 hours and then 175 ° C. for 3 hours, or 150 ° C. for 2 hours and then 175 ° C. for 3 hours. Next, a fiber-reinforced resin molded article can be suitably obtained by heat treatment at 230 ° C. for 4 hours.

  The allylphenol novolak resin composition of the present invention can be suitably used in various applications such as a sealing material, a molding material, and an adhesive material.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

A method for measuring the characteristics used in the following examples is shown below.
(1) Viscosity The viscosity of allylphenol novolak was measured using a TVH type E type viscometer manufactured by Toki Sangyo Co., Ltd.
(Measurement condition)
Measurement temperature: 25 ° C
Sample volume: 1.2 mL

(2) Fluidity The fluidity of the melt-mixed sample was evaluated using a Koka flow tester CFT-500 manufactured by Shimadzu Corporation. As a guideline for evaluating the fluidity, a temperature at which the fluidity became high and the stroke reached 15 mm was used. Note that the temperature at which the stroke reaches 15 mm corresponds to the temperature at which the sample rapidly fluidizes.
(Measurement condition)
Temperature rising condition: 3 ° C./min Sample amount: 1.2 g
Die hole diameter: 0.5 mm
Die length: 10.0mm
Atmosphere: In the air

(3) Glass transition temperature (DMA method (tensile method))
The obtained cured product was cut into a shape having a thickness of 1 to 1.5 mm, a width of 4 mm, and a length of 40 to 50 mm to obtain a test piece. The storage elastic modulus of the test piece was measured under the following conditions using a dynamic viscoelasticity measuring device RSA-G2 manufactured by TA Instruments. The glass transition temperature was defined as the temperature at the intersection where the two linear portions of the storage elastic modulus change curve were extended.
(Measurement condition)
Temperature rising condition: 3 ° C / min Measurement upper limit: 400 ° C
Atmosphere: In the air

(4) Flexural strength and flexural modulus The obtained cured product was cut into a shape of 4 mm thickness x 6 mm width x 80 mm length to obtain a test piece. The stress and elastic modulus by the three-point bending test of the test piece were measured under the following conditions using a universal testing machine with a thermostatic bath manufactured by A & D.
(Measurement condition)
Test speed: 2 mm / min Distance between fulcrums: 60 mm
Atmosphere: 25 ° C

(5) Linear expansion rate The obtained cured product was cut into a shape of thickness 10 mm × width 4 mm × length 6 mm to obtain a test piece. The linear expansion coefficient in the temperature range below the glass transition temperature of the test piece was measured under the following conditions using TA-600 manufactured by Shimadzu Corporation.
(Measurement condition)
Temperature rising condition: 3 ° C / min Measurement upper limit: 400 ° C
Atmosphere: Under nitrogen flow of 30 mL / min

(6) 5% mass reduction temperature (measurement conditions)
Equipment: TG-DTA manufactured by Shimadzu Corporation
Temperature rising condition: 10 ° C / min Measurement upper limit: 500 ° C
Sample amount: 10 mg
Atmosphere: under nitrogen flow of 55 mL / min

The materials used in the following examples are shown below.
(1) Bismaleimide compound BMI-1000 4,4′-diphenylmethane bismaleimide (N, N′-diphenylmethane bismaleimide or 4,4′-bismaleimide diphenylmethane) manufactured by Daiwa Kasei Kogyo Co., Ltd., represented by the following chemical formula And purity: 92.8% by mass.

(2) o, o′-diallylbisphenol A
DABPA (purity: 90.7 mass%) manufactured by Daiwa Kasei Kogyo Co., Ltd. represented by the following chemical formula, an allyl group equivalent of 154 g / eq, and a high-viscosity liquid having a viscosity of 20.8 Pa · s at 25 ° C. Using.

(3) Allylphenol novolac resin A
The allylphenol novolak resin represented by the chemical formula (1) was used in a liquid form having a hydroxyl group equivalent of 141 g / eq, an allyl group equivalent of 141 g / eq, and a viscosity at 25 ° C. of 1.7 Pa · s.

(4) Allylphenol novolac resin B
The allylphenol novolak resin represented by the chemical formula (1) was used in a liquid form having a hydroxyl group equivalent of 144 g / eq, an allyl group equivalent of 144 g / eq, and a viscosity at 25 ° C. of 2.4 Pa · s.

(5) Radical initiator (dicumyl peroxide)
Park Mill D (purity: 99.9 mass%) manufactured by NOF Corporation, represented by the following chemical formula, was used.

[Example 1]
23.4 g of allylphenol novolac resin A was heated and stirred at 130 ° C., 36.6 g of 4,4′-diphenylmethane bismaleimide was added in several portions, and the mixture was melt-mixed while stirring. The mixture was stirred until 4,4′-diphenylmethane bismaleimide was completely melted and mixed air bubbles disappeared to obtain an allylphenol novolac resin composition.
The fluidity of this composition was measured. The results are shown in Table 1. The measured chart is shown in FIG.
The obtained allylphenol novolak resin composition was degassed in vacuum, then poured into a mold, and heat treated at 150 ° C. for 2 hours, 175 ° C. for 3 hours, and then at 230 ° C. for 4 hours. A cured product of 4 mm × width 60 mm × length 150 mm was obtained.

[Example 2]
25.0 g of allylphenol novolak resin A was heated and stirred at 130 ° C., 35.0 g of 4,4′-diphenylmethane bismaleimide was added in several portions, and the mixture was melted and mixed with stirring. The mixture was stirred until 4,4′-diphenylmethane bismaleimide was completely melted and mixed air bubbles disappeared to obtain an allylphenol novolac resin composition.
The obtained allylphenol novolak resin composition was degassed in vacuum, then poured into a mold, and heat treated at 150 ° C. for 2 hours, 175 ° C. for 3 hours, and then at 230 ° C. for 4 hours. A cured product of 4 mm × width 60 mm × length 150 mm was obtained.

Example 3
23.4 g of allylphenol novolac resin A was heated and stirred at 130 ° C., 36.6 g of 4,4′-diphenylmethane bismaleimide was added in several portions, and the mixture was melt-mixed while stirring. The mixture was stirred until 4,4′-diphenylmethane bismaleimide was completely melted and mixed air bubbles disappeared. Further, 1.0 g of dicumyl peroxide was added and stirred to obtain an allylphenol novolac resin composition.
The obtained allylphenol novolak resin composition was degassed in vacuum, then poured into a mold, and heat-treated at 150 ° C. for 2 hours and then at 175 ° C. for 3 hours to obtain a thickness of 4 mm × width of 60 mm × length. A cured product having a thickness of 150 mm was obtained.

Example 4
The allylphenol novolak resin composition obtained in the same manner as in Example 3 was degassed in vacuum, and then poured into a mold, which was cast at 150 ° C. for 2 hours, at 175 ° C. for 3 hours, and then at 230 ° C. for 4 hours. A cured product having a thickness of 4 mm, a width of 60 mm, and a length of 150 mm was obtained by heat treatment.

Example 5
23.8 g of allylphenol novolac resin B was heated and stirred at 130 ° C., 36.2 g of 4,4′-diphenylmethane bismaleimide was added in several portions, and the mixture was melt-mixed while stirring. The mixture was stirred until 4,4′-diphenylmethane bismaleimide was completely melted and mixed air bubbles disappeared to obtain an allylphenol novolac resin composition.
The fluidity of this composition was measured. The results are shown in Table 1.
The obtained allylphenol novolak resin composition was degassed in vacuum, then poured into a mold, and heat-treated at 150 ° C. for 2 hours and then at 175 ° C. for 3 hours to obtain a thickness of 4 mm × width of 60 mm × length. A cured product having a thickness of 150 mm was obtained.

Example 6
The allylphenol novolak resin composition obtained in the same manner as in Example 5 was vacuum degassed and then poured into a mold, and the mixture was cast at 150 ° C. for 2 hours, 175 ° C. for 3 hours, and then at 230 ° C. for 4 hours. A cured product having a thickness of 4 mm, a width of 60 mm, and a length of 150 mm was obtained by heat treatment.

Example 7
23.8 g of allylphenol novolac resin B was heated and stirred at 130 ° C., 36.2 g of 4,4′-diphenylmethane bismaleimide was added in several portions, and the mixture was melt-mixed while stirring. The mixture was stirred until 4,4′-diphenylmethane bismaleimide was completely melted and mixed air bubbles disappeared. Further, 1.0 g of dicumyl peroxide was added and stirred to obtain an allylphenol novolac resin composition.
The obtained allylphenol novolak resin composition was degassed in vacuum, then poured into a mold, and heat-treated at 150 ° C. for 2 hours and then at 175 ° C. for 3 hours to obtain a thickness of 4 mm × width of 60 mm × length. A cured product having a thickness of 150 mm was obtained.

Example 8
The allylphenol novolak resin composition obtained in the same manner as in Example 7 was degassed in vacuum, and then poured into a mold, which was cast at 150 ° C. for 2 hours, at 175 ° C. for 3 hours, and then at 230 ° C. for 4 hours. A cured product having a thickness of 4 mm, a width of 60 mm, and a length of 150 mm was obtained by heat treatment.

[Comparative Example 1]
A composition was obtained in the same manner as in Example 1, except that 26.7 g of o, o′-diallylbisphenol A and 33.3 g of 4,4′-diphenylmethane bismaleimide were used.
A cured product having a thickness of 4 mm, a width of 60 mm, and a length of 150 mm was obtained using the obtained composition in the same manner as in Example 1.

[Comparative Example 2]
A composition was obtained in the same manner as in Example 1 using 29.8 g of allylphenol novolac resin A and 30.2 g of 4,4′-diphenylmethane bismaleimide.
A cured product having a thickness of 4 mm, a width of 60 mm, and a length of 150 mm was obtained using the obtained composition in the same manner as in Example 1.

[Comparative Example 3]
A composition was obtained in the same manner as in Example 1 using 30.9 g of allylphenol novolac resin A and 29.1 g of 4,4′-diphenylmethane bismaleimide.
A cured product having a thickness of 4 mm, a width of 60 mm, and a length of 150 mm was obtained using the obtained composition in the same manner as in Example 1.

  About the hardened | cured material of Examples 1-8 and Comparative Examples 1-3, glass transition temperature, bending strength, bending elastic modulus, linear expansion coefficient, and 5% mass reduction temperature were measured. Moreover, the fluidity | liquidity of the allylphenol novolak resin composition of Example 1,5,6 was measured. The results are shown in Table 1.

As can be seen from the flowability measurement results of Examples 1, 5, and 6, the allylphenol novolak resin composition of the present invention is highly fluidized by heating to a relatively low temperature of about 80 ° C., preferably about 70 ° C. It can be made.
In addition, in Examples 1 and 2 in which the equivalent ratio [number of maleimide group equivalents / number of allyl group equivalents] is in the range of 0.85 to 1.30, as can be seen from the measurement results of the glass transition temperature and linear expansion coefficient of the cured product The obtained cured product has a glass transition temperature as high as about 90 ° C. and a linear expansion coefficient as low as about three-quarters compared with the cured products obtained in Comparative Examples 2 and 3 having an equivalent ratio smaller than the above range. The expansion rate is achieved.

Next, examples of a prepreg using the allylphenol novolak resin composition of the present invention and a laminate (copper-clad laminate) which is a fiber-reinforced resin molded article using the prepreg will be described. First, the evaluation method of the laminate used in the following examples is shown below.
(1) Peel strength A laminate obtained by forming a strip-like copper foil having a width of 10 mm by etching was used as a test piece. Using an autograph (“AG-5000D” manufactured by Shimadzu Corporation), the 90 ° copper foil peel strength was measured at a test speed of 50 mm / min.

(2) Glass transition temperature Using a dynamic viscoelastic device (TA Instruments (RSA-G2)), the laminate obtained by removing the copper foil by etching and cutting out to 10 mm × 40 mm was increased at 3 ° C./min. Measured at temperature rate. Let the temperature of the intersection which extended two linear parts with respect to the change curve of a storage elastic modulus be a glass transition temperature (Tg).

The materials used in the following examples are shown below.
(1) Bismaleimide compound BMI-1000 4,4′-diphenylmethane bismaleimide (N, N′-diphenylmethane bismaleimide or 4,4′-bismaleimide diphenylmethane) manufactured by Daiwa Kasei Kogyo Co., Ltd., represented by the following chemical formula And purity: 92.8% by mass.

(2) Allylphenol novolac resin C
The allylphenol novolak resin represented by the chemical formula (1) was used in a liquid form having a hydroxyl group equivalent of 141 g / eq, an allyl group equivalent of 141 g / eq, and a viscosity at 25 ° C. of 2.4 Pa · s.

(3) Radical initiator (dicumyl peroxide)
Park Mill D (purity: 99.9 mass%) manufactured by NOF Corporation, represented by the following chemical formula, was used.

(4) Glass cloth Non-alkali treated glass cloth M2116: manufactured by Arisawa Manufacturing Co., Ltd. was used.

(5) Copper foil Electrolytic copper foil CF-T9B-THE: Fukuda metal foil powder industry company make, 35 micrometers in thickness was used.

Example 9
100 parts by mass of allylphenol novolac resin C was heated and stirred at 130 ° C., 137 parts by mass of 4,4′-diphenylmethane bismaleimide was added in several portions, and the mixture was melt-mixed while stirring. The mixture was stirred until 4,4′-diphenylmethane bismaleimide was completely melted and mixed air bubbles disappeared. Next, the temperature of the mixture was set to 100 ° C., 5.7 parts by mass of dicumyl peroxide was added, and the mixture was further stirred to obtain an allylphenol novolac resin composition.
The obtained allylphenol novolac resin composition was adjusted to 80 ° C. and impregnated with a 150 mm × 95 mm glass cloth to obtain a prepreg. Next, after four prepregs are stacked, the copper-clad laminate is formed by sandwiching between copper foils, pressurizing with a hot press heated to 170 ° C. for 15 minutes, and heat-treating at 200 ° C. for 90 minutes under normal pressure. Obtained. Evaluation was performed on the laminate after removing unnecessary portions of the copper foil on the surface of the copper-clad laminate with an etching solution and washing. The evaluation results are shown in Table 2. Moreover, the storage elastic modulus, loss elastic modulus, and tan-delta measurement result which measured the laminated body with the dynamic viscoelasticity apparatus are shown in FIG.

  From the chart of measuring the dynamic viscoelasticity of the laminate of FIG. 2, no change curve is observed in the storage elastic modulus in the measurement temperature range, so that the glass transition temperature of the laminate exceeds at least 350 ° C. I understand.

  As described above, when the allylphenol novolak resin composition of the present invention was used, a copper-clad laminate that was a fiber-reinforced resin molded body could be obtained without using a solvent. Moreover, it turned out that the obtained copper-clad laminated body is excellent in heat resistance.

  According to the present invention, it is easy to handle with low viscosity and can be cured at a low temperature. The cured product has mechanical properties, heat resistance (for example, glass transition temperature of 255 ° C. or higher), low expansion (low expansion). An improved allylphenol novolac resin composition having excellent rate) can be obtained.

Claims (8)

An allylphenol novolac resin composition containing an allylphenol novolac resin and a bismaleimide compound,
The allylphenol novolac resin is a liquid having a viscosity of 10 Pa · s or less at 25 ° C., and the ratio of the allyl group equivalent number of the allylphenol novolak resin and the maleimide group equivalent number of the bismaleimide compound [maleimide group equivalent number / allyl group equivalent number] ] Is the range of 0.85-1.30, The allylphenol novolak resin composition characterized by the above-mentioned. The allylphenol novolak resin composition according to claim 1, wherein the allylphenol novolak resin is represented by the following chemical formula (1).

(In the formula, n is an integer of 0 to 20.)   The allylphenol novolak resin composition according to claim 1 or 2, wherein the bismaleimide compound is a bismaleimide compound having an aliphatic cyclic structure and / or an aromatic cyclic structure.   The allylphenol novolac resin composition according to any one of claims 1 to 3, wherein the allylphenol novolac resin and the bismaleimide compound are uniformly melt-mixed at a temperature of 30 to 150 ° C.   Furthermore, the radical initiator is contained, The allylphenol novolak resin composition in any one of Claims 1-4 characterized by the above-mentioned.   Hardened | cured material obtained by heat-processing the allyl phenol novolak resin composition in any one of Claims 1-5.   A fiber-reinforced resin molded article, wherein the matrix resin comprises the allylphenol novolac resin composition according to any one of claims 1 to 5.   The manufacturing method of the hardened | cured material characterized by obtaining the hardened | cured material by heat-processing the allylphenol novolak resin composition in any one of Claims 1-5 at the temperature of 150-280 degreeC.

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