JP2003012747A - Acetynyl group-containing curable resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new curable resin having excellent heat resistance and mechanical characteristics of cured material and improved flame retardance. SOLUTION: This curable resin is characterized by comprising a dihydronaphthoxazine ring containing a substituent group having at least one terminal acetylene bond, attached to nitrogen constituting the dihydronaphthoxazine ring. The curable resin is exemplified by a curable resin which is represented by formula (1) (R is hydrogen, a 1-6C alkyl group, cyclohexyl group, phenyl group, a substituted phenyl group, naphthyl group or a substituted naphthyl group) and contains an acetynyl group and the dihydronaphthoxazine ring.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermosetting resin which gives a cured resin excellent in heat resistance and curing characteristics, and more particularly to a thermosetting resin having at least one acetinyl group and a dihydronaphthoxazine ring. It concerns a resin.

[0002]

2. Description of the Related Art Various thermosetting resins such as epoxy resin, phenol resin, polyimide resin, melamine resin, and polyimide resin have been developed and applied to fields suitable for their respective resin characteristics. Recently, copper-clad laminates for printed wiring boards, adhesives for multilayer wiring boards, sealing materials for semiconductors, adhesives for semiconductor mounting, semiconductor mounting modules, or parts used for automobiles, aircrafts, building members, etc. In the curable resin used for the above, a resin material excellent in stability and reliability under high temperature and high humidity is required. Further, from the viewpoint of environmental load reduction, a halogen-free flame-retardant resin material is strongly desired.

In recent years, it has been reported that a dihydrobenzoxazine resin is a resin having a cured product having better heat resistance and moisture resistance than a conventional phenol resin (H. Ishid).
a, et al., J. Polym. Sci., Vol. 32, p921 (1994),
H. Ishida, et al., J. Appl. Polym. Sci., Vol. 61, 15
95 (1996)). Further, since these resins have ring-opening polymerization reactivity, they exhibit low curing shrinkage, and the cured product after the ring-opening reaction has various characteristics such as low thermal expansion. (H. Ishida, et al., J. Poly
m. Sci., Vol.34, 1019 (1994),). Furthermore, these are
It has also been shown to be reactive as an epoxy resin and to be effective as a curing agent (JP-A-4-227922). However, these conventional resins and resin compositions have a glass transition temperature of about 160 ° C. and cannot be said to have sufficient characteristics in heat resistance and flame retardancy, and in order to obtain good characteristics, a high curing temperature and a long curing temperature are required. It had the drawback of requiring a curing time. That is, JP-B-49-47378 and JP-A-2-69567.
Resins using a compound having a dihydrobenzoxazine ring as disclosed in JP-A No. 4-227922 or JP-A No. 4-227922 are known, but these cannot obtain sufficient heat resistance and mechanical properties. It was Further, recently, a thermosetting resin having an acetinyl group in the molecule has been developed as an organic compound having high heat resistance.

[0004]

SUMMARY OF THE INVENTION The present invention provides a novel thermosetting resin having excellent heat resistance and flame retardancy.

[0005]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventor has found that a resin having a dihydronaphthoxazine structure containing an acetinyl group is
We have found that it is possible to greatly improve heat resistance and mechanical properties, and completed the present invention.

The present invention is a curable resin having a dihydronaphthoxazine ring characterized in that the nitrogen constituting the dihydronaphthoxazine ring is substituted with a substituent having at least one acetinyl group. Further, the present invention provides the following general formula (1)

[Chemical 2] (In the formula, R represents hydrogen or an alkyl group having 1 to 6 carbon atoms), which is the curable resin having the dihydronaphthoxazine ring. In the general formula (1), it is a preferred embodiment that the substitution position of the oxygen atom with respect to the naphthalene ring is the 1,5-, 1,6- or 2,7-position.

Further, the present invention is characterized in that aminoarylacetylene, formaldehyde and monohydroxynaphthalene or dihydroxynaphthalene having two hydroxy groups each at one ring are reacted at 70 to 120 ° C. It is a method for producing a curable resin having a sagin ring. Further, the present invention, a curable resin having the dihydronaphthoxazine ring, an epoxy resin,
It is a curable resin composition obtained by mixing another resin having an oxazine ring or both of them. Furthermore, the present invention is a curable resin having the dihydronaphthoxazine ring or a curable resin obtained by thermosetting the curable resin composition.

The curable resin of the present invention is a curable resin having a dihydronaphthoxazine ring in which nitrogen constituting the dihydronaphthoxazine ring is substituted with a substituent having at least one acetinyl group. There may be one dihydronaphthoxazine ring or two or more dihydronaphthoxazine rings in one molecule, and one benzene ring constituting the dihydronaphthoxazine ring is a condensed benzene ring, that is, a naphthalene ring or the like. Besides, it may have a substituent such as an alkyl group. Substituents with at least one acetinyl group are>N-R'-
(Ac) _n (where N is nitrogen constituting the dihydronaphthoxazine ring, R ′ is a 1 + n-valent organic group, Ac is an acetinyl group, and n is 1
It is represented by the above integer), but is preferably a phenylene group substituted with one acetinyl group (a lower alkyl group or the like can be nuclear-substituted).

A preferred specific example of the curable resin having a dihydronaphthoxazine ring of the present invention is represented by the above formula (1). In the above formula (1), R is hydrogen or has 1 to 6 carbon atoms.
, An alkyl group, a cyclohexyl group, a phenyl group or a substituted phenyl group, a naphthyl group or a substituted naphthyl group, and the like, preferably hydrogen or an alkyl group having 1 to 6 carbon atoms. Further, in the general formula (1), the substitution position of the oxygen atom with respect to the naphthalene ring is preferably at the 1,5-, 1,6- or 2,7-position.

Since the curable resin having a dihydronaphthoxazine ring of the present invention has a dihydronaphthoxazine structure, it is heated at a temperature of 150 ° C. or higher to cause a ring-opening reaction of the dihydronaphthoxazine ring to cause curing. It has excellent physical properties such as heat resistance and flame retardancy. Furthermore, since it contains an acetylinyl group, the crosslinking reaction by the acetylene group proceeds at a temperature of 300 ° C. or higher, and a cured product having a high heat resistance of 350 ° C. or higher is obtained.

The curable resin having a dihydronaphthoxazine ring of the present invention can be obtained by reacting an aldehyde with a phenol by a known method except that aminoarylacetylene is used. Known compounds such as formaldehyde, acetaldehyde, and benzaldehyde can be used as the aldehydes, but formaldehydes are preferred. Known compounds such as phenol, naphthol, hydroquinone, and bisphenol can be used as the phenols, but monohydroxynaphthalene or dihydroxynaphthalene having two hydroxy groups each is preferable. As the aminoarylacetylene, known compounds such as aniline, alkylaniline, and naphthylaniline in which the terminal is substituted with an acetylinyl group can be used, but paraaminophenylacetylene is preferable.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION An example of a method for producing a curable resin having a dihydronaphthoxazine ring is represented by the following reaction formula.
In this example, a compound having a naphtholic hydroxyl group at at least one of the α-position and β-position of the naphthalene ring is used, and the compound can be synthesized from primary amines and aldehydes.

[Chemical 3] In the above reaction formula, R represents an alkyl group having at least one acetinyl group and having 1 to 6 carbon atoms, a cyclohexyl group, a phenyl group or a substituted phenyl group.

The compound having a naphtholic hydroxyl group may have a substituent such as halogen and an alkyl group, but it does not have a substituent or has an alkyl group having 1 to 3 carbon atoms (lower alkyl group).
Those having 2 to 2 are preferable. The compound having a naphtholic hydroxyl group may have one or more hydroxyl groups, but the number is 4 or less, preferably 1 or 2. It also has one substitutable hydrogen at the ortho position adjacent to the hydroxyl group.

Examples of the compound having a naphtholic hydroxyl group include 1-naphthol, 2-naphthol, 1,5-naphthalenediol, 1,6-naphthalenediol, 1,7-naphthalenediol and 1,4-naphthalenediol. Preferred examples include: In addition, the following general formula (2)

[Chemical 4] (In the formula, R represents an alkylene group having 1 to 6 carbon atoms, a xylylene group, or a substituted xylylene group, and n represents a number of 1 to 10) are also preferable. The compound having these naphtholic hydroxyl groups is a compound having one naphtholic hydroxyl group on one or both of the two rings constituting the naphthalene ring and at least one substitutable hydrogen at the ortho position of the hydroxyl group. It is preferable from the viewpoint of cured product characteristics. These may be used alone or in combination of two or more.

As the primary amines, aliphatic amines such as methylamine, butylamine, and cyclohexylamine having an acetinyl group, and aromatic amines such as aniline, toluidine, and anisidine can be used. These are one or more acetinyl groups. It is also possible to use a combination of amines having groups. The primary amine is represented by R—NH ₂ , and R may be an alkyl group having at least one acetinyl group, an aryl group, or the like, but is preferably a primary amine represented by the formula (3). is there. In equation (3),
Ar is an aromatic group, but is preferably a p-phenylene group or a lower alkyl-substituted p-phenylene group.

[Chemical 5]

The aldehydes are not limited to formaldehyde, and aliphatic aldehydes and aromatic aldehydes represented by R-CHO can be used, but formaldehyde is preferred. In the general formula (1), R is R—CH.
Derived from aldehydes represented by O, R can be hydrogen or an alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, a phenyl group or a substituted phenyl group, a naphthyl group or a substituted naphthyl group, and the like. When formaldehyde is used as the aldehyde, it can be used in any form as an aqueous formalin solution or paraformaldehyde.

In order to synthesize the curable resin of the general formula (1) showing an example of the curable resin of the present invention, hydrogen is bonded to at least one of the α-position and the β-position as shown in the above reaction formula. A compound having a naphtholic hydroxyl group present is reacted with a primary amine and aldehydes. When the number of hydroxyl groups contained in the compound having a naphtholic hydroxyl group is Y,
Primary amine 0.8 to 1.2 × Y mol, preferably 0.9 to 1 mol of the compound having a naphtholic hydroxyl group.
1.1 × Y moles were used and 1.6-2.
It is preferable to use 4 × Y mole, preferably 1.8 to 2.2 × Y mole. If aldehydes are used in excess, the phenol resin unit will be easily produced as a by-product.

The method for producing the thermosetting resin having a dihydronaphthoxazine ring of the present invention is not particularly limited, but the production method of the present invention is preferable. A preferred example of the production method of the present invention is as follows. After reacting by a method of gradually adding the primary amine having an acetinyl group to formaldehyde, a compound having a naphthol-based hydroxyl group is added, and 20 minutes to 24 hours, 70 to Keep at 120 ° C. At this time, an organic solvent can be used if necessary.
After the reaction, the product is isolated and purified by a synthetic chemical method such as extraction, and the volatile component such as condensed water is dried and removed to obtain the target curable resin having a dihydronaphthoxazine ring.

Preferred specific examples of the curable resin having a dihydronaphthoxazine ring of the present invention are shown below.

[Chemical 6]

[0020]

[Chemical 7]

[0021]

[Chemical 8]

[0022]

[Chemical 9]

The curable resin of the present invention undergoes a ring-opening polymerization reaction by heating to form a naphtholic hydroxyl group without generating a volatile component and form a crosslinked structure having excellent properties. This cured product exhibits low hygroscopicity, high glass transition temperature, high strength / high elastic modulus and low curing shrinkage, and is also excellent in flame retardancy.

The curable resin of the present invention can also be used in combination with various epoxy resins. As the epoxy resin used, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, or hydrogenated bisphenol A type epoxy resin, various alicyclic epoxy resins, further Examples of the epoxy resin include various epoxy resins having a naphthalene structure, brominated epoxy resins, and the like, but they can be used without limitation. Furthermore, these can be used alone or in combination of two or more.

Further, the curable resin of the present invention may be used in combination with another resin having a dihydrobenzoxazine ring. When a resin composition containing an epoxy resin or another resin having a dihydrobenzoxazine ring is mixed, the mixing ratio is 100 parts by weight of the curable resin of the present invention, and a resin having another dihydrobenzoxazine ring. 1 ~ 1
A range of 00 parts by weight is preferred. The epoxy resin is preferably in the range of 1 to 100 parts by weight based on 100 parts by weight of the curable resin of the present invention or 100 parts by weight of the curable resin of the present invention and another resin having a dihydrobenzoxazine ring.

As the other resin having a dihydrobenzoxazine ring, a known resin having a dihydrobenzoxazine ring can be used. A resin having a dihydrobenzoxazine ring synthesized using the following raw materials is preferable. Examples of phenols having hydrogen bonded to at least one of the ortho positions as a raw material include polyfunctional phenols, bisphenols, trisphenols such as 1,1,1-tris (4-hydroxyphenyl) ethane, and phenols. From the viewpoint of thermosetting properties, a compound having two or more phenolic hydroxyl groups in which hydrogen is bonded to at least one of the ortho positions is preferable in one molecule. Specific examples thereof include catechol, resorcinol, hydroquinone as polyfunctional phenols, and bisphenol A, bisphenol S, bisphenol F, hexafluorobisphenol A, etc. as bisphenols. Examples of the phenol resin include phenol novolac resin, resole resin, phenol-modified xylene resin, alkylphenol resin, melamine phenol resin, polybutadiene-modified phenol resin and the like. These may be used alone or in combination of two or more kinds. As the primary amine as a raw material, aliphatic amines such as methylamine, butylamine and cyclohexylamine, and aromatic amines such as aniline, toluidine, anisidine and the like can be used, and these can be used alone or in combination of a plurality of amines. Can also be used. Formaldehyde as a raw material can be used in any form as an aqueous formalin solution or as paraformaldehyde.

Preferred specific examples of the other resin having a dihydrobenzoxazine ring are shown below, but the resin is not limited to these, and one kind or a combination of two or more kinds can be used.

[Chemical 10]

[0028]

[Chemical 11]

[0029]

[Chemical 12]

The curable resin of the present invention may contain various phenol resins, melamine resins, polyamide resins, polyimide resins and the like, if necessary, in addition to the components described above. Further, it may contain a filler, a reinforcing material, a release agent, a coupling agent, a plasticizer, a flame retardant, a curing aid, a coloring agent, a coupling agent, carbon black, or the like.

Further, if necessary, a compound having a phenolic hydroxyl group having an effect of opening the dihydronaphthoxazine ring, for example, bisphenol A, a novolac resin, a resole resin, or a compound having an amino group is used. You can also Further, as an effective catalyst for the reaction between the epoxy resin and the phenolic hydroxyl group, for example, an imidazole compound, a dicyandiamide compound, or a phosphorus compound can be used. Further, for the purpose of further improving the flame retardancy of the resin, it is also possible to use various organic phosphorus compounds such as phosphines such as triphenylphosphine, phosphoric acid esters, phosphinic acid esters, phosphorous acid esters, and phosphine oxides. it can.

[0032]

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

Example 1 0.4 mol (46.85 g) of 4-aminophenylacetylene was dissolved in 200 ml of dioxane, and a formaldehyde solution (36
(-38% aqueous solution) 67 g was added dropwise and reacted at room temperature for 5 hours. Then, 0.2 mol of 1,5-naphthalenediol (32.03
g) was added, and the mixture was reacted at 100 ° C to 120 ° C for 5 hours with stirring. After the reaction was completed, the precipitated solid was collected by filtration to obtain 72 g of a curable resin (A) having an acetinyl group-containing dihydrobenzoxazine ring. The results of infrared analysis and mass spectrum analysis of this curable resin (A) are shown in FIGS. 1 and 2.

Example 2 10 g of the above curable resin (A) was cured on a hot plate kept at 180 ° C. for 1 hour, and then the physical properties were measured.
As a result, the glass transition temperature was 230 ° C and the coefficient of thermal expansion was 40 ppm.
/ ℃, thermal decomposition start temperature was 340 ℃, flexural strength was 240MPa, flexural modulus was 4.6Gpa. Furthermore, after heating at 350 ° C for 1 hour, the physical properties of the cured product were measured. As a result, the glass transition temperature was 350 ° C, the coefficient of thermal expansion was 30 ppm / ° C, the thermal decomposition initiation temperature was 440 ° C, the bending strength was 300 MPa, and the bending strength was 300 MPa. The elastic modulus was 4.8 Gpa. The disappearance of triple bonds based on the acetinyl group was also confirmed.

The glass transition temperature is a dynamic viscoelasticity measuring device (DMA), and the thermal expansion coefficient is a thermomechanical analyzer (TMA).
The thermal decomposition starting temperature (5% weight loss temperature) was measured using a thermogravimetric analyzer (TGA).
The measurement was performed according to 11. In addition, the water absorption rate was measured by measuring the weight change before and after the PCT treatment after preparing a 3 mm thick cured product and treating the cured product under PCT (121 ° C, 2 atm) treatment time of 20 hours. It was 1.7 wt% when calculated. Further, the flame retardancy was V0 when the flame retardancy of a 1.6 mm thick cured product was evaluated according to the method of UL standard.

[0036]

EFFECT OF THE INVENTION The acetylinyl-containing curable resin of the present invention has an acetylene structure, a dihydronaphthoxazine ring, and a naphthalene structure in the molecule, and therefore has excellent heat resistance and can improve flame retardancy. Since it is possible to give a cured resin having good characteristics and mechanical properties, it can be used as a laminated board for printed wiring boards, a printed wiring board, a semiconductor encapsulating material, a semiconductor mounting module, other various electronic component peripheral members, automobiles, Aerospace equipment parts, building parts, etc.
Furthermore, it can be used as a binder or a matrix resin for carbon fibers, carbon electrodes, various composite materials and the like.

[Brief description of drawings]

FIG. 1 IR analysis chart

FIG. 2 Mass spectrum analysis chart

Claims (6)

[Claims] 1. A curable resin having a dihydronaphthoxazine ring, wherein nitrogen constituting the dihydronaphthoxazine ring is substituted with a substituent having at least one acetinyl group. 2. The following general formula (1): The curable resin having a dihydronaphthoxazine ring according to claim 1, wherein R is hydrogen or an alkyl group having 1 to 6 carbon atoms. 3. The dihydronaphthoxazine ring according to claim 2, wherein the substitution position of the oxygen atom with respect to the naphthalene ring in the general formula (1) is 1,5-, 1,6- or 2,7-position. Curable resin that has. 4. Curing having a dihydronaphthoxazine ring characterized by reacting aminoarylacetylene, formaldehydes, monohydroxynaphthalene or dihydroxynaphthalene having two hydroxy groups each at 70 to 120 ° C. Of producing a flexible resin. 5. A curable resin composition obtained by mixing the curable resin according to claim 1 with an epoxy resin or another resin having an oxazine ring. 6. A curable resin obtained by thermosetting the curable resin according to claim 1 or the curable resin composition according to claim 5.