JPH03181508A - Allylic ester-based thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, composed of an allylic ester oligomer and maleic acid derivative in a specific proportion, excellent in curability and adhesion (especially adhesion to metal) and useful as molding materials, decorative boards, etc. CONSTITUTION:The objective composition composed of (A) 50-99wt.%, preferably 25-99wt.% allylic ester oligomer [e.g. a compound expressed by the formula (R is organic residue derived from bifunctional saturated carboxylic acid; B is organic residue derived from a dihydric saturated alcohol)], (B) 1-50wt.% maleic acid derivative (e.g. maleic anhydride or N-methylmaleimide) and preferably (C) 1-50wt.% acrylic acid derivative [e.g. (meth)acrylic acid] and/or diallylic monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel allyl ester thermosetting resin composition. More specifically, the present invention provides curable and adhesive properties,
In particular, it relates to an allyl ester thermosetting resin composition that has excellent adhesion to metals.

[Conventional technology and its problems] Diallyl resins, which are mainly composed of prepolymers derived from diallyl orthophthalate, diallyl isophthalate, and diallyl terephthalate, have been known to have excellent retention of electrical properties at high temperatures and high humidity. Because of this, it has been used for many years in electrical and electronic applications that require high reliability.

The above-mentioned diallyl phthalate resin also has excellent dimensional stability, heat resistance, moisture resistance, water resistance, and other properties, but it also has the drawback of lacking adhesiveness. Diaryl phthalate resin is usually used in combination with various reinforcing materials, fillers, etc., so if mutual adhesion or wetting is insufficient, it will be difficult to obtain a reinforcing effect and the resin will not be able to demonstrate its performance. Can not. Furthermore, some molded products have metal parts inserted, encapsulated, or adhered to each other, and in such cases, mutual adhesion is also strongly required. Many efforts have been made to meet these demands, including modification and blending of resins, but no fully satisfactory results have yet been obtained.

Furthermore, since diallylphthalate resins are polymerized by allyl groups, they have the disadvantage of slow curing speed. Recently, there has been a strong demand for shorter molding cycles in order to improve productivity, and the current curing characteristics cannot meet this demand.

Furthermore, the present inventors have developed an allyl ester oligomer having an allyl ester group at the end and the following structure derived from a polyvalent saturated carboxylic acid and a polyvalent saturated alcohol inside (Japanese Patent Application No. 262217).

CH2”CHCIT20(CORCOOBO)nCOR
COOCH2C1'l''CHz In this case, if terephthalic acid, which has particularly excellent symmetry, is used as the polyvalent saturated carboxylic acid, a cured product with extremely excellent physical properties can be obtained.However, in order to improve the physical properties, it is necessary to increase the molecular weight beyond a certain level. However, it has the disadvantage that the double bond concentration decreases as the polymer increases, and the polymerization rate decreases extremely.

An object of the present invention is to solve these problems and provide an allyl thermosetting resin composition that has excellent adhesiveness and curability while retaining the excellent properties of conventional diallyl phthalate resins.

[Means for Solving the Problems] The present inventors conducted intensive studies to achieve the above object, and as a result, completed the present invention.

That is, the present invention provides an allyl ester having an allyl ester group at the end and whose interior is derived from a poly@Ii saturated carboxylic acid and a polyhydric saturated alcohol, maleic anhydride or a derivative thereof, and optionally acrylic acid or its derivative. It is characterized by exhibiting extremely high curing speed and adhesive properties by combining derivatives and/or diallyl monomers.

The allyl ester oligomer used here is represented by the following general formula.

(+) CH2: (HCH20(CORCOO
BO),, C0RCOOCH2CH: CI'+2 or (2) An oligomer with an allyl ester group at the end and the following repeating unit -(-C0RCOOBO← Structure-A -+C0RCOOh-Z -0-C0RCOO-Structure-
B-(-BOCO)r-humanC0O-BO-Structure-C [wherein, R is an organic residue derived from a divalent saturated carboxylic acid, and B is an organic residue derived from a divalent saturated alcohol. ,
A represents an organic residue derived from a polyvalent saturated carboxylic acid having a valence of 3 or more, and Z represents an organic residue derived from a saturated alcohol having a valence of 3 or more.

X and y represent positive integers of 2 or more. ] Examples of divalent saturated carboxylic acids that give R here include oxalic acid,
Malonic acid, succinic acid, curtaric acid, adipic acid, β-methyladipic acid, pimelic acid, corkic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid,
1,2- or 1,3- or 1. 4-cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, diphenyl-p,p'-dicarboxylic acid, diphenyl-m+m'-dicarboxylic acid, 1.4- or 1,5- or 2.6- or 2. 7-naphthalene dicarboxylic acid,
diphenylmethane-p,p'-dicarboxylic acid, diphenylmethane-m1m'-dicarboxylic acid, benzophenone-
4,4'-dicarboxylic acid, p-phenylene diacetic acid, p-
These include carboxyphenylacetic acid, methylterephthalic acid, and tetrachlorophthalic acid. Among them, terephthalic acid and 2,6
- Divalent saturated carboxylic acids with high symmetry, such as naphthalene dicarboxylic acid, provide particularly excellent physical properties.

Examples of dihydric saturated alcohols that give B include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, sameethylene glycol, and heptamethylene glycol. Fur, octamethylene glycol, nonamethylene glycol, decamethylene glycol, undecamethylene glycol,
Dodakamethylene glycol, tridecamethylene glycol, niocosane methylene glycol, hydrogenated bisphenol A, 1,4-cyclohexane dimetatool, 2-ethyl-2,5-bentanediol, 2-ethyl-1,3
- Saturated glycols consisting only of carbon such as hexanediol and styrene glycol, and ether groups such as diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, ethylene oxide adducts of bisphenol A, and propylene oxide adducts of bisphenol A. Dihydric saturated alcohols containing bromine and glycols containing bromine such as dibromoneopentyl glycol are also included. Among these, diols that yield polyesters with high crystallinity, such as terephthalic acid and 2,6-naphthalene dicarboxylic acid, such as ethylene glycol, neopentyl glycol, and 1,4-butanediol, provide particularly excellent physical properties. In addition, glycols such as propylene glycol, 1,3-butanediol, and dipropylene glycol are particularly preferred because they have good compatibility with maleic anhydride and acrylic acid derivatives, and the formulation can be changed over a wide range.

Examples of trivalent or higher polyvalent saturated carboxylic acids that give A include trimellitic acid, pyromellitic acid, and the like.

Examples of trivalent or higher polyhydric saturated alcohols that give 2 include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, and the like.

In the present invention, diallyl monomers are mixed in when synthesizing the allyl ester oligomer, but they do not adversely affect the curing speed or adhesive properties even if used as they are. It can also be actively added to the resin composition for the purpose of increasing Tg; such diallyl monomers include diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl chlorendate, diallyl endeic acid, diallyl maleate. , diallyl fumarate, diallyl adipate, and the like. The amount of these to be used is not very preferable since excessive use leads to an increase in shrinkage rate, a decrease in mechanical strength, etc. Therefore, it is 45% by weight or less, preferably 30% by weight or less.

Maleic acid and its derivatives include maleic anhydride, maleimide, N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-methylphenylmaleimide, N-chlorophenylmaleimide, There are N-substituted maleimides such as N-carboxylphenylmaleimide, among which maleic anhydride itself provides extremely fast curing rates.

Examples of acrylic acid or its derivatives include unsaturated carboxylic acids such as acrylic acid and methacrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and octyl (meth)acrylate. acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate,
Alkyl (meth)acrylates such as cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, (iso)bornyl (meth)acrylate, adamantyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, 1-naphthyl (meth)acrylate, fluorophenyl (meth)
acrylate, chlorophenyl (meth)acrylate,
Bromophenyl (meth)acrylate, tribromophenyl (meth)acrylate, methoxyphenyl (meth)
Acrylate, cyanophenyl (meth)acrylate,
Aromatic acrylic esters such as piphenyl (meth)acrylate and bromobenzyl (meth)acrylate, 2-
Hydroxyethyl (meth)acrylate, (meth)acrylic acid polyethylene glycol ester, etc., (meth)acrylic acid esters such as glycidyl (meth)acrylate, alkylamino (meth)acrylate, (meth)acrylamide, NI N-dimethyl There are (meth)acrylamides such as (meth)acrylamide and N,N-diethyl (meth)acrylamide. Also, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,3-butyreglycol Di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanesioldi(meth)acrylate, 1,6-hexanethiol di(meth)acrylate, neobentylglycol di(meth)acrylate ) acrylate, hydroxypivalic acid neopentyl glycol ester di(meth)acrylate, oligoester di(meth)acrylate, polybutadiene di(meth)acrylate, 2,2-bis(4-(meth)acryloyloxinphenyl)propane, 2 .2-bis(4-(ω-(meta)
acryloyloxypolyethoxy)phenyl)propane, 2,2-bis(4-(ω-(meth)acryloyloxypolyethoxy)dibromophenyl)propane, 2,2
- Di(meth)acrylates such as bis(4-(ω-(meth)acryloyloxypolypropoxy)phenyl)propane, bis(4-(ω-(meth)acryloyloxypolyethoxy)phenyl)methane, trimethylolethanetri (meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri
Trifunctional crosslinking monomers such as (meth)acrylates,
Multifunctional acrylates such as tetrafunctional crosslinking monomers such as pentaerythritol tetra(meth)acrylate can also be used. Among these, acrylic acid and lower esters of acrylic acid give excellent results in terms of curability. Here, the fact that electrical properties do not deteriorate even when acid anhydrides such as maleic anhydride are used, and that the allyl group in allyl ester, which is generally said to polymerize slowly, can be cured faster by maleic anhydride. cannot be predicted from conventional knowledge, and represents the disclosure of a new method.

In addition, physical properties such as bending strength of the resulting cured product are improved, which could not be predicted from conventional knowledge and represents the disclosure of a novel method.

In the present invention, if the amount of maleic acid and its derivatives is too large, maleic anhydride may sublimate during heating for curing, maleic anhydride may remain during polymerization, or the alkali resistance after curing may deteriorate. This is not preferable because it has negative effects such as a decrease in

If the amount is too small, no effect on adhesiveness or curability can be obtained, which is not preferable. Therefore, the amount of maleic anhydride blended is 1 to 50% by weight, preferably 2 to 30% by weight based on the total resin.

In addition, from the viewpoint of curing speed, it is most preferable to use equimolar amounts based on the total amount of allyl groups in the allyl ester oligomer and diallyl monomer, and if you want to maximize the curing speed, the iodine value of the allyl ester oligomer It is preferable to use maleic anhydride whose double bond concentration is calculated to be equimolar.

Further, if the curing speed is insufficient with maleic anhydride alone, it is possible to further increase the curing speed by using acrylic acid or a derivative thereof. In this case, if the amount used is too high, the Tg will decrease,
There are drawbacks such as deterioration of electrical properties, and adhesion is lower than when maleic anhydride is used alone. Also, if the amount is too low, the desired effect will not be achieved.
When blended, it is 0.1 to 50% by weight, preferably 1 to 20% by weight of the total resin.

Furthermore, other monomers may be added to the resin composition of the present invention as long as the physical properties and curability are not impaired.

Such reactive monomers include, for example, aromatic vinyl compounds, unsaturated dibasic acids and derivatives thereof, vinyl esters of saturated aliphatic or aromatic carboxylic acids and derivatives thereof, vinyl cyanide compounds such as (meth)acrylonitrile, unsaturated Examples include hydrocarbons, halogenated unsaturated hydrocarbons, and the like.

Examples of aromatic vinyl compounds include styrene or α-substituted styrenes such as α-methylstyrene, α-ethylstyrene, and α-chlorostyrene, and nuclear-substituted styrenes such as fluorostyrene, chlorostyrene, bromostyrene, chloromethylstyrene, and methoxystyrene. can be mentioned.

Unsaturated dibasic acids and their derivatives include fumaric acid,
Itaconic anhydride, citraconic anhydride, endic anhydride, and their mono- or dialkyl esters,
Examples include di- or monoalkyl esters of maleic acid such as dimethyl maleate and monoallyl maleate.

Vinyl esters of saturated aliphatic or aromatic carboxylic acids and derivatives thereof include vinyl acetate, vinyl propionate, vinyl benzoate, vinyl n-butyrate, and the like.

Examples of unsaturated hydrocarbons include 1-hexene, 1-octene, 4-vinylcyclohexene, and the like.

Examples of halogenated unsaturated hydrocarbons include vinyl chloride and vinyl bromide.

Crosslinkable polyfunctional monomers can also be used, such as diallyl carbonate, diethylene glycol diallyl carbonate, divinylbenzene, N
+ Bifunctional crosslinking monomers such as N'-m-phenylene bismaleimide; Trifunctional crosslinking monomers such as tri(meth)allyl isocyanurate and triallyl trimellitate.

Further, polymers having double bonds such as unsaturated polyesters can also be used in the same manner as reactive monomers.

The blending ratio of the reactive monomer depends on the required performance properties, but is 20% by weight or less, preferably 5% by weight or less, based on the total amount of resin in the composition of the present invention.

If it exceeds 20% by weight, the curing rate will be unduly delayed, the internal distortion of the molded product will increase significantly due to an increase in curing shrinkage rate, etc., which is not preferable.

The curing agent used in the present invention may be any type of radical polymerization initiator as long as it can generate radicals by heat, microwaves, infrared rays, or ultraviolet rays. It can be appropriately selected depending on the blending ratio and the curing method of the curable composition.

Examples of radical polymerization initiators that can be used in polymerization using heat, microwaves, and infrared rays include 2.2'-azobisisobutyronitrile, 2°2'-azobisisovaleronitrile, and 2.21azobis(2,4 -dimethylvaleronitrile), ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutylene ketone peroxide, cyclohexanone peroxide, acetylacetone peroxide, imbutyryl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 0-methyl Diacyl peroxides such as benzoyl peroxide, lauroyl peroxide, p-chlorobenzoyl peroxide, 2,4.4
-) Hydroperoxides such as dimethylpentyl-2-hydroperoxide, diisopropylbenzene peroxide, cumene hydroperoxide, tart-butyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide, di-tert-butyl peroxide, tris(tert-butyl peroxide) -butylperoxy)triazine and other alkyl peroxides, 1,1-di-tert-
Butylperoxycyclohexane, 2,2-te
tert-butylperoxyoxykecurs, tert-butylperoxide valley), tert-butylperoxy-2-ethylhexanony), tert-butylperoxyisobutyrate, di-tert-butylperoxyhexahydroterephthalate, di-tert-butyl Alkyl peresters such as peroxyazelate, tert-butylperoxy-3.5.5-trimethylhexanoate, tert-butylperoxyacetate, tert-butylperoxybenzoate, di-tert-butylperoxymethyl adipate, diisobrobyl peroxy Examples include percarbonates such as dicarbonate, di-5ec-butylberoxydicarbonate, and tert-butylperoxyisopropyl carbonate.

Examples of radical polymerization initiators that can be used in polymerization using ultraviolet light include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-jethoxyacetophenone, and 4'isopropyl-2-hydroxy-
2-Methylpropiophenone, 2-hydroxy-2-methylpropiophenone, 4.4' bis(diethylamino)benzophenone, benzophenone, methyl(0-benzoyl)benzoate, 1-phenyl-I.

2-propanedione-2-(o-ethoxycarbonyl)
Oxime, 1-phenyl-1,2-propanedione-2
-(o-benzoyl)oxime, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin isooctyl ether methyl ketal, benzyl diethyl ketal, carbonyl compounds such as diacetyl, methylanthraquinone, chloroanthraquinone, chloro Examples include anthraquinone or thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone, and sulfur compounds such as diphenyl disulfide and dithiocarbamate.

Practically, peroxides commonly used for diallyl phthalate resins, such as dicumyl peroxide, tert-butyl peroxide, benzoyl peroxide, etc., can be used as they are. The appropriate blending amount is 0.1 to 6% by weight based on the resin content.

The composition of the present invention may optionally contain fillers, polymerization accelerators, polymerization inhibitors, internal mold release agents, coupling agents, pigments, flame retardants, and other additives, as in the case of conventional diallylphthalate compositions. Additives may be added within a range that does not impair the properties of the composition to improve moldability or physical properties of the molded article.

As a method for molding the composition of the present invention, known molding methods and molding conditions similar to those for conventional diallyl phthalate resins can be applied as they are. That is, a casting method in which the composition of the present invention is injected into a mold and cured, an injection molding method or a transfer molding method in which the composition is heated to a fluid state, and then placed in a mold and heated to harden. A compression molding method in which the composition is cured by heating and pressurizing it in a mold. A laminate molding method in which the resin is cured in a sheet, a coating method in which a fine powder or solution of the composition is applied to a substrate and cured on the substrate, and a printing paper etc. is impregnated with the composition solution and after drying. An example of a molding method is a decorative board molding method in which the material is cured by heating and pressing on a substrate. An example of the heating temperature for curing during molding is about 60 to 220°C. Further, when the pressurized condition is adopted, the pressure may be approximately 5 to 1000 kg/cm2.

Furthermore, unlike conventional diallylphthalate resins, some of the compositions of the present invention are liquid at room temperature, and the same molding method as for liquid unsaturated polyesters can be applied to these. Therefore, it has become possible to expand the scope of use of the resin of the present invention.

The composition of the present invention takes advantage of its fast curing properties and adhesive properties and is used as a molding material in a wide range of fields such as the following.

For example, connectors, motor commutators, governors, coil bobbins, relays, switches, terminal boards, ignitions, breakers, sockets, binders for sliding resistors, printed wiring boards, sealing materials for electronic parts and elements, coil encapsulation, etc. Electrical and electronic fields, such as insulating materials in the light to heavy electrical field; Also, for example, plastic brake pistons and other mechanical fields; Tableware and other daily necessities fields; Medical fields, such as trays and containers that require chemical or steam sterilization It is useful as a molding material in the materials field.

Further, the composition is impregnated or applied to a fibrous sheet such as paper, nonwoven fabric, glass cloth, etc. in the presence or absence of a solvent, and the composition is pressed and cured to a wood, paper, metal, or other inorganic substrate, or it is precured. The resulting product is applied to the above base material in the form of a decorative board and is useful for various building materials, furniture, interiors, cabinets, kitchen equipment, axles, ship interior materials, and other fields.

In addition, if the resin is directly impregnated into wood and cured, it becomes a wood-plastic composite (so-called WPC), which can be used in fields such as floorboards, decks, roof decks, architectural structural materials, sporting goods, etc. In addition, it can be used for glass cloth, etc. As a laminate made by impregnating and laminating a fibrous sheet structure, it can be used in fields that require high-temperature, high-humidity properties, such as terminal plates, motor wedges, insulation collars, slot armor coil separators, and other rotating machine-related fields. , duct piece,
It is useful in static machine related fields such as barriers, terminal plates, operating rods, panels such as switchboards, printed wiring boards, and PC insulation supports.It also has excellent dimensional stability and good mechanical strength even under severe temperature and humidity changes. Fields that require this, such as laser domes, missile blades,
Rocket nozzles, jet aircraft air ducts, etc.
Fields that require chemical resistance for various chemical equipment parts, fields that require weather resistance, chemical resistance, and mechanical strength such as antennas, skis, ski poles, fishing rods, etc., and mold materials for molding paints and resins. A wide range of applications, including hot stamping resins, UV curing inks, materials for lenses and other optical applications, binders for glass fibers and carbon fibers, and resins for resist films in phosphorography using light, electron beams, or X-rays. It can be provided to

[Example code] Hereinafter, the present invention will be explained in more detail with reference to Examples.

The typical operation for synthesis of allyl ester oligomer is as follows. 11 equipped with distillation equipment
800 g of diallyl ester monomer in a Mitsuro flask.
Ethylene glycol 78.4g 1 diptyltin oxide 0
．． 1 g was charged and heated to 180° C. under a nitrogen stream, and the produced allyl alcohol was distilled off. When about 140g of allyl alcohol has been distilled out, the inside of the reaction system is adjusted to 50mmHg.
The distillation rate of allyl alcohol was increased.

After the theoretical amount of allyl alcohol was distilled off, the reaction was continued for an additional hour and the reaction mixture was cooled. After the reaction product was solidified, it was crushed into small lumps, and then poured into methanol 11 and vigorously stirred for about 1.0 hour while crushing the oligomer to form a powdered oligomer. After filtering to separate methanol, the mixture was dried and ground to obtain 496 g of oligomer. Table 1 shows the physical properties of the obtained allyl ester oligomer.

Physical property values of oligomers obtained by changing reaction conditions and isolation conditions are also listed in Table 1.

A composition having the formulation shown in Table 2 was kneaded with appropriate heating and stirring in a Brabender blast mill if the allyl ester oligomer was solid, or in a flask if it was liquid. The obtained composition was placed on a heating plate at 130° C., and the time until it stopped becoming stringy was measured, which was determined as the gel time. Further, the composition was dissolved in methyl ethyl ketone to obtain a varnish, and the varnish was polished with a #240 file and degreased (room m/- night/triclean) to an adherend (mild steel plate, J
6850) on IS-, and after removing the solvent at 90°C for 30 minutes, it was fixed with adhesive and cured at 180°C for 71 hours. The results are shown in Table 3.

The treatment was carried out in the same manner as in the example except that L-barrel, maleic anhydride, and acrylic acid derivative were not mixed. The blending conditions and physical property measurement results are shown in Table 2.3.

[Effects of the Invention] According to the present invention, curability and adhesiveness can be dramatically improved compared to conventional diallyl phthalate resins,
It can be used not only for molding materials and decorative laminates, but also for electronic and electrical materials, paints, and other fields that require uniform hardness and adhesive properties, and its industrial value is extremely high.

Claims (2)

[Claims] (1) An allyl ester thermosetting resin composition comprising 50 to 99 wt% of allyl ester oligomer and 1 to 50 wt% of maleic acid derivative. (2) An allyl ester thermosetting resin composition comprising 25 to 99 wt% of allyl ester oligomer, 1 to 50 wt% of maleic acid derivative, and 1 to 50 wt% of at least one of an acrylic acid derivative and a diallyl monomer.