KR940010214B1 - Thermosetting resin composition - Google Patents

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Description

Thermosetting resin composition

The present invention relates to a thermosetting diallyl phthalate resin composition useful as a molding material in the manufacture of molded articles such as laminates, electrical parts, electronic parts, mechanical parts and medical care products.

The present invention can provide molded articles having excellent heat resistance, size stability, chemical resistance, mechanical strength and electrical insulation, and particularly high surface hardness.

A plurality of resin-impregnated fibrous substrates of the present invention, or resin-impregnated fibrous substrates laminated to plywood or metal plates, coalescing them under heat and pressure, and molding the resin to cure the resin, and top plates such as decorative plates, desks and checkout counters, and Provided are suitable thermosetting resins for impregnation resins in the manufacture of laminates such as printed circuit boards.

More specifically, the present invention relates to electrical devices such as commutators, motor commutators, governors, coil bobbins, relays, switch terminal boards, ignitions, breakers, sockets, encapsulants for electronic components and devices, and insulating materials. Provides thermosetting resin compositions useful as molding materials for medical and sanitary materials such as electronic components, mechanical parts such as pistons of plastic brakes, tableware and other daily necessities, and ashtrays or containers that can be sterilized with chemicals or steam. .

Laminated plates and other various molded articles obtained from the thermosetting resin composition of the present invention exhibit characteristics that meet the requirements of the separate application and have greatly improved surface hardness and heat resistance. [Especially cigarette resistance].

Molded articles made from molding materials containing an initial polymer or precopolymer of diallyl phthalate as the resin component have difficulties in their properties and have been desired to improve such properties. In particular, heat resistance and surface hardness cause problems and place restrictions on the use of conventional diallyl phthalate resin compositions.

When a molding material containing an initial polymer or initial copolymer of diallyl phthalate as the resin component is to be used for the production of a laminate such as a decorative board, it has excellent moldability and secondary formability, and the resulting cosmetic board has excellent physical and chemical properties. Characteristic and calm appearance and feel. However, when using such a plate as a top plate of a desk and a checkout counter, it is often damaged by various containers made of cigarette or knife, forks or glass, porcelain, etc., which are often burnt. Thus, such molding materials have not been highly appreciated for these applications.

When conventional molding materials containing initial polymers or initial copolymers of diallyl phthalate as the resin component are used for the production of molded articles such as electrical or electronic parts, the resulting molded articles have excellent size stability and mechanical properties even under harsh atmospheres such as high temperature, high humidity. And as a highly-reliable material having electrical properties. However, in the case of decorative plates, such shaped articles do not have sufficient surface hardness and are still susceptible to damage. These detrimental effects of low hardness also pose problems for use as mechanical parts, commodities such as tableware, and medical supplies. This drawback occurs in the form of whitening on the surface of the molded part when removing the burr, for example as a deflasher or tumbling mixer. In use, the tableware, for example, suffers in the form of surface damage by knives, spoons, forks, and the like.

To date, there have been many proposals for compositions containing combinations of initial polymers of diallyl phthalate with polyacrylates or polymethacrylates of polyalcohols, for example Japanese Patent Publication Nos. 15074/1969, 25234/1969 and 103358/1974 (corresponding to British Patent Application Publication No. 1198259 West German Patent Application Publication No. 1694930).

Polyacrylates or polymethacrylates (hereinafter referred to as "poly (meth) acrylates") of the polyhydric alcohols used in these conventional proposals are, for example, glycerol trimethacrylate, trimethylolpropane trimethacrylate and Pentaerythritol tetramethacrylate. However, according to the inventors' investigation, when the polyhydric alcohol poly (meth) acrylate is used, the surface hardness and thermal stability (particularly tobacco resistance) of the laminated board or various molded articles prepared from the resulting composition are not as high as required. Can not do it. For example, deeper damage occurs when the plucking hardness is measured by increasing the load on a laminate surface from a conventional composition containing polyhydric alcohol poly (meth) acrylates. In addition, when the surface of the molded article from the composition is rubbed with very fine steel wool, the gloss retention of the surface is significantly reduced. When a lit cigarette is placed on a laminated board surface from a polyhydric alcohol poly (meth) acrylate, the back plate is susceptible to coloration or carbonization. In particular, when left for more than 2 minutes, the lowering of the plate is quick.

The present inventors have developed thermosetting diallyl phthalate resin compositions which can overcome the aforementioned drawbacks or shortcomings of molding materials containing initial polymers or initial copolymers of diallyl phthalate as resin components and also the above mentioned drawbacks or drawbacks of the prior art. It was investigated for development.

As a result of these investigations, the use of a specific combination of the above-mentioned resin component with a polyacrylate or polymethacrylate of a specific polyacrylamide can obtain very improved properties and excellent test results from the above-mentioned tests; It has been found that this particular combination leads to thermosetting resin compositions that can provide laminates or molded articles having surface hardness and heat resistance that can withstand practical conditions completely.

The inventors further investigated on the basis of the above findings to provide molded articles having significantly superior properties, in particular surface hardness and heat resistance, of a thermosetting resin composition containing a combination of components (A) and (B) shown below. Found.

(A) 60 to 95% by weight of the initial polymer or initial copolymer selected from the group consisting of the following (A-1), (A-2) and (A-3), (A-1) initial polymer of diallyl phthalate , (A-2) diallyl terephthalate of the following formula (1) and

Aromatic benzyl hydrocarbons having one or more hydrogen atoms in the benzyl position and represented by the following formula (2):

Wherein each of R¹ and R² is a member selected from the group consisting of a hydrogen atom and a lower alkyl group, n is an integer of 1 to 3, and an initial copolymer of diallyl terephthalate derived from (A-3) A mixture of (A-1) and (A-2), and (B) a polyacrylate or polymethacryl of dipentaerythritol represented by the following formula having at least four acryloyl or methacryloyl groups in the molecule: 50 to 5% by weight

이고, 적어도 4개의 R³기는 -COCH=CH₂또는

를 나타낸다.Wherein each R³ is a hydrogen atom, -COCH = CH ₂ or

At least four R 3 groups are -COCH = CH ₂ or

Indicates.

Accordingly, an object of the present invention is to provide a new type of thermosetting resin composition containing an initial polymer or initial copolymer of diallyl phthalate as a resin component useful for providing molded articles having improved properties.

The above and other objects and advantages of the present invention will become more apparent from the following description.

The initial polymer or initial copolymer (A) used as the resin component in the composition of the present invention is selected from the group consisting of (A-1), (A-2) and (A-3).

The prepolymer (A-1) of diallyl phthalate is well known and prepared by a known method which polymerizes o-, m- or p-diallyl phthalate of the following formula in solution or bulk in the presence of a radical initiator. can do.

)이 1,000∼30,000이다. 초기 중합체는 후-중합될 수 있다. 요오드가 점도 및

을 디알릴프탈레이트의 형태(o-, m- 또는 p-)에 따라 적절히 선택할 수 있다. 바람직하기로는, 요오드가는 오르토-초기 중합체에 대하여 55∼65, 이소-초기 중합체에 대하여 65∼90이고, 테레-초기 중합체에 대하여 85∼95이다. 30℃의 50중량% 메틸에틸케론 용액에 대하여 측정한 용액 점도는 바람직하기로는 오르토-초기 중합체에 대하여 70∼110cp, 이소-초기 중합체에 대하여 50∼90cp이고, 테레초기 중합체에 대하여 50∼200cp이다. GPC법에 따라 폴리스티렌으로 계산된 수평균 분자량은 바람직하기로는 오프토-초기 중합체에 대하여 2,000∼20,000, 이소-초기 중합체에 대하여 1,000∼20,000이고, 테레-초기 중합체에 대하여 2,000∼30,000이다.Preferably, the initial polymer (A-1) has an iodine of 55 to 95 as measured by the Wijs method and a viscosity of 50 to 200 cps at 30 ° C for a 50% by weight methylethyl ketone solution. centipoise), and the number average molecular weight (measured by gel permeation chromatography (GPC) and calculated by polystyrene)

) Is 1,000 to 30,000. The initial polymer may be post-polymerized. Iodine has a viscosity and

Can be appropriately selected depending on the form (o-, m- or p-) of the diallyl phthalate. Preferably, the iodine number is 55 to 65 for the ortho-initial polymer, 65 to 90 for the iso-initial polymer and 85 to 95 for the tere-initial polymer. The solution viscosity measured for a 50 wt% methylethylkeron solution at 30 ° C. is preferably 70 to 110 cps for ortho-initial polymers, 50 to 90 cps for iso-initial polymers and 50 to 200 cps for tere initial polymers. . The number average molecular weight calculated by polystyrene according to the GPC method is preferably 2,000 to 20,000 for the offto-initial polymer, 1,000 to 20,000 for the iso-initial polymer and 2,000 to 30,000 for the tere-initial polymer.

Initial copolymers (A-2) of diallyl terephthalate and aromatic benzyl hydrocarbons and methods for their preparation are well known and described in detail, for example, in US Pat. No. 4,518,764 (corresponding to UK Pat. No. 2,131,036). Instead of describing in detail the component (A-2) and its preparation, the above-mentioned U.S. Patent is incorporated herein by reference. Suitable initial polymers for the present invention are described below.

The initial copolymer (A-2) used as the resin component in the present invention is a terephthalate of the following formula (1) and

Aromatic benzyl hydrocarbons having at least one hydrogen atom in the benzyl position and represented by the following formula (2):

Wherein each of R¹ and R² is a member selected from the group consisting of a hydrogen atom and a lower alkyl group, n is an integer of 1 to 3, an initial copolymer of diallyl phthalate.

Preferably the initial copolymer (A-2) is an initial copolymer of diallyl terephthalate having the following structural features (a) and (b).

또는

에 결합된다.(a) This initial copolymer has an allyl group of the monomer unit of formula (1) in which one monomer unit of formula (2) is

or

Is coupled to.

(b) The number of monomer units of formula (1) in the carbon-carbon bonded molecular chain segment formed from the allyl group of the monomer unit of formula (1) in the initial copolymer is 3-11.

The structure of the initial copolymer (A-2) is also described in the above cited US Pat. No. 4,518,764. When toluene (R¹ = R² = H, n = 1) is used as the compound of formula (2), the structure of the initial copolymer can be represented by the following formula (A ₁ ).

(X = 3 ~ 11)

In formula (A ₁ ), R is a chain derived from an unreacted allyl group and / or an allyl group constituting another molecular chain segment of the initial copolymer.

Indicates. As an example, there is a structural part represented by the following formula (C ₁ ).

Formula (A ₁₎ an allyl group in the structure of the carbon formed - the number of monomer units of formula (1) in the carbon bonded molecular chain segment is 3-11, as shown in formula (A _1). This carbon-carbon bonded molecular chain segment is a head-to-head bond segment of formula (B ₂ )

And a head-to-tail bond shown in formula (A ₁ ), ie, a bond of formula (B ₁ ).

Within the structure of formula (C ₁ ), the monomer unit of formula ( ₁ ) constitutes a side chain point that couples two structural units of formula (B ₁ ) and (B ₂ ) via two ester bonds.

R At this time, the unreacted allyl date may be represented by the structural unit formula (C _2).

The structural moiety of formula (C ₂ ) forms a crosslinking site upon curing of the diallyl terephthalate initial copolymer.

이 4,000∼10,000이고, 중량평균 분자량

이 70,000∼200,000이고

대

의 비율로 나타낸 분자량 분포가 10∼40이고, (h) 브라벤더 플라스토그래피로 측정한 브라벤더 응용점도가 250∼2,600m.g.이고 브라벤던 플라스토그래프로 측정한 가공시간이 5∼65분이다.In the present invention, it is preferable that the initial copolymer (A-2) further has the following characteristics: (c) 1.20 to 1.25 of the iodide at 40 to 85 and (d) 25 deg. (e) softening temperature range of about 50 ° C. to 120 ° C., and (f) a viscosity determined at 30 ° C. for a 50% by weight methylethyl ketone solution, measured by gel permeation chromatography (GPC). Average molecular weight that can be calculated with polystyrene

It is 4,000-10,000, and a weight average molecular weight

Is 70,000-200,000

versus

The molecular weight distribution represented by the ratio is 10 to 40, (h) the Brabender application viscosity measured by Brabender Plasography is 250 to 2,600 mg, and the processing time is 5 to 65 minutes as measured by Brabdendon platograph.

The preparation of the initial copolymer (A-2) described above is set out in US Pat. No. 4,518,764, cited above. For example, the reaction conditions may be appropriately selected and matched to provide an initial copolymer having structural properties (a) and (b), and preferably also properties (c) to (h). It can be prepared by copolymerizing diallyl terephthalate of formula (1) and aromatic hydrocarbon of formula (2) in the presence of the same catalyst.

In formula (2) representing an aromatic hydrocarbon, each of R 1 and R 2 is selected from a hydrogen atom and a lower alkyl group. The lower alkyl group is a C ₁ ~C ₅ alkyl group.

Examples of the compound of formula (2) include toluene, ethylbenzene, n-propylbenzene, isopropylbenzene, n-butylbenzene, isobutylbenzene, sec-butylbenzene, n-amylbenzene, sec-amylbenzene, iso Amylbenzene, (2-methylbutyl) -benzene, o-xylene, m-xylene, p-xylene, xylene isomer mixture. Pseudocumene, 1,2-diethylbenzene, 1,3-diethylbenzene, 1,4-diethylbenzene, 1,2-dipropylbenzene, 1,3-dipropylbenzene, 1,4- Dipropylbenzene, diisopropylbenzene, p-cymene, 1,2-dibutylbenzene, 1,3-dibutylbenzene, 1,4-dibutylbenzene, 1,2-diisoimylbenzene, 1,3- Diisoamylbenzene, 1,4-diisoamylbenzene, and 1,2,3-trimethylbenzene.

Examples of organic peroxides and azo compounds used as catalysts to form diallyl terephthalate copolymers (A-2) include di-tert-butyl peroxide, di-sec-butyl peroxide, tert-butyl-sec-butyl Dialkyl peroxides such as peroxides and dicumyl peroxides; Diaryl peroxide; Diacyloyl or diacyl peroxide, such as bennoyl peroxide; Alkyl esters of percarboxylic acids such as di-tert-butyl peroxalate and tert-butyl perbenzoate: 2,2'-azobis isobutyronitrile, 2,2'-azobis- (2-methylbuty Ronitrile), 2,2'-azobis- (2-methyl-haptanitrile), 1,1'-azobis- (1-cyclohexylcarbonitrile), methyl 2,2'-azobis isobutyrate, 4 Azo compounds such as, 4'-azobis- (4-cyano-pentanoic acid), and azidobenzene; And tert-butylhydroperoxide, sec-butyl hydroperoxide, tetralin hydroperoxide, cumyl hydroperoxide, benzene hydroxide peroxide, benz hydryl hydroperoxide, decalin hydroperoxide, acetyl peroxide, cyclohexyl hydro Peroxides, and hydroperoxides such as n-decyl hydroperoxide. Moreover, as molecular oxygen, the compound which is easy to oxidize can also be used. For example, diallyl terephthalate, an aromatic hydrocarbon of formula (2) having at least one hydrogen atom in the benzyl position, and the copolymer of the present invention correspond to such an oxidizing compound. If these are oxidized with air or oxygen before or during the copolymerization reaction to form peroxides, these can also be used as catalysts for the copolymerization reaction.

The use of diallyl terephthalate initial copolymer (A-2) to impart to the compositions of the present invention is effective and desirable for imparting higher impact strength to laminates or molded articles. In the falling dart test, which shows the impact strength of the curing-product of the diallyl O-phthalate initial polymer, the drop height leading to failure is up to 70 mm, whereas that of the cured product of diallyl terephthalate earth copolymer is about 180 mm. As high as.

The composition of the present invention uses diallyl phthalate initial polymer (A-1), diallyl terephthalate initial copolymer (A-2), or a mixture of both (A-3) in any ratio. In the mixture, in order to secure the impact strength of the diallyl terephthalate initial copolymer, the diallyl terephthalate initial copolymer (A-2) is at least 1% by weight, preferably at least 5% by weight, more preferably at 20% by weight. It is good to exist anymore.

In addition to the initial polymer or initial copolymer (A) as an essential resin component, the thermosetting resin composition of the present invention contains a small amount of another resin compatible with component (A). For example, unsaturated polyester resins may be further blended in order to obtain good cure rates and good affinity with fillers and to increase economic effectiveness. As for the mixing amount of an unsaturated polyester, 40 weight% or less is preferable with respect to component (A) and the total amount of unsaturated polyester resin. If the mixing amount exceeds 40% by weight, the excellent intrinsic properties of the diallyl phthalate prepolymer (A-1) or diallyl terephthalate prepolymer (A-2) are greatly lowered and prepared from the resulting thermosetting resin composition. The moisture resistance of the laminate or molded article is undesirably reduced.

Examples of unsaturated polyester resins include mixtures of one or more polybasic unsaturated acids such as maleic acid, fumaric acid and ataconic acid with one or more polybasic saturated acids such as phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid and succinic acid; It is an unsaturated polyester resin obtained by making 1 or more types of polyhydric alcohols, such as diethylene glycol, propylene glycol, dipropylene glycol, and neopentyl glycol, react. Preferably, the unsaturated polyester resin has an acid value of about 5 to 100, a viscous liquid at room temperature (18 to 25 ° C), or a solid having a flash point of 150 ° C or less.

The resin component (A) in the composition of the present invention may be mixed with a vinyl monomer that contributes to increasing the crosslink density of the resin during curing. The mixing amount of the vinyl monomer is preferably 5% by weight or less based on the total amount of it and the component (A). If this exceeds 5% by weight, it causes disadvantages. For example, the curing speed is delayed too much during resin curing, or the curing shrinkage is increased to increase the internal distortion of the molded product.

Examples of vinyl monomers include allyl esters such as diallyl ortho-phthalate, diallyl isophthalate and diallyl terephthalate; Styrene monomers such as styrene and alpha-chlorostyrene; And acrylate monomers such as methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate and propylene glycol dimethacrylate. There is.

The thermosetting resin composition of the present invention is a polyacrylate or polymethacrylate (B) of dipentaerythritol having at least four acryloyl or methacryloyl groups in its molecule as (A-1), (A -2) and in combination with the initial polymer or initial copolymer (A) selected from (A-3).

Component (B) is represented by the following formula:

이고, 적어도 4개의 R³기는 -COCH=CH₂또는

이다.Wherein R 3 each represents a hydrogen atom, -COCH = CH ₂ or

At least four R 3 groups are -COCH = CH ₂ or

to be.

Component (B) contributes to the improvement of the surface hardness and heat resistance (especially tobacco resistance) of the laminated board or molded article manufactured from the thermosetting resin composition of this invention in combination with component (A). As examples of component (B), dipentaerythritol dihydroxy tetraacrylate, dipentaerythritol dihydroxy tetramethacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol monohydroxypentametha Methacrylate, dipentaerythritol nuxaacrylate and dipentaerythritol nuxamethacrylate. These may be used alone or in combination.

When using dipentaerythritol poly (meth) acrylate having three or less acryloyl or methacryloyl groups as component (B) of the composition of the present invention, the surface hardness of the laminate or molded article produced from the composition And the heat resistance is not sufficiently improved, and also the moisture resistance of the laminate or the molded article is markedly reduced.

The mixing ratio of component (A) is 60 to 95% by weight, preferably 70 to 90% by weight, and the mixing ratio of component (B) is 40 to 5% by weight, preferably 30 to 10% by weight. If the proportion of component (B) is less than 5% by weight, the effect of improving the properties is not sufficient. If this exceeds 40% by weight, the composition causes blocking during molding and the molding product increases in shrinkage. Therefore, accurate molding is impossible. Otherwise, the impact strength of the laminate or molded article is reduced.

Admixture of dipentaerythritol poly (meth) acrylate as component (B) in the compositions of the present invention is also effective to increase curing in molding and thus shorten the molding cycle.

The composition of the present invention may be blended with a transition agent in order to facilitate the curing of the resin component (A) and to enhance the crosslinking effect by the component (B). As the curing agent, for example, an organic peroxide used for curing the diallyl phthalate initial polymer or the initial copolymer may be used. Specific examples thereof include benzoyl peroxide, t-butyl peroxy benzoate, dicumyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, lauroyl peroxide, t-butyl peroxyacetate t-butyl Peroxypivalate and t-butyl peroxyoctoate. Of these, benzoyl peroxide, t-butyl peroxybenzoate and dicumyl peroxide are preferred. The addition amount of a hardening | curing agent is suitably selected, for example, 1-10 weight part per 100 weight part.

Depending on the end use of the laminate and other molded articles to be produced from this thermosetting resin composition, various additives may be further mixed in the resin composition. Examples of these additives are fillers, polymerization promoters, compatibility inhibitors, internal mold release agents, coupling agents, pigments and flame retardants.

Fillers are inorganic and / or organic fillers used alone or in combination. The amount of filler used is, for example, about 1 to 500% by weight based on the weight of the resin component (A). Specific examples include talc, mica, asbestos, glass powder, silica, clay, silas, titanium oxide, magnesium oxide, carbon calcium, alumina, aluminum hydroxide, asbestos fiber, silica fiber, glass fiber, silicate glass fiber, alumina fiber, carbon fiber, Inorganic fillers such as boron fibers, beryllium fibers, steel fibers, and whiskers; And organic fillers such as natural fibers (eg cellulose), pulp, acrylic fibers, polyester fibers (eg polyethylene terephthalate fibers), cotton, rayon and polyvinyl alcohol fibers (eg vinylon).

Examples of polymerization promoters are, for example, metal soaps such as cobalt, vanadium, and manganese salts of naphthenic acid and octoic acid, and aromatic tertiary amines such as dimethylaniline and diethylaniline. The amount of the polymerization accelerator is, for example, about 0.005 to about 6% by weight based on the weight of the resin component (A) of the present invention.

Examples of polymerization inhibitors include quinones such as p-benzoquinone and naphthoquinone, hydroquinones, p-tert-butylcatechol, polyhydric phenols such as hydroquinone monomethylether and p-cresol, and quaternary ammonium salts such as trimethyl ammonium chloride. have. The amount of the polymerization inhibitor is, for example, about 0.001 to about 0.1% by weight based on the weight of the resin component (A).

Examples of internal release agents are metal salts of stearic acid such as calcium stearate, zinc stearate and magnesium stearate. The amount of the internal mold release agent is, for example, about 1 to about 5% by weight based on the weight of the resin component (A).

Examples of coupling agents are gamma-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane and allyltrimethoxysilane. The amount of coupling agent is about 0.01 to about 3% by weight based on the weight of the resin component (A).

Examples of pigments are carbon black, iron black, cadmium yellow, benzidine yellow, cadmium orange, rad iron oxide, cadmium rad, cobalt blue, and anthraquinone blue. The amount of the pigment is, for example, about 0.1 to about 10% by weight based on the weight of the resin component (A).

Examples of flame retardants include inorganic compounds such as antimony oxide and aluminum hydroxide, phosphorus containing compounds such as tris (chloroethyl) phosphate, tris (2-bromo-3-chloropropyl) phosphate and ammonium polyphosphate, chlorinated paraffin and di Chlorine-containing compounds such as allylchloratedate, and bromine-containing compounds such as decabromodiphenylether and tetrabromophthalic anhydride. These compounds are known as flame retardants for diallyl phthalate type resins. The use amount of the flame retardant is, for example, about 1 to 30% by weight based on the weight of the resin component (A).

In using the composition of the present invention for producing a laminate, the composition is dissolved in a suitable organic solvent to prepare an impregnated resin solution. Examples of the solvent include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, aromatic compounds such as benzene, toluene, xylene and isopropylene benzene, esters such as ethyl acetate and butyl acetate. Total non-volatile content (i.e., amount of composition excluding solvent) in the substrate impregnated with the composition of the present invention by coating or impregnating the resulting solution on or in a substrate such as printing paper, woven fabric, nonwoven fabric, or a single wooden board. According to the end use of the resultant laminated board, it is made into the range of 30 to 90 weight%. After drying, the resin impregnated substrate is superimposed on the surface of, for example, plywood, particle board, hard board, cement-asbestos plate, gypsum board or resin impregnated kraft paper and the entire assembly is molded under heat and pressure to give the desired laminate. . Alternatively, the resin-impregnated substrate is heated to cure the resin and laminated to a metal plate such as an aluminum plate using an adhesive to form a laminate. It is also possible to stack two or more resin impregnated substrates and mold the assembly under heat and pressure to produce a laminate. In this case, the numerical impregnation substrate may be the same or a combination of two or more substrates of different colors and materials. If the impregnated or coated substrate of the present invention is used as the surface layer of the laminate, the resin impregnated substrate of the lower layer need not be impregnated with the composition of the present invention.

When the laminate thus obtained is cut along a plane intersecting the laminate plane, individual laminated layers appear on the cut plane. By using the cosmetic effect of the laminated layers, this laminate can be used, for example, in the manufacture of upholstery, interior finishes, furniture, attachments and other various handmade articles.

The resin-impregnated substrate used in the manufacture of the laminate is, for example, a nonwoven fabric, paper or a mat composed of natural or synthetic fibers, or a single wooden board. Specific examples of these substrate materials include inorganic fibers such as cellulose, natural fibers such as cotton and asbestos, ceramics, glass fibers and alumina fibers, and polyamide fibers, polyimide fibers, polyimideamide fibers, polyester fibers, and polyvinyl. Organic fibers such as alcohol fibers and acrylic fibers. These substrates are often used in practical use with a reference weight of 10 to 200 g / m 2 and a thickness of 0.02 to 1 mm. These are printed or non-printed. As a substrate for resin impregnation, a single wood board obtained by thinly cutting a paulownia tree, birch tree, wangwang, hawthorn, beech, cherry, etc. to a thickness of 0.1 to 3 mm may be used.

Molding conditions for the manufacture of laminates are those known for producing laminates using diallyl phthalate initial polymer or initial copolymer as the resin component. For example, by molding for 1 to 60 minutes at a temperature of 100 to 160 ° C. under a pressure of 1 to 100 kg / cm 2, a laminate having good surface hardness and heat resistance intended by the present invention can be obtained.

When the composition of the present invention is intended to be used as a raw material for the manufacture of molded articles, for example, electric and electronic parts, mechanical parts, tablewares and daily necessities and medical supplies, the composition is known as a mixing and grinding machine or a Henschel mixer. Mix using a mixer. The mixture is kneaded in a roll mill or kneader heated at 50 to 110 ° C. for 2 to 30 minutes and then pulverized to form raw materials for various molding methods such as compression molding, transfer molding and injection molding. Appropriate molding conditions are used for each molding method. For example, compression molding requires a mold temperature of 150 to 170 DEG C, a molding pressure of 50 to 100 kg / cm < 2 > and a curing time of 40 to 180 seconds per mm of thickness of the grade. The trans-P molding may be carried out under a molding pressure of 30 to 600 kg / cm 2 for a curing time of 30 to 120 seconds per mm of thickness of the molded article at a molding temperature of 150 to 170 ° C.

Injection molding is preferably carried out under the following conditions:

Cylinder temperature: 50-100 ℃ (front)

20-50 ℃ (rear)

Screw Speed: 30-80rpm

Mold temperature: 160-180 ℃

Molding pressure: 300-1500kg / ㎠

Curing time: 20-120 seconds per mm of molded part thickness

Molded articles obtained by the molding methods have particularly good surface hardness and heat resistance.

The following examples illustrate the invention in detail.

[Examples 1-3 and Comparative Examples 1-5]

In each run, the components shown in Table 1 were mixed well to form a resin solution for impregnation. The resulting solution was dipped in printing paper printed with ivory color on the basis of 100 g / m 2 and then taken out and dried at 80 ° C. for 5 minutes to obtain a resin impregnated paper having a solid impregnation amount of 130 g / m 2.

Separately, the same diallyl orthophthalate initial polymer shown in Table 1 was mixed with the curing agent shown in Table 1 and the mixture was dissolved in a mixed solvent of acetone and toluene. Two krafts having a reference weight of 140 g / m 2 in the resulting solution. The sheet was immersed and dried as above to obtain two kraft paper sheets having a solid impregnation amount of 100 g / m 2.

The paper impregnated with the composition of the present invention made as above was placed on two numerically impregnated kraft paper sheets. This assembly was introduced into a glass whose hot plate temperature was maintained at 130 ° C. A glossy caul plate was placed on the printing side of the assembly and the assembly was compressed to a pressure of 30 kg / cm 2 and introduced into a press and cooled with water for 20 minutes.

The surface flicking hardness and tobacco resistance of the resultant decorative plate were measured by the following method, and the results are shown in Table 1.

[Surface flicking hardness]

For each specimen, the Flicking Hardness A test was performed on special plywood mold F in accordance with the JAS standard (Japanese Agricultural and Forestry Standard), and the average depth of damage on these specimens was calculated and defined as the surface flicking hardness.

Methods: Each specimen was fixed horizontally on the holder and loaded with 200 g or 300 g using a diamond needle. Three linear damages of 50 mm length were provided on the surface of the specimen and the depth of the damage was measured.

[Cigarette resistance]

10mm thick particle board [200 type HDR, manufactured by Ada Sangyo Co., Ltd .; The specimen was placed face up on a 10 mm thick, density 0.74 g / cm 3]. Both ends of the specimens were fixed with cellophane tape. After placing the lit cigarette on the specimen and leaving it for 2, 3, 4 or 5 minutes, the tobacco was cleaned with methanol and the appearance of the cosmetic surface was observed. The results were evaluated according to the following standard.

◎: no color change

○: No color change but traces remain

△: color change observed on the surface layer

×: color change observed to deep layer

Partially carbonized and bubbles or cracks are generated.

TABLE 1

Footnotes to (1)-(6) in Table 1

(1) An initial polymer having a viscosity of 96.5 cps, a iodine value of 56.7 and a number average molecular weight of 5,100 according to the GPC method, determined for a 50% by weight methyl ethyl ketone solution at 30 ° C.

(2) An initial polymer having a viscosity of 77 cps at 30 ° C. for a 50% by weight methyl ethyl ketone solution, an iodine value of 83.0 determined by the Wigies method, and a number average molecular weight of 4,700 according to the GPC method.

(3) Initial copolymer of Preparation Example 2 shown in Table 2 below.

(4) A commercially available unsaturated polyester resin having an acid value of 34.5 and prepared from 1 mol of maleic acid, 1 mol of phthalic acid and 2 mol of propylene glycol.

(5) "DR-20S", brand name of product of Osaka Soda Co., Ltd.

(6) "Carplex", a brand name for products of Shionogi Pharmaceutical Co., Ltd.

[Examples 4 to 10 and Comparative Examples 6 to 13]

In each run, the ingredients shown in Table 3 were mixed with a Henschel mixer, kneaded for 2-30 minutes with a roll mill heated to 50-110 ° C. and ground with a hammer mill to form a molding material.

In Comparative Example 9, in which the amount of dipentaerythritol sexaacrylate was excessively high, the molding material was sticky during grinding, and stuck to the hammer and the screen. Therefore, it could not grind smoothly. Also, when left for 1 day at room temperature (23 ° C), it was colored.

The various properties shown in Table 4 were tested for the resulting molding materials. The test method is as follows:

[Required Curing Time]

The molding material was compression molded into a circular plate 100 mm in diameter and 1 mm thick at a mold temperature of 160 ° C. under a molding pressure of 100 kg / cm 2. The surface conditions of the molded article were observed after the molded article was immersed in boiling chloroform for 1 hour. The molding time which does not cause surface roughness or gloss was determined as the required curing time per unit thickness of the molded article.

Rockwell Hardness [(M Scale), ASTM D785], Flexural Strength (ASTM D790), Charpy Impact Strength (V Notched), ASTM D256, Heat Distortion Temperature (48.5kg / ㎠, ASTM D648)

[Volume Resistivity [After Dynamic, ASTM D257]]

Tested according to ASTM. Specimens were prepared by molding at a mold temperature of 160 ° C. under a molding pressure of 100 kg / cm 2. The molding time is obtained by multiplying the required curing time by the thickness of the specimen.

The resins shown in Table 3 are as follows:

The diallyl ortho-phthalate prepolymer and diallylisophthalate prepolymer were the same as those shown in Table 1.

The unsaturated polyester resin was an unsaturated polyester resin having an acid value of 28.0, a softening temperature of 80 DEG C, made from 0.5 mol of maleic anhydride, 0.5 mol of phthalic anhydride, and 1 mol of propylene glycol.

The diallyl terephthalate prepolymers (1) and (2) were prepared in Preparation Example 1 and Preparation Example 2 shown below, respectively. 600 mm inner diameter, 120 liter capacity, turbine blade type variable stirrer, jacketed stainless steel (SUS 304) polymerization tank with double pipe supply nozzle for monomer and catalyst supply, nitrogen washing opening, exposure valve, color coupling, thermometer and pressure gauge Used. The double-tubular feed nozzle for monomer and catalyst supply was secured in the part of the main body of the polymerization tank below the liquid level, and the inner diameter of the inner tube was 1.5mm at the position starting from the position before introduction into the polymerization tank to minimize the residence time in the supply pipe. Was adjusted. Three such nozzles were provided for nozzle occlusion. A sampling section was also provided to the main body of the polymerization tank so that the liquid layer could be sampled using the internal pressure of the polymerization tank during the polymerization reaction. An oil-rotating vacuum pump and a nitrogen-containing vessel were connected to the nitrogen washing openings so that they could be replaced as needed.

60 kg of aromatic hydrocarbon (HC) of formula (2) shown in Table 2 was introduced into the polymerization tank, and the internal pressure of the polymerization tank was reduced at room temperature using a vacuum pump, and then reduced to atmospheric pressure with nitrogen gas. This operation was repeated three times to replace the air in the polymerization bath with nitrogen. Then, the pressure was reduced again and the polymerization tank was closed. The stirrer was operated and stirred at 240 rpm to allow steam to pass through the jacket and to raise the temperature of the polymerization tank to 140 ° C.

Stirring speed was increased to 720 rpm. (Molar ratio 0.5: 1) mixture of diallyl terephthalate and di-tert-butyl peroxide (DTBPO) and aromatic hydrocarbon (HC) of formula (2) was pumped under a discharge pressure of 70 kg / cm 2, and the outer tube of the double tube nozzle Were simultaneously supplied to the polymerization bath at a predetermined rate from. During this time, steam was controlled to maintain the polymerization bath at 140 ° C. The diallyl terephthalate (DAT) of formula (1) to be fed was cooled to 15 ° C. and the mixture of di-tert-butylperoxide and aromatic hydrocarbon was cooled to 5 ° C. The line leading to the polymerization tank was kept cold. The pressure of the polymerization tank was 0.3-2 kg / cm 2 -G. When the feed of the predetermined amount of diallyl terephthalate, aromatic hydrocarbon and di-tert-butyl peroxide was complete the steam feed was terminated and the stirring speed was lowered to 240 rpm. The polymerization tank was cooled by passing cooling water through the jacket. After cooling to near room temperature, the leak valve was opened to reduce the pressure to atmospheric pressure and terminate the polymerization reaction.

During the polymerization, the reaction mixture was sampled appropriately and the reaction was observed by the refractive index and GPC of the sample product.

The feed rates and feed amounts of diallyl terephthalate, aromatic hydrocarbons and di-tert-butylperoxide are shown in Table 2.

A thin film evaporator was used to evaporate the volatiles from the resulting polymerization reaction, and the weight ratio of unreacted aromatic hydrocarbon in the volatile residue to the sum of the copolymer and the unreacted diallyl terephthalate was adjusted to 0.3: 1. Then, the evaporated residue was added dropwise to a stirring tank filled with 5 times the weight of diallyl terephthalate supplied of methanol and stirred to precipitate a copolymer. The precipitated copolymer was washed well with the same amount of methanol, filtered, dried and ground to form a powdery copolymer.

The yields and properties of the copolymers are shown in Table 2.

TABLE 2

Each note for Table 2

(* 1): Calculation was carried out for the plastiret by gel permeation chromatography using a 150CGPC device manufactured by Waters.

(* 2): Light transmission type automatic melting point measuring device (made by "PF61" metallurgy) is used.

(* 3): Measured value by Brabender Plasography manufactured by Brabender Co., Ltd. (West Germany)

Capacity of dough room: 50cc

Rotor type: W50H

Sample: Sample 50g + Yellow Stearate 0.5

Temperature of dough room: 130 ℃

Rotor Speed: 22rpm

The dough was kneaded under the above conditions until the kneading resistance reached 5000 m.g. The minimum torque value was defined as the Brabender melt viscosity from the torque curve on the recording paper, and the time from the end of the sample introduction until the kneading resistance was 5000 m.g was defined as the processing time.

In Table 3, the silane coupling agent used "A-174" of Japan Unicar Co., Ltd. and glass fiber manufactured by Asahi Glass Fiber Co., Ltd. was used.

Molding materials prepared from the respective compositions of Examples and Comparative Examples were adjusted to a 36-pin square connector at a mold temperature of 170 ° C. under an injection pressure of 1000 kg / cm 2 by adjusting the front of the cylinder to 80 ° C. using a 2-cavity mold. Injection molding.

This connector was treated with a deflater to examine whitening of the surface. The results are shown in Table 4.

Walnut shell was used as a deflector, and it was deflashed by spraying time 30 second under an air pressure of 5 kg / cm <2>.

In comparison, the molding material of 9 suffered severe occlusion and thus stuck to the material feed offer. Therefore, the supply of raw materials could not be smoothed and the connector could not be molded.

Specimens (circular plates 100 mm in diameter and 3 mm in thickness) were prepared from each of the molding materials prepared from the compositions shown in Table 3 by compression molding. The surface of this test piece was rubbed 100 times with the steel mat (BONSTAR No. 0000 by the Japan steel wool company), and the change of the surface gloss was measured. The results are shown in the gloss retention rate in Table 4. The glossiness was measured by making the incident angle 60 degrees with the gloss meter (model VG-2PD by Nippon Denshoku Industrial Co., Ltd.).

TABLE 3a

(1): Initial copolymer of the preparation example 1 of Table 2

(2): Initial copolymer of the preparation example 2 of Table 2

TABLE 3b

TABLE 3c

Table 3d

TABLE 4a

TABLE 4

(*): Injection molding was impossible and could not be tested.

From Table 4, the molded articles obtained from the composition of the present invention containing dipentaerythritol poly (meth) acrylate in Example 4-10 are inherent properties of the cured product of diallyl phthalate initial polymer or diallyl terephthalate initial copolymer. It can be seen that it has a much improved surface hardness without breaking.

On the other hand, the product of Comparative Example 6-8, which had resinous delivery without dipentaerythritol poly (meth) acrylate, had a much lower surface hardness. In Comparative Example 9 in which the amount of dipentaerythritol nuxaacrylate is excessively high, the molding material is tacky and poor in handling. In Comparative Example 10, in which the dipentaerythritol trihydroxytriacrylate contained only three acryloyl groups in the molecule, the water resistance (volume resistivity after boiling) of the product was considerably lowered and the surface hardness improvement effect was also low. In Comparative Example 11-13, using the poly (meth) acrylate of the polyhydric alcohol conventionally, the effect of improving the surface hardness was not sufficient.

Claims (5)

(A) 60-95% by weight of the initial polymer or initial copolymer selected from the group consisting of (A-1), (A-2) and (A-3), (A-1) initial polymer of diallyl phthalate , (A-2) diallyl terephthalate of formula (1)

Aromatic benzyl hydrocarbons having at least one hydrogen atom in the benzyl position and represented by the following formula (2):

An initial copolymer of diallyl terephthalate derived from [where each of R 1 and R 2 is a member selected from the group consisting of a hydrogen atom and a lower alkyl group, n is an integer of 1-3], and (A-3) said ( A mixture of A-1) and (A-2) and (B) a polyacrylate or polymethacrylate of dipentaerythritol having at least four acryloyl or methacryloyl groups and represented by the following formula: 40-5% by weight

[Wherein each R³ is a hydrogen atom, -COCH = CH₂ or

At least four R 3 groups are -COCH = CH₂ or

A thermosetting resin composition containing the. The initial polymer (A-1) has an iodine value of 55-95 as measured by Wiegs' method and a viscosity of 50-200 chencps as determined for a 50% by weight methylethylketone solution at 30 ° C. Number average molecular weight measured by gel permeation chromatography and calculated by polystyrene

It is 1,000-30,000. The thermosetting resin composition characterized by the above-mentioned. The thermosetting resin composition according to claim 1, wherein the initial copolymer (A-2) has the following properties (a) and (b). (a) The initial copolymer (A-2) is a monomeric unit of formula (2) is a benzyl position through the carbon-carbon bond

or

Both are bound to the allyl group of the monomeric unit of formula (1), and (b) the monomeric unit of formula (1) in the carbon-carbon bonded molecular chain segment formed from the allyl group of the monomeric unit of formula (1) in the initial copolymer The number is 3-11. The thermosetting resin composition according to claim 3, wherein the initial copolymer (A-2) further has the following properties (c)-(h). (c) the iodine value measured by the Wiegs method is 40-85, (d) the specific gravity at 25 ° C is 1.20-1.25, (e) the softening temperature displacement is about 50 ° C to about 120 ° C, and (f) 30 ° C. The viscosity determined for a 50% by weight methyl ethyl ketone solution at 80-300 cps, (g) number average molecular weight measured by gel permeation chromatography (GPC) and calculated by polystyrene

4,000-10,000, weight average molecular weight

Is 70,000-200,000,

versus

The molecular weight distribution expressed by the ratio of is 10-40, (h) the Brabender melt viscosity measured by Brabender Plasography is 250-2,600 mg and the processing time estimated by Brabender Plasography is 5-65 minutes. The thermosetting resin composition according to claim 1, further comprising about 1 to about 10 parts by weight of a curing agent per 100 parts by weight of the initial polymer or initial copolymer (A).