JP3035700B2 - Curable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel curable composition useful as a modifier for a polymer material or various polymers.

[0002]

2. Description of the Related Art Hitherto, as polyfunctional compounds having a polymerizability and being used as a modifier for various polymers and having a double bond in a molecule, dialkyl fumarate such as dibutyl fumarate, ethylene glycol bis (Isopropyl fumarate), diol bisalkyl fumarate such as bisphenol A bis (secondary butyl fumarate) (JP-A-62-45561, JP-A-62-10)
No. 6059, JP-A-62-235902, JP-A-63
No. 14747), unsaturated carboxylic acid ester compounds such as unsaturated alkyd resins and unsaturated polyester resins.

However, among these compounds, dialkyl fumarate has a drawback that it has only one double bond in the molecule, has no crosslinkability, and is poor in polymerizability. Further, diol bisalkyl fumarate has two double bonds in the molecule and improves the above-mentioned disadvantages of dialkyl fumarate, but the polymerizability is still insufficient, and the resulting polymer Since the crosslinking density is insufficient, there is a disadvantage that physical properties such as heat resistance, chemical resistance and mechanical strength are not sufficient.

An unsaturated alkyd resin is usually produced by polycondensing an unsaturated dibasic acid such as maleic acid with a glycol component such as ethylene glycol, but has a disadvantage that it has a high viscosity and is difficult to handle. Further, in the case of an unsaturated polyester resin obtained by diluting the resin with styrene, styrene is volatilized and a strong odor is generated, which causes a problem that the working environment is deteriorated and environmental pollution is caused.

The present applicant has previously developed a polymerizable fumarate derivative which eliminates the above-mentioned drawbacks of the carboxylic acid ester-based compound, provides a polymer having excellent polymerizability and crosslinkability, and is excellent in heat resistance and the like. (Japanese Patent Laid-Open No. 7-304709)
issue). However, a curable composition in which a general-purpose vinyl polymerizable monomer is blended with this polymerizable fumarate derivative has sufficient polymerizability, but the strength and elongation of the polymer and the balance between them, that is, the toughness, are not necessarily. It was not enough.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a curable composition which is excellent in curability, has a small cure shrinkage, and can provide a cured product having excellent physical properties such as toughness and heat resistance. Is to do.

[0007]

The present inventors have made intensive studies to solve the above-mentioned problems of the prior art, and as a result, have found that certain polymerizable fumarate derivatives, particularly urethane (meth)
The inventors have found that a composition containing an acrylate can achieve the above object, and have completed the present invention.

That is, the present invention relates to (A)

[0009]

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[In the formula, R ₁ and R ₂ are the same or different and each is a halogen-substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a halogen-substituted or unsubstituted carbon group having 6 to 1 carbon atoms.
8 represents an organic group containing a benzene ring, a cycloalkyl group having 3 to 20 carbon atoms, a tetrahydrofurfuryl group or a pyridyl lower alkyl group. R ₃ is a group

[0011]

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FIG. Here, X is a hydrogen atom, carbon number 1
4 to 4 alkyl groups or halogen atoms. D is a direct bond,

[0013]

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Wherein R ₄ is

[0015]

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Is shown. i is an integer of 1 to 4, l is 0 to 3
M represents an integer of 0 to 30; p represents an integer of 1 to 12; n shows 1.1-4.0 by an average value. ] A polymerizable fumarate derivative 10 represented by the formula:
0 parts by weight, (B) urethane (meth) acrylate 1-2
00 parts by weight, 0 to 199 parts by weight of (C) vinyl polymerizable monomer, and the total of components (B) and (C) is 1 to 200 parts by weight.
The present invention relates to a curable composition containing 0.01 to 10% by weight based on the total weight of (D) the polymerization initiator (A), (B) and (C).

The curable composition of the present invention is a low-viscosity liquid, easy to handle, and has excellent curability, that is, excellent in polymerizability and crosslinkability, high crosslink density, and can provide a polymer excellent in toughness and heat resistance. . Therefore, it is suitable as a polymer material or a crosslinking modifier for various polymers.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) of the curable composition of the present invention is a polymerizable fumaric acid ester derivative represented by the aforementioned general formula (I), and is composed of (anhydride) maleic acid or fumaric acid. An average degree of condensation n derived from a certain unsaturated dibasic acid and a diol having a bisphenol skeleton is 1.1 to 4.0.
Is obtained by esterifying both ends of a condensate with a monohydric alcohol.

R _{3 in the} general formula (I) is a residue of a diol component. By using a diol having a bisphenol skeleton, the heat resistance of the resulting polymerizable fumarate derivative and the polymer of the composition are obtained. Etc. are improved.

Examples of the diol having a bisphenol skeleton include 4,4'-isopropylidenebisphenol (hereinafter, referred to as bisphenol A), 4,4'-methylenebisphenol (hereinafter, referred to as bisphenol F), and 4,4'-sulfonyl. Diphenol (hereinafter referred to as bisphenol S), 4,4′-oxybisphenol, bis (4-hydroxyphenyl) methanone,
4′-isopropylidenebis (2,6-dibromophenol) (hereinafter referred to as tetrabromobisphenol A), 4,4′-methylenebis (2,6-dibromophenol) (hereinafter referred to as tetrabromobisphenol F) and the like. Can be Of these, nuclear-substituted or unsubstituted bisphenol A and bisphenol F are preferable from the viewpoint of the heat resistance of the resulting polymerizable fumarate derivative and the heat resistance and toughness of the polymer of the composition.

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an iso-propyl and an n-propyl group.
-Butyl, sec-butyl, t-butyl and the like.

Examples of the halogen atom in the group X in the general formula (I) include a chlorine atom, a bromine atom and an iodine atom.

Examples of the oxyalkylene group represented by R ₄ O in the R ₃ group of the general formula (I) include an oxyethylene group derived from ethylene glycol or ethylene oxide, an oxypropylene group derived from propylene glycol or propylene oxide, A hydroxyoxypropylene group from epichlorohydrin;

As the group represented by R ₃ in the general formula (I), an oxyalkylene group-added bisphenol is preferred. The reason is that bisphenols such as bisphenol A and bisphenol F are solid, but become liquid by the addition of an oxyalkylene group,
This is because the esterification reaction becomes easy, and the viscosity of the resulting polymerizable fumaric acid ester derivative itself becomes low, so that it becomes easy to handle.

L in the group represented by R ₃ in the above general formula (I)
And m is an integer of 0 to 30, preferably 0 to 20. When l or m exceeds 30, the polymerizability of the composition containing the polymerizable fumarate derivative or the heat resistance of the polymer of the composition, chemical resistance, and physical properties such as mechanical strength are preferably reduced. Absent. P is an integer of 1 to 12, preferably 1 to 4. When p exceeds 12, the bisphenols become solid and difficult to handle, and at the same time, the resulting polymerizable fumarate derivative has a high viscosity, making it difficult to handle, and the heat resistance, chemical resistance, and mechanical properties of the polymer of the composition. It is not preferable because physical properties such as strength are reduced.

R ₁ and R _{2 in} the general formula (I) are monohydric alcohol component residues used for terminal esterification (blocking), and may be the same or different, and may be halogen-substituted or unsubstituted. An organic group having a benzene ring having 6 to 18 carbon atoms, a halogen-substituted or unsubstituted alkyl group,
An ester residue that is a cycloalkyl group having 3 to 20 carbon atoms, a tetrahydrofurfuryl group or a pyridyl lower alkyl group.

Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group and a sec-
Butyl group, tert-butyl group, n-hexyl group, n-
Examples thereof include linear or branched alkyl groups such as an octyl group, a 2-ethylhexyl group, and an n-dodecyl group.

Examples of the halogen-substituted alkyl group having 1 to 12 carbon atoms include a chloroethyl group, a 2,3-dibromopropyl group and a tribromoneopentyl group.

Halogen-substituted or unsubstituted C6-C18
Examples of the organic group having a benzene ring include a phenyl group, a phenyl group substituted with a halogen nucleus, an alkyl group having 1 to 4 carbon atoms, a phenyl group substituted with a nucleus, a benzyl group, a benzyl group substituted with a halogen nucleus, and an alkyl group nucleus having 1 to 4 carbon atoms. Examples include a substituted benzyl group, a phenethyl group, and a 2-phenoxyethyl group.

The cycloalkyl group having 3 to 20 carbon atoms includes cyclohexyl, cyclooctyl, cyclonanonyl, cyclodecanyl, cyclododecanyl, cyclotridecanyl, cyclotetradecanyl, cyclooctadecanyl and the like. , A cyclonanodecanyl group and the like.

Examples of the pyridyl lower alkyl group include a pyridylmethyl group (picolyl group), a pyridylethyl group and a pyridylpropyl group.

R ₁ and R ₂ are an organic group having a halogen-substituted or unsubstituted benzene ring having 6 to 18 carbon atoms,
A cycloalkyl group having 3 to 20 carbon atoms, a tetrahydrofurfuryl group or a pyridyl lower alkyl group is preferred, and a phenoxyalkyl group, a cyclohexyl group, a tetrahydrofurfuryl group or a picolyl group is particularly preferred.

In the polymerizable fumaric acid ester derivative of the general formula (I), the average value of n is 1.1 to 4.0, preferably 1.5 to 3.0, and therefore, double It has an average of 2.1 to 5.0 bonds. If the average value of n is more than 4, the molecular weight becomes high, the viscosity becomes high, the handling becomes difficult, and it becomes unsuitable for use as a crosslinking modifier or the like. On the other hand, when the average value of n is less than 1.1, the curability is reduced, and the crosslinked density of the cured product of the composition is insufficient, and the physical properties such as heat resistance and mechanical strength are not sufficient, which is not preferable.

Therefore, only when the average value of n is in the range of 1.1 to 4.0, the composition is a low-viscosity liquid and easy to handle, and the composition containing the polymerizable fumaric acid ester derivative has excellent curability and crosslinkability. It is suitable as a bulking agent, and the cured product has a sufficient crosslink density, and is excellent in physical properties such as heat resistance and mechanical strength.

Formula (I) used in the composition of the present invention
Preferred specific examples of the polymerizable fumarate derivative include, but are not limited to, combinations of R ₁ , R _2, and R ₃ shown in Table 1 below.

[0036]

[Table 1]

The polymerizable fumarate derivative used in the present invention can be prepared as follows.

For example, a maleic acid monoester is obtained by reacting (anhydride) maleic acid with a predetermined molar amount of a monohydric alcohol corresponding to the degree of condensation, and this is reacted with an amount of diol corresponding to the degree of condensation in the presence of an acidic catalyst. To a fumaric acid ester in the presence of an acidic catalyst such as hydrochloric acid or a basic catalyst such as morpholine. The isomerization may be performed before the esterification of maleic acid monoester and diol. Also, a polymerizable fumaric acid ester derivative can be obtained by a process in which fumaric acid is used instead of (anhydride) maleic acid and the isomerization reaction is omitted.

When preparing a polymerizable fumaric acid ester derivative in which R ₁ and R ₂ are different, maleic acid or fumaric acid (anhydride) is mixed with the respective monohydric alcohol to carry out an esterification reaction. The monoester is obtained by reacting separately without mixing a hydric alcohol, and then the dehydration condensation reaction with a diol is carried out in the same manner as described above to obtain the desired product.

As another method, the desired product can be obtained by a reverse process of the above, ie, a method in which maleic acid or fumaric acid (anhydride) is first reacted with a diol component, and then a monohydric alcohol is reacted to carry out terminal esterification. Is obtained.

Further, (anhydrous) maleic acid or fumaric acid,
The target product can also be obtained by a method in which a diol and a monohydric alcohol are simultaneously charged and reacted at the same time.

In the curable composition of the present invention, (A) a polymerizable fumarate derivative is added to (B) urethane (meth)
It is essential to mix acrylate. The component (B) is a urethane (meth) acrylate having a main skeleton of a urethane bond formed by a reaction between a polyisocyanate and a polyol, and having one or more acryloyl groups and / or methacryloyl groups.

The urethane (meth) acrylate is usually obtained by reacting a polyisocyanate compound (a) with a polyol (b) and a (meth) acrylate (c) having a hydroxyl group.

Examples of the polyisocyanate compound (a) include aromatic or aliphatic diisocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate and isophorone diisocyanate, and dimethyl triphenylmethane tetraisocyanate. And polyfunctional isocyanates such as triphenylmethane triisocyanate. These polyisocyanate compounds may be used alone or in combination of two or more.

Examples of the polyol (b) include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, hexamethylene glycol, polyethylene glycol, bisphenol A, bisphenol F and bisphenol used in the general formula (I). Bifunctional alcohols such as oxyalkylene-added bisphenols in which an oxyalkylene group is added to a bisphenol skeleton such as S, and polyfunctional alcohols such as trimethylolpropane and pentaerythritol. More preferred.

The (meth) acrylate (c) having a hydroxyl group is an unsaturated hydroxy compound having one or more hydroxyl groups and one or more (meth) acryloyl groups in the molecule, for example, 2-hydroxyethyl (meth) Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, N-
Hydroxymethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, trimethylolpyropane mono (meth) acrylate, trimethylolpropane di (meth) acrylate, glycerin mono (meth)
Acrylate, glycerin di (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycidyl (meth)
Examples include, but are not limited to, equimolar reaction products of acrylate and (meth) acrylic acid.
These can be used alone or in combination of two or more.

The amounts of the compounds (a), (b) and (c) when synthesizing the urethane (meth) acrylate are usually determined by the ratio of the hydroxyl groups of (b) and (c) to the isocyanate groups of (a). With a reaction equivalent or higher, preferably a hydroxyl group / isocyanate group ratio of 1.0
Used at a rate of about 1.5. There is no particular limitation on the reaction order of (a), (b) and (c).
(B) and (c) are reacted simultaneously, (a) and (b) are reacted, and then (c) is reacted. The reaction temperature is usually about 40 to 70 ° C., and unreacted isocyanate groups are The reaction is usually continued for about 2 to 5 hours until consumed. A normal reaction catalyst such as triethylamine or dibutyltin dilaurate may be used to promote the reaction, or a polymerization inhibitor such as benzoquinone, hydroquinone, hydroquinone monomethyl ether, catechol, or phenothiazine may be used to prevent polymerization during the reaction. it can.

The molecular weight of the urethane (meth) acrylate is not particularly limited, but it is preferable that the viscosity does not increase in handling the composition.
About 00 to 3000 is preferable.

(Meth) of urethane (meth) acrylate
The number of acryloyl groups is one or more on average per molecule, but preferably one to four.

In the curable composition of the present invention, a vinyl polymerizable monomer (C) can be used in combination as a polymerizable monomer. The component (C) also functions as a diluent for the components (A) and (B) having relatively high viscosity.

The vinyl polymerizable monomer includes (meth)
Acrylic acid ester, styrene, vinyl toluene, methyl nucleus substituted styrene, α-methyl styrene, para-t-butyl styrene, chloro nucleus substituted styrene, bromo nucleus substituted styrene, divinyl benzene, diallyl orthophthalate,
Diallyl isophthalate, diallyl terephthalate, triallyl (iso) cyanurate, vinyl benzoate, diallyl tetrachlorophthalate, vinyl ethers, vinyl acetate, vinyl propionate, (meth) acrylamide,
(Meth) acrylonitrile, diethylene glycol bisallyl carbonate, N-vinylpyrrolidone, (meth)
Acryloylmorpholine and the like can be mentioned, and they can be used alone or in combination. Examples of the (meth) acrylic acid ester include methyl (meth) acrylate and ethyl (meth)
Acrylate, n-butyl (meth) acrylate, iso
-Butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate,
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, dicyclo Pentenyl (meth) acrylate, dicyclopentenyl
Monofunctional (meth) acrylates such as oxyethyl (meth) acrylate and isobornyl (meth) acrylate, polyethylene glycol di (meth) acrylate,
Bifunctional (meth) acrylates such as 1,6-hexanediol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and trimethylolpropanetri (Meth) acrylate, pentaerythritol tri (meth)
Examples include, but are not limited to, trifunctional (meth) acrylates such as acrylates. Among these monomers, styrene, alkyl (meth) acrylate having an alkyl group having 1 to 18 carbon atoms, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl Oki Shiechiru (meth)
When one or two or more selected from acrylate and (meth) acryloylmorpholine are used, the cured product is particularly excellent in physical properties such as tensile strength, elongation, heat resistance and the like, and is preferable.

The composition of the present invention further contains a polymerization initiator (D) for each of the above components (A), (B) and (C).

Of the polymerization initiators (D) used in the composition of the present invention, the thermal polymerization initiators are cured at room temperature (normally 5).
-40 ° C.) method, for example, a combination of benzoyl peroxide with an accelerator such as a dialkylaniline or a toluidine derivative, a curing agent of a room temperature curing system such as methyl ethyl ketone peroxide alone or methyl ethyl ketone peroxide, and cobalt naphthenate or dialkyl. The redox reaction is carried out in combination with an accelerator such as aniline or a toluidine derivative. In the medium-temperature curing (normally about 40 to 90 ° C.) method and the high-temperature curing method (normally about 90 to 150 ° C.), benzoyl peroxide, diisopropyl peroxydicarbonate,
Di-n-propylperoxycarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, t-butylperoxydiisobutyrate, t-butylperoxyneodecanoate, −
Examples include radical initiators that decompose at relatively high temperatures, such as 2-ethylhexylperoxydicarbonate, lauroyl peroxide, t-butylperoxybenzoate, azobisisobutyronitrile, azobisdimethylvaleronitrile, ammonium persulfate, and potassium persulfate. Can be used alone or in combination.

As the photopolymerization initiator, a general initiator which is decomposed by irradiation with light to generate radicals and the like is used.
Although not particularly limited, for example, benzoin alkyl ethers such as benzyl, benzophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin propyl ether; 2,2-diethoxyacetophenone; and 2,2-dimethoxy-2-phenylacetophenone; Acetophenone, 2-hydroxy-2-
Methylpropiophenone, propiophenones such as 2-hydroxy-2-methylpropiophenone, thioxanthones, benzyldimethylketal, α-hydroxyisobutylphenone, 1-hydroxycyclohexyl phenyl ketone, tetramethylthiuram disulfide, diphenyl sulfide, Examples include triphenylphosphine, chloronaphthoquinone, anthraquinone, and benzoyl peroxide, which are used alone or in combination. Tertiary amines such as triethylamine and alkylmorpholine can also be used as sensitizers to increase the photopolymerization rate.

The proportion of the constituent components of the curable composition of the present invention is usually (A) the polymerizable fumarate derivative 10
The urethane (meth) acrylate (B) is 1 to 200 parts by weight, preferably 20 to 150 parts by weight, and the (C) vinyl polymerizable monomer is 0 to 199 parts by weight, preferably 10 to 10 parts by weight, based on 0 part by weight. 100 parts by weight, and the total of the components (B) and (C) is 1 to 200 parts by weight. Further, the amount of the polymerization initiator (D) used generally depends on the component (A),
0.01 to 1 based on the sum of the components (B) and (C)
0% by weight, preferably 0.05 to 5% by weight. If the amount is less than 0.01% by weight, the curing is insufficient and the surface of the cured product remains tacky. If it exceeds 10% by weight, curing is not particularly accelerated, which is economically disadvantageous.

In the composition of the present invention, if necessary, for example, vinyl chloride resin, polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene.
Styrene resins such as styrene copolymers, thermoplastic resins such as polycarbonate and polystyrene-modified polyphenylene ether resins, and thermosetting resins such as phenol resins, epoxy resins, and diallyl phthalate resins can be used in combination.

Also, heat stabilizers such as dibutyltin maleate, dibutyltin mercaptide, metal soaps, lead compounds, etc., antioxidants, ultraviolet absorbers, lubricants such as stearic acid ester, stearyl alcohol, polyethylene wax, calcium carbonate, glass Fillers such as fibers, pigments such as titanium oxide, dyes, plasticizers and the like can be added.
Furthermore, other modifiers can be used in combination.

The curable composition of the present invention can be obtained by mixing, stirring, etc. each component at room temperature or, if necessary, under heating.

In preparing the composition, (B)
The urethane (meth) acrylate as a component may be separately synthesized and mixed with other components. However, if the viscosity of the component (B) is high and the polymerization is easy during the synthesis, the polymerization prepared in advance may be used. When the reaction is performed in the presence of the soluble fumaric acid ester derivative (A), the viscosity becomes lower, and the synthesis and handling become easier. In order to synthesize the component (B) in this way, the components (A) and (B) may be reacted so as to have a predetermined composition when the component (B) is synthesized. In this case, the components (A) and (B) do not react with each other.

The curable composition of the present invention has excellent curability by heat, ultraviolet light, electron beam or radiation, and produces a crosslinked polymer having excellent physical properties. Although the curing conditions of the present composition are not particularly limited, for example, in the case of thermal polymerization, usually 5
It can be cured by heating at about 150 ° C. for about 1 to 24 hours. In the case of photopolymerization, the actinic light sources include low-pressure mercury lamps, high-pressure mercury lamps, fluorescent lamps for ultraviolet rays, carbon arc lamps, xenon lamps, zirconium lamps,
Sunlight or the like can be used. For example, a high-pressure mercury lamp (80 W / c
m), when the irradiation distance is about 15 cm, 5 to 300
It can be cured by irradiating ultraviolet rays for about a second. If necessary, curing may be performed by two-stage curing.

The composition of the present invention can be used alone or as a modifier incorporated in various polymers for a wide range of uses such as paints,
Development as a raw material or modifier for image forming materials such as coating agents, printing inks, varnishes, adhesives, photosensitive printing materials, photoresists, etc., and for the modification of molding materials and various synthetic resins Is possible. When molding, for example,
Ordinary FRP such as cast molding method to cure directly in desired mold
The same molding method can be used.

[0062]

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

Synthesis Example 1 Synthesis of polymerizable fumaric acid ester derivative (A) In a 2 L four-necked flask equipped with a stirrer, a thermometer and a distillate removing device, 196 g of maleic anhydride and cyclohexano-
200 g of toluene were reacted in 300 g of toluene at 90 ° C. for 5 hours to synthesize monocyclohexylmalate. Next, 10 g of 35% hydrochloric acid was added as an isomerization catalyst,
For 6 hours to obtain monocyclohexyl fumarate.

The isomerization was analyzed by gel permeation chromatography (GPC), and it was confirmed that the isomerization was nearly 100% complete by peak shift.

To this were added 664 g of bisphenol A di (pentaethylene glycol) (abbreviated as BPA · 10EO) and 10 g of paratoluenesulfonic acid as a catalyst.
A dehydration reaction was performed at 0 ° C. for 6 hours. After washing with water, toluene, unreacted alcohol and the like were distilled off to obtain 1004 g of a yellow viscous liquid polymerizable fumarate derivative (A).

Synthesis Examples 2 to 4 Synthesis of Polymerizable Fumarate Derivatives (B) to (D) Synthesis Example 1 was repeated except that the monohydric alcohol shown in Table 2 was used instead of cyclohexanol in Synthesis Example 1. In the same manner as in the above, yellow viscous liquid polymerizable fumaric acid ester derivatives (B), (C) and (D) were obtained.

Synthesis Example 5 Synthesis of Comparative Polymerizable Fumarate Derivative (E) In a 2 L four-necked flask equipped with a stirrer, thermometer, and distillate remover, 98 g of maleic anhydride and 100 g of cyclohexanol were added to toluene. The reaction was carried out at 90 ° C. for 5 hours in 400 g to synthesize monocyclohexylmalate. To this, 101 g of triethylamine was added, 143 g of thionyl chloride was added dropwise in an ice bath, and the mixture was reacted at room temperature for 10 hours. Then, triethylamine hydrochloride was filtered off to obtain monocyclohexyl fumaric acid chloride. This toluene solution of cyclohexyl fumaric acid chloride was treated with bisphenol A di (pentaethylene glycol) (abbreviated as BPA · 10EO) 332.
g and 150 g of pyridine / toluene (1/1) were added dropwise under ice-cooling, and reacted at room temperature for 10 hours. Then, pyridine hydrochloride was filtered off, and the filtrate was washed with water and toluene was distilled off to obtain 486 g of a comparative polymerizable fumarate derivative (E) as a yellow viscous liquid for comparison. This compound corresponds to the polymerizable fumarate derivative (A) having a different degree of condensation.

Synthesis Examples 6 to 8 Synthesis of Comparative Polymerizable Fumarate Derivatives (F) to (H) Same as Synthesis Example 5 except that cyclohexanol in Synthesis Example 5 was changed to a monohydric alcohol shown in Table 2. And the comparative polymerizable fumarate derivatives (F), (G),
(H) was obtained. This compound has polymerizable fumarate derivatives (B), (C), and (D) having different degrees of condensation.
Corresponding to

The composition and viscosity of each of the polymerizable fumarate derivatives used in Examples and Comparative Examples of the present invention obtained in Synthesis Examples 1 to 8 were measured by the following methods.

[Composition Analysis] The composition of each polymerizable fumaric acid ester derivative was analyzed by GPC.
The composition ratios of 0 to 5 were calculated, and the average value of n was calculated from the composition ratios.

[Viscosity] The viscosity of each polymerizable fumaric acid ester derivative was measured using a B-type viscometer.

From the results of the composition analysis, the polymerizable fumaric acid ester derivatives (A) to (D) used in Examples have an average value of n in the general formula (I) in the range of 1.1 to 4.0. Turned out to be something. On the other hand, each of the polymerizable fumaric acid ester derivatives (E) to (H) used in the comparative examples was synthesized under a condition at which a transesterification reaction did not occur at a low temperature. It turned out that it was obtained.

Table 2 shows the raw materials, yields, compositions and viscosities of the polymerizable fumaric acid ester derivatives.

[0074]

[Table 2]

The urethane methacrylate shown below is
It was synthesized as follows. That is, urethane methacrylate (U-1) is synthesized in the presence of the polymerizable fumarate derivatives (A) to (D) obtained in Synthesis Examples 1 to 4, and (A) / (U-1) , (B) / (U-1), (C)
/ (U-1) and (D) / (U-1). In addition, the synthesis of urethane methacrylates of Synthesis Examples 10 to 12 described below were similarly performed in the presence of a polymerizable fumarate derivative. Further, the urethane methacrylates (U-1), (U-2) and (U-4) used in Comparative Examples also have the presence of the polymerizable fumaric acid ester derivative having a low degree of condensation obtained in Synthesis Examples 5 to 8. Synthesized below.

Synthesis Example 9 Urethane methacrylate (U
Synthesis of -1) Urethane methacrylate (U-1) used in Example 1
Is mixed with a polymerizable fumarate derivative (A) and a urethane methacrylate (U-1) in a ratio of 50/50 wt.
% Was determined. That is, in the presence of 1004 g of the polymerizable fumaric acid ester derivative (A), 275 g of 2,4-tolylene diisocyanate was charged into a 2 L four-necked flask equipped with a stirrer and a thermometer, and heated to about 50 ° C. to give methoxyhydroquinone. 205 g of 2-hydroxyethyl methacrylate solution in which about 0.2 g is dissolved
React with additional time, and add bisphenol A
After charging 524 g of di (pentaethylene glycol), the mixture was reacted and aged at about 60 ° C. to obtain a composition comprising a polymerizable fumarate derivative (A) / urethane methacrylate (U-1).

Similarly, as (U-1) used in Example 2, urethane methacrylate (U-1) was synthesized in the presence of the polymerizable fumarate derivative (B). That is, in the presence of 977 g of the polymerizable fumarate derivative (B), a 2 L four-necked flask equipped with a stirrer and a thermometer was prepared.
268 g of 2,4-tolylene diisocyanate was charged,
2-hydroxyethyl methacrylate solution 20 in which about 0.2 g of methoxyhydroquinone was dissolved by heating to about 50 ° C.
0 g was reacted in about 2 hours while adding 511 g of bisphenol A di (pentaethylene glycol), and then reacted and aged at about 60 ° C.
A polymerizable fumarate derivative (B) / urethane methacrylate (U-1) composition was obtained.

Similarly, in Examples 3 and 4 (U-
As 1), urethane methacrylate (U-1) in the presence of a polymerizable fumarate derivative (C) or (D)
Was synthesized.

The urethane methacrylate (U-1) used in Examples 1 to 4 has an average of two methacryloyl groups per molecule regardless of the type of the polymerizable fumarate derivative present at the time of synthesis. The number average molecular weight is 1300 (GPC analysis, polystyrene equivalent value,
The same applies hereinafter).

Synthesis Example 10 Synthesis of urethane methacrylate (U-2) As a diisocyanate compound, isophorone diisocyanate was used instead of 2,4-tolylene diisocyanate. That is, in the presence of 1004 g of the polymerizable fumaric acid ester derivative (A), 2 stirrer and thermometer were attached.
In an L four-necked flask, add isophorone diisocyanate 32
6 g, heated to about 50 ° C., and reacted while adding 191 g of 2-hydroxyethyl methacrylate solution in which about 0.2 g of methoxyhydroquinone was dissolved in about 2 hours, and further 485 g of bisphenol A di (pentaethylene glycol). After being charged, the mixture is reacted and aged at about 60 ° C. to give a polymerizable fumarate derivative (A)
/ Urethane methacrylate (U-2) composition was obtained.

The obtained urethane methacrylate (U-
2) had an average of two methacryloyl groups per molecule, and had a number average molecular weight of 1,400.

Synthesis Example 11 Synthesis of Urethane Methacrylate (U-3) In the presence of 1004 g of the polymerizable fumarate derivative (A), a 2 L four-necked flask equipped with a stirrer and a thermometer was placed.
Charge 491 g of 2,4-tolylene diisocyanate,
A 2-hydroxyethyl methacrylate solution 36 heated to about 50 ° C. and about 0.2 g of methoxyhydroquinone dissolved therein
After reacting while adding 7 g in about 2 hours, 149 g of diethylene glycol was charged, and the mixture was reacted and aged at about 60 ° C. to obtain a polymerizable fumarate derivative (A) / urethane methacrylate (U-3) composition. I got

The obtained urethane methacrylate (U-
3) had an average of two methacryloyl groups per molecule and had a number average molecular weight of 700.

Synthesis Example 12 Synthesis of urethane methacrylate (U-4) Urethane methacrylate was synthesized using glycerin dimethacrylate instead of 2-hydroxyethyl methacrylate as the methacrylate. That is,
In the presence of 1004 g of the polymerizable fumarate derivative (A), a 2 L four-necked flask equipped with a stirrer and a thermometer was added.
239 g of 2,4-tolylene diisocyanate was charged,
Approximately 313 g of glycerin dimethacrylate in which about 0.3 g of methoxyhydroquinone was dissolved by heating to about 50 ° C.
React with additional time, and add bisphenol A
After charging 451 g of di (pentaethylene glycol), the mixture was reacted and aged at about 60 ° C. to obtain a polymerizable fumarate derivative (A) / urethane methacrylate (U-4) composition.

The obtained urethane methacrylate (U-
4) had an average of 4 methacryloyl groups per molecule, and had a number average molecular weight of 1500.

Example 1 Polymerizable fumarate derivative (A) / urethane methacrylate (U-1) = 50/50 wt% composition 100
2 g of 55% methyl ethyl ketone peroxide and 6% of cobalt naphthenate as a thermal polymerization initiator.
1 g was added and mixed to obtain a curable composition of the present invention. This was poured into a Teflon mold of the size for a test piece according to ASTM D-648 and cured by two-step curing.
That is, after curing at room temperature (at about 20 ° C. for 24 hours), the composition was almost completely cured at 120 ° C. for 2 hours as a post cure to prepare a heat resistant test piece.

On the other hand, in place of the thermal polymerization initiator, 5 g of “Irgacure 651” (trade name, benzyldimethyl ketal, manufactured by Ciba-Geigy) was added as a photopolymerization initiator.
By mixing, a curable composition of the present invention was obtained. The bottom of the Teflon mold whose top and bottom are released is held down by a glass plate that has been subjected to a mold release treatment with a polyester film, the curable composition of the present invention is injected, and after the injection, the upper surface of the mold is subjected to the same treatment as described above. The plate was pressed with a plate, and irradiated with a high-pressure mercury lamp (80 W / cm) at a distance of 15 cm on each side for 2 minutes on each side to prepare a test piece for measuring physical properties other than heat resistance.

Examples 2 to 7 Examples 1 to 10 were prepared by using a composition comprising a polymerizable fumarate derivative of the type shown in Table 3 below and urethane methacrylate.
The same amount of a thermal polymerization initiator or a photopolymerization initiator was added and mixed to obtain a curable composition of the present invention. Using this, Example 1
A test piece was prepared in the same manner as described above.

Example 8 Polymerizable fumarate derivative (A) / urethane methacrylate (U-1) = 50/50 wt% composition 100
50 g of acryloyl morpholine as a vinyl polymerizable monomer was added to g, and the same amount of a thermal polymerization initiator or a photo polymerization initiator as in Example 1 was added and mixed to obtain a curable composition of the present invention. Was. Using this, a test piece was prepared in the same manner as in Example 1.

Examples 9 to 11 In the same manner as in Example 8, except that 50 g of the vinyl polymerizable monomer shown in Table 3 was added instead of acryloylmorpholine as the vinyl polymerizable monomer. The curable composition of the present invention was obtained. Using this, a test piece was prepared in the same manner as in Example 1.

Comparative Examples 1-2 A curable composition for comparison was obtained in the same manner as in Example 1 or 2, except that urethane methacrylate was not used. Using this, a test piece for measuring physical properties was prepared in the same manner as in Example 1.

Comparative Examples 3 to 5 Compositions of polymerizable fumaric acid ester derivatives (F) to (H) / urethane methacrylate (U-1) having a low degree of condensation obtained in Synthesis Examples 6 to 8 = 50/50 wt% Using 100g,
A comparative curable composition was obtained using the same formulation as in Example 1. Using this, a test piece was prepared in the same manner as in Example 1.

Comparative Examples 6 to 8 Using the polymerizable fumaric acid ester derivative (E) obtained in Synthesis Example 5 and 100 g of a urethane methacrylate composition of the type shown in Table 4, the same formulation as in Example 1 was used. A curable composition for use was obtained. Using this, a test piece was prepared in the same manner as in Example 1.

For the test pieces obtained by heat-curing or photo-curing the curable compositions obtained in Examples 1 to 11 and Comparative Examples 1 to 8, the hardness, polymerization shrinkage, tensile strength and elongation of the cured product were obtained. And heat resistance were measured by the following methods.

[Hardness] In accordance with ASTM, D-2583,
Barcol hardness was measured using the photopolymerized test piece.

[Polymerization Shrinkage] The specific gravity p of the blended liquid and the specific gravity q of the photopolymer were measured and calculated according to the formula of (1-p / q) × 100.

[Tensile strength, elongation] ASTM, D-63
No. 8 No. 1 dumbbell-shaped test piece having a thickness of 2 mm was prepared by photopolymerization, and the strength and elongation at a tensile speed of 10 mm / min were measured.

[Heat resistance] According to ASTM, D-648,
A test piece having a length of 127 mm, a width of 10 mm and a thickness of 13 mm was prepared by thermal polymerization, and the deflection temperature under load at a load of 18.6 kg / cm ² was measured.

Further, the polymerization rate as an index of curability of each composition was measured by the following method.

(1) Thermal Polymerization 10 g of the mixture shown in Table 3 or Table 4 was placed in a test tube, 0.05 g of benzoyl peroxide was charged as a thermal polymerization initiator, and after purging with nitrogen, polymerization was carried out at 80 ° C. for 5 hours. . After polymerization, the cured polymer was Soxhlet extracted with toluene for 5 hours,
The conversion was determined.

(2) Photopolymerization 1% by weight of benzyl dimethyl ketal (trade name: Irgacure 651 manufactured by Ciba-Geigy Co., Ltd.) was added as a photopolymerization initiator to the mixture shown in Table 3 or 4, and the curable composition of the present invention was added. The bottom surface of the Teflon mold whose top and bottom are released is held down by a glass plate that has been release-treated with a polyester film, and the curable composition of the present invention is injected. It was pressed with a glass plate treated in the same way, and irradiated on both sides for 2 minutes each side from a place of 15 cm under a high-pressure mercury lamp (80 W / cm), and the polymerization rate was determined in the same manner as in the case of thermopolymerization.

Tables 3 and 4 show the compositions and test results of the curable compositions of Examples 1 to 11 and Comparative Examples 1 to 8.

[0103]

[Table 3]

[0104]

[Table 4]

When Examples 1 and 2 and Comparative Examples 1 and 2 shown in Tables 3 and 4 are compared, when compared with the case where the polymerizable fumaric acid ester derivative is used alone, the urethane ( It can be seen that when (meth) acrylate is blended, the polymerization rate, the hardness, strength, elongation, and heat resistance of the obtained cured product are all excellent. In addition, comparing Examples 1 to 7 and Comparative Examples 3 to 8, even if urethane (meth) acrylate is blended, the average value of n is 1.1 to 4.0, that is, the average of double bonds is 2.1. The composition of the present invention using the polymerizable fumarate derivative containing 〜5.0 or less and the comparative composition containing the equivalent of n = 1 (two double bonds) of the derivative are better in the composition of the present invention. It turns out that it is excellent in various physical properties.

In the case of a composition further containing a vinyl polymerizable monomer (Examples 8 to 11), it was also found that the obtained cured product had more excellent physical properties.

[0107]

The curable composition of the present invention is excellent in heat or light curability, has a small curing shrinkage, and has a high curing shrinkage ratio due to the addition of urethane (meth) acrylate to a specific polymerizable fumarate derivative. The hardness, the strength and the elongation of the cured product are large and well balanced, that is, a cured product having excellent toughness and excellent physical properties such as heat resistance is obtained, and is extremely suitable as a polymer material or a crosslinking modifier.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI // C07C69 / 60 C07C69 / 60 C08F2 / 46 C08F2 / 46 C09D 175/06 C09D 175/06 C09J 175/06 C09J 175 / 06 (56) References JP-A-7-304709 (JP, A) JP-A-62-45561 (JP, A) JP-A-63-14757 (JP, A) JP-A-2-21811 (JP, A) JP-A-48-12834 (JP, A) JP-A-3-227390 (JP, A) JP-A-3-227389 (JP, A) JP-A-54-81398 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08F 290/00-290/14 C08F 2/46-2/50 C08F 22/00-22/40 C08F 222/00-222/40 C08F 283/00-283 / 01 C08F 299/00-299/08 C09D 1/00-201/10 C09J 1/00-201/10 C07C 69/60

Claims (6)

(57) [Claims] (A) General formula (A) [Wherein, R ₁ and R ₂ are the same or different and are each a halogen-substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a halogen-substituted or unsubstituted organic group containing a benzene ring having 6 to 18 carbon atoms, A cycloalkyl group having 3 to 20 carbon atoms, a tetrahydrofurfuryl group or a pyridyl lower alkyl group. R ₃ is a group Is shown. Here, X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom. D is a direct bond, And R ₄ is Is shown. i is an integer of 1 to 4, l is an integer of 0 to 30,
m represents an integer of 0 to 30; p represents an integer of 1 to 12; n shows 1.1-4.0 by an average value. 100 parts by weight of a polymerizable fumarate derivative represented by the formula:
(B) 1 to 200 parts by weight of urethane (meth) acrylate, (C) 0 to 199 parts by weight of a vinyl polymerizable monomer, and the total of components (B) and (C) is 1 to 200 parts by weight, and (D) A curable composition comprising a polymerization initiator in an amount of 0.01 to 10% by weight based on the total of the components (A), (B) and (C). 2. In the formula (I), R ₁ and R ₂ are the same or different and each have a halogen-substituted or unsubstituted C 6 -C 6.
The curable composition according to claim 1, which is an organic group having 18 benzene rings, a cycloalkyl group having 3 to 20 carbon atoms, a tetrahydrofurfuryl group or a picolyl group. 3. The curing method according to claim _1, wherein R ₁ and R _{2 in the} formula (I) are the same or different and each is a phenoxyalkyl group, a cyclohexyl group, a tetrahydrofurfuryl group or a picolyl group. Composition. 4. The method according to claim 1, wherein the urethane (meth) acrylate (B) is
The curable composition according to claim 1, wherein the curable composition is a reaction product of a polyol, a polyisocyanate compound, and a (meth) acrylate having a hydroxyl group. 5. The urethane (meth) acrylate (B) is
The number average molecular weight is 400 to 3,000, and has an average of 1 to 4 (meth) acryloyl groups in one molecule.
A composition according to claim 1. 6. The vinyl polymerizable monomer (C) is styrene,
Having an alkyl group having 1 to 18 carbon atoms (meth) acrylic acid alkyl ester, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, di
Cyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate and (meth)
The curable composition according to claim 1, which is at least one member selected from the group consisting of acryloylmorpholine.