JP2000169532A - Vinyl ester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain flexible resin compositions which retain a large elongation, simultaneously have toughness and do not leave unreacted monomers behind and are rich in reactivity without causing change in hardness and short in curing time even at low temperatures. SOLUTION: Vinyl ester resin compositions comprise (a) a vinyl ester resin composed of an epoxy acrylate having a (meth)acrylate group at the molecular terminal obtained by reacting an epoxy resin with an α,β-unsaturated monobasic acid and (b) a mixture of polymerizable unsaturated monomers, the homopolymer of each of which has an average glass transition temperature (Tg) of -10 to 99 deg.C, and the polymerizable unsaturated monomer containing a (meth)acryloyl group, with a ratio of component (a) to component (b) of 2/8 to 8/2 to retain a required flexibility.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION This invention relates to a wide range of civil engineering and construction applications such as paints, floor and wall coatings, road markings, castings, laminates, adhesives, linings, corrugated plates, etc. The present invention relates to a radical-curable vinyl ester resin composition having excellent low-temperature curability.

[0002]

2. Description of the Related Art The following resins are conventionally known as radical-curable flexible resins. For example, Japanese Patent Application Laid-Open
In JP-A-196268, there are acrylic syrups, and in JP-A-56-92917, there are unsaturated polyester resins and the like in which the amount of unsaturated dibasic acid is extremely reduced to impart flexibility.

[0003] The above-mentioned resins have their respective characteristics, but have the following problems.

The former comprises a (meth) acrylic acid ester polymer, a (meth) acrylic acid monomer, and a plasticizer as main components, and has a number average molecular weight of 20,000 to 6 as a production method.
After preparing many (meth) acrylic acid ester polymers by suspension polymerization or the like in advance, this is a step of dissolving and mixing the polymer with the monomer and the remaining raw material group. Therefore, there is a problem that the production time becomes very long, but the polymer / monomer ratio is reduced to about 1/100 for viscosity adjustment considering workability.
It becomes 2. This is disadvantageous in that since the amount of the monomer is large, the curing shrinkage increases, and at the same time, the anaerobic property increases, and the surface drying properties of the coating film and the like deteriorate.

In the latter case, on the other hand, the main components consist of glycol and a saturated dibasic acid, a small amount of unsaturated dibasic acid is added to the polyester polymer, and then about 40% of styrene is mixed as a crosslinking monomer. You. Although the number of crosslinking points is small, flexibility is imparted. However, since the number of double bonds on the polymer side to be crosslinked with styrene is small, 50% or more of the total styrene amount becomes surplus. For this reason, styrene exists as a monomer, and gradually reacts with the lapse of time to make the resin harder. 6 resin cured products with initial Shore A hardness of about 40
After a month, it will double to around 80.

Further, Japanese Patent Publication No. 57-28487 discloses a method for imparting flexibility to a vinyl ester resin.
A flexible resin composition comprising a vinyl ester resin obtained by reacting an epoxy compound with a polybutadiene polymer containing a terminal carboxy group or a butadiene-acrylonitrile copolymer and an unsaturated-basic acid, and a polymerizable vinyl monomer has been proposed. ing. However, this resin is very poor in flexibility, judging from the examples.

As a crosslinking monomer which reacts with a polymer of a polymerizable monomer-crosslinking type thermosetting resin such as an unsaturated polyester resin, an epoxy acrylate resin and a polyester acrylate resin, styrene is usually used in most cases. . As a partly modified cross-linking monomer, other monomers may be used in combination with styrene, but the average homopolymer glass transition temperature of the cross-linking monomer is 100 ° C. or higher, which is due to the presence of the unreacted monomer as described above. There is an adverse effect on physical properties, particularly a change in hardness.

Further, in the conventional radical-curing type thermosetting resin, the flexibility is imparted at the polymer portion, so that there is a disadvantage that the curing reaction time becomes extremely long at the cost of the flexibility.

[0009]

That is, according to the present invention, there is provided a flexible resin composition having the above-mentioned disadvantages, large elongation, and toughness, without leaving unreacted monomers,
An object of the present invention is to obtain a resin composition which does not cause a change in hardness, has high curing reactivity, and has a short curing time even at a low temperature.

[0010]

Means for Solving the Problems The present inventors have found that when a vinyl ester resin having an acryloyl group introduced into a polymer portion is used and (meth) acrylic acid ester is used as a monomer to be used, the curing reactivity is remarkably improved. It was found that there was almost no unreacted momer on curing. Furthermore, it has been found that by adjusting the average glass transition temperature (Tg) of the homopolymer of the monomer group used, a resin composition having the required flexibility can be obtained freely, and the present invention is completed. Reached.

The present invention relates to (a) an epoxy resin having α, β-
Unsaturated- (Meth) is added to the molecular end obtained by the reaction with basic acid.
A vinyl ester resin comprising an epoxy acrylate having an acrylate group, (b) an average glass transition temperature (Tg) of -10 when the monomer used becomes a homopolymer.
C. to 99.degree. C., wherein the polymerizable unsaturated monomer contains a (meth) acryloyl group, and the ratio of (a) / (b) is 2/8 to 8 / 2
A vinyl ester resin composition characterized by having the required flexibility, preferably, Tg is represented by the following formula.

1 / Tg = w1 / Tg1 + w2 / Tg2 +
+ Wn / Tgn Tg: Average glass transition temperature of all monomers (° K) Tg1: Average glass transition temperature of monomer 1 (° K) Tg2: Average glass transition temperature of monomer 2 (° K) ・ Tgn: Monomer average glass transition temperature of n (° K) w1: weight ratio of monomer 1 w2: weight ratio of monomer 2 wn: weight ratio of monomer n, w1 + w2 +... wn = 1, n is an integer of 2 or more .

Preferably, it contains a thermoplastic resin, preferably the unsaturated monomer mixture (b)
Contains at least one member selected from unsaturated alcohol monomers, polyfunctional unsaturated monomers, and unsaturated monomers having an air-drying property, and preferably has a polymerizable monomer-crosslinked unsaturated group-containing polymer having an air-drying property. And preferably provides a vinyl ester resin composition whose composition is used for a coating material.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The vinyl ester resin (a) of the present invention is an epoxy acrylate having a (meth) acrylate group at a molecular terminal, and the terminal of an epoxy skeleton (epoxy resin) is an α, β unsaturated dibasic acid. Epoxy acrylate obtained by reacting with an equivalent ratio of 1: 2 to an unsaturated polyester (meth) acrylate, or a saturated or unsaturated polyester (meth) acrylate obtained by adding a carboxyl group at the terminal of an unsaturated polyester to an unsaturated glycidyl compound. And mixtures thereof.

Polyester (meth) acrylate is
A mixture containing at least one (meth) acrylate group in one molecule and a polymerizable unsaturated monomer. The polyester (meth) acrylate is represented by the following general formula.

[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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M: (meth) acrylic acid residue G: glycol residue Tr: triol residue Te: tetraol residue D1: dibasic acid residue D2: tribasic acid residue D3: tetrabasic acid residue Group J: glycol residue based on monoepoxyside X: m-valent organic residue based on reaction with carboxyl group of m-valent epoxy compound Y: n-valent organic residue based on reaction with hydroxyl group of n-valent isocyanate compound Organic residue a, b, c, d: an integer of 1 or more p: 0 or 1 m: an integer of 2 to 10 n: an integer of 2 to 5, and a plurality of groups in parentheses are repeated May have different constituent components for each repeating unit.

The glycol unit in the above formula includes, for example, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, hexylene glycol, dimethylolcyclohexane, 2,4,4-
Alkylene glycols such as trimethyl-1,3-pentanediol; polyalkylene glycols such as diethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, and polybutylene glycol; bisphenol A, bisphenol F, bisphenol S And addition reaction products of dihydric phenols typified by titrabrom bisphenol A and alkylene oxides typified by ethylene oxide and propylene oxide.

As the triol unit, glycerin, trimethylolpropane, trimethylolethane, 1,2,2
6-hexanetriol and the like. As the tetraol unit, pentaerythritol, diglycerol,
There are 1,2,3,4-butanetetriol and the like.

As the dibasic acid (anhydride) unit, o-
Phthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic acid, tetrabromophthalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, 1,1,2-dodecanoic acid, maleic acid, fumaric acid,
Examples include itaconic acid, himittic acid, and heptic acid. The tribasic acid units include trimellitic acid, aconitic acid, butanetricarboxylic acid, and 6-carboxy-3-methyl-
1,2,3,6-hexahydrophthalic acid and the like;
Examples of the basic acid unit include pyromellitic acid and butanetetracarboxylic acid.

Examples of the monoepoxide unit include ethylene oxide, propylene oxide, epichlorohydrin, styrene oxide, phenyldaricidyl ether and the like.

As the m-valent epoxy compound unit, a so-called epoxy resin can be suitably used. For example, a plastic material course 1 “Epoxy resin” published by Nikkan Kogyo Shimbun (published on May 10, 1938, Kuni Hashimoto This is an epoxy resin described on pages 19 to 48.

As the n-valent isocyanate compound unit, a polyvalent isocyanate compound known in the polyurethane industry can be suitably used. For example, a plastic material course 2 “Polyurethane resin” published by Nikkan Kogyo Shimbun (June 1969) Published by Keiji Iwata on March 30), p. 46, No. 1
Polyvalent isocyanate compounds described on pages 75 to 178. The resin having the above structure may be produced by an esterification reaction of a dihydric, trihydric or tetrahydric alcohol with acrylic acid and / or methacrylic acid and a polybasic acid, or by the general formula [2] MG-OH ( (However, the meanings of M and G are the same as above.)

Of the above formulas, polyester (meth) acrylates of formulas [1] and [2] are preferred. The above-mentioned phenyl saturated polyester is defined as α, β
-Produced by polycondensation of an unsaturated dibasic acid or an acid anhydride thereof with an aromatic saturated dibasic acid or an acid anhydride thereof, and glycols, and optionally using an aliphatic or aliphatic saturated dibasic acid as an acid component And unsaturated polyester produced by the above method.

Examples of the α, β-unsaturated dibasic acid or its acid anhydride include maleic acid, maleic anhydride,
Fumaric acid, itaconic acid, citraconic acid, chlormaleic acid and esters thereof and the like, as aromatic saturated dibasic acid or its acid anhydride, phthalic acid, phthalic anhydride,
Isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, halogenated phthalic anhydride and esters thereof, and the like, as aliphatic or alicyclic saturated dibasic acid, oxalic acid, There are malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride and esters thereof, and these are used alone or in combination.

The glycols include ester glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol,
4-butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, Ethylene glycol carbonate, 2,2-di- (4-hydroxypropoxydiphenyl) propane and the like can be mentioned, and they are used alone or in combination. In addition, adducts such as ethylene oxide and propylene oxide can also be used. Also,
Polycondensates such as polyethylene terephthalate can also be used as part of the glycols and acid components.

The unsaturated glycidyl compound of the present invention includes glycidyl esters of unsaturated-basic acids such as acrylic acid and methacrylic acid, for example, glycidyl acrylate and glycidyl methacrylate. Glycidyl acrylate is preferred as such an unsaturated glycidyl compound. The number average molecular weight of such an unsaturated polyester acrylate is preferably from 1500 to 3000, particularly preferably from 1800 to 2800. If the molecular weight is less than 1500, the resulting cured product will be tacky or have poor strength properties. On the other hand, if it is larger than 3000, the curing time becomes longer, and the productivity becomes poor.

The epoxy acrylate resin of the present invention is:
Bisphenol-type epoxy resin alone or a resin obtained by mixing a bisphenol-type epoxy resin and a novolak-type epoxy resin, the epoxy resin having an average epoxy equivalent preferably in the range of 150 to 450 and an unsaturated-basic acid. Epoxy vinyl ester obtained by reacting in the presence of an esterification catalyst.

Here, typical examples of the above-mentioned bisphenol type epoxy resin include glycidyl having two or more epoxy groups in one molecule obtained by reacting epichlorohydrin with bisphenol A or bisphenol F. Ether type epoxy resin, dimethyl glycidyl ether type epoxy resin obtained by reacting methyl epichlorohydrin with bisphenol A or bisphenol F, or epoxy resin obtained from alkylene oxide adduct of bisphenol A and epichlorohydrin or metal epichlorohydrin. . Typical examples of the novolak type epoxy resin include an epoxy resin obtained by reacting phenol novolak or cresol novolac with epichlorohydrin or methyl epichlorohydrin.

Representative examples of the above unsaturated-basic acids include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid,
Examples include monomethyl malate, monopropyl malate, monobutene malate, sorbic acid or mono (2-ethylhexyl) malate. These unsaturated-basic acids may be used alone or as a mixture of two or more.

The reaction between the epoxy resin and the unsaturated-basic acid is preferably carried out at 60 to 140 ° C., particularly preferably at 80 to 140 ° C.
It is carried out using an esterification catalyst at a temperature of １２０120 ° C. As the esterification catalyst, for example, a tertiary ammon such as triethylamine, N, N-dimethylbenzylamine, N, N-dimethylaniline or diazabicyclooctane; or a known catalyst such as diethylamine hydrochloride can be used as it is. .

The number average molecular weight of such an epoxy acrylate is preferably 900 to 2500, particularly preferably 1 to 2.
300 to 2200. If the molecular weight is smaller than 900, the resulting cured product may have tackiness or the strength properties may be reduced. On the other hand, if it is larger than 2500, the curing time becomes longer and the productivity becomes poor.

The unsaturated monomer (b) of the present invention includes an unsaturated monomer or an unsaturated oligomer capable of undergoing a cross-linking reaction with the vinyl ester resin (a), and particularly preferably a monomer or oligomer containing an acryloyl group. Yes, (meth) acrylate monomers are preferred. When a monomer containing no acryloyl group is used and the amount thereof is increased, the copolymerizability with the vinyl ester resin is deteriorated and the curing time is prolonged. Specific examples of these monomers containing an acryloyl group include methyl acrylate, ethyl acrylate, n-butyl acrylate, iso-butyl acrylate, and t-acrylate.
-Butyl, 2-ethylhexyl acrylate, n-octyl acrylate, decyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, β-ethoxyethyl acrylate, 2-cyanoethyl acrylate, cyclohexyl acrylate , Diethylaminoethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, decyl methacrylate, lauryl methacrylate, stearyl methacrylate, 2-methacrylic acid
Hydroxyethyl, 2-hydroxypropyl methacrylate, phenyl carbitol acrylate, noniphenyl carbitol acrylate, noniphenoxypropyl acrylate, N-vinylpyrrolidone, polycaprolactone acrylate, acryloyloxyethyl phthalate, acryloyloxy succinate, and further cured resin Each derivative of dicyclopentanedien, silicyldecane, and triazine for improving the surface drying property of dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, tricyclodecanyl acrylate, tricyclodecanyl methacrylate, tris (2- (Hydroxyethyl) isocyanuric acrylate. Of course, the copolymerizability during the crosslinking reaction is slightly inferior, but other vinyl monomers may be used in combination. For example, allyl monomers such as styrene, vinyl acetate, vinyl toluene, α-methylstyrene, diallyl phthalate, diallyl isophthalate, triallyl isocyanurate, diallyl tetraprom phthalate; acrylonitrile, glycidyl methacrylate, n-methylol acrylamide-butyl ether, n -Hard monomers such as methylolacrylamide and acrylamide.

The unsaturated alcohol of the present invention has an acryloyl group and a hydroxyl group.
2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate and the like. It is used when the composition of the present invention is used for those using asphalt.

The polyfunctional unsaturated monomer of the present invention is a compound having at least two polymerizable double bonds in one molecule, and has abrasion resistance, scratch resistance and sliding resistance on the surface of a cured product. It is preferably used for the purpose of improving chemical resistance and the like. Preferably, it is a polyfunctional (meth) acrylate monomer, for example, ethylene glycol di (meth)
Alkanediol di- (meth) acrylates such as acrylate, 1,2-propylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate; Propylene glycol di (meth)
Polyoxyalkylene-glycol di (meth) acrylates such as acrylate, triethylene glycol (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol (meth) acrylate, divinylbenzene, diallyl phthalate, triallyl phthalate, triaryl Lucyanurate, triallyl isocyanurate, allyl (meth) acrylate, diallyl fumarate and the like can be mentioned, and these can be used alone or in combination of two or more.

The average glass transition temperature of the polymerizable unsaturated monomer of the present invention is in the range of -10 to 99 ° C, and particularly preferably -10 to 80 ° C for improving the tear strength of the mixture (b). When the transition point temperature is -10 ° C or lower, tackiness remains on the surface of the cured resin, and the tensile strength and the like further decrease.
On the other hand, when the temperature exceeds 99 ° C., the amount of strain during curing of the cured product increases, and when used in the state of a coated film, it leads to peeling from the substrate and turning over. Also, the elongation becomes too small and the crack resistance becomes poor.

The vinyl ester resin (A) of the present invention /
(B) A preferable ratio of the unsaturated monomer mixture is 2/8
８8/2. If (a) is smaller than 2, the curability of the cured resin product will be poor. When it is larger than 8, the viscosity of the composition becomes high and handling becomes difficult.

The polymerizable unsaturated monomer having an air-drying property of the present invention is, for example, an acrylic acid derivative such as dicyclopentadiene, tricyclodecane, etc., such as dicyclopentenyloxyethyl acrylate, tricyclo [5-2-1-02 , 6)
And dendritic acrylate. Drying oils and epoxy-reactive diluents described below can also be used.

The polymerizable monomer-crosslinkable unsaturated group-containing polymer having an air-drying property is obtained by introducing an air-drying component as an essential component into an unsaturated polyester, a vinyl ester resin or the like.

The method for introducing an air-drying component as an essential component into the unsaturated polyester polymer, vinyl ester polymer or the like as the above-mentioned polymer to be cross-linked includes the following.

A compound containing an allyl ether group represented by -0-CH2-CH = CH2 is used in combination with the glycol component. A compound containing a cycloaliphatic unsaturated polybasic acid and its derivative is used in combination with the acid component. A compound containing dicyclopentadiene is used in combination. Use drying oil and epoxy reactive diluent together.

Among these compounds, any known allyl ether group-containing compound can be used, and typical examples thereof include ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, and triethylene glycol monoallyl ether. Allyl ether, polyethylene glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, tripropylene glycol monoallyl ether, polypropylene glycol monoallyl ether, 1,2-butylene glycol monoallyl ether, 1,3-butylene Glycol monoallyl ether, hexylene glycol monoallyl ether, octylene glycol monoallyl ether, trimethylolpropane monoallylate Le, trimethylolpropane diallyl ether, glycerol monoallyl ether,
Allyl ether compounds of polyhydric alcohols such as glycerin diallyl ether, pentaerythritol monoallyl ether and pentaerythritol triallyl ether; allyl ether compounds having an oxirane ring such as allyl glycidyl ether;

Other glycol components used in combination include ethylene glycol, propylene glycol,
Diethylene glycol, dipropylene glycol, 1,
3-butanediol, 1,4-putindiol, 2-methylpropane-1,3-diol, hopentyl glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A,
Ethylene glycol carbonate, 2,2-di (-4-
(Hydroxypropoxydiphenyl) propane and the like, alone or in combination. Other oxides such as ethylene oxide and propylene oxide can also be used. In addition, a polycondensate such as polyethylene terephthalate can be used as a part of the glycol and the acid component.

Compounds comprising the above cycloaliphatic unsaturated polybasic acids and derivatives thereof include tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, α-terphine-maleic anhydride adduct. Rosin, ester gum and the like.

The α, β-unsaturated dibasic acids or acid anhydrides used alone or in combination with these are maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chlormaleic acid. And esters thereof, and aromatic saturated dibasic acids or anhydrides thereof include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, halogenated phthalic anhydride and esters thereof. , Aliphatic or alicyclic saturated dibasic acids include oxalic acid, malonic acid, succinic acid,
Adipic acid, sebacic acid, aceleic acid, glutaric acid,
Hexahydrina phthalic anhydride and their esters are used alone or in combination.

Further, a resin obtained by reacting a reactive monomer having a glycidyl group with a terminal carboxyl group of an unsaturated alkyd resin synthesized from glycol and an acid can also be used. Representative examples of the reactive monomer having a glycidyl group include glycidyl acrylate and glycidime methacrylate.

Also, β-PMAA unit compounds can be used, which are cis-3-methyl-4-cyclohexene-cis-1,2-dicarboxylic acids represented by the following [IA] and [IB]. And its anhydride (abbreviated as βPMAA), which is an adduct of trans-piperylene and maleic anhydride, or a ring-opened acid anhydride group in this adduct. is there.

[0057]

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[0058]

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Representative examples of the compound containing dicyclopentanediene include a hydroxylated dicyclopentanediene represented by the following formula [II].

[0060]

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As the drying oil, linseed oil, soybean oil,
Examples include cottonseed oil, peanut oil, coconut oil and the like, or a reaction product of these fatty oils with a polyhydric alcohol such as glycerin.

The epoxy-reactive diluent includes a monoepoxy compound and a polyepoxy compound. The former includes allyl glycidyl ether, n-butyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylate, Khadura E and the like, and the latter includes UNOX 206, Epicoat 812, DGE, B
DO and the like.

An unsaturated polyester vinyl ester resin,
When producing an epoxy vinyl ester resin, it is recommended to use a polymerization inhibitor for the purpose of preventing gelation and for adjusting the storage stability or curability of the produced resin. Here, typical examples of the polymerization inhibitor used include hydroquinones such as hydroquinone, pt-butylcatechol and mono-t-butylhydroquinone; hydroquinone monomethyl ether and di-t-butyl-p. Phenols such as cresol: p-benzoquinone, naphthoquinone or p-
Quinones such as tolquinone; copper salts such as copper naphthenate;

The ratio of the polymerizable unsaturated monomer to the total amount of the polymerizable unsaturated monomer (b) and the vinyl ester resin (a) is preferably 30 to 60% by weight.
The preferred viscosity of the mixture (b) is in the range of 0.5 to 5 poise. When the viscosity is high, kneading with other components described below becomes difficult, and when the viscosity is low, the components are easily separated.

The vinyl ester resin composition of the present invention comprises
It is also preferred to include a curing agent, which includes organic peroxides. Specifically, known materials such as diacyl peroxide, peroxyester, hydroperoxide, dialkyl peroxide, ketone peroxide, peroxyketal, alkylperester, and percarbonate are used. , Kneading conditions, curing temperature and the like are appropriately selected.

The amount of addition is a commonly used amount, preferably 0.01 to 4 parts by weight per 100 parts by weight of the resin composition.
Parts by weight. The above curing agents may be used in combination.

Further, a curing accelerator, that is, a substance capable of decomposing an organic peroxide of the curing agent by a redox reaction and facilitating generation of active radicals is, for example, a metal such as a cobalt-based, vanadium-based, and manganese-based metal. Soaps, 3rd
Quaternary amines, quaternary ammonium salts, mercaptans and the like.

A thermoplastic resin can be added to the resin composition of the present invention for the purpose of improving the air curability of the cured resin and reducing the cure shrinkage. Specific examples of the thermoplastic resin include lower alkyl esters of acrylic acid or methacrylic acid such as methyl methacrylate, etal methacrylate, butyl methacrylate, methyl acrylate and ethyl acrylate, and monomers such as styrene, vinyl chloride and vinyl acetate alone. Polymers or copolymers, at least one of the above vinyl monomers, lauryl methacrylate, isovinyl methacrylate, acrylamide, methacrylamide, hydroxyalkyl acrylate or methacrylate, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, cetyl In addition to at least one copolymer of stearyl methacrylate, cellulose acetate butyrate and cellulose acetate propionate, polyethylene, polyethylene Propylene, it may be mentioned saturated polyester. The addition amount is preferably from 0 to 50 parts by weight, particularly preferably from 0 to 35 parts by weight, based on 100 parts by weight of the resin composition.

The resin composition according to the present invention may contain a filler, an aggregate, a coloring agent such as a pigment or a dye, in addition to the above additives.

The fiber reinforcing material used in the present invention includes:
For example, glass fibers, organic fibers such as amide, aramid, vinylon, polyester, and phenol, carbon fibers, metal fibers, ceramic fibers, or a combination thereof are used. In consideration of workability and economy, glass fibers and organic fibers are preferable. In addition, the form of the fiber includes plain weave, satin weave, non-woven fabric, mat shape and the like, but the mat shape is preferable from the construction method, thickness maintenance and the like, and the glass roving is cut into 20 to 100 mm to make chopped strands. It is also possible to use.

As the filler, calcium carbonate powder, clay, alumina powder, silica stone powder, talc, barium sulfate, silica powder, glass powder, glass beads, mica, aluminum hydroxide, cellulose thread, silica sand, river sand, cold water stone, Known materials such as marble chips and crushed stones may be mentioned. Among them, glass powder, aluminum hydroxide, barium sulfate and the like are preferable because they impart translucency when cured.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, where “parts” and “%” are on a weight basis unless otherwise specified.

The abbreviations in the table are as follows. MMA methyl methacrylate EMA 〃ethyl n-BMA 〃n-butyl MA methyl acrylate EA エ チ ル ethyl n-BA ｎn-butyl 2-EHA ２−2-ethylhexyl iso-PMA isopropyl methacrylate 2-HEMA 〃2-hydroxyethyl HPMA @ hydroxypropyl DEGDA diethylene glycol diacrylate TMPTA trimethylolpropane triacrylate

Synthesis Example 1 [Epoxy acrylate (VE-
Preparation of 1)] In a three-necked flask equipped with a thermometer, a stirrer, and a condenser, “Epiclon 85” having an epoxy equivalent of 185 obtained by the reaction of bisphenol A and epichlorohydrin was added.
0 "[Epoxy resin manufactured by Dainippon Ink and Chemicals, Inc.]
Of 1850 g (equivalent to 10 epoxy groups), 860 g of methacrylic acid (equivalent to 10 carboxyl groups), 1.36 g of hydroquinone and 10.8 g of triethylamine, and the temperature was raised to 120 ° C., and the reaction was carried out at the same temperature for 10 hours. By continuing the process, a liquid epoxy acrylate having an acid value of 3.5, an epoxy equivalent of 1500 or more, and a color number of 2 was obtained.

Synthesis Example 2 [Epoxy acrylate (VE-
Preparation of 2)] In a three-necked flask equipped with a thermometer, a stirrer, and a cooler, "Epiclon 850" (manufactured by Dainippon Ink and Chemicals, Inc.) having an epoxy equivalent of 190 obtained by the reaction of bisphenol A and epichlorohydrin was prepared. Epoxy resin) 443.7 g and "Hiker CTBN1300 x 13"
110.1 g of (butadiene-acrylonitrile copolymer having a terminal carboxyl group manufactured by Goodrich, USA) was charged,
After raising the temperature to 95 ° C. and reacting for 2 hours, 0.25 g of hydroquinone, 180.4 g of methacrylic acid and 2.1 g of triethylamine were added, and the temperature was raised again to 95 ° C., and the reaction was continued. After a time, when the acid value became 6, the reaction temperature was lowered to 60 ° C. to stop the reaction, and the specified monomer was gradually added to completely dissolve the contents.

Air-drying resin compositions UPE-1 to UPE
Preparation of PE-2. Synthesis Example 3 [Preparation of saturated polyester (UPE-1)] 2.0 mol of terephthalic acid, 1.5 mol of diethylene glycol, and 1 mol of pentaerythritol / triallyl ether were heated and dehydrated under known conditions to obtain a saturated polyester having an acid value of 20. .

Synthesis Example 4 [Unsaturated polyester (UPE-
Preparation of 2)] β-PMAA 1.0 mol, isophthalic acid 1.0 mol, fumaric acid 0.5 mol, bisphenol A ethylene oxide 10
1.5 moles of the molar adduct and 1.3 moles of diethylene dalicol were heated and dehydrated and condensed under known conditions to obtain an unsaturated polyester having an acid value of 18.

Synthesis Example 5 [Unsaturated polyester (UPE-
3) Preparation of orthophthalic acid 7 mol, maleic anhydride 3 mol, ethylene glycol 3 mol, triethylene glycol 7 mol,
Toluhydroquinone 50 ppm was heated and condensed at 200 to 220 ° C. to synthesize unsaturated polyester UPE-3.

<Test Method> A uniaxial tensile test was carried out on a test piece (300 mm × 300 mm × 70 mm) with a fine-grained asphalt mixture (13), page 50 of the Asphalt Pavement Guidelines (63rd edition) at 20 ° C. It was left for one week in an atmosphere of a relative humidity of 65%, cut, and a 40 mm × 40 mm steel jig was bonded using an epoxy resin. After the adhesive was cured, it was tested at 20 ° C. at a loading speed of about 1 kgf / cm ² / sec using a hydraulic adhesion tester manufactured by Yamamoto Houkiki Co., Ltd.

The method for calculating the tensile adhesive strength is as follows.

[0081]

<Measurement Method of Curing Characteristics> (Method A) A BPO paste (50
%) 2PHR, DMA0.5PHR are collected in a beaker, and 25 ° C.
Time until gelation in constant temperature water bath (Method B) For 100 PHR of resin, MEKPO1.0 PHR,
Mix with 6% cobalt naphthenate 0.4PHR and DMA 0.1PHR, and the measurement conditions are the same as in Method A.

<Measurement Method for Strength Test> A test piece was prepared from a cast plate and measured according to the JIS-K-7113 tensile test method.
With N = 5, the method of calculating absorbed energy (resilience) is represented by an integrated value of stress (σ) and elongation (ε). RS
= Resilience, but

[0084]

(Equation 1)

R S measurement method Personal image analysis system LA-5 manufactured by Pierce Co., Ltd.
Measured at 00. Hardening Shrinkage Measurement Test It was measured using a hardening shrinkage measuring device manufactured by Inteco Corporation. The measurement principle is as follows.

A pair of detecting plates facing each other are placed in the compound, and the stress accompanying the solidification of the compound generated between the respective detecting plates is measured. Each detecting plate is subjected to a load servo so that the stress is always zero. Moved by mechanism. Since the relative position between the two detection plates can be automatically recorded by a separately provided displacement detector, the contraction displacement can be accurately measured regardless of the intermolecular binding force due to the solidification of the compound.

The measurement of the shrinkage was performed by the following method.

In order to measure the shrinkage of the material itself, the measurement was performed on a fluorine-formed plate (3 mm) having a small binding force on the lower plate. That is, a four-sided frame made of polyethylene foam is provided on a fluorine-molded plate, and a compound (resin / 5 silica sand = 1/3) of a sample to be measured is formed into a frame having a thickness of 15 mm, and the detection plate is formed. The above measurements were made.

<Surface Drying Test Method> The two types of coating films were tested for surface drying properties one hour after gelation. (Note) WaX (No.1) → Polyethylene WaX Slip Aid SL-18 manufactured by San Nopco Co., Ltd.

[0090] (Note) WaX (No.2) → microcrystalline wax, Hi-Mic-1045 made by Wax made in Japan

[0091]

Examples 1 to 4 and Comparative Examples 1 to 3 The resins obtained in the above synthesis examples were subjected to the above-mentioned tests with the formulations shown in Tables 1 and 2, and the evaluation results are shown in the same table.

Examples 5 to 6 The resins obtained in the above synthesis examples were tested for the asphalt adhesive strength and the drying property with the compositions shown in Table 3, and the evaluation results are shown in the same table.

Examples 7 to 8 The resins obtained in the above synthesis examples were blended as shown in Table 4 and tested for surface drying property and curing shrinkage, and the evaluation results were shown in the same table.

Example 9 and Comparative Example 4 The resins obtained in the above Synthesis Examples were tested for the surface dryness with the formulations shown in Table 5, and the evaluation results were shown in the same table.

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[Table 1]

[0097]

[Table 2] Table-2

[0098]

[Table 3] Table-3

[0099]

[Table 4] Table-4

[0100]

[Table 5] Table-5

[Effects of the Invention] Usually, the functions of the resin composition such as flexibility, toughness, strength characteristics, water resistance, chemical resistance and physical characteristics are imparted by modifying the polymer portion. Is the idea.

The basic composition of the radical-curable resin was composed of a polymer portion / crosslinking monomer portion, and the monomer portion was almost constant, and only a small portion of the monomer portion could contribute to the basic properties. As described above, the basic properties of the resin were determined by the polymer portion. Further, in the radical-curable thermosetting resin, the degree of influence on the basic properties is much greater in the polymer portion than in the monomer portion. For example, when synthesizing a resin having a large elongation, there is a method of using a material that imparts flexibility as a raw material used for the polymer portion, but the resin has poor durability performance such as water resistance. In other words, the properties that are in the opposite relationship tend to be noticeable.

It is considered that the technical idea of providing characteristics by combining various types of monomer portions while keeping the polymer portion constant as in the present invention is novel.

The resin composition of the present invention has high elongation, toughness, and flexibility, is excellent in low-temperature curability, and has no unreacted monomer. Flooring and wall coating materials, flooring materials, civil engineering and architectural covering materials such as road marking materials, cast products, laminated products, adhesives, lining materials, sealing materials, corrugated boards, decorative boards, electrical insulating substrates, optical communications It can be used for glass fiber coating materials, biomedical materials, resin capsule anchors, etc.

Claims (5)

[Claims] 1. An epoxy resin having α, β-unsaturation-
A vinyl ester resin comprising an epoxy acrylate having a (meth) acrylate group at the molecular end obtained by reacting a basic acid, (b) the average glass transition temperature (Tg) when the monomer used becomes a homopolymer, -10 ° C to 9
A mixture of polymerizable unsaturated monomers having a temperature of 9 ° C., wherein the polymerizable unsaturated monomer contains a (meth) acryloyl group, and the ratio of (a) / (b) is 2/8 to 8/2; A vinyl ester resin composition having required flexibility. 2. The polymerizable unsaturated monomer mixture (b) is
2. The vinyl ester resin composition according to claim 1, comprising one or more selected from unsaturated alcohol monomers, polyfunctional unsaturated monomers, and unsaturated monomers having air-drying properties. 3. The vinyl ester resin composition according to claim 1, further comprising a thermoplastic resin. 4. The method according to claim 1, which further comprises a polymerizable monomer-crosslinked unsaturated group-containing polymer having air drying properties.
3. The vinyl ester resin composition of 3. 5. The vinyl ester resin composition according to claim 1, wherein the resin composition is a covering material for civil engineering and construction.