JP5845935B2 - Radical polymerizable resin composition - Google Patents

Description

  The present invention relates to a radical polymerizable resin composition having excellent curing characteristics at room temperature.

  Civil engineering and building materials such as road waterproofing materials and road pavement materials have been provided with a coating layer so that, for example, even if the underlying concrete is cracked, it will not follow and deteriorate its aesthetics and performance. ing. The coating layer preferably has tensile physical properties such as tensile elongation and tensile strength for following the base.

  Examples of the coating layer material having tensile properties include a polymerizable unsaturated resin having two or more polymerizable unsaturated double bonds in one molecule, a hydroxyalkyl (meth) acrylate, and one molecule. A curable unsaturated resin composition characterized by containing an unsaturated compound which is liquid at room temperature and has one or more cyclohexene rings and two or more allyl ether groups is known (for example, Patent Documents). 1).

  Since the coating layer material has excellent tensile properties, it contributes to long-term durability of the road without lowering the strength of the road or the like even if the underlying concrete cracks or the like. . However, in order to provide the coating layer as described above, it is required that the coating layer material is cured in a room temperature environment during construction. According to the coating layer material, it has a practically usable level of room temperature curability, but in response to a recent demand for further shortening of the construction time, a material with improved room temperature curability has been demanded. Yes.

JP 2003-40949 A

  The problem to be solved by the present invention is to provide a radical polymerizable resin composition excellent in room temperature curability.

The inventors of the present invention, while pursuing research to solve the above-mentioned problems, paid attention to the radical polymerizable monomer used in combination with the radical polymerizable resin, and conducted earnest research.
As a result, it was found that only when a specific amount of allyl ester compound was used, a radical polymerizable resin composition having good tensile properties and room temperature curability was obtained, and the present invention was completed.

That is, the present invention includes at least one radical polymerizable resin (A) selected from the group consisting of unsaturated polyester resins, epoxy (meth) acrylate resins, urethane (meth) acrylate resins, and polyester (meth) acrylate resins, ( radically polymerizable monomer having an meth) acryloyl group (B), a Riruesuteru compound (C), and a melting point contains petroleum wax (D) is in the range of 43-72 ° C., the allyl ester compound (C) Is used in a range of 1 to 10% by mass relative to the total mass of the radical polymerizable resin (A), the radical polymerizable monomer (B) and the allyl ester compound (C). A radical polymerizable resin composition is provided.

The radical polymerizable resin composition of the present invention uses a specific amount of allyl ester compound. It has excellent room temperature curability. In addition, the radical polymerizable resin composition of the present invention is excellent in tensile physical properties such as tensile strength and tensile elongation, and is also excellent in low odor.
Therefore, the radically polymerizable resin composition of the present invention can be suitably used in fields such as civil engineering, architecture, railways, and roads. Among these, it can be particularly suitably used for road pavement materials, road waterproofing materials, flooring materials, and the like.

  The unsaturated polyester resin is obtained, for example, by reacting a dibasic acid containing an α, β-unsaturated dibasic acid with a polyhydric alcohol.

  Examples of the α, β-unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride and the like.

  As other dibasic acid, saturated dibasic acid can be used, for example, phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydro Phthalic acid, hexahydrophthalic anhydride, hexahydroterephthalic acid, hexahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid, 2,6-naphthalenedicarboxylic acid, 2 , 7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid anhydride, 4,4′-biphenyldicarboxylic acid, and dialkyl esters thereof.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, and 2-methyl-1. , 3-propanediol, 1,3-butanediol, neopentyl glycol, hydrogenated bisphenol A, 1,4-butanediol, an adduct of bisphenol A and propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,3-propanediol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane Glycol, 1,4-cyclohexanedimethanol, paraxylene glycol, vinyl Kurohekishiru 4,4' Geo - le, 2,6-decalin glycolate - le, 2,7-decalin glyco - can be used Le like.

  Further, as the unsaturated polyester resin, an air-drying imparting unsaturated polyester resin may be used.

  The air-drying imparted unsaturated polyester resin includes, for example, those using a compound containing a cycloaliphatic unsaturated polybasic acid and a derivative thereof as a dibasic acid component, and a hydroxyl group having an allyl ether group as a polyhydric alcohol component. Those using a compound, those using a dicyclopentadiene compound, those using linseed oil and tung oil as a drying oil, and the like can be used.

  Examples of the cycloaliphatic unsaturated polybasic acid and derivatives thereof include, for example, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, α-terpinene / maleic anhydride adduct, trans-piperylene / anhydride A maleic acid adduct or the like can be used.

  Examples of the hydroxy compound having an allyl ether group include ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl 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 Diallyl ether, glyceryl diallyl ether, pentaerythritol triallyl ether It can be used ether, and the like.

  The epoxy (meth) acrylate resin is obtained by reacting an bisphenol-type epoxy resin alone or an epoxy resin obtained by mixing a bisphenol-type epoxy and a novolac-type epoxy resin with an unsaturated monobasic acid.

  Examples of the bisphenol type epoxy resin include a glycidyl ether type epoxy resin having two or more epoxy groups in one molecule obtained by reaction of epichlorohydrin and bisphenol A or bisphenol F, methyl epichlorohydrin and bisphenol A or bisphenol F, and the like. A dimethyl glycidyl ether type epoxy resin obtained by reacting bisphenol A, an epoxy resin obtained by reacting an alkylene oxide adduct of bisphenol A with epichlorohydrin or methyl epichlorohydrin, and the like can be used.

  As the novolac type epoxy resin, for example, an epoxy resin obtained by reacting phenol novolac or cresol novolak with epichlorohydrin or methyl epichlorohydrin can be used.

  Examples of the unsaturated monobasic acid include (meth) acrylic acid, cinnamic acid, crotonic acid, monomethylmalate, monopropylmalate, monobutenemalate, sorbic acid, mono (2-ethylhexyl) malate, and the like. be able to.

  Examples of the urethane (meth) acrylate resin include those obtained by reacting a polyol, polyisocyanate, and a (meth) acrylic compound having a hydroxyl group.

  Examples of the polyol include acrylic polyol, polycaprolactone polyol, polybutadiene polyol, polyether polyol, polycarbonate polyol, and polyester polyol.

  The polyisocyanate has two or more isocyanate groups in the molecule. For example, aromatic diisocyanates such as phenylene diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, Aliphatic or aliphatic cyclic structure-containing diisocyanates such as isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, xylylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, polyphenylene poly Methylene polyisocyanate Sulfonate, formalin condensate of methylene diphenyl dicyanamide Socia titanate, can be used aromatic polyisocyanates such as carbodiimide modified products, etc. 4,4'-diphenylmethane diisocyanate.

  Examples of the (meth) acrylic compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like. (Meth) acrylic acid alkyl ester having a hydroxy group, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate and the like can be used.

  In the present invention, “(meth) acrylate” refers to one or both of methacrylate and acrylate, and “(meth) acryloyl group” refers to one or both of methacryloyl group and acryloyl group. “Acrylic acid” refers to one or both of methacrylic acid and acrylic acid, and “(meth) acrylic compound” refers to one or both of an acrylic compound and a methacrylic compound.

  The polyester (meth) acrylate resin is a saturated polyester or unsaturated polyester having two or more (meth) acryloyl groups in one molecule. The saturated polyester is a condensation reaction of a saturated dibasic acid and a polyhydric alcohol, and the unsaturated polyester is a condensation reaction of an α, β-unsaturated dibasic acid and a polyhydric alcohol. All have a (meth) acryloyl group at the terminal.

  The saturated dibasic acid, the α, β-unsaturated dibasic acid and the polyhydric alcohol can be the same as those used for the unsaturated polyester resin.

  As a method for introducing a (meth) acryloyl group into the polyester (meth) acrylate resin, it is preferable to use a glycidyl ester compound of (meth) acrylic acid, and it is particularly preferable to use glycidyl (meth) acrylate.

  As the radical polymerizable resin (A), an epoxy (meth) acrylate resin, a urethane (meth) acrylate resin, or a polyester (meth) acrylate resin is used from the viewpoint of further improving room temperature curability among the above-described ones. Preferably, from the viewpoints of room temperature curability and tensile physical properties, an epoxy (meth) acrylate resin and a polyester (meth) acrylate resin are more preferable, and a polyester (meth) acrylate resin is particularly preferable.

  The radical polymerizable monomer (B) is a reactive diluent for the radical polymerizable resin (A), and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic acid n. -Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate , 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, β-ethoxyethyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) Diethylaminoethyl acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, polycaprolacto (Meth) acrylate, diethylene glycol monomethyl ether mono (meth) acrylate, dipropylene glycol monomethyl ether mono (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meta ) Acrylate, tris (2-hydroxyethyl) isocyanuric (meth) acrylate, phenoxyethyl (meth) acrylate, and the like can be used. These radically polymerizable monomers (B) may be used alone or in combination of two or more. Among these, it is preferable to use methyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and phenoxyethyl (meth) acrylate. From the viewpoint of improvement, dicyclopentenyloxyethyl methacrylate, dicyclopentenyl methacrylate, and phenoxyethyl methacrylate are particularly preferable.

  The mass ratio [(A) / (B)] of the radical polymerizable resin (A) and the radical polymerizable monomer (B) ranges from 20 to 80/80 to 20 from the viewpoint of tensile properties and the like. The range of 30-60 / 70-40 is more preferable, and the range of 30 / 70-50 / 50 is particularly preferable.

  The allyl ester compound (C) is an essential component from the viewpoints of room temperature curability, tensile physical properties, and the like. For example, diallyl phthalate, diallyl isophthalate, diallyl tetrabromophthalate, triallyl phthalate, and the like can be used. Among these, diallyl phthalate is particularly preferable from the viewpoint of further improving room temperature curability and tensile properties.

  The use ratio of the allyl ester compound (C) is 1 to 10% by mass with respect to the total mass of the radical polymerizable resin (A), the radical polymerizable monomer (B) and the allyl ester compound (C). In order to solve the problem of the present invention, it is essential to be in the range. When the use ratio of the allyl ester compound (C) is less than 1% by mass, the room temperature curability is insufficient, and when it exceeds 10% by mass, the tensile strength is lowered, so that the molded product can be handled. Have difficulty. As the use ratio of the allyl ester compound (C), room temperature curability, tensile physical properties, compatibility with the radical polymerizable resin (A), and the like are more preferable. The range of 1-8 mass% is further more preferable with respect to the total mass of the body (B) and the allyl ester compound (C), and the range of 3-6 mass% is particularly preferable.

  The radical polymerizable resin composition of the present invention contains the radical polymerizable resin (A), the radical polymerizable monomer (B), and the allyl ester compound, but contains other additives as necessary. May be.

  The other additives include, for example, petroleum wax, curing agent, curing accelerator, antioxidant, anti-aging agent, pigment, thixotropic agent, solvent, filler, process oil, plasticizer, UV inhibitor, reinforcement Materials, aggregates, flame retardants, stabilizers and the like can be used. Among these, from the viewpoint of improving the compatibility with the radical polymerizable monomer (B) and the allyl ester compound (C) and further improving the room temperature curability and the tensile physical properties, it may contain a petroleum wax. preferable. Moreover, when further improving room temperature curability, it is preferable to contain a hardening | curing agent and a hardening accelerator.

  The petroleum wax prevents curing inhibition by oxygen, and the use of petroleum wax (D) having a melting point of 43 to 72 ° C. makes it possible to use the radical polymerizable monomer (B) or the allyl ester compound (C). From the viewpoint of compatibility with oil, a petroleum wax having a melting point of 48 to 66 ° C is more preferred, and a petroleum wax having a temperature of 48 to 60 ° C is particularly preferred. As the petroleum wax (D), specifically, paraffin wax, microcrystalline wax, petrolactam and the like can be used, and the radical polymerizable monomer (B) and the allyl ester compound (C) can be used. It is particularly preferable to use paraffin wax from the viewpoint of compatibility. In addition, melting | fusing point of the said petroleum wax (D) shows melting | fusing point measured based on JISK2235.

  The petroleum wax (D) is used in a proportion of 100 parts by mass of the allyl ester compound (C) from the viewpoint of compatibility with the radical polymerizable monomer (B) and the allyl ester compound (C). The range is preferably 1 to 35% by mass, more preferably 2 to 20% by mass, and particularly preferably 5 to 10% by mass.

  As the curing agent, it is preferable to use an organic peroxide from the viewpoint of room temperature curing. For example, diacyl peroxide, peroxyester, hydroperoxide, dialkyl peroxide, ketone peroxide, peroxide Oxyketal type, alkyl perester type, percarbonate type and the like can be used. These curing agents are appropriately selected depending on curing conditions and the like.

  The amount of the curing agent used is from the viewpoint of room temperature curability to the total mass of the radical polymerizable resin (A), the radical polymerizable monomer (B), and the allyl ester compound (C). The range of 5-10 mass% is preferable, and the range of 1-5 mass% is more preferable.

  The curing accelerator is a substance having an action of decomposing an organic peroxide of the curing agent by a redox reaction and facilitating generation of active radicals. For example, a cobalt-based organic material such as cobalt naphthenate or cobalt octylate. Metal soaps such as acid salts, zinc octylate, vanadium octylate, copper naphthenate, barium naphthenate, metal chelates such as vanadium acetyl acetate, cobalt acetyl acetate, iron acetylacetonate, aniline, N, N-dimethylaniline N, N-diethylaniline, p-toluidine, N, N-dimethyl-p-toluidine, N, N-dimethyl-p-toluidine ethylene oxide adduct, N, N-bis (2-hydroxyethyl) -p -Toluidine, 4- (N, N-dimethylamino) benzaldehyde, 4- [N, N -Bis (2-hydroxyethyl) amino] benzaldehyde, 4- (N-methyl-N-hydroxyethylamino) benzaldehyde, N, N-bis (2-hydroxypropyl) -p-toluidine, N-ethyl-m-toluidine , Triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, N, N-bis (hydroxyethyl) aniline, diethanolaniline, N, N-substituted anilines, N, N-substituted-p-toluidine , 4- (N, N-substituted amino) benzaldehyde and other amines can be used.

  As the usage-amount of the said hardening accelerator, it is 0.05-5 mass% with respect to the total mass of the said radically polymerizable resin (A), the said radically polymerizable monomer (B), and the said allyl ester compound (C). Is preferable, and the range of 0.5 to 3% by mass is more preferable.

  Hereinafter, the present invention will be described in detail with reference to examples.

[Synthesis Example 1] Synthesis of epoxy methacrylate resin (A-1) Epoxy equivalent obtained by reaction of bisphenol A and epichlorohydrin in a four-necked flask equipped with a thermometer, stirrer, inert gas inlet and reflux condenser And 1850 parts by mass of Epicron 850 (manufactured by DIC Corporation), 860 parts by mass of methacrylic acid, 1.36 parts by mass of hydroquinone and 10.8 parts by mass of triethylamine were heated to 120 ° C. and reacted for 10 hours in the same time. Thus, an epoxy methacrylate resin (A-1) having an acid value of 3.5 was obtained.

[Synthesis Example 2] Polyester methacrylate resin (A-2)
A four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser was charged with 969 parts by weight of adipic acid, 551 parts by weight of methyltetrahydrophthalic anhydride, and 690 parts by weight of neopentyl glycol as an esterification catalyst. 11 parts by mass of monobutyltin oxide was added and reacted at 205 ° C. for 11 hours. Then, it cooled to 140 degreeC, then, 941 g of glycidyl methacrylate was thrown in, and it was made to react for 10 hours, and polyester methacrylate resin (A-2) was obtained.

[Example 1]
40 parts by mass of the epoxy methacrylate resin (A-1), 55 parts by mass of dicyclopentenyloxyethyl methacrylate, 5 parts by mass of diallyl phthalate, and 0.3 parts by mass of paraffin wax having a melting point of 54 ° C. are mixed. Thus, a radical polymerizable resin composition was obtained.

[Examples 2-3, Comparative Examples 1-3]
Except that the types and / or amounts of the radical polymerizable resin (A), the radical polymerizable monomer (B), and the allyl ester compound (C) used were changed as shown in Table 1, the same manner as in Example 1 was performed. A radical polymerizable resin composition was obtained.

[Evaluation method of room temperature curability]
The room temperature curability was evaluated by the value of [Drying Time] / [Gelging Time] from [Drying Time] and [Gelging Time] shown below.
In addition, it evaluated as follows with the value of said [drying time] / [gelling time].
If it is 2.0 or less, “◎”
If it is more than 2.0 and 3.0 or less, “○”
If it exceeds 3.0, “×”
If measurement is not possible, "-"

[Drying time]
For 50 parts by mass of the radical polymerizable resin compositions obtained in Examples and Comparative Examples, 0.25 parts by mass of 8% cobalt octylate, 0.5 parts by mass of paratoluidine-ethylene oxide 2 mol adduct, peroxidation A coating film having a thickness of 0.25 mm was prepared using an applicator on a glass plate at 25 ° C., and the drying time of the coating film surface was measured by touch. Specifically, after the coating film was prepared, the time (seconds) until the absorbent cotton did not remain on the coating film surface was measured even if the absorbent cotton was pressed three times against the coating film.
In addition, the thing whose tensile strength was inadequate and it was difficult to handle a molding was set to “−” because the drying time could not be measured accurately.

[Gelification time]
For 50 parts by mass of the radical polymerizable resin compositions obtained in Examples and Comparative Examples, 0.25 parts by mass of 8% cobalt octylate, 0.5 parts by mass of paratoluidine-ethylene oxide 2 mol adduct, peroxidation 0.5 parts by mass of benzoyl was added, collected in a beaker, and the time (seconds) until gelation in a 25 ° C. constant temperature water bath was measured.
In the case where the tensile strength was insufficient and it was difficult to handle the molded product, the gelation time could not be accurately measured, and therefore, “-” was given.

It turned out that the thing of Examples 1-3 which is a radically polymerizable resin composition of this invention is excellent in normal temperature curability.
On the other hand, Comparative Examples 1 and 2 were embodiments that did not contain an allyl ester compound, but were found to have poor room temperature curability.
Moreover, although the comparative example 3 is an aspect with many amounts of an allyl ester compound, it turned out that tensile strength is inadequate and handling of a molded article is difficult.

Claims (4)

One or more radically polymerizable resins (A) selected from the group consisting of unsaturated polyester resins, epoxy (meth) acrylate resins, urethane (meth) acrylate resins and polyester (meth) acrylate resins, having a (meth) acryloyl group radical polymerizable monomer (B), a Riruesuteru compound (C), and a melting point contains petroleum wax (D) is in the range of from 43 to 72 ° C., the proportion of the allyl ester compound (C), wherein Radical polymerizable resin characterized by being in a range of 1 to 10% by mass relative to the total mass of radical polymerizable resin (A), radical polymerizable monomer (B) and allyl ester compound (C). Composition.   The radically polymerizable resin composition according to claim 1, wherein the allyl ester compound (C) is diallyl phthalate.   2. The radical polymerizable monomer (B) is at least one selected from the group consisting of phenoxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate and dicyclopentenyl (meth) acrylate. Or the radically polymerizable resin composition of 2. The radically polymerizable resin according to any one of claims 1 to 3 , wherein a proportion of the petroleum wax (D) used is in the range of 1 to 35% by mass with respect to 100 parts by mass of the allyl ester compound (C). Composition.