JPS6071669A - Photosetting composition for protecting face of slope - Google Patents

Abstract

PURPOSE:The titled composition having improved storage stability, providing a film with improved corrosion resistance, water resistance, adhesivity to base material, crack resistance, and weather resistance, comprising an epoxy resin, an Al compound, and a specific silicon compound as essential components. CONSTITUTION:The desired composition comprising (A) an epoxy resin (e.g., glycidyl ether type epoxy resin, etc.), (B) preferably 0.001-10wt% based on the component A of an Al compound such as trispropyl acetoacetonato aluminum, etc.), and (C) preferably 0.1-20wt% based on the component A of a silicon compound (preferably one containing any of peroxysilane group, o-nitrobenzyloxy group, alpha-ketosilyl group, such as trissalicyl-aldehyde aluminum, etc.) forming silanol group by light irradiation as essential components.

Description

Detailed Description of the Invention [Technical Field of the Invention] The present invention relates to a photocurable slope protection composition, and more particularly, the present invention relates to a photocurable slope protection composition, and more particularly, it has excellent storage stability, is cured by light to form a coating film, and is The present invention relates to a photocurable slope protection composition in which the film has excellent corrosion resistance, water resistance, adhesion to a substrate, crack resistance, and has weather resistance.

[Technical background of the invention and its problems] Conventionally, techniques such as mortar spraying, wire mesh covering, concrete pouring, and planting of vegetation have been known for protecting slopes such as bedrock. However, these techniques have many problems such as crack peeling, corrosion, and poor workability. As a way to deal with this problem, as a slope preservation agent,
Unsaturated polyester resin compositions are known from the viewpoint of cost.

However, since the cracks shrink significantly when hardened, the distortion causes insufficient adhesion to slopes such as rock and poor crack resistance, resulting in problems in terms of weather resistance overall.

[Object of the invention] The present invention eliminates the above-mentioned drawbacks of unsaturated polyester resin compositions, has excellent storage stability,
The object of the present invention is to provide a photocurable slope retention composition capable of forming a cured film in a short time.

[Summary of the Invention] The photocurable slope care composition of the present invention is characterized by comprising an epoxy resin, an aluminum compound, and a silicon compound that generates silanol groups when irradiated with light.

The epoxy resin which is the first essential component of the composition of the present invention includes -functional epoxy compounds and polyfunctional epoxy compounds. -Functional epoxy compounds include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, phenyldalicidyl ether, butyglycidyl ether, and the like. In addition, examples of polyfunctional epoxy compounds include, but are not limited to, bisphenol A epoxy resins; bisphenol F epoxy resins; phenol novolac epoxy resins; alicyclic epoxy resins; triglycidyl isocyanate, pidantoin epoxy, and the like. Heterocyclic epoxy resin; hydrogenated bisphenol A type epoxy resin; propylene glycol-dicrindyl ether, pentae I
Aliphatic epoxy (51 fat) such as polyglycidyl ether; epoxy resin obtained by reaction of aromatic, aliphatic or alicyclic carboxylic acid with epichlorohydrin; spiro ring-containing epoxy resin; 〇- A glycidyl ether type epoxy resin which is a reaction product of an arylphenol novolac compound and epichlorohydrin; ○- of each hydroxyl group of bisphenol A
Examples include glycidyl ether type epoxy resins, which are the reaction products of diallylbisphenol compounds having an allyl group in the position and epichlorohydrin, and one or more selected from these can be used as desired.

The aluminum compound, which is the second essential component of the H composition of the present invention, is an organoaluminium complex in which an alkoxy group, phenoxy group, acyloxy group, β-diketonato group, 0-carbonylphenorad & etc. are bonded to an aluminum atom. Preferably, it is a compound.

Here, the alkoxy group preferably has 1 to 10 carbon atoms, and examples include butoxy, ethoxy, impropoxy, butoxy, bentoxy, etc.; examples of the phenoxy group include phenoxy group, 0-methylphenoxy, 0-methoxyphenoxy group, p-nitrophenoxy group, 2.6-
Examples of dimethylphenoxy include acetate, propionate, impropionate, and acyloxy groups.
Ligands include butyrad, stearado, ethylacetoacetate, provylacetoacetate, butylacetoacetate, diethylmalato, dipivaloylmethanato;
Examples of the β-diketonato group include acetylacetonato, trifluoroacetylacetonato, hexafluoroacetylacetonato, CH3"CH3; examples of the 0-carbonylphenorad group include,
Examples include salicylaldehydate.

Specific examples of such aluminum compounds include trismethoxyaluminum, trisethoxyaluminum, trisisopropoxyaluminum, trisphenoxyaluminum, trisparamethylphenoxyaluminum, impropoxyjethoxyaluminum, trisbutoxyaluminum, trisacetoxyaluminum, trissteer. Radoaluminum, trisbutyradaluminum, trispropionatoaluminum, trisinpropionatoaluminum, trisacetylacetonadoaluminum, tristrifluoroacetylacetonadoaluminum, trishexafluoroacetylacetonadoaluminum, trisethylacetoacetatoaluminum, trissalicyl Aldehyda aluminum, tris-diethylmalorado aluminum, trispropylacetoacetato aluminum, trisbutyl acetoacetato aluminum, tris-divival methanato aluminum, diacetylacetonatodipivaloyl methanato aluminum, and the like.

These aluminum compounds may be used alone or in a mixed system of two or more, and the amount added is from o to 10%, preferably from 1 to 5%, based on the weight ratio to the epoxy resin. Range 1]. The blending amount is 0.0010
If it is less than 1% by weight, sufficient curing properties of the slope protection film cannot be obtained, and if it exceeds 10% by weight, the cost will increase and moisture resistance tends to decrease. This is not desirable because it can be seen.

The third essential component of the composition of the present invention is a silicon compound that generates silanol groups upon irradiation with light.

Preferably, such a silicon compound is a silicon compound containing any one of a peroxinerane group, an 0-nitrobenzylpoxy group, and an α-ketosilyl group.

Among these silicon compounds, those having a peroxysilane group have the following formula'('')r+-8I+00n')
4゜(In the formula, R+1.B2 may be the same or different, and each represents a hydrogen atom) ・Represents a rogene atom, an alkyl group or an aryl group having 1 to 5 carbon atoms, and n is O
Represents an integer from ~3. ).

In the above formula, examples of the alkyl group having 1 to 5 carbon atoms include:
Methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, sec-F7+
/ thread, n-pentyl group, methoxy method, ethoxy method, and chloromethyl group; Examples of the aryl group include phenyl group and naphthyl group.

Examples include anthranil patch and benzyl stout; carbon number 1-5
The alkyl group and aryl group may have a substituent such as a rogen atom, a nitro group, a cyano group, or a methoxy group.

Specific examples of such silicon compounds include the following H2 Examples include compounds shown in the following.

In the formula C, which has an 0-nitrobenzyloxy group,
R1, R2, and B3 may be the same or different, and each of them is a hydrogen atom; - rogene atom; a vinyl group; an allyl group; an unsubstituted or substituted argyl group having 1 to 0 carbon atoms; ~10 alkoxy group; unsubstituted or substituted aryl group; aryloxy; siloxy group, R4 is a hydrogen atom; unsubstituted or substituted alkyl group having 1 to 10 carbon atoms; to phenyl: substituted phenyl group Representation,
R5, R,6, B7, B, and 8 may be the same or different, and each represents a hydrogen atom; a nitro group; a cyano group; a hydroxy group; a mercapto group; a halogen atom; an acetyl group; an allyl group; Alkyl group having 1 to 5 carbon atoms; Alcoquine group having 1 to 5 carbon atoms; Unsubstituted or substituted aryl group; represents aryloxy, p, q, , r
is 0≦p, q.

It is a compound represented by "represents an integer satisfying the condition of ≦3.1≦p+q+r≦3."

Examples of the unsubstituted or substituted alkyl group having 1 to 10 carbon atoms include butyl group, ethyl group, propyl group, butyl group, t-
Examples include butyl group, bentyl group, chloromethyl group, chloroethyl group, fluoromethyl group, cyanmethyl group, etc., and examples of alkoxy groups having 1 to 10 carbon atoms include methoxy group, ethoxy, n-propoquine, n-butoxy. Examples include bases.

Examples of the unsubstituted or f11-substituted aryl group include phenyl group, p-methoxyphenyl group, p-chlorophenyl group,
Examples of the p-trifluoromethylphenyl group include p-trifluoromethylphenyl, and examples of the aryloxy group include phenoxy.

In addition, the silicon compound has an 0-nitrobenzyloxysilyl group as a terminal group, and the main chain has the following formula: where n represents O or an integer of 1 or more, and 1 and B2 have the same meanings as above. and X and Y may be the same or different,
Each represents an oxygen atom, an alkylene group, an aryl group, etc.

) may be a compound consisting of a group represented by

Non-fitm directly bonded to silicon atoms used in the present invention
Specific examples of silicon compounds having a substituted 0-nitrobenzyloxy group include trimethio(0-nitrobenzyloxy)silane, dimethylphenyl(0-nitrobenzyloxy)7rane, and diphenylmethyl(0-nitrobenzyloxy). oxy)silane, ) IJ phenyl(0-
nitrobenzyloxy)silane, vinylmethylphenyl(0-nitrobenzyloxy)silane, t--7'
thylmethylphenyl(0-nitrobenzyloxy)silane, triethyl(0-nitrobenzyloxy)silane,
) IJ (2-chloroethyl)-〇-nitrobenzyloxysilane, fluoroxy''silane, triphenyl(α-ethyl-〇-nitrobenzyloxy)silane, trimethyl(3-methyl-2-nitrobenzyloxy)silane, dimethyl Phenyl (3,4,5-)
Liftoxy-2-nitrobenzyloxy)silane, oxy)silane, triphenyl(4,5-dimethyl-2-nitrobenzyloxy)silane/, vinylmethylphenyl(4,5-')
Chloro-2-nitrobenzyloxy/)silane, triphenyl(2,6-cinitrobenzyloxy/)silane, diphenylmethyl(2,4-dinitrobenzyloxy)silane, triphenyl(3-methoxy-2-nitrobenzyl) oxy) 7rane, vinylmethylphenyl (3,
4-dimethoxy-2-nitrobenzyloxy7) silane, dimethyldi(0-nitrobenzyloxy)/ran, methylphenyldi(0-nitrobenzyloxy)silane, vinylphenyldi(0-nitrobenzyloxy)silane,
t-methylphenyldi(O-nitrobenzyloxy)silane, jetyldi(0-nitrobenzyloxy)silane, 2-chloroethylphenyldi(0-nitrobenzyloxy)silane, diphenyldi(0-nitrobenzyloxy)silane, diphenyldi(3-methoxy-2-nitrobenzyloxy)silane, diphenyldi(3,4-dimethoxy-2-nitrobenzyloxy)silane, diphenyldi(2,6-dinitrobenzyloxy)silane, diphenyldi(2-nitrobenzyloxy)silane ,4-dinitrobenzyloxy)silane,
Methyltri(0-nitrobenzyloxy)silane, Phenylto IJ(0-nitrobenzyloxy)silane, p-
Examples include bis(0-nitrobenzyloxydimethylsilyl)benzene, and silicon compounds produced by the reaction of 5i(J-containing silicone resin and O-nitrobenzyl alcohol).

Finally, those having an α-ketosilyl group have the following formula: (3) (where l, m, and n represent numbers of 0, 1, 2.3,
What is more than 13 + n + m id 3?
1, 几2. R3 and 几4 may be the same or different, and each represents a hydrocarbon group such as an alkyl group having 1 to 10 carbon atoms, an aryl group, an allyl group, or a vinyl group, an aryloxy group, or an aryloxy group having 1 to 10 carbon atoms. It represents an alkoxy compound, and these are compounds in which a substituent such as a halogen atom, MO2, CN, -0CR3, etc. is present ((optionally 0)) in the molecule.

in particular, Compounds such as

The amount of these silicon compounds added is 0.1 to 20% by weight, preferably 1 to 10% by weight based on the epoxy resin.
is within the range of If the amount is less than 0.1 part by weight, sufficient curing properties will not be obtained, and although it is possible to use more than the weighted part, it may result in high costs and decomposition products of the catalyst component. This is not desirable as it may cause problems.

Slope protection set of the present invention 1. The composition has the above-mentioned three components as essential components, that is, epoxy resin, aluminum compound, and silicon compound, but also contains hydrous silicic acid, silicic anhydride, calcium carbonate, glass powder, Frey, as a physical property modifier, as appropriate.
It is also possible to use a mixture of asbestos powder, mica powder, etc.

The composition of the present invention can be applied to preserve slopes such as rocks by brush coating, air type, or airless type, and after lining the slope, it is cured by a solar curing method. It can be put to practical use.

[Example of the invention 1jlu] Examples 1 to 6 As the epoxy resin, ERL4221 (trade name UC
Manufactured by Company C; alicyclic, epoxy equivalent weight 145, molecular weight 290)
, Epicor) 828 (trade name manufactured by Shell Chemical Co., Ltd.; bisphenol A type, epoxy equivalent 190-210, molecule 1
380), Epicote 1001 (trade name, manufactured by Shell Chemical Co., Ltd.; bisphenol A type, epoxy equivalent 450-52
5, molecular weight 900) and Epicote 152 (trade name, manufactured by Shell Chemical Co., Ltd.; phenol novolac type, epoxy equivalent weight 172-179), and as the organoaluminum compound, trispropylacetoaceketaluminum (
TPAAA),) lissalicylaldehydatoaluminum (TSADA), and t-butylperoxytriphenylsilane (TBTPS) were used as the organosilicon compound.
)It was used.

The above materials were uniformly mixed in the proportions shown in Table 1 (expressed in parts by weight) to prepare a photocurable slope 1 protection composition of the present invention.

On the other hand, for comparison, 0.3 mole of diethylene glycol and 08 mole of phlopylene gelicol were added to acid components of 0.8 mole of maleic anhydride, 0.1 mole of phthalic acid, and 0.1 mole of adipic acid at a temperature of 180 to 220'. A heating dehydration reaction was carried out in step c, and the reaction was completed at an acid value of 40 to obtain an ester.

An unsaturated polyester consisting of 55 parts by weight of this ester, 45 parts by weight of styrene, 17 parts by weight of cobal naphthenate as a curing accelerator, and 11 parts by weight of methyl ethyl ketone peroxide (5° weight ratio dimethyl phthalate solution) as a hardening agent. A composition was prepared and designated as Comparative Example 1.

The various compositions described above were applied onto rock using a spray gun, and the performance of the silicide on the rock was investigated. The results are collectively shown in Table 2.

Table 2 As shown in Table 2, the photocurable slope retention composition of the present invention maintained sufficient performance over a long period of time, but the composition of the comparative example had poor adhesion, crack resistance, It had various drawbacks, such as poor film resistance, and was not worthy of being used as a slope preservation composition.

Examples 7 to 12 Epoxy resins include Ell, L4221, Epicote 828, Epicote 1001, and Epicote 100.
4 (trade name, manufactured by Shell Chemical Co., Ltd.: bisphenol Am, epoxy equivalent: 900-1000, molecular weight 1400), and the organoaluminum compounds include triacetylacetonadoaluminum (TAAA), triethylacetoacetatoaluminum (Tll'l, AACA). ),)
Lith-lobe thylacedoacet aluminium (TNB)
AACA) and trissalicylaldehyde aluminum (TSADA) as the organosilicon compound.
Triphenyl(0-nitrobenzyloxy)silane (T
PONBS), diphenyldi(0-nitrobenzyloxy)silane (DDONBS), t-butyldiphenyl(5-meth-2-nitrobenzyloxy)silane (T
BDPM) and hydriphenyl(2,6-cinitrobenzyloxy)silane (TPDNBS) were used.

The proportions of the above listed in Table 3 (expressed in parts by weight)
were mixed uniformly to prepare a photocurable slope preservation composition of the present invention.

On the other hand, for comparison, an ester was obtained in the same manner as in Comparative Example 1 by adding 1.0 mole of propylene glycol to 0.3 mole of maleic anhydride, 0.6 mole of phthalic acid, and 0.1 mole of adipic acid. 55 parts by weight of this ester, 40 parts by weight of styrene, 5 parts by weight of methyl methacrylate, 0.7 parts by weight of cobalt naphthenate as a curing accelerator, and 1 part by weight of methyl ethyl ketone peroxide (50 parts by weight of methyl phthalate solution) as a curing agent. An unsaturated polyester composition was prepared and designated as Comparative Example 2.

9. Apply the above various compositions onto the rock using a spray gun and harden the rock. 'Uno sex fii: ii! 11 beds. The results are collectively shown in Table 4.

・As shown in Table 4 of Table 3, the photocurable slope protection composition of the present invention maintained sufficient performance over a long period of time, but the composition of the comparative example had poor surface hardness, adhesion, and weather resistance. It had various drawbacks, such as poor performance, and was not worthy of being used as a slope protection composition.

Examples 13 to 18 Epoxy street resins include ERL4221 and Epicote 82.
8. Using Epicoat 1001 and Epicoat 1004, the organic aluminum compounds were trisacetylacetonadoaluminum (TAAA), trisethylacetoacetatoaluminum (TEAACA) and trissalicylaldehydatoaluminum (TsA, DA). As the compounds, triphenylbenzoylsilane (TPBS) and diphenyl-methyl-benzoylsilane (NDBS) were used.

The above materials were mixed uniformly in the proportions shown in Table 5 (expressed in parts by weight) to prepare the photocurable slope protection composition of the present invention.

On the other hand, for comparison, 0.6 mol of maleic anhydride and 0.4 mol of phthalic acid were added to propylene glycol 0.8 mol.
mol, diethylene glycol 0.3 mol, ester obtained in the same manner as in Comparative Example 1, 55 parts by weight of the obtained ester,
35 parts by weight of styrene, methyl methacrylate) 10
A composition of an unsaturated polyester system consisting of 0.7 parts by weight of cobalt naphthenate as a hardening agent and 1 part by weight of methyl ethyl peroxide (50% by weight dimethyl phthalate solution) as a hardening agent was prepared. Comparative example 3.
Closed.

The various compositions described above were applied onto rock using a spray gun, and the performance of the cured products on the rock was examined. The results are summarized in Table 6.

As shown in Table 6, the photocurable slope protection composition of the present invention maintained sufficient performance over a long period of time, but the composition of the comparative example had poor adhesion and crack resistance. It had various drawbacks such as poor performance and was not worthy of being used as a slope protection composition.

[Effects of the Invention] As is clear from the above explanation, the photocurable slope protection composition of the present invention forms a lining film with excellent adhesion, crack resistance, and weather resistance, and is useful for protecting slopes such as rock. , has a wide range of uses as a lining agent for the protection of historic sites, etc., and its industrial value is extremely high.
given name)

Claims (1)

[Scope of Claims] (1) A photocurable slope protection composition comprising an epoxy resin, an aluminum compound, and a silicon compound that generates silanol groups upon irradiation with light. (2) The photocurable slope protection composition according to claim 1, wherein the aluminum compound is an organic aluminum compound. (a) The silicon compound has a peroxysilane group, 0-
The photocurable slope protection composition according to claim 1, which is a silicon compound having either a nitrobenzyloxy group or an α-ketosilyl group. (4) The amounts of the aluminum compound and the silicon compound are each 0.0 based on the weight of the epoxy resin.
The photocurable slope protection composition according to claim 1, which has a weight ratio of 01 to 10 and 0.1 to 20% by weight.