JP3060089B2 - Photocurable coating composition for flooring - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photocurable coating composition for flooring. More specifically, it cures at high speed by irradiation with light such as ultraviolet rays, has excellent adhesion to vinyl chloride resin (hereinafter simply referred to as PVC) flooring, and imparts abrasion resistance and stain resistance. The present invention relates to a cationic photocurable coating composition containing a propenyl ether terminal group compound.

[0002]

2. Description of the Related Art In recent years, PVC floor covering materials using an organic solvent have problems in terms of toxicity to workers, danger of fire, environmental pollution, drying speed, and waste of the solvent. Solvent-free coating agents that do not contain as an essential component but use curing by irradiation with active energy rays such as ultraviolet (UV) light have been studied. Examples of the solvent-free photocurable coating agent include radically polymerizable unsaturated polyesters, polyester (meth) acrylates, and urethane (meth) acrylates (for example, see JP-A-3-215515).
And JP-A-6-279556), photo-radical polymerization-type curing generally causes volume shrinkage, easily reduces the adhesion to the PVC substrate surface, and the acrylic composition has a peculiar odor. However, there is a problem that the working environment is deteriorated and skin irritation is high. Furthermore, when air (oxygen) is interposed during UV curing, the radical curing reaction is inhibited, so it is necessary to perform UV irradiation in an inert gas atmosphere.
There were also restrictions on the equipment. An epoxy photocationic curable resin has been proposed to improve such a problem. However, since the resin has low photoreactivity, a large amount of U.S.C.
Requires V energy. Therefore, there are drawbacks that a high UV energy irradiation device is required and irradiation time is long. As a method for improving the low reactivity of the photocationic curable resin, a method using an alicyclic epoxy compound as a base resin or a diluent is known (Japanese Patent Application Laid-Open No. 5-186755, etc.).

[0003]

However, the reaction rate of an alicyclic epoxy compound using an alicyclic epoxy compound is lower than that of a conventional photo-radical curable resin. It was limited, and it was difficult to obtain one that could satisfy practical performance. The present invention does not contain organic solvents, irritating monomers and oligomers, cures rapidly by irradiating active energy rays such as UV, has excellent adhesion to PVC resin, and has good abrasion resistance to flooring materials. It is an object of the present invention to provide a cationic photocurable coating composition that imparts properties, stain resistance, and the like. The coating composition of the present invention significantly improves various problems in the prior art, that is, harm to workers, environmental pollution, odor control, curing speed, coating film properties, and the like.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies on a coating material for a PVC flooring material that solves the above problems, and as a result, have reached the present invention. That is, the photocurable coating composition for a floor covering of PVC of the present invention is characterized by a (poly) ether oligomer having a propenyl ether terminal group, a polyester oligomer having a propenyl ether terminal group, and propenyl represented by the general formula (1). Urethane oligomer having an ether terminal group and at least two propenyls in a molecule selected from the group of monomers having a propenyl ether terminal group represented by the general formula (6), (6 ′) or (7) One or more compounds having ether terminal groups (A) and a cationic photopolymerization initiator (B) are essential components.

[0005]

X ¹ [—O— (AO) m—R ¹ ] n (1) In the formula, n is an integer of 3 to 200;
An integer of 200, and at least one of m is 1 or more. At least two of the n R ¹ groups are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. A is an alkylene having 2 to 12 carbon atoms, arylene, aralkylene or cycloalkylene group,
When m is 2 or more, A may be the same or different,
The (AO) m portion may be random addition or block addition. X ¹ is a polyhydric alcohol residue. ｝

X ¹ [—OR ¹ ] n (6) wherein n is an integer of 2 to 200, and X ¹ is a residue of polyglycerin (2 to 18-mer of glycerin). is there.
At least two of the n R ¹ are propenyl groups, and the rest may be alkyl, acyl or aryl groups. ｝

X ¹ [—O—R ¹ ] n (6 ′) wherein n is an integer of 2 to 200, and X ¹ is a residue of a 2- to 3-trimer of trimethylolalkane. . n R
^At least two of 1 are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝

Embedded image Y ¹ [—CO—X ² O—R ¹ ] n (7) ‖ In the formula, n is an integer of 2 to 200, and X ² is a residue of any one of alkylene diol, arylene diol, polyether diol, polyurethane diol and polycarbonate diol represented by HOX ² OH, Y ¹ is a polyvalent carboxylic acid residue. At least two of the n R ¹ groups are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION As (A) of the present invention, a urethane oligomer having a propenyl ether terminal group is particularly preferred.

In the general formula (1), A represents 1 to 1 carbon atoms.
2, a divalent group selected from the group consisting of alkylene, arylene, aralkylene and cycloalkylene groups, and examples of usable alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, Examples thereof include an alkylene group having 1 to 14 carbon atoms such as octylene, nonylene, decylene, undecylene, and dodecylene. Examples of arylene groups include phenylene,
Examples include naphthylene, anthrylene, phenanthrylene and the like. Examples of aralkylene include benzylene, 1-phenylene, 2-phenylene, 3-phenylpropylene, 2-phenylpropylene, 1-phenylpropylene, and the like. Examples of cycloalkylene groups include cyclopentylene, cyclohexylene, cycloheptylene,
And cyclooctylene. Of these, an ethylene group and a propylene group are preferred. If the alkylene group has more than 12 carbon atoms, the solubility of the cationic photopolymerization initiator (B) described later will be poor.

X ¹ is a polyhydric alcohol residue. Examples of the polyhydric alcohol include glycerin, polyglycerin (2 to 18-mer of glycerin, such as diglycerin, triglycerin, tetraglycerin, etc.) and glycidol ring opening. Polymers (compounds having a degree of polymerization of 2 to 5000), trimethylolalkanes (trimethylolethane, trimethylolpropane, trimethylolbutane and the like) and their dimers and trimers, monopentaerythritol, dipentaerythritol, 3,5-pentaerythritol, sorbitol, sorbitan sorbitan glycerin condensate, and the like. Of these, particularly preferred are glycerin, polyglycerin, and trimethylolalkane and its dimers and trimers.

In the general formula (1), n m is usually an integer of 0 to 200, and at least one of m is 1 or more, preferably 1 to 80, particularly preferably an integer of 1 to 5. is there. When m exceeds 200, the viscosity increases (B).
Becomes difficult to dissolve.

N is usually 2 to 200, preferably 3
To 100, particularly preferably an integer of 3 to 5. n is 2
If it exceeds 00, the viscosity increases and the dissolution of the initiator (B) becomes difficult. At least two of the n R ¹ groups are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups.

The polyester oligomer having a propenyl ether terminal group in the present invention includes a compound represented by the following general formula (2), (3) or (4).

[0012] In the formula, m is an integer of 1 to 200, n is an integer of 2 to 200, and X ² and X ³ are HOX ² OH and HOX ³ OH, respectively.
Represented by an alkylene diol, arylene diol,
Polyether diol, a residue of any of the diols of the polyurethane diols or polycarbonate diols, Y ¹ is a polyvalent carboxylic acid residue, Y ² is a divalent carboxylic acid residue. At least two of the n R ¹ groups are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝

X ² in the general formula (2) is HOX ² O
H is a residue of any of diols of alkylene diol, arylene diol, polyether diol, polyurethane diol and polycarbonate diol.

Specific examples of the alkylene diol represented by HOX ² OH include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, and 1,9-nonane. Diol, neopentyl glycol, 1.4-cyclohexanediol and the like. Of these, ethylene glycol and propylene glycol are preferred.

Specific examples of arylene diols represented by HOX ² OH include catechol, bis (2-hydroxyphenyl) methane, bis (4-hydroxyphenyl)
Examples include methane and bisphenol A. Of these, bisphenol A is preferred.

Specific examples of the polyether diol represented by HOX ² OH include poly (oxyethylene) diol, poly (oxypropylene) diol, poly (oxytetramethylene) diol, ethylene oxide adduct of bisphenol A, bisphenol And propylene oxide adduct of A. Of these, poly (oxyethylene) diol and poly (oxypropylene) diol are preferred.

The degree of polymerization of the above polyether diol is usually from 1 to 200, preferably from 2 to 100, particularly preferably from 3 to 3.
-20.

Examples of the polyurethane diol represented by HOX ² OH include reaction products of the following (i) and (ii). (I) H (OX ⁵⁾ diol represented by m-OH (provided that, m is an integer of 1 to 200, X ⁵ is a carbon number 2 to 1
And 2 divalent groups selected from the group consisting of alkylene, arylene, aralkylene and cycloalkylene groups. ) (Ii) a diisocyanate represented by OCN-Z ³ -NCO (However, Z ³ is a divalent group selected from the group consisting alkylene, arylene, a group aralkylene and cycloalkylene.)

In the above diol (i), m is an integer of usually 1 to 200, preferably 3 to 20.

In the diol of the above (i), X ⁵ is 2 selected from the group consisting of alkylene, arylene, aralkylene and cycloalkylene groups having 2 to 12 carbon atoms.
Examples of the alkylene group that is a valent group and may be used include methylene, ethylene, propylene, butylene, pentylene,
Hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene and the like can be mentioned. Examples of the arylene group include phenylene, naphthylene, anthrylene, phenanthrylene and the like. Examples of aralkylene include benzylene, 1-phenylene, 2-phenylene, 3-phenylpropylene, 2-phenylpropylene, 1-phenylpropylene, and the like. Examples of cycloalkylene groups include cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene and the like. Of these, particularly preferred are an ethylene group and a propylene group. When the carbon number of the alkylene group is 12
If the ratio exceeds the above range, the solubility of the polymerization initiator (B) becomes poor.

Examples of the diisocyanate (ii) include toluene diisocyanate (TDI), p- and m-phenylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 2,2 4,4-trimethylhexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI), 4,4'-diphenylmethane diisocyanate (MDI), 3,3'-dimethyl-4,4 '-Diphenylmethane diisocyanate,
1,5-tetrahydronaphthalene diisocyanate, naphthalene-1,5'-diisocyanate, bis (2-methyl-3-isocyanatophenyl) methane, 4,4'-
Examples include diphenylpropane diisocyanate, tetramethylxylene diisocyanate (TMXDI), and isophorone diisocyanate (IPDI). Of these, TDI, MDI, IPDI, TMX are preferred.
DI, hydrogenated MDI and HDI.

Examples of the polycarbonate diol represented by HOX ² OH include compounds represented by the following general formula. (However, m is an integer of 1 to 200, and X ⁶ is a divalent group selected from the group consisting of alkylene, arylene, aralkylene, and cycloalkylene having 2 to 12 carbon atoms.)

M in the above general formula is usually from 1 to 200,
Preferably it is an integer of 3 to 20.

X ⁶ in the above general formula has 2 to 12 carbon atoms.
Alkylene, arylene, aralkylene and a divalent group selected from the group consisting of cycloalkylene, examples of alkylene groups that can be used include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, Octylene, nonylene, decylene, undecylene, dodecylene and the like can be mentioned. Examples of the arylene group include phenylene, naphthylene, anthrylene, phenanthrylene and the like. Examples of aralkylene include benzylene, 1-phenylene, 2-phenylene, 3-phenylpropylene, 2-phenylpropylene, 1-phenylpropylene, and the like. Examples of cycloalkylene groups include cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene and the like. Of these, an ethylene group and a propylene group are preferred.

X ³ in the general formula (2) is:
The same as those exemplified as X ^{2 in the} formula (2) can be mentioned, and X ² and X ³ may be the same or different.

In the general formula (2), Y ¹ is a divalent or higher polyvalent carboxylic acid residue, and Y ² is a divalent carboxylic acid residue. Examples of the dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, oxalic acid, malonic acid, succinic acid,
Glutaric acid, adipic acid and the like can be mentioned. Examples of the trivalent or higher polycarboxylic acid include trimellitic acid and pyrimellitic acid. Among these, it is preferable that both Y ¹ and Y ² are one or more selected from isophthalic acid, terephthalic acid and adipic acid.

In the general formula (2), m is usually from 1 to 20.
It is an integer of 0, preferably 1 to 80, particularly preferably 1 to 20. When m exceeds 200, the viscosity becomes high and the dissolution of the polymerization initiator (B) becomes difficult.

In the general formula (2), n is usually 2 to 20.
It is an integer of 0, preferably 3 to 100, particularly preferably 3 to 20. When n exceeds 200, the viscosity becomes high and the dissolution of the initiator (B) becomes difficult. Further, at least two of the n R ¹ groups are a propenyl group, and the rest are hydrogen atoms,
It may be an alkyl, acyl or aryl group.

Next, the polyester oligomer represented by the following general formula (3) will be described. 中 wherein, m is an integer of 1 to 200, n is an integer of 2 to 200, X ² is an alkylene or an arylene group,
X ¹ is a polyhydric alcohol residue. At least two of the n R ¹ groups are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝

X ¹ in the general formula (3) is the same as that represented by the general formula (1).
X ² , m and n are the same as those represented by the general formula (2).

Next, the polyester oligomer represented by the following general formula (4) will be described. In the formula, m is an integer of 1 to 200, n is an integer of 2 to 200, and X ² and X ³ are an alkylene diol, an arylene diol, a polyether diol, a polyurethane represented by HOX ² OH and HOX ³ OH, respectively. X ¹ is a residue of a diol of either diol or polycarbonate diol, and X ¹ is a polyhydric alcohol residue. At least two of the n R ¹ groups are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝

X ¹ in the general formula (4) is the same as that represented by the general formula (1).
X ² , X ³ , m and n are the same as those represented by the general formula (2). X ² and X ³ may be the same or different.

The urethane oligomer having a propenyl ether terminal group in (A) in the present invention is a compound represented by the following general formula (5). {Wherein, m is 0 to 200, n is an integer of 2 to 200, Q ¹ is -OX ² O-or ^{-N (R 2) -X 4 -N} (R
² )-and Q ² is a group represented by -OX ² O-. X ² is an alkyl diol, aryl diol, polyether diol represented by HOX ² OH,
It is a residue of a diol of either polyester diol or polycarbonate diol. -N (R ²⁾ -X ⁴
—N (R ² ) — is a diamine residue represented by HN (R ² ) —X ⁴ —N (R ² ) H, and X ⁴ is alkylene, arylene, aralkylene or cycloalkyl having 2 to 12 carbon atoms. An alkylene group, and R ² is an alkyl, aryl, aralkyl or cycloalkyl group having 2 to 12 carbon atoms. Z
¹ is a polyvalent isocyanate residue, and Z ² is a divalent isocyanate residue. At least two of the n R ¹ groups are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝

In the general formula (5), ² in Z 2
Examples of the multivalent isocyanate include the same ones as those described in the above formula (ii). As the polyvalent isocyanate for Z ^1, in addition to the above-mentioned divalent isocyanate, lysine ester triisocyanate, modified isocyanate (isocyanurate trimer, buret trimer,
Trimethylolpropane adduct), triphenylmethane triisocyanate, polyphenylmethane polyisocyanate and the like.

In the general formula (5), Q ¹ is —OX ² O—
Or ^{-N (R 2) -X 4 -N} (R 2) - in a group represented, Q ² is a group represented by -OX ² O-. X ² is H
Alkylene diol represented by OX ² OH, ant - diol, polyether diol, a residue of any of the diol polyester diols or polycarbonate diols, X ² is the same as X ² in the general formula (2) Things.

When the HOX ² OH is a polyester diol, the following reaction products of (iii) and (iv) can be mentioned. ^{(Iii) H (OX 7)} m-OH in the diol represented (wherein, m is an integer of 1 to 200, X ⁷ is a carbon number 2 to 1
And 2 divalent groups selected from the group consisting of alkylene, arylene, aralkylene, and cycloalkylene groups. (Iv) Dicarboxylic acid represented by HOOC-Y ³ —COOH (where Y ³ is a divalent group selected from the group consisting of alkylene, arylene, aralkylene and cycloalkylene).

In the diol of the above (iii), m is usually an integer of 1 to 200, preferably 3 to 20.

In the diol of the above (iii), X ⁷ is a divalent group selected from the group consisting of alkylene having 2 to 12 carbon atoms, arylene, aralkylene and cycloalkylene. Is methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene,
Decylene, undecylene, dodecylene and the like can be mentioned.
Examples of the arylene group include phenylene, naphthylene, anthrylene, phenanthrylene and the like. Examples of aralkylene include benzylene, 1-phenylene, 2-phenylene, 3-phenylpropylene, 2-phenylpropylene, 1-phenylpropylene, and the like.
Examples of cycloalkylene groups include cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene and the like. Of these, an ethylene group and a propylene group are preferred. The alkylene group has 1 carbon atom
If it exceeds 2, the solubility of the polymerization initiator (B) becomes poor.

Examples of the dicarboxylic acid (iv) include phthalic acid, isophthalic acid, terephthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, polycarboxylic acid and the like. Preferred among these are isophthalic acid, terephthalic acid and adipic acid. X ⁴ is the same as X ² in the general formula (2), R ² is the same as A shown in the general formula (1), and m and n are The same as those represented by the general formula (2) can be mentioned.

The monomer having a propenyl ether terminal group in (A) of the present invention is a compound represented by the following general formula (6) or (7). X ¹ [—O—R ¹ ] n (6) In the formula, n is an integer of 2 to 200, and X ¹ is a polyhydric alcohol residue. At least two of the n R ¹ groups are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝

In the general formula (6), n is usually 2 to 2
00, preferably an integer of 2 to 6. If n exceeds 200, the viscosity is high and the handling becomes poor. X ¹ is the same as that shown in the general formula (1).

[0042] In the formula, n is an integer of 2 to 200, X ² is a residue of any one of alkylene diol, arylene diol, polyether diol, polyurethane diol and polycarbonate diol represented by HOX ² OH, and Y ¹ Is a polyvalent carboxylic acid residue. At least two of the n R ¹ groups are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups.に お い て In the general formula (7), n is an integer of usually 2 to 200, preferably 2 to 6. If n exceeds 200, the viscosity is high and the handling becomes poor. Y ¹ and X ² are the same as those represented by the general formula (2).

As the cationic photopolymerization initiator (B) used in the present invention, known cationic photopolymerization initiators can be used. Specific examples of (B) include triphenylsulfonium hexafluoroantimonate, triphenylsulfonium phosphate, p- (phenylthio)
Phenyldiphenylsulfonium hexafluoroantimonate, p- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, bis [4-diphenyl-sulfonio) phenyl Sulfide-bis-hexafluorophosphate, bis [4-diphenyl-sulfonio) phenyl] sulfide-bis-hexafluoroantimonate, (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe-hexafluorophosphate and the like. These are readily available from the market. Examples of commercially available products include “SP-150” and “SP-150” manufactured by Asahi Denka Co., Ltd.
170 ";" Irgacure 26 "manufactured by Ciba Geigy
"UVR-697" manufactured by Union Carbide
4 "," UVR-6990 "and the like.

In the present invention, a reactive diluent (C) can be used if necessary for the purpose of adjusting the viscosity of the composition.

As the compound (C), a compound represented by the following general formula (8) can be mentioned. CH ₃ —CH ＝ CH—O—X ² —O—R ³ (8) wherein X ² is an alkylene diol, arylene diol, polyether diol, polyurethane diol or polycarbonate diol represented by HOX ² OH R ³ is a residue of any diol, and R ³ has 2 to 2 carbon atoms.
12 alkyl, aryl, aralkyl, cycloalkyl groups or hydrogen atoms. ｝

X ² in the above general formula (8) is the same as that represented by the above general formula (2).
³ is an alkyl, aryl, aralkyl, cycloalkyl group or hydrogen atom having 2 to 12 carbon atoms.

In the present invention, the weight ratio of (A) :( B) is usually (95-99.9) :( 0.01-
5), preferably (96-98): (2-4).
If the ratio of (B) is less than 0.05, a sufficient effect of initiating polymerization cannot be obtained, and if it exceeds 5, the effect of further improving the curing speed is uneconomical.

When the reactive diluent (C) is used, the amount of the (C) is usually 5 to 60% by weight, preferably 10 to 30% by weight based on the total weight of (A) and (B). is there.
When the amount of (C) exceeds 60% by weight, the curing speed decreases.

If necessary, the composition of the present invention may contain a known photo-radical polymerizable composition (D).
The amount of (D) is per 100 parts by weight of the composition of the present invention,
It is usually 0 to 100 parts by weight, preferably 0 to 40 parts by weight.

The composition of the present invention may further comprise, if necessary,
Known epoxy resins (bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetrabromobisphenol A type epoxy resin, novolak type epoxy resin, etc.), pigments, colorants, inorganic fillers, non-reactive resins (rosin derivatives, etc.), A leveling agent, an antistatic agent, an organic solvent, and other various additives can be contained.

The cationic photocurable coating material for flooring made of the composition of the present invention is applied to, for example, a sheet-like or tile-like vinyl chloride base material and then cured at high speed by irradiation with light energy such as UV. Forms a film with excellent adhesion, stain resistance, etc. In addition, unlike the conventional radical photocuring type, photocuring does not cause curing inhibition due to oxygen, and there is almost no shrinkage during curing, so that warpage during coating is extremely small.

The flooring substrate to which the composition of the present invention is applied includes:
It may be any of hard, semi-rigid, soft or foam. There is no particular limitation on the method of coating the substrate, and a known method (roll coating, gravure coating, knife coating, curtain coating, spray coating, etc.) can be used. Examples of light that can be used include UV emitted from a high-pressure mercury lamp, a metal halide lamp, a low-pressure mercury lamp, and the like.

[0053]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto. The numerical values in the composition column are parts by weight.

Examples 1 to 6 and Comparative Examples 1 to 3 Liquid compositions prepared according to the formulation shown in Table 1
It was applied to the surface of a soft PVC sheet having a thickness of 70 μm to a thickness of 70 μm, and the photoreactivity, adhesion and stain resistance were evaluated according to the following evaluation methods and evaluation criteria. Table 1 shows the obtained evaluation results. Photoreactivity: Curing property was observed by irradiating a predetermined amount of ultraviolet rays (UV) to the surface coated with the composition. The curability was evaluated according to the following criteria based on the degree of adhesion of the uncured product to cotton by rubbing the coated surface after irradiation with UV of a certain energy amount with a cotton swab. Evaluation criteria: ○ Surface completely cured (tack-free) △ Some surface uncured part × Surface uncured Adhesion: Covered sheet (floor material) obtained by irradiating 900 mJ / cm ² UV with the coated surface facing outside The coating was evaluated by the presence or absence of peeling and cracking of the coating layer. Evaluation criteria: ○ No abnormality × Peeling or cracking Stain resistance: Gauze that was marked with black magic ink on the coated surface of the same coated sheet as that used in the above adhesion test, and was allowed to contain ethanol after 24 hours And the degree of contamination after wiping was evaluated.

[0055]

[Table 1]

The compounds used in the formulations shown in Table 1 are as follows. The CH ₃ —CH ＝ CH— group (propenyl group) is abbreviated as Pr. Propenyl ether end groups Compound (1): Pr-O- ( CH 2 CH 2 O) 12 -Pr propenyl ether end groups of compound (2): (Y: Terephthalic acid residue) Propenyl ether terminal group compound (3): (X: triethylene glycol residue) (Z: 4,4'-diphenylmethane diisocyanate residue) Propenyl ether terminal group compound (4): (X: triethylene glycol residue) Propenyl ether terminal group compound (5): R [O- (CH ₂ CH ₂ O) ₁₂ -Pr] ₃ (R: glycerin residue) propenyl ether terminal group compound (6): (X ¹ : triethylene glycerin residue) (Y: terephthalic acid residue) (X ² : polyurethane diol residue of the following formula) (Z: 4,4′-diphenylmethane diisocyanate residue) Acrylate terminal compound (7): Epoxy terminal compound (8): "Epicoat 828"
(Bisphenol type epoxy resin manufactured by Yuka Shell Co., Ltd.) Alicyclic epoxy terminal group compound (9): "ERL-422
1 "(manufactured by Union Carbide Corporation, alicyclic epoxy resins) reactive diluent (10): Pr-O- CH 2 CH 2 -OH reactive diluent (11): 2-hydroxyethyl acrylate reactive diluent ( 12): "BRL-4206" (manufactured by Union Carbide Co., Ltd., alicyclic epoxy resin diluent) Photocationic polymerization catalyst (13): "UVR-6974"
<< 50% ethylene carbonate solution of a mixture of p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate and bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate, manufactured by Union Carbide Co., Ltd. (14): “Irgacure 18
4 "(made by Ciba-Geigy)

[0057]

The photocationically curable floor covering coating composition containing a compound having a propenyl ether terminal group according to the present invention has better surface curability than conventional radical polymerization type acrylate-based ones, This has the effect of providing excellent adhesion to materials and stain resistance. In addition, it has a high-speed curing property as compared with those using a conventionally known epoxy UV cation curing resin. Because of the above effects, the photocationically curable coating composition of the present invention is extremely useful as a solventless coating, especially for PVC flooring.

────────────────────────────────────────────────── (5) References US Pat. No. 5,334,772 (US, A) “J. Macromol. Sci., Pure Appl. Chem.”, 1994, A31 (12), p. 1927-1941 (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 4/00 C08F 299/06 C09D 167/07 C09D 175/16 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (8)

(57) [Claims] 1. A (poly) ether oligomer having a propenyl ether terminal group, a polyester oligomer having a propenyl ether terminal group, a urethane oligomer having a propenyl ether terminal group represented by the general formula (1), and a compound represented by the general formula (6): At least one compound (A) having at least two propenyl ether terminal groups in a molecule selected from the group of monomers having a propenyl ether terminal group represented by the general formula (6 ′) or (7), And a photocurable coating composition for PVC flooring, comprising a cationic photopolymerization initiator (B) as an essential component. X ¹ [—O— (AO) m—R ¹ ] n (1) In the formula, n is an integer of 3 to 200, and n m is 0 to
An integer of 200, and at least one of m is 1 or more. At least two of the n R ¹ groups are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. A is an alkylene having 2 to 12 carbon atoms, arylene, aralkylene or cycloalkylene group,
When m is 2 or more, A may be the same or different,
The (AO) m portion may be random addition or block addition. X ¹ is a polyhydric alcohol residue. X ¹ [—OR ¹ ] n (6) wherein n is an integer of 2 to 200, and X ¹ is a residue of polyglycerin (2 to 18 mer of glycerin) It is.
At least two of the n R ¹ are propenyl groups, and the rest may be alkyl, acyl or aryl groups. X ¹ [—O—R ¹ ] n (6 ′) wherein n is an integer of 2 to 200, and X ¹ is a residue of a trimer of trimethylolalkane. is there. n R
^At least two of 1 are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝ Embedded image Y ¹ [—CO—X ² O—R ¹ ] n (7) ‖ In the formula, n is an integer of 2 to 200, and X ² is a residue of any one of alkylene diol, arylene diol, polyether diol, polyurethane diol and polycarbonate diol represented by HOX ² OH, Y ¹ is a polyvalent carboxylic acid residue. At least two of the n R ¹ groups are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝ 2. The composition according to claim 1, wherein the polyester oligomer having a propenyl ether terminal group is an oligomer represented by the following general formula (2), (3) or (4). Embedded image Y ¹ [—CO— (X ² O—CY ² C—O) m—X ³ O—R ¹ ] n (2) ‖ ‖ ‖ O O O ｛In the formula, m is an integer of 1 to 200, n is an integer of 2 to 200, and X ² and X ³ are HOX ² OH and HOX ³ OH, respectively.
Represented by an alkylene diol, arylene diol,
Polyether diol, a residue of any of the diols of the polyurethane diols or polycarbonate diols, Y ¹ is a polyvalent carboxylic acid residue, Y ² is a divalent carboxylic acid residue. At least two of the n R ¹ groups are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝ Embedded image X ¹ [—O— (CX ² O) m—R ¹ ] n (3) ‖ In the formula, m is an integer of 1 to 200, n is an integer of 2 to 200, X ² is an alkylene or an arylene group,
X ¹ is a polyhydric alcohol residue. At least two of the n R ¹ groups are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝ Embedded image X ¹ [-(OX ² OC) m-OX ³ O-R ¹ ] n (4) ‖ In the formula, m is an integer of 1 to 200, n is an integer of 2 to 200, and X ² and X ³ are respectively HOX ² OH, alkylene diol represented by HOX ³ OH, arylene diol, polyether diol, X ¹ is a residue of a diol of either polyurethane diol or polycarbonate diol, and X ¹ is a polyhydric alcohol residue. At least two of the n R ¹ groups are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝ 3. The composition according to claim 1, wherein the urethane oligomer having a propenyl ether terminal group is an oligomer represented by the following general formula (5). Embedded image Z ¹ [-NC- (Q ¹ -C-NZ ² NC) m-Q ² -R ¹ ] n (5) ｜ ‖ ｜ ｜ ｜ ‖ H O O H During H O {wherein, m is 0 to 200, n is an integer of 2 to 200, Q ¹ is -OX ² O-or ^{-N (R 2) -X 4 -N} (R
² )-and Q ² is a group represented by -OX ² O-. X ² is a residue of any one of alkyl diol, aryl diol, polyether diol, polyester diol and polycarbonate diol represented by HOX ² OH. -N (R ²⁾ -X ⁴ -
N (R ² ) — is a diamine residue represented by HN (R ² ) —X ⁴ —N (R ² ) H, and X ⁴ is an alkylene, arylene, aralkylene or cycloalkylene group having 2 to 12 carbon atoms. R ² is an alkyl, aryl, aralkyl or cycloalkyl group having 2 to 12 carbon atoms Z ¹ is a polyvalent isocyanate residue, and Z ² is a divalent isocyanate residue. At least two of the n R ¹ groups are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝ 4. The weight ratio of (A) :( B) is (95-9)
9.9): The composition according to any one of claims 1 to 3, which is (0.01 to 5). 5. The method according to claim 1, further comprising a reactive diluent (C), wherein the content of (C) is 5 to 60% by weight based on the total weight of (A) and (B). 5. The composition according to any of 4. 6. The composition according to claim 5, wherein (C) is a reactive diluent represented by the following general formula (8). CH ₃ —CH ＝ CH—O—X ² —O—R ³ (8) wherein X ² is an alkylene diol, arylene diol, polyether diol, or polyurethane diol represented by HOX ² OH Or a residue of any diol of polycarbonate diol, wherein R ³ has 2 to 2 carbon atoms.
12 alkyl, aryl, aralkyl, cycloalkyl groups or hydrogen atoms. ｝ 7. A photocurable coating composition for PVC flooring, wherein the composition according to claim 1 further contains an epoxy resin. 8. A PVC flooring material which is obtained by applying the composition according to claim 1 by roll coating, gravure coating, knife coating, curtain coating or spray coating, and then irradiating the coated surface with light to cure the floor. Production method.