KR950006945B1 - Photo-cure type coating composition - Google Patents

Abstract

A thermoplastic acryl resin oligomer(II; R4= H or methyl, R6= H, methyl, ethyl, propyl, butyl and glycidyl, m= 1-500, n= 1-500, o= 1-10, x= C2-8 alkylene) and a composition containing urethane acrylate(I; R1= H, methyl, R2= (CH2)1, l= 1-6, R3= aliphatic or cyclic aliphatic or aromatic compound, Y= polyol or polyester polyol) were reacted at 40 degree C with a reactive monomer, a photoinitiator, a levelling agent and other additives to give the coating composition.

Description

Photocurable coating composition and flooring using the same

The present invention is coated on a vinyl chloride sheet to improve the durability, chemical resistance, heat resistance, fouling resistance, abrasion resistance, weather resistance, etc. of the sheet, especially UV curable coating composition used for the purpose of improving the stain resistance, wear resistance, weather resistance and the like and the same It relates to the vinyl chloride sheet used.

In terms of use, vinyl chloride flooring is divided into heavy-duty walks and warning walks, which are used in offices, department stores, general stores, and gymnasiums.In order to increase abrasion resistance, durability, pollution resistance, and chemical resistance, UV-curable varnishes are used. It has been used to coat, and the trend of using UV-curable varnish coating to the flooring for the alarm line used in the living room, kitchen, bedroom of apartments and general houses. However, the conventional UV-curable varnishes played a role in improving the appearance, wear resistance, durability, stain resistance, and chemical resistance of vinyl chloride sheets, but were not at a level that could fully satisfy the needs of consumers. Poor wear resistance and scratches due to dust, shoes, etc., and poor contamination resistance, so it does not erase well after staining contaminants (Creon, Magic, Kimchi soup, Okdo period, shoe polish, etc.). There is a change in color (lateral change) or other physical and mechanical properties.

The present invention completely compensates for the disadvantages of abrasion resistance, stain resistance, and weather resistance, so that there are few scratches upon friction with foreign substances, and easily erased after contact with contaminants, and do not discolor (yellowing) even after prolonged exposure to sunlight and physical properties. The present invention relates to an ultraviolet curable coating film composition excellent in wear resistance, fouling resistance, and weather resistance that do not fall off.

Another object of the present invention is to provide a vinyl chloride sheet using the ultraviolet curable coating composition according to the present invention.

In order to achieve the above object, the ultraviolet curable coating composition of the present invention is a mixture of a urethane acrylate and a thermoplastic acrylic resin as an oligomer, and is composed of a reactive monomer, a photoinitiator, a leveling agent, an additive, and the like, and has a viscosity of 300 at 25 ° C. A coating film composition that is -5000 CPS.

The present invention is a conventional UV curable coating composition (US Pat. Nos. 3,782,961, 3,829,531, 3,850,770, 3,874,906, 3,864,113, 3,891,523, 3,895,171, 3,899,611, 3,907,574, 3,912,516). No. 3,932,356, 4,301,209), the use of thermoplastic acrylic resin is characterized in that the curing speed is high, and wear resistance, pollution resistance, weather resistance is particularly excellent.

The present invention is described in volume as follows.

The photocurable coating composition of the present invention is a photocurable coating composition comprising urethane acrylate of the following general formula (I), a thermoplastic acrylic resin of the following general formula (II), a reactive monomer, a photoinitiator, a leveling agent, a quencher and other additives. It is composed.

Wherein R ¹ is hydrogen or a methyl group, R ² is (CH ₂ ) ₁ 1 is an integer of 1 to 6, R ³ is an aliphatic, cyclic aliphatic or aromatic compound, and Y is a polyol or polyester polyol.

Wherein R ⁴ is hydrogen or methyl, R ⁵ is hydrogen or methyl, ethyl, propyl, butyl and lycidyl and the like, m is 1-500, n is 1-500, o is 1-10, X is a C2-C8 alkylene group.

The general formula (I) is a urethane acrylate oligomer prepared by adding a polyol or polyester polyol to an aliphatic, cyclic aliphatic or aromatic diisocyanate with a hydroxyl group-containing acrylate of the following general formula (III) It can be used 10 to 70% by weight based on the whole, if less than the amount, the adhesion and fouling resistance is lowered, in many cases the viscosity is high, workability is poor and the coating film is strong. It is preferable to use 25 to 60% by weight in consideration of the physical properties of the coating film and the viscosity of the varnish.

In formula, R <^6> is hydrogen or methyl group P is a water purifier of 2-6.

General formula (I) The polyol used for urethane acrylate manufacture is poly tetrahydrofuran (PTHF) represented by the following general formula (IV), and its molecular weight is 500-3000.

Particularly, although PTHF-650, PTHF-1000, PTHF-2000, etc. may be used by BASF Co., Ltd., but the PTHF-1000, PTHF-2000, etc., the varnish viscosity is high coating PTHF-650 is recommended to use due to inconvenience in working.

G is an integer of 6-42 in said formula.

The polyester polyol used in the preparation of the urethane acrylate of the general formula [I] may be represented by the following general formula [V], which may be obtained by a condensation reaction of an acid having two carboxyl groups and an alcohol having two hydroxyl groups, At this time, in consideration of the flexibility of the cured coating film and the viscosity of the varnish, it is preferable to use a polyester polyol having a hydroxyl value of 200 to 250 and a molecular weight of 450 to 560.

In the above formula, R ⁷ is an aliphatic, cyclic aliphatic or aromatic compound having 2 to 10 carbon atoms, R ⁸ is an aliphatic, cyclic aliphatic or aromatic compound having 2 to 10 carbon atoms, and r is 1 to 3.

Here, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, phthalic acid, maleic acid, terephthalic acid, and the like are used for the acid having two carboxyl groups, and for the alcohol having two hydroxyl groups, ethylene glycol, diethylene glycol, neopentyl glycol Etc.

The molar ratio of the polyol / polyester polyol used in the reaction with one isocyanate of diisocyanate is suitably 1/3 to 3/1 considering the flexibility of the coating film and other physical properties.

A urethane acrylate oligomer is prepared by a known method by adding a hydroxy group-containing acrylate of the general formula [III] to another isocyanate which is an intermediate obtained by addition reaction of a polyol or a polyester polyol to diisocyanate. Useful include hydroxy ethyl acrylate, hydroxy ethyl methacrylate, hydroxy propyl acrylate, hydroxy propyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxy pentyl acrylate, hydroxy Pentyl methacrylate, hydroxy hexyl acrylate, hydroxy hexyl methacrylate and the like.

Diisocyanates used in preparing urethane acrylate oligomers include isophorone diisocyanate (3-isocyanate methyl 3,5,5trimethyl cyclohexyl isocyanate), 4,4′-dicyclohexyl methane-diisocyanate, trimethyl-hexamethylene- Diisocyanate, 1,6-hexamethylene diisocyanate, 2,4,4-trimethyl 1,6-hexamethylene diisocyanate, octadecylene diisocyanate, 1,4-cyclohexylene diisocyanate, 2,4-toluene Diisocyanate, 2,6-toluene diisocyanate, and the like, which is most suitable for the UV curable coating composition for double sheets is 3-isocyanate methyl 3,5,5-trimethylcyclohexyl isocyanate or 4,4′-hexyl hexyl Methane-diisocyanate.

In the present invention, a thermoplastic acrylic resin of the general formula [II], which is a non-reactive oligomer, is used to increase the curing property of the varnish and to improve the fouling resistance, weather resistance, and abrasion resistance of the coating film. There is an advantage to improve the wear resistance, fouling resistance and weather resistance of the coating film.

Such a non-reactive oligomer may be selected from an acrylic monomer and an acrylate monomer having a double bond in a molecule and reacted in the presence of a catalyst to obtain a thermoplastic acrylic resin having a molecular weight of 1,500 to 100,000.

Acrylate monomers capable of preparing such non-reactive oligomers include methyl methacrylate, butyl acrylate, acrylic acid, methacrylic acid, glycidyl methacrylate, hydroxy ethyl acrylate, hydroxypropyl acrylate, hydroxy propyl meta Acrylate, methyl acrylate, hydroxyethyl methacrylate, polypropylene glycol, polytetrimethylglycol, colyethylene glycol, polytetra methylene glycol, ethylene glycol, propylene glycol and the like.

Such non-reactive oligomers may be used in an amount of 5 to 50% by weight based on the total composition when preparing the varnish, but it is preferable to use 5 to 30% by weight in consideration of workability such as viscosity of the varnish.

If the amount of the non-reactive oligomer is 5% by weight or less, abrasion resistance, fouling resistance, and weather resistance may occur. If the content is 50% by weight or more, problems with chemical resistance and solvent resistance may occur.

The reactive monomer of the present invention may be polymerized with the urethane acrylate oligomer to affect the physical properties of the coating film, and one or more monomers may be used. The monomers mainly used are monomers having an acrylate ester monomer and a monofunctional vinyl group.

Acrylic esters are prepared by esterification of alcohols with unsaturated carboxylic acids, 1,4 butanediol diacrylate, 1,6 hexane diol diacrylate, neopentyl glycol diacrylate, pentaerythritol tetra methacrylate, trimethylol propane Triacrylate, ethyl hexyl acrylate, ethylhexyl methacrylate, pentyl acrylate, hexyl acrylate, cyclohexyl methacrylate, 1,4 butanediol diacrylate, tripropylene glycol, diacrylate, etc. It can be used with a rate oligomer with a 1 / 9-9 / 1 weight ratio, It is preferable to use with a 1 / 3-3 / 1 weight ratio.

Monomer vinyl monomers include N-vinyl-2 pyrrolidone, vinyl acetate, vinyl butyrate, vinyl isobutylate, vinyl caprate, vinyl caproate, vinyl captylate, vinyl cetyl ether, and vinyl cyclohexanol. , Vinyl-n-decanoate, vinyl decyl ether, vinyl isodecyl ether, vinyl laurate, vinyl octadecyl ether, etc. The coating of varnish is easy to adjust the viscosity and increase the curing rate is N- Vinyl-2-pyrrolidone is usefully used, and can be used in an oligomer with a weight ratio of 1/9 to 9/1, and is preferably used in a weight ratio of 1/3 to 3/1.

In addition, the reactive monomers are related to the viscosity of the varnish, the flexibility of the coating film, the hardness, the adhesion, and the like.

The photoinitiator uses a conventional polymerization initiator activated by ultraviolet rays, and in particular, 0.5 to 10% by weight of the benzophenone series, benzyl dimethyl ketal series, acetophenone series andhraquinone thioxanthone series, and the like are used.

As such photoinitiators, hydroxy-cyclohexyl phenyl ketone, 2.2-dimethoxy-2-phenyl, acetophenone, benzophenone, phenyl-2-hydroxy 2-propyl ketone and the like are mainly used.

The relubricating agent uses a silicone diacrylate-based or silicone polyacrylate-based compound in an amount of 0.1 to 5% by weight of the total composition. When semi-gloss or matte is required for the coating film composition, a matting agent may be used. The silica-based matting agent may be used in an amount of 1 to 10% by weight based on the required glossiness.

Other additives can use a well-known compound by changing the addition amount according to various requirements.

The following Examples and Comparative Examples will be described in more detail the efficacy, the effect of the UV-curable coating film composition of the present invention and a vinyl chloride sheet using the same, but is not intended to limit the scope of the present invention.

Unless otherwise specified, "parts" means "parts by weight".

Example 1

40 parts of urethane acrylate prepared by condensing adipic acid and neopentyl glycol to 1 mol of isophorone diisocyanate and reacting with 0.3 mol of polyester polyol, 0.2 mol of PTHF-650, and 1 mol of 2-hydroxyethyl acrylate, 10 parts of a non-reactive oligomer prepared by reacting 620 parts of methyl methacrylate, 7 parts of methyl acrylate, 50 parts of butyl acrylate and 100 parts of polypropylene glycol monoacrylate with a benzyl peroxide catalyst in the presence of methyl isobutyl ketone. 10 parts 6-hexanediol diacrylate, 10 parts 2-ethylhexyl acrylate, 25 parts N-vinyl-2-pyrrolidone, 2.5 parts benzophenone, 2 parts hydroxycyclohexyl phenyl ketone, silicone polyacrylate 0.5 parts of Ebecryl 360 from UCB was stirred at 40 ° C to prepare an ultraviolet curable varnish having a viscosity of 800 cps at 25 ° C.

Example 2

UV curable varnish with the same composition and content as in Example 1, except that the non-reactive oligomer of Example 1 was reacted with 600 parts of methyl methacrylate, 50 parts of hydroxy propyl methacrylate, and 10 parts of butyl acrylate. Was prepared.

Example 3

An ultraviolet curable varnish was prepared in the same composition and content as in Example 1 except that 35 parts of the urethane acrylate and 15 parts of the non-reactive oligomer were used.

Example 4

An ultraviolet curable varnish was prepared in the same composition and content as in Example 1 except that 10 parts of the urethane acrylate and 40 parts of the non-reactive oligomer were used.

Comparative Example 1

An ultraviolet curable varnish was prepared in the same composition and content as in Example 1 except that 50 parts of the urethane acrylate of Example 1 was used and no non-reactive oligomer was used.

TABLE 1

* Curing condition: High pressure mercury lamp, 80 watts / cm 2 lamp, fully cured at 10cm

* Dry film thickness: 10 ~ 15㎛ (* 3 is 120㎛)

* How to paint: Except * 3, paint with LOLAKOTA on the floor

(* 3 produces cured film)

* 1: Measurement of discoloration (yellowing) in 130 ℃ oven

* 2: measured according to JIS D0202 (Cross-Cut)

* 3: measured by INSTRON, measuring temperature 25 ℃, humidity RH55%

* 4: Use of dual abrasion measuring instrument (model 505)

* 5: Coating state after room temperature x 48 hours (swelling, discoloration)

* 6: The state of coating film washed with ethanol after room temperature × 24 hours

* 7: Observation of discoloration (yellowing) after 7 days of sunlight

When the UV curable varnish of the present invention was prepared and coated on a vinyl chloride sheet to evaluate physical properties, the non-reactive oligomer used as shown in Table 1 shows excellent physical properties in heat resistance, abrasion resistance, chemical resistance, fouling resistance, weather resistance, and the like. In the case of Example 4, which was used in an excessive amount, the adhesion and acidity were lowered, which was not suitable.

Claims (4)

The photocurable type which adds the non-reactive oligomer which is a thermoplastic acrylic resin of general formula (II) to the composition which consists of a well-known urethane acrylate of general formula (I), a reactive monomer, a photoinitiator, a leveling agent, and other additives. Coating composition. Wherein R ¹ is hydrogen (H) or methyl group (CH ₃ ), R ² is (CH ₂ ) ₁ , 1 is an integer from 1 to 6, R ³ is an aliphatic, cyclic aliphatic or aromatic compound, Y is Polyols or polyester polyols. Wherein R ⁴ is hydrogen or methyl, R ⁶ is hydrogen or methyl, ethyl, propyl, butyl and lycidyl and the like, m is 1 to 500, n is 1 to 500, o is 1 to 10, X is a C2-C8 alkylene group. The photocurable coating film composition according to claim 1, wherein the urethane acrylate of the general formula [I] is 10 to 70% by weight based on the final total composition. The photocurable coating composition according to claim 1, wherein the non-reactive oligomer, which is a thermoplastic acrylic resin having a molecular weight of 1,500 to 100,000, is 5 to 50% by weight based on the total composition. A vinyl flooring cured by coating the composition of any one of claims 1 to 3 to a thickness of 0.1 to 10 mils.