KR100509419B1 - Manufacturing method of photocurable urethane acrylate oligomer - Google Patents

Abstract

The present invention relates to a method for preparing a thermosetting silicone-modified resin and a coating composition containing the same, which have excellent storage stability at room temperature, have almost no increase in viscosity during storage, and crosslinking reaction as the resin itself when heat of 150 to 200 ° C. is applied. The cured resin composition is excellent in heat resistance and can withstand a long period of time at 250 to 400 ° C., which can be used for an adhesive requiring heat resistance, and is particularly suitable for use as a heat-resistant paint. The method of the present invention prepares a silicone-modified resin using a polyol containing an average of two or more reactive hydroxyl groups in one molecule and a silicone intermediate containing two or more reactive silanol or alkoxy groups per average molecule, and thus prepared silicone The heat-curable silicone-modified resin composition made of a silane containing two or more modified resins and reactive alkoxy groups compensates for the high temperature curability and the weak mechanical properties of the cured product, which are easily cured even at a relatively low temperature, thereby providing excellent mechanical properties. It is suitable for heat-resistant paints because it is characterized by having excellent heat resistance properties of silicon.

Description

Manufacturing method of photocurable urethane acrylate oligomer

The present invention relates to a method for producing a photocurable urethane acrylate oligomer having good durability and chemical resistance and particularly excellent antistatic ability.

More specifically, it is applied to a photocurable varnish, and when the photocurable varnish is coated on a vinyl chloride sheet or a plastic molded article, the coating film has excellent durability, chemical resistance, contamination resistance, abrasion resistance, weather resistance, and the like, and particularly, provides antistatic ability. Urethane acrylate with antistatic ability to reduce the degree of contamination of the coating film by lowering the electrical resistance of the coating film and to allow the contaminated material (first, tee, hair, etc.) to fall off easily to prevent scratching from the contaminant. It is to provide a method for preparing an oligomer.

The use of vinyl chloride flooring is divided into heavy-duty walks and warning walks, which are used in offices, department stores, hotels, general stores, and gymnasiums. In order to increase the stain resistance and chemical resistance, the coating film composition containing the photocurable oligomer has been coated since early. There is a trend to use a coating composition containing a photo-curable oligomer also in the flooring for alarms used in living rooms, kitchens, bedrooms of apartments and general houses.

However, the coating composition containing the conventional photocurable oligomer has the unique appearance, wear resistance and durability of vinyl chloride sheet. It played a role of improving pollution resistance and chemical resistance, but it was not a level that could fully satisfy the needs of consumers.

In the case of plastic molded products, acrylonitrile-butadiene-styrene copolymer (ABS), polycarbonate (PC), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polystyrene (PS), etc. Is widely used in telephones, cosmetic containers, various accessories, and other plastic molded products, and the coating composition containing the conventional photocurable oligomer plays a role of improving the hardness, durability, chemical resistance, and wear resistance of the molded products. It was not enough to fully satisfy the desire.

In addition, in the case of vinyl chloride flooring, excellent flexibility is also required for the photocurable coating composition to meet the inherent flexibility of the sheet. In the case of a plastic molded article, hardness, chemical resistance, and durability are required for the photocurable coating composition according to the purpose of the molded article.A conventional coating film (paint) composition containing a photocurable oligomer, for example, Korean Patent No. 74985, US Patent Although the coating compositions disclosed in Nos. 3,782,961, 3,829,531, 3,874,905, 3,897,523, 3,895,171, 3,899,611, 3,912,516, 3,932,356, and 4,301,209 were used, the curability and other poor hardenability Has been the cause.

In particular, since the conventional vinyl chloride flooring and plastic molded products have high electrical resistance on the inherent surface or the surface of the photocurable coating film, they are easily charged by friction or peeling and are adsorbed by dust to damage the appearance. Have

As a method for solving such a problem, a method of mixing an antistatic agent such as a surfactant having a low molecular weight, for example, glycerol monostearate, into the composition, a method of modifying the surface structure of the coating composition by plasma treatment, or the like Proposed.

However, this method cannot give permanent antistatic capability. The reason for this is that since the antistatic agents are present in the thin coating film (10 to l5 탆) of the vinyl chloride flooring material or the plastic molded article, these antistatic agents are easily removed by washing with water, friction, or the like, thereby losing the antistatic ability. In addition, the method of plasma treatment of the surface structure of the coating composition is not only expensive, but also has a problem in that physical properties of the photocurable composition are lowered.

The present invention was completed in order to solve the above problems, the object of the present invention is good hardness, chemical resistance, durability, flexibility, etc. without sacrificing the general properties of the photocurable coating film composition, permanent antistatic ability It is to provide a photocurable urethane acrylate oligomer that can provide.

The photocurable urethane acrylate oligomer for achieving the above object is reacted with an isocyanate functional group (NCO) of an aliphatic, cyclic aliphatic, aromatic diisocyanate or oligomers of these isocyanate compounds of the following general formula (2) , And reacting a part of the remaining isocyanate with a polyalkylene glycol macromer containing a hydroxy group at the terminal of the following general formula (3) and adding the remaining unreacted isocyanate with a hydroxy group-containing acrylate of the general formula (4) And urethane acrylate oligomers having an antistatic ability represented by the following general formula (1).

Wherein R ₁ is aliphatic, cyclic aliphatic, aromatic compound or oligomer of these compounds.

X ₁ and X ₂ are different from each other, and a residue of formula (3) or (4),

Y is a residue of the polyether polyol of the formula (2).

Since the urethane acrylate oligomer of the present invention of the general formula (1) includes a (-R-O-) having an antistatic function in the oligomer to form a cured coating film, it has a permanent antistatic function until the coating film disappears after coating.

HO- (-R ₂ -0-) _n -H (2)

R ₂ is an alkylene group having 2 to 6 carbon atoms,

m is 1-90.

Where R ₃ is hydrogen or a methyl group,

R ₄ is an alkylene group having 2 to 6 carbon atoms,

n is 2-40.

CH ₂ = CCOR ₅ -OH (4)

Where R ₃ is hydrogen or a methyl group,

R <_5> is a C2-C6 alkylene group.

The present invention will be described in more detail as follows.

The polyether polyol of the general formula (2) used in the preparation of the urethane acrylate oligomer of the general formula (1) is glycol having two hydroxyl groups, that is, ethylene glycol, propylene glycol butylene glycol, pentylene glycol, hexanediol and the like. It is preferable to use the thing obtained by the ether condensation reaction of the thing, and having a hydroxyl value of 30-1,100 and a molecular weight of 100-4,000 in consideration of curability, hardened | cured material property, etc.

The hydroxyl group-containing polyalkylene glycol macromers of the general formula (3) used in the production of the photocurable urethane acrylate oligomer of the present invention are polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate. , Polypropylene glycol monomethacrylate, polybutylene glycol monoacrylate, polybutylene glycol monomethacrylate, polypentylene glycol monoacrylate, polypentylene glycol monomethacrylate, polyhexylene glycol monoacrylate And polyhexylene glycol monomethacrylate and the like, having a hydroxyl value of 15 to 550 and a molecular weight of 100 to 4000 is preferable; The hydroxy group-containing acrylate of formula (4) is hydroxy ethyl acrylate, hydroxy ethyl methacrylate, hydroxy propyl acrylate, hydroxy propyl methacrylate, hydroxy butyl acrylate, hydroxy butyl methacryl Acrylate, hydroxy pentyl acrylate, hydroxy pentyl decacrylate, hydroxy hexyl acrylate, hydroxy hexyl methacrylate and the like.

Inosyanates used in the synthesis of the photocurable urethane acrylate oligomer of the present invention include isophorone diisocyanate (3-isocyanate methyl 3,5,5-trimethyl cyclohexyl isocyanate), 4,4-dicyclo Hexyl 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 oligomers of these compounds. In particular, the isocyanate oligomer may be a trifunctional triisocyanate of the biuret, isocyanurate structure of the diisocyanate, or a composite structure thereof and the like.

The equivalent ratio of the isocyanate compound and the polyether polyol is suitably used in an amount of 0.2 to 1 equivalent of the polyether polyol for 2 equivalents of isocyanate. If the polyol is 0.2 equivalent or less, the adhesion and mechanical properties of the coating film are inferior, and if it is 1.5 equivalent or more, the curability is This is bad. More preferred equivalent ratio is 0.5-1.2 equivalents of polyether polyol to 2 equivalents of isocyanate.

together. The urethane acrylate oligomer is prepared by a known method of addition reaction seeker to the unreacted isocyanate of the intermediate obtained by the addition reaction of the polyether polyol to the hydroxyl group-containing compound of the general formulas (3) and (4), wherein the hydroxyl group The equivalent ratio of the compound is preferably 0.5 to 1.8 equivalents of the hydroxyl group-containing compound to 2 equivalents of the isocyanate compound. If the hydroxyl group-containing compound is 0.5 equivalent or less, curability is poor, and preferably 0.8 to 1.5 equivalents.

Here, the hydroxy group-containing polyalkylene macromer of the general formula (3) and the hydroxy group-containing acrylate equivalent ratio of the general formula (4) can be appropriately adjusted according to the physical properties required for the possession, but 9.9: 0.1 to 1: 9 is suitable, when the content of the hydroxy group-containing polyalkylene macromer of the general formula (3) is high, the curability and chemical resistance are poor, and the content of the hydroxy group-containing acrylate of the general formula (4) is large The adhesion and the flexibility of the coating film are poor, and the antistatic ability is poor. Therefore, considering the curability, durability, adhesion, chemical resistance and antistatic ability, the equivalent ratio is preferably 8: 2 to 2: 8.

As described above, the photocurable urethane acrylate oligomer having excellent antistatic ability is characterized by excellent antistatic ability and adhesion, durability, chemical resistance, flexibility, fouling resistance, and abrasion resistance by polyether polyols and hydroxyl group-containing polyalkylene macromers. It will exhibit weather resistance and is prepared by the following synthesis method.

That is, the isocyanate is weighed and attached to the synthesis apparatus in a four-necked round flask equipped with a thermometer, and then the polyether polyol and the appropriate amount of catalyst are weighed into a dropping tube and mounted in the flask, and the reaction temperature is maintained at 50 to 60 ° C. While the contents of the dropping tube are added to the dropping tube for 30 to 120 minutes, and the content of the isocyanate content is determined, and the hydroxy group-containing polyalkylene glycol macromer and the hydroxy group-containing acrylate mixture are appropriately added if necessary. The polymerization inhibitor was added to the dropping tube in the basis of equilibrium, and the flask was added to the flask. The reaction temperature was maintained at 50 to 70 ° C for 30 to 120 minutes, and the mixture in the dropping tube was constantly added to react with the final isocyanate. When the urethane acrylate oligomer is prepared by terminating the reaction It is.

Hereinafter, it will be described in detail through a preferred embodiment of the present invention. In an embodiment, the oligomer of the present invention is prepared by varying the components, and then, a paint is prepared using a known method, and the coating is coated on a vinyl chloride flooring material to be compared with the conventional one.

Example 1

0.3 equivalent of polyethylene glycol (product of Korea Polyol, product name Konix PEG-1000) with 2 equivalents of isophorone diisocyanate trimer (product of OLIN, product name Luxate ITM 800), polypropylene glycol monomethacrylate (UK The urethane acrylate oligomer was prepared using BP Co., Ltd. product name Bisomer PPM6E) 1 equivalent, and hydroxy ethyl acrylate 0.2 equivalent.

Example 2

The same composition as in Example 1 except that polyethylene glycol having a molecular weight of 400 (product name: Konix PEG-400, manufactured by Korean Polyol Co., Ltd.) was used instead of polyethylene glycol having a molecular weight of 1000. Urethane acrylate oligomers were prepared by content and method.

Example 3

A urethane acrylate oligomer was prepared in the same composition, content and method as in Example 1 except that polyethylene glycol monoacrylate (trade name Bisomer PEA9E manufactured by EP Company, UK) was used instead of polypropylene glycol monomethacrylate.

Example 4

A urethane acrylate oligomer was prepared in the same composition, content and method as in Example 1 except that 0.5 equivalent of polypropylene glycol monomethacrylate and 0.5 equivalent of hydroxy ethyl acrylate were used.

Comparative Example 1

Instead of polyethylene glycol having a molecular weight of 1000, a polyester polyol prepared by condensation of adipic acid and ethylene glycol by a known method was used and hydroxy instead of 1 equivalent of polypropylene glycol monomethacrylate and 0.2 equivalent of hydroxy ethyl acrylate. A urethane acrylate oligomer was prepared in the same composition, content and method as in Example 1 except that 1.5 equivalents of ethyl acrylate alone was used.

60 parts by weight of the present invention and the conventional urethane acrylate oligomer prepared in the above, 20 parts by weight of hexanediol diacrylate, 10 parts by weight of tripropylene glycol diacrylate, 5,5 parts by weight of trimethylolpropane triacrylate, 1 4.5 parts by weight of hydroxycyclohexyl-phenyl ketone (manufactured by Ciba-Geigy, Switzerland, Irgacure 184) and 0.5 parts by weight of silicone polyacrylate (manufactured by UCB, Belgium, product name Ebecryl 350) at 40 to 50 ° C A photocurable paint having 600 to 1200 centipoise (cps) at 25 ° C. was prepared and coated on a vinyl chloride flooring material with a thickness of 20 μm and cured with a curing energy of 800 mJ / cm 2 (UV irradiation device, manufactured by American Ultrabiore Inc., USA). After the comparison test results are shown in Table 1 below.

Table 1 Property comparison test results according to Examples and Comparative Examples

* Legend ○: Good, △: Normal, ×: Poor

* 1) Measured by JIS DO202 (Cross-Cut).

* 2) Use a dual wear meter (Model 505 from Teledtne Taber).

* 3) Contamination of the coating film with contaminants such as magic ink, bitumen, and kimchi soup, left at room temperature for 24 hours.

* 4) Coating state after immersion in 1% sulfuric acid solution at room temperature for 10 minutes.

* 5) Coating state after immersion in 1% sodium hydroxide solution at room temperature for 10 minutes.

* 6) Coating state after immersion in 3% sodium chloride solution at room temperature for 10 minutes.

* 7) Using resistance measuring instrument (Model SM-8210 of Toa Electronics of Japan), measure at 25 ℃ and 55 ± 5% relative humidity.

As described in detail above, when the photocurable urethane acrylate oligomer according to the present invention is applied to a paint, it is possible to exhibit wear resistance, fouling resistance, chemical resistance and excellent antistatic ability of the applied base.

Claims (4)

The polyether polyol of general formula (2) is reacted with an aliphatic, cyclic aliphatic, aromatic diisocyanate or some isocyanate functional group (NCO) in the oligomer of these isocyanate compounds, and then a portion of the remaining isocyanates is added to the terminal of general formula (3) Addition reaction with a polyalkylene glycol macromer containing a hydroxy group, and the remaining unreacted isocyanate is reacted with a hydroxy group containing acrylate of the following general formula (4). A method of producing a photocurable urethane acrylate oligomer represented by the general formula (1), wherein the hydroxy group-containing polyalkylene macromer and the hydroxy group-containing acrylate are reacted at a ratio of 9.9: 0.1 to 1: 9. . Wherein R ₁ is aliphatic, cyclic aliphatic, aromatic compound or oligomer of these compounds, X ₁ and X ₂ are different from each other, and a residue of formula (3) or (4), Y is a residue of the polyether polyol of the formula (2). HO- (-R ₂ -O-) _m -H (2) here. R ₂ is an alkylene group having 2 to 6 carbon atoms m is 1-90. Where R ₃ is hydrogen or a methyl group, R ₄ is an alkylene group having 2 to 6 carbon atoms n is 2-40. Where R ₃ is hydrogen or a methyl group, R <_5> is a C2-C6 alkylene group. The method of claim 1, Polyether polyol is a polyalkylene glycol obtained by ether condensation reaction of a glycol having two hydroxyl groups selected from ethylene glycol, propylene glycol, butylene glycol, pentylene glycol and hexane diol, having a hydroxyl value of 30 to 1100 and a molecular weight of 100 to 4000. Method for producing a photocurable urethane acrylate oligomer characterized by. The method of claim 1, The hydroxyl group-containing polyalkylene macromers are polyethylene glycol monoacrylate polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, polybutylene glycol mono acrylate, polybutylene glycol mono Methacrylate, polypentylene glycol monoacrylate polypentylene glycol monomethacrylate, polyhexylene glycol monoacrylate and polyhexylene glycol monomethacrylate, having a hydroxyl value of 15 to 550, molecular weight of 100 to 4000 Method for producing a photocurable urethane acrylate oligomer, characterized in that. The method of claim 1, The hydroxy group-containing acrylates are hydroxy ethyl acrylate, hydroxy ethyl methacrylate hydroxy propyl acrylate hydroxy propyl methacrylate, hydroxy butyl acrylate hydroxy butyl methacrylate, hydroxy pentyl acrylate, hydroxy A process for producing a photocurable urethane acrylate oligomer, characterized in that selected from the group consisting of hydroxy pentyl methacrylate, hydroxy hexyl acrylate and hydroxy hexyl methacrylate.