JP3093856B2 - UV curable resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an ultraviolet-curable resin composition, particularly to woodworking-related products, electrical appliances, automobile interior materials, etc., having improved recoatability such as coating property, adhesiveness, overcoating and restoration of an adhesive interface. The present invention relates to a useful ultraviolet curable resin composition.

[0002]

2. Description of the Related Art Many ultraviolet curable resins are already known. However, these ultraviolet curable resins satisfy both of these properties at the same time because of their contradictory properties of stain resistance and adhesiveness. There is a disadvantage that it is difficult to obtain.

[0003] For this reason, this compounded composition is intended to improve the stain resistance by adding a silicone-based or Teflon-based slipping agent, or the oligomer (prepolymer), which is a constituent material of the ultraviolet-curable resin, is polarized. A method of improving the adhesiveness by bonding to a group, or improving the crosslink density by combining with a monofunctional or polyfunctional monomer, and reducing the porous portion of the coating to improve the stain resistance are also performed. .

[0004]

However, even though the addition of the silicone-based or Teflon-based slip agent is effective in improving the stain resistance, it has the disadvantage of lowering the adhesiveness and the recoating property. There is a need to add a thermoplastic resin to bond a polar group to a prepolymer or the like to improve adhesiveness, or to combine a monofunctional or polyfunctional monomer with a photoinitiator or sensitizer. In this case, however, there is a disadvantage that the stain resistance is reduced. In addition, it is effective to bind oligomer soft segments to improve workability, especially elongation workability. However, this is poor in stain resistance, easily affected by oxygen inhibition, and contaminates rolls and glossy plates. However, in extreme cases, there is a phenomenon that they adhere to each other and the productivity is poor.

[0005]

According to the present invention, there is provided an ultraviolet curable resin having the following formula:

Embedded image The acetylene alcohol derivative represented by the formula (1) is used in an amount of 0.5 to 5.
It is an ultraviolet curable resin composition to which 0% by weight is added.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION That is, the present inventors have developed adhesive properties,
As a result of various studies to develop a UV curable resin that retains stain resistance and has a recoating property, adding an acetylene alcohol derivative to the UV curable resin makes this UV curable resin excellent in adhesiveness and stain resistance. And
In addition, they have found that they have improved workability and have recoating properties, and have studied on the types and amounts of acetylene alcohol derivatives used here and completed the present invention. This is described in more detail below.

The ultraviolet-curable resin used in the present invention is:
Any known materials may be used, and a photopolymerization initiator, a sensitizer, or the like may be blended with a prepolymer or monomer.

The prepolymer gives the basic properties of the cured product and is an important component constituting the skeleton of the resin. The prepolymer is roughly classified into three types, namely, polyester acrylate, epoxy acrylate and urethane acrylate. The prepolymer used in the present invention may be any of these prepolymers, but urethane acrylate is preferred because it has excellent curability, provides a tough and flexible coating film, and is less susceptible to oxygen inhibition.

The monomer used here has a role of adjusting the viscosity, imparting adhesion to the object to be coated, and the like. This is based on the consideration of practical workability of the resin compound. Is done. There are monofunctional and polyfunctional monomers.Polyfunctional monomers play a role as a cross-linking agent between polymers, and monofunctional ones play a role of viscosity adjustment and a role of initiator and solvent of additives. The polyfunctional monomers include dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, 1,3-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, and neopentyl glycol diacrylate. Acrylate, polyethylene glycol
400 diacrylate, hydroxypiparic acid ester neopentyl glycol diacrylate, tripropylene glycol diacrylate, 1,3-bis (3-acryloxyethoxy-2-hydroxypropyl) -5,5-dimethylhydantoin, hydroxypiparic acid Ester neopentyl glycol derivative diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, etc., and monofunctional monomers as 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate,
Examples include 2-hydroxypropyl acrylate, 2-hydroxyethyl acryloyl phosphate, tetrahydrofurfuryl acrylate, and acrylates of tetrahydrofurfuryl derivatives, and these are considered in consideration of their viscosity, solubility, volatility, safety, and the like. You can select it.

The prepolymer and the monomer are blended with a photoinitiator, a sensitizer and the like in order to make the prepolymer and the monomer ultraviolet-curable, and all of them may be known. Therefore, as the photoreaction initiator, biacetyl, acetophenone, benzophenone,
Michler's ketone, benzyl benzoin, benzoin isobutyl ether, benzyl dimethyl ketal, tetramethylthiuram sulfide, azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, 1-hydroxycyclohexyl phenyl ketone,
2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-
Methylpropan-1-one, 2-chlorothioxanthone, methylbenzoylformate and the like are exemplified, and the amount may be in the range of 0.1 to 5% by weight based on the above prepolymer.

The sensitizer added here may be a known sensitizer, such as acetophenone, 3-methylacetophenone, propiophenone, benzophenone, or
Chlorobenzophenone, 4-ethylbenzophenone, 4
-Hydroxybenzophenone, benzoin, xanthone, fluorenone, fluorene, benzaldehyde, anthraquinone, triphenylamine, carbazole, benzoin ethyl ether and the like. The amount of the sensitizer may be determined depending on the type, the curing speed required for the composition, and the like.
The range may be 10% by weight.

Next, the acetylene alcohol derivative to be added to the above-mentioned ultraviolet-curable resin for producing the ultraviolet-curable resin composition of the present invention has a transparent, pale yellow physical property and a specific gravity of about 0. .97, flash point 132.2
° C (270 ° F) or more, viscosity is 160 cps or more, and surface tension is 32.6 dyne / cm or more.

Embedded image It is shown by.

If the amount of the acetylene alcohol derivative is less than 0.5% by weight, the effect is not sufficiently obtained. If the amount is more than 5% by weight, the adhesiveness,
Even though the recoating property can be maintained, the gloss-plate resistance deteriorates. Therefore, it is necessary to set this in the range of 0.5 to 5% by weight.

The UV-curable resin composition of the present invention thus obtained has a porous surface after curing because the conventional UV-curable resin is added with a monomer or a solvent having low volatility. Therefore, when viewed from the microscopic viewpoint, the contact area is reduced, the number of polar groups is reduced due to high-density crosslinking, the intermolecular distance is reduced, and the adhesive force and the recoating property are reduced. An acetylene alcohol derivative is added to the resin composition, and the acetylene alcohol derivative penetrates the porous surface to form a molecular film such that the OH groups are on the inside, and the resin film is arranged, so that the surface energy increases and the Adhesion and recoating properties are increased by the intermolecular force and anchor effect, and the stain resistance is maintained by the outer CH ₃ group. Since the acetylene alcohol derivative film of (1) is arranged on the surface and blocks oxygen in the air, there is an advantage that curing failure due to oxygen inhibition can be avoided.

[0015]

EXAMPLES Next, examples and comparative examples of the present invention will be described. In the examples, parts indicate parts by weight, and the measurement of physical properties in the examples indicates the following measurement results. It is. [Cross-cut peeling test 1] A cellophane tape is stuck, and after standing at room temperature, it is rapidly peeled at 90 ° (JIS K5400). [Cross-cut peeling test 2] A cellophane tape was stuck and 20 ° C２０60 ° C was applied to each for 4
After 10 cycles of cooling and heating, 90
Abrupt peeling at ° (JIS K5400). [Coin Scratch] The test is carried out with a 10-yen coin without an outer knurl. ◎… No abnormality ×… Scratch

[Stain resistance 1] This shows the measurement results according to JIS K6902. ◎… No abnormality ○… Slight color residue [Stain resistance 2] Contact the hard coat sheet with the stainless steel plate heated to 150 ° C and let it stand at room temperature to check the stain condition and peeling force of the stainless steel plate . ◎: No abnormality ○: Slightly cloudy (bleed) ×: Transfer [Stain resistance 3] Sprinkle carbon and then wipe with a cotton cloth. ◎… No abnormality ○… Some scratches ×… Scratch

Examples 1-3, Comparative Examples 1-2 Prepolymer, polyester-based urethane acrylate:
UN-1255 [trade name of Negami Kogyo Co., Ltd.], prepolymer, epoxy acrylate: UN-EP-A [trade name of Negami Kogyo Co., Ltd.], monomer, 2-hydroxyl-ethylmethyl acrylate: 2-HEMA [ Kyoeisha fats and oils], photoreaction initiator, 2-hydroxy-2-methyl-1-phenyl-propan-1-one: Darocure 11
73 [trade name, manufactured by Merck Japan Ltd.], sensitizer, 1-hydroxycyclohexyl phenyl ketone: Irgacure
184 (trade name, manufactured by Ciba Geigy), acetylene alcohol derivative: Surfynol SE (trade name, manufactured by Air Product) and slip agent, silicone: 10-2
8 (T) (trade name, manufactured by Dainichi Seika Co., Ltd.) in an amount shown in Table 1 was further added with an amount of isopropyl alcohol (IPA) shown in Table 1 to cure the ultraviolet rays by five kinds. A resin composition was prepared.

Next, the resin of the comparative example was replaced with 0.1 mm hard PVC.
Coating at # 25 bar coater, the solvent was dried, and then adjusted to a coating film of 10 [mu], is cured with irradiation energy of a mercury lamp 230mmj / cm ^2, to make a hard coat coating sheet,
Thereafter, the resin of the example including the comparative example was coated on the hard coat-coated sheet, and cured under the same curing conditions as a sample for confirming the adhesiveness (recoating property), and the physical properties thereof were examined. As a result, the results as shown in Table 2 were obtained.

This UV-curable resin composition is applied to 0.1 mm hard PVC under the above conditions, cured, and vertically mirror-finished at 150 ° C. and 30 kgf / cm ^2. ) Was sampled and the degree of contamination of the stainless steel plate was determined.
The result as shown in was obtained.

[0020]

[Table 1]

[Table 2]

[0021]

The present invention relates to an ultraviolet curable resin composition, which is obtained by adding 0.5 to 5.0% by weight of an acetylene alcohol derivative to an ultraviolet curable resin as described above. The addition of the acetylene alcohol derivative has the advantage of having adhesiveness, stain resistance and excellent recoatability.

Continuation of the front page (51) Int.Cl. ⁷ identification code FI C09D 5/00 C09D 5/00 C (C08F 290/06 238: 00) (58) Field surveyed (Int.Cl. ⁷ , DB name) C08F 290/00-290/14 C08F 2/46-2/56 C08F 38/00-38/04 C08F 238/00-238/04 C08L 1/00-101/16 C09D 1/00-201/10

Claims (1)

(57) [Claims] 1. An ultraviolet curable resin having the following formula : ## STR1 ## In 0.5 to 5 and A isethionate alkylene alcohol derivative represented.
An ultraviolet curable resin composition characterized by being added at 0% by weight.