JP2003342525A - Ultraviolet-curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an ultraviolet-curable composition with which an anchor coat having excellent adhesivity to a topcoat film is formed in a multicoated ultraviolet-cured coating film. <P>SOLUTION: The ultraviolet-curable composition is obtained by using an isocyanate compound and a hydroxy compound as raw materials and comprises one or more kinds of unsaturated urethane compounds obtained by using an unsaturated bond-containing compound in at least one of the raw materials. At least a part of the whole unsaturated bonds which one or more kinds of the unsaturated urethane compounds have comprises an allyl group-derived unsaturated bond. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a UV-curable composition for UV-curing coating film (hereinafter, also referred to as "multi-coating UV-curing coating film") which is multiply coated on the surface of various articles, and more particularly to a multi-layer coating composition. It is intended to provide an ultraviolet curable composition capable of forming a high adhesion between cured coatings that are stacked on each other.

[0002]

2. Description of the Related Art Conventionally, in plastic products (molded products) such as polyvinyl chloride, polycarbonate, polyethylene terephthalate, etc., for the purpose of reinforcing various physical properties such as hardness, acid resistance, alkali resistance and solvent resistance, The surface of the product is coated with a cured coating film of a composition mainly containing an ultraviolet curable unsaturated compound (that is, an ultraviolet curable composition).

[0003] By the way, when multiple coatings of a cured coating film made from such an ultraviolet-curable composition are applied in multiple layers, generally, a cured coating film on the lower side (anchor coat film) and an upper cured coating film on top of it (top coating) In order to improve the adhesion with the coating film), the ultraviolet curable composition at the time of forming the cured film on the lower side is slowly cured (that is, the lower coating film (the ultraviolet curable composition). ) Is shortened to leave an uncured portion by shortening the UV irradiation time), and at the time of curing the ultraviolet curable composition when forming the upper cured coating film, the lower coating film together with the ultraviolet curable composition is cured. The film (ultraviolet curable composition) is completely cured. However, as a result of the research conducted by the present inventors, when the lower coating film is incompletely cured to leave an uncured portion, the variation in the curing degree in the coating film is caused by the lower coating film and the upper coating film. It was found that this is the reason why the adhesive force between the films cannot be made sufficiently high.

In addition, in the case of a multi-coat UV curable coating film (particularly a two-layer multi-coat coating film), from the viewpoint of adhesion to the upper cured coating film (top coat film), the lower cured coating film (anchor) is used. For the coating film, it is common to use an ultraviolet-curable composition that forms a relatively soft film even when completely cured. However, the lower cured coating film (anchor coat film) is subjected to buff molding (polishing), and the upper cured coating film (top coat film) is formed on top of it, and the adhesion between the upper and lower cured coating films is increased. If the hardness of the lower cured coating (anchor coating) is too soft, the coating may fall off during buffing (polishing), and the durability of the multiple coating UV cured coating From the viewpoint of properties (mechanical strength), it is desirable that the cured coating film (anchor coat film) on the lower side also has a relatively high hardness, and the entire coating film of multiple coating has a high hardness. Therefore, an ultraviolet curable composition capable of achieving a lower cured coating film (top coat film) that can be adhered to the upper cured coating film (top coat film) with high adhesion while having a relatively high hardness is provided. It has been demanded.

[0005]

SUMMARY OF THE INVENTION In view of the above circumstances, an object of the present invention is to UV-cure a multi-coat UV-curable coating film for an anchor coat film capable of forming a sufficiently high adhesion with a topcoat film. To provide a sex composition. Also,
The anchor coat film and the top coat film adhere to each other with a sufficiently high adhesion, and also have excellent physical properties (scratch resistance, acid resistance,
(EN) It is intended to provide an ultraviolet-curable composition having alkali resistance, solvent resistance, etc.) and capable of realizing a highly functional and highly durable multiple-coating ultraviolet-curing coating film.

[0006]

Means for Solving the Problems As a result of intensive studies aimed at achieving the above object, the present inventors have found that among unsaturated bonds, an unsaturated bond derived from an allyl group, which has the slowest ultraviolet curing reaction rate, is formed. When a saturated urethane compound is applied to the anchor coat film, unreacted unsaturated bonds are uniformly present in the incompletely cured anchor coat film, and it is high between the uncoated unsaturated bond and the top coat film formed on it. It has been found that adhesion can be obtained, and the present invention has been completed based on the finding.

That is, the present invention is as follows. (1) An unsaturated urethane compound obtained by using an isocyanate compound and a hydroxyl compound as raw materials and using a compound having an unsaturated bond in at least one of the raw materials
An ultraviolet curable composition containing one or more species, characterized in that at least a part of the unsaturated bonds contained in the one or more unsaturated urethane compounds comprises an unsaturated bond derived from an allyl group. An ultraviolet curable composition for an anchor coat film of a multi-coat ultraviolet curable coating film. (2) The proportion of unsaturated bonds derived from an allyl group in the unsaturated bonds of one or more unsaturated urethane compounds is 8%.
The ultraviolet curable composition according to the above (1), which is the above. (3) The ultraviolet ray according to (1) or (2) above, wherein the unsaturated bond contained in the one or more unsaturated urethane compounds is an unsaturated bond derived from an allyl group and an unsaturated bond derived from a (meth) acryloyl group. Curable composition. (4) The average per molecule of the compound having an unsaturated bond derived from a (meth) acryloyl group is an unsaturated bond derived from a methacryloyl group and used in one or more unsaturated urethane compounds. The ultraviolet curable composition according to the above (3), wherein the product of the number of unsaturated bonds and the average number of isocyanate groups per molecule of the isocyanate compound is 6.0 or more. (5) The average per molecule of the compound having an unsaturated bond derived from a (meth) acryloyl group is an unsaturated bond derived from an acryloyl group and used in one or more unsaturated urethane compounds. The ultraviolet-curable composition according to (2) above, wherein the product of the number of unsaturated bonds in (4) and the average number of isocyanate groups per molecule of the isocyanate compound is 4.0 or more. (6) The isocyanate compound has 2 isocyanato groups.
(1) to (1), which comprises the above isocyanate compound
The ultraviolet curable composition according to any one of (5). (7) The ultraviolet curable composition according to any one of (1) to (6) above, wherein the hydroxyl compound has an unsaturated bond. (8) An unsaturated urethane compound obtained by using an isocyanate compound and a hydroxyl compound as raw materials and using a compound having an unsaturated bond in at least one of the raw materials is 1
An ultraviolet-curable composition containing one or more species, wherein the unsaturated bond of the one or more unsaturated urethane compounds comprises an unsaturated bond derived from an allyl group and an unsaturated bond derived from a (meth) acryloyl group. In addition, the ratio of the unsaturated bond derived from the allyl group is 8% or more, and the following condition 1 or condition 2 is satisfied, and the ultraviolet curable composition for multiple coating ultraviolet curable coating film is characterized. object. Condition 1: An average per molecule of a compound having an unsaturated bond derived from a (meth) acryloyl group is an unsaturated bond derived from a methacryloyl group and used in one or more unsaturated urethane compounds. The product of the number of unsaturated bonds and the average number of isocyanato groups per molecule of the isocyanate compound is 6.0 or more. Condition 2: The average per molecule of the compound having an unsaturated bond derived from a (meth) acryloyl group is an unsaturated bond derived from an acryloyl group and used in one or more unsaturated urethane compounds. The product of the number of unsaturated bonds and the average number of isocyanato groups per molecule of the isocyanate compound is 4.0 or more. (9) The isocyanate compound has 2 isocyanato groups.
The ultraviolet curable composition according to (7) above, which comprises the above isocyanate compound. (10) The ultraviolet-curable composition according to the above (8) or (9), wherein the hydroxyl compound has an unsaturated bond.

In the above and subsequent description of the present specification, unless otherwise specified, the term "anchor coat film" refers to a UV curable coating film to be applied in multiple layers, which is the lower side on which the UV curable coating film is applied. The ultraviolet-curing coating film is referred to, and the "top coat film" refers to the uppermost coating film among the ultraviolet-curing coating films which are applied in multiple layers. That is, for example, in the case of a multi-coat ultraviolet curable coating film in which two layers are overcoated, the first cured coating film is the "anchor coat film" and the second cured coating film is the "top coat film". In the case of a multi-coat UV curable coating film in which three layers are overcoated, the first cured film and the second cured film are “anchor coat film”,
The third cured coating film is the "top coat film".

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. The ultraviolet curable composition of the present invention is used for at least an anchor coat film in a multi-coat ultraviolet curable coating film, and is preferably used for both an anchor coat film and a top coat film.

The ultraviolet curable composition of the present invention (hereinafter also simply referred to as "composition") contains an unsaturated urethane compound as a main component. The “unsaturated urethane compound” is obtained by using a compound having an unsaturated bond in at least one of the two raw material compounds using an isocyanate compound and a hydroxyl compound as raw materials, and having a urethane bond and an unsaturated bond in the molecule. It is a compound that has. The term "unsaturated bond" as used herein means a carbon-carbon double bond that exhibits a radical polymerization, anionic polymerization, or cationically polymerizable curing reaction (polymerization reaction) when irradiated with ultraviolet rays, and examples thereof include allyl. Examples thereof include a group, an acryloyl group, a methacryloyl group (hereinafter, the “acryloyl group” and the “methacryloyl group” are collectively referred to as “(meth) acryloyl group”), and a vinyl group.

The ultraviolet curable composition of the present invention contains at least one kind of the above-mentioned unsaturated urethane compound, and at least a part of the unsaturated bond of the one or more kinds of unsaturated urethane compound is derived from an allyl group. Its main characteristic is that it consists of unsaturated bonds. That is, at least a part of the compound (that is, at least one of the isocyanate compound and the hydroxyl compound) having an unsaturated bond of the raw material of the unsaturated urethane compound (one or more unsaturated urethane compound) in the composition is derived from an allyl group. A compound having an unsaturated bond is used.

In the present invention, the compound having an unsaturated bond which is a raw material of the unsaturated urethane compound preferably has an average number of unsaturated bonds per molecule of 2.0 or more. That is,
When the compound having an unsaturated bond used for the unsaturated urethane compound in the composition is one kind of compound, a compound having an unsaturated bond in the molecule of 2 or more is used, and the compound having an unsaturated bond is used. When two or more compounds are used, two or more compounds should be selected and used so that the average number of unsaturated bonds per molecule calculated as follows is 2.0 or more. Is preferred. For example, when the compound A having the number of unsaturated bonds in the molecule is x mol and the compound B having the number of unsaturated bonds in the molecule is y mol as the compound having the unsaturated bond, The average number of unsaturated bonds per molecule is a value obtained by the formula of (ax + by) / (x + y). In the present invention, the calculated value is rounded off to one decimal place.

In the present invention, the average number of unsaturated bonds per molecule in the compound having an unsaturated bond is more preferably 2.5 or more, and the upper limit is preferably 6.0 or less.

In the ultraviolet curable composition of the present invention,
An unsaturated bond derived from an allyl group is uniformly present in the coating film in an incompletely cured state by using it, and an ultraviolet curable composition is further applied onto the coating film to form an ultraviolet ray. When the curing (complete curing) is performed, a compound bond is uniformly formed at the boundary between the two overlapping cured coating films, and the two cured coating films are brought into close contact with each other with high adhesion. That is, by applying the ultraviolet-curable composition of the present invention to an anchor coat film in a multi-coating ultraviolet-curing coating film, recoatability (adhesion with an ultraviolet-curing coating film (top coat film) to be coated thereon) ), It is possible to realize an anchor coat film.

In the present invention, the proportion of the unsaturated bond derived from the allyl group in the unsaturated bond of the unsaturated urethane compound (one or more unsaturated urethane compound) in the composition is 8% or more. Preferably, particularly preferably 12%
That is all. When the unsaturated bond derived from the allyl group in the unsaturated bond is less than 8%, it is difficult to obtain the desired anchor coat film having excellent recoatability, which is not preferable. In addition,
"Percentage of unsaturated bond derived from an allyl group in the unsaturated bond of the unsaturated urethane compound in the composition",
"Ratio of the number of moles of unsaturated bonds derived from an allyl group to the total number (mole number) of unsaturated bonds of the compound having an unsaturated bond used as the raw material of the unsaturated urethane compound in the composition" . For example, the isocyanate compound as one raw material used for the unsaturated urethane compound in the composition does not have an unsaturated bond, and as the hydroxyl compound as the other raw material, a number of unsaturated bonds derived from an allyl group, X mol of the hydroxyl compound A having b unsaturated bonds other than the unsaturated bond derived from the allyl group and hydroxyl compound B having c unsaturated bonds other than the unsaturated bond derived from the allyl group (unsaturated bond derived from the allyl group (Having no bond) in y mol, "the ratio of the unsaturated bond derived from the allyl group in the unsaturated bond of the unsaturated urethane compound in the composition" is represented by the formula: [ax / (ax + bx + cy )] × 100 (%)

In the composition of the present invention, all unsaturated bonds contained in the unsaturated urethane compound (one or more unsaturated urethane compounds) in the composition may be unsaturated bonds derived from an allyl group, but a top coat film Unsaturation in the composition when an anchor coat film for buffing (polishing) to obtain higher adhesion with is intended (that is, when the anchor coat film also needs to have a certain high hardness) The unsaturated bond that the urethane compound has is an unsaturated bond derived from an allyl group,
The curing reaction rate by UV irradiation (polymerization rate) is faster than the unsaturated bond derived from the allyl group, and it is preferable that the unsaturated bond derived from the (meth) acryloyl group or vinyl group is mixed, and among them, It is more preferable that the unsaturated bond derived from the allyl group and the unsaturated bond derived from the (meth) acryloyl group are mixed. Further, the composition of such an aspect can form a cured coating film having a relatively high hardness, and thus can be used as a top coat film in a multiple coating ultraviolet curing coating film. That is, in the case of the composition of this aspect, by forming an anchor coat film and a top coat film sequentially using this composition, the adhesion between the overcoated coating films is high, and the hardness of the surface (uppermost layer) is high. It is possible to form a sufficiently high multi-coating UV-curable coating film. In the case of the composition of this aspect, 8 to 50% (preferably 12 to 5) of the unsaturated bonds of the unsaturated urethane compound are contained.
0%) is occupied by an unsaturated bond derived from an allyl group, and the remaining 92
~ 50% (preferably 88 to 50%) has a faster curing reaction rate (polymerization rate) by UV irradiation than an unsaturated bond derived from an allyl group, from an unsaturated bond derived from a (meth) acryloyl group or a vinyl group. Is more preferable, and more preferable results can be obtained when the following Condition 1 or Condition 2 is satisfied.

Condition 1: The unsaturated bond of the unsaturated urethane compound (one or more kinds of unsaturated urethane compound) in the composition is composed of an unsaturated bond derived from an allyl group and an unsaturated bond derived from a methacryloyl group. Average number of unsaturated bonds per molecule of the compound having an unsaturated bond used for the unsaturated urethane compound (one or more kinds of unsaturated urethane compound) in the product, and average isocyanate per molecule of the isocyanate compound The product of the cardinal number is 6.0 or more.

Condition 2: The unsaturated bond of the unsaturated urethane compound (one or more unsaturated urethane compound) in the composition is composed of an unsaturated bond derived from an allyl group and an unsaturated bond derived from an acryloyl group, Average number of unsaturated bonds per molecule of the compound having an unsaturated bond used for the unsaturated urethane compound (one or more kinds of unsaturated urethane compound) in the product, and average isocyanate per molecule of the isocyanate compound The product of the cardinal number is 4.0 or more.

Under the above conditions 1 and 2, the average number of unsaturated bonds per molecule of the compound having an unsaturated bond is the value calculated by the above-mentioned procedure. "Average number of isocyanato groups" is the average number of isocyanato groups per molecule in all the isocyanate compounds used as the raw material of the unsaturated urethane compound (one or more unsaturated urethane compound) in the composition, and for example, isocyanato group When x mol of the isocyanate compound A having the number of groups a and y mol of the isocyanate compound B having the number of isocyanato groups of b are used, the formula is calculated by (ax + by) / (x + y). In the present invention, the calculated value is rounded off to the second decimal place.

If a composition satisfying the above conditions 1 or 2 is used, an anchor coat film and a top coat film are sequentially formed by using the composition, so that the anchor coat film having a relatively high hardness is scratch-resistant. It is possible to obtain a highly functional and highly durable multi-coating ultraviolet curable coating film in which a top coat film having excellent properties and excellent solvent resistance, alkali resistance and acid resistance is stacked with high adhesion.

In the present invention, the compound having an unsaturated bond in the raw material of the unsaturated urethane compound (isocyanate compound, hydroxyl compound) is at least one of an isocyanate compound and a hydroxyl compound, but at least the hydroxyl compound is an unsaturated bond. It is preferable to use a hydroxyl compound having an unsaturated bond.

Examples of the hydroxyl compound having an unsaturated bond include a hydroxyl compound having an unsaturated bond derived from an allyl group, a hydroxyl compound having an unsaturated bond derived from a (meth) acryloyl group, and an unsaturated bond derived from a vinyl group. Examples thereof include a hydroxyl compound and the like, and one kind or two or more kinds of these compounds can be used.

Examples of the hydroxyl compound having an unsaturated bond derived from an allyl group include a reaction product of an allyl glycidyl ether and an unsaturated carboxylic acid. In the reaction product of the allyl glycidyl ether and the unsaturated carboxylic acid, as the unsaturated carboxylic acid, acrylic acid, acrylic acid dimer, crotonic acid, methacrylic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid Examples thereof include mono- or dicarboxylic acids, and among these, acrylic acid, methacrylic acid, and acrylic acid dimer are preferable, and acrylic acid or methacrylic acid is particularly preferable. That is, 2-hydroxy-3
-Allyloxypropyl (meth) acrylate is particularly preferred.

A hydroxyl compound having an unsaturated bond derived from a (meth) acryloyl group (the hydroxyl compound having an unsaturated bond derived from the (meth) acryloyl group has an unsaturated bond other than an unsaturated bond derived from a (meth) acryloyl group). Not included), for example, hydroxyalkyl (meth) acrylate, hydroxycycloalkyl (meth) acrylate, polyalkylene glycol mono (meth) acrylate, an adduct of glycidyl (meth) acrylate and (meth) acrylic acid. , Ring-opening reaction products of these (meth) acrylate compounds and ε-caprolactone, adducts of glycidyl ether and (meth) acrylic acid, phenylglycidyl ether and (meth) acrylic acid adduct, and the like, and preferably Hydroxyalkyl (meth) acry It is over door.

In the hydroxyalkyl (meth) acrylate, the alkyl part is a linear or branched alkyl having 2 to 100 carbon atoms, preferably 2 to 60 carbon atoms, and the alkyl has a substituent. The substituent may be, for example, a group derived from phenoxy or caprolactam-modified diol. Specific examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate and 2
-Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, etc. (Meth) acrylate; trimethylolpropane di (meth) acrylate, trimethylolethanedi (meth) acrylate, glycidol dimethacrylate, 2-hydroxy-3-
Examples thereof include di (meth) acrylates such as (meth) acrylooxypropyl (meth) acrylate; tri (meth) acrylates such as tetramethylolmethane tri (meth) acrylate; dipentaerythritol penta (meth) acrylate. Among these, 2-hydroxy-
3- (meth) acrylooxypropyl (meth) acrylate, tetramethylolmethane tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferred.

In the hydroxycycloalkyl (meth) acrylate, the cycloalkyl part has 3 to 3 carbon atoms.
It is 0, preferably 4 to 20 cycloalkyl, and the cycloalkyl may have a substituent, and examples of the substituent include a group derived from methyl, ethyl, and ethoxylated bisphenol. To be Specific examples of the hydroxycycloalkyl (meth) acrylate include cyclohexanedimethanol mono (meth) acrylate, cycloheptanedimethanol mono (meth) acrylate, cyclooctanedimethanol mono (meth) acrylate.
Examples thereof include acrylate, caprolactam-modified mono (meth) acrylate, and spiroglycol-modified mono (meth) acrylate.

In the polyalkylene glycol mono (meth) acrylate, the alkyl part has 1 to 10 carbon atoms.
It is 0, preferably 2 to 60, linear or branched alkyl, and each alkyl part may be bonded via an oxygen atom. Specific examples of the polyalkylene glycol mono (meth) acrylate include mono (meth) s such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and polytetramethylene oxide mono (meth) acrylate.
Examples thereof include acrylates and (meth) acrylic acid adducts of ethylene-propylene glycol block polymers.

In the present invention, examples of the isocyanate compound include a monoisocyanate compound, a diisocyanate compound, a polyisocyanate compound and modified products thereof. Among them, the diisocyanate compound,
Polyisocyanate compounds and modified products thereof are preferred. That is, the isocyanate compound is preferably an isocyanate compound having 2 or more isocyanato groups. In general, the isocyanate compound is preferably one that does not have an unsaturated bond. In the present invention, as the isocyanate compound, one kind or two or more kinds of compounds can be used.

Examples of the monoisocyanate compound include an aliphatic monoisocyanate compound, an alicyclic monoisocyanate compound, an aromatic monoisocyanate compound, and the like, and the aliphatic monoisocyanate compound is preferable. The aliphatic monoisocyanate compound is preferably one in which the fat part is composed of a linear or branched saturated hydrocarbon group having 1 to 36 carbon atoms, preferably 6 to 16 carbon atoms, and specific examples include methyl isocyanate. , Ethyl isocyanate, n-hexyl isocyanate, 2-ethylhexyl isocyanate, n-heptyl isocyanate, octyl isocyanate, nonyl isocyanate, decyl isocyanate, undecyl isocyanate, dodecyl isocyanate, tridecyl isocyanate, tetradecyl isocyanate, pentadecyl isocyanate, hexadecyl isocyanate , Icosyl isocyanate, triacontyl isocyanate, and the like. Moreover, as what has an unsaturated bond, for example, 2-isocyanate ethyl (meth) acrylate,
Methacryloyl isocyanate, m-isopropenyl dimethyl benzyl isocyanate, vinyl isocyanate, etc. are mentioned.

Examples of diisocyanate compounds include aliphatic diisocyanate compounds, alicyclic diisocyanate compounds and aromatic diisocyanate compounds. The fatty part in the aliphatic diisocyanate compound is preferably a linear or branched saturated hydrocarbon group having 1 to 20 carbon atoms, preferably 6 to 10 carbon atoms, and the fat part has 1 or 2 or more carbon atoms. It may be substituted with a substituent. Examples of the substituent include monovalent or higher valent groups derived from isophorone, methylenebiscyclohexane and the like; carboxyl groups and the like. Specific examples of the aliphatic diisocyanate compound include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate,
1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-bis (isocyanatomethyl) hexane Acid etc. are mentioned.

The alicyclic portion in the alicyclic diisocyanate compound is preferably a saturated or unsaturated alicyclic hydrocarbon group having 3 to 20 carbon atoms, preferably 6 to 10 carbon atoms. Two or more hydrocarbon groups may be present, in which case they are bonded to each other via a linear or branched alkylene having 1 to 12 carbon atoms, preferably 6 to 10 carbon atoms. Moreover, the said alicyclic part may be substituted by 1 or 2 or more substituents, and as a substituent in this case, carbon number is preferably 4-12, more preferably 6-.
Examples thereof include linear or branched alkyl of 10. Specific examples of the alicyclic diisocyanate compound include 1,3-cyclopentene diisocyanate and 1,4
-Cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) -3,3,5-trimethylcyclohexane,
4,4'-methylenebis (cyclohexyl isocyanate), 2,4-cyclohexane diisocyanate, 1,
3-bis (isocyanatomethyl) cyclohexane, 1,
4-bis (isocyanatomethyl) cyclohexane, 1,
Examples thereof include 3-cyclopentene diisocyanate.

The aromatic moiety in the aromatic diisocyanate compound is preferably benzene or naphthalene, more preferably naphthalene, and two or more of these aromatic rings may be present, in which case they are single bonds. ,
Alternatively, the carbon number is preferably 1 to 20, more preferably 6
-12 is a linear or branched alkylene, or bonded via an oxygen atom. The aroma moiety may be substituted with one or two or more substituents, in which case the substituent has 2 to 20 carbon atoms, preferably 6 to 1 carbon atoms.
2 include straight chain or branched chain alkyl and amino. Specific examples of the aromatic diisocyanate compound include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-biphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,
4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenyl ether diisocyanate, isophorone diisocyanate, 1,
6-hexane diisocyanate; 1,3- or 1,
4-xylylene diisocyanate, or a mixture of 1,3-xylylene diisocyanate and 1,4-xylylene diisocyanate, ω, ω′-diisocyanato-1,
4-diethylbenzene, 1,3- or 1,4-bis (1-isocyanato-1-methylethyl) benzene or 1,3-bis (1-isocyanato-1-methylethyl) benzene and 1,4-bis (1 -Isocyanato-1-
A mixture with methylethyl) benzene and the like can be mentioned.

Examples of the polyisocyanate compound include an aliphatic polyisocyanate compound, an alicyclic polyisocyanate compound, an aromatic polyisocyanate compound, and the like, and the aliphatic polyisocyanate is particularly preferable. Further, the polyisocyanate compound preferably has 3 or more isocyanato groups. The fat part in the aliphatic polyisocyanate compound is a linear or branched saturated hydrocarbon group having preferably 1 to 20, and more preferably 6 to 10 carbon atoms. Also, the fat part is 1
Alternatively, it may be substituted with two or more substituents. Examples of the substituent include monovalent or higher valent groups derived from isophorone, cyclohexane and the like. Specific examples of the aliphatic polyisocyanate compound include 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, and 1,3. , 6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane, and the like.

The alicyclic portion of the alicyclic polyisocyanate compound preferably has 3 to 20 carbon atoms, more preferably 3 to 20 carbon atoms.
10 saturated alicyclic hydrocarbon groups, the saturated alicyclic hydrocarbon groups may exist in two or more to form a condensed ring, and further, these alicyclic hydrocarbon groups may exist in two or more. , May be bound to each other via a methylene group. Further, the alicyclic portion may be substituted with one or two or more substituents, and the substituent has, for example, preferably 4 to 4 carbon atoms.
12, more preferably linear or branched alkyl having 6 to 10 and linear or branched alkylene having preferably 4 to 12 carbon atoms. Specific examples of the alicyclic polyisocyanate compound include:
1,3,5-triisocyanatocyclohexane, 1,
3,5-Tris (isocyanatomethyl) cyclohexane, 2- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) bicyclo [2.2.1] heptane, 2- (3-isocyanatopropyl) ) -2,6-Di (isocyanatomethyl) bicyclo [2.2.1] heptane, 3- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) bicyclo [2.2.1] Heptane, 5- (2-isocyanatoethyl) -2- (isocyanatomethyl) -3- (3-isocyanatopropyl) bicyclo [2.2.1] heptane, 6- (2-isocyanatoethyl) -2 -(Isocyanatomethyl) -3- (3-isocyanatopropyl) bicyclo [2.2.1] heptane, 5- (2-isocyanatoethyl) -2- (isocyanatomethyl) -2- (3-i Cyanatopropyl) bicyclo [2.2.1] heptane, 6- (2-isocyanatoethyl) -2- (isocyanatomethyl) -2- (3-isocyanatopropyl) bicyclo [2.2.1] heptane And so on.

The aromatic ring portion in the aromatic polyisocyanate compound is preferably benzene, naphthalene, etc., more preferably naphthalene, and two or more of these aromatic rings may be present, in which case Have a single bond with each other, and preferably have 2 to 2 carbon atoms.
It may be bonded via a straight-chain or branched alkylene having 0, more preferably 6 to 12, and the like. Further, the aromatic ring portion may be substituted with one or more substituents, and as the substituent, for example, a linear chain having 2 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms is preferable. Or branched-chain alkyl, preferably 2 to 2 carbon atoms
Examples thereof include linear or branched alkylene having 0. Specific examples of the aromatic polyisocyanate compound include triphenylmethane-4,4 ′, 4′-triisocyanate, 1,3,5-triisocyanatobenzene,
2,4,6-triisocyanatotoluene, 4,4'-diphenylmethane-2,2 ', 5,5'-tetraisocyanate, 1,3,5-triisocyanatomethylbenzene and the like can be mentioned.

Examples of the modified diisocyanate compound and the modified polyisocyanate compound include burettes, isocyanurates, and adducts obtained by urethanization reaction with various polyhydroxy compounds.
Examples thereof include allophanate bodies, oxadiazinetrione bodies, and uretdione bodies, and specific examples thereof include those obtained by modifying the compounds (one or more kinds) listed as specific examples of the above diisocyanate compound and polyisocyanate compound. To be

The modified product is preferably an isocyanurate compound, and a specific example of the isocyanurate compound is a tris (isocyanatoalkyl) -substituted isocyanurate compound (“alkyl” has 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms).
Is a linear or branched chain (ethyl, butyl, hexyl, etc.). ), Of which Tris (6-
Isocyanatohexyl) isocyanurate is particularly preferred. In addition, specific examples of the other isocyanurate body include the isocyanurate body represented by the following general formula (I).

[0038]

[Chemical 1]

Specific examples of the modified burette include those represented by the following formula (II).

[0040]

[Chemical 2]

Further, in the present invention, the modified product includes
A modified TMP represented by the following general formula (III) (R in the formula has the same meaning as that in formula (I)) can also be used.

[0042]

[Chemical 3]

In the present invention, the urethanization reaction of the isocyanate compound and the hydroxyl compound for obtaining the unsaturated urethane compound is carried out by reacting the isocyanate compound and the hydroxyl compound with an isocyanate group preferably 0.9 to 1 relative to the hydroxyl group. 0.1 equivalent, and more preferably, 1.0 to 1.05 equivalent can be used in such an amount. This urethanization reaction can be carried out without solvent or in a solvent inert to the isocyanato group and the hydroxyl group. Examples of such an inert solvent include ethyl acetate, butyl acetate, acetone, ethyl methyl ketone, chloroform, chloromethane, toluene, tetrahydrofuran and the like. When the urethanization reaction is carried out in a solvent, the amount of the solvent used varies depending on the scale of the reaction and the like, and is determined by the handling suitability.

The above-mentioned urethanization reaction is usually 0 to 120.
It can be carried out in the temperature range of 0 ° C, and in order to allow the reaction to proceed efficiently, it is preferably carried out at 30 to 90 ° C. If the reaction temperature is lower than 0 ° C, the urethanization reaction may not proceed or by-products may easily occur.

When the urethanization reaction does not proceed sufficiently due to the nature of the reaction raw material, a catalyst for promoting the reaction may be used. Examples of the catalyst include organic tin compounds (for example, dibutyltin laurate, dibutyltin octoate, dibutyltin dimethoxide, etc.), amine compounds (for example, triethylamine, diethanolamine,
Such as dimethylbutylethanolamine) is suitable. In addition to these, titanium compounds, aluminum compounds, zirconium compounds, and the like are also included. The amount of the catalyst used is preferably 0.01-
The amount is 2.5% by weight, more preferably 0.1 to 1.5% by weight, and may be appropriately adjusted according to the kind and amount of the reaction raw material.

In the present invention, an appropriate amount of a polymerization inhibitor may be further added to the reaction system in order to prevent the resulting unsaturated urethane compound from polymerizing in the reaction system. Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, and 2,6-di-tert-butyl-4-methylphenol. The amount of these polymerization inhibitors used is preferably 0.0001 to 1.
The content is 0% by weight, more preferably 0.001 to 0.1% by weight, and may be appropriately adjusted according to the kind and amount of the reaction raw material. If the amount of the polymerization inhibitor used is too large, the curability of the composition of the present invention is deteriorated, and if it is too small, the stability of the composition of the present invention is deteriorated, and gelation may occur during storage or reaction. become.

The ultraviolet-curable composition of the present invention contains an unsaturated urethane compound and usually an ultraviolet (light) curing agent.

The ultraviolet curing agent used in the present invention includes:
For example, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4-
(Methylthio) phenyl] -2-morpholinopropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl ) -Butane-1
-One, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-
1-one, bisacylphosphine oxide, acylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethylbenzoyldiphenylphosphine oxide, benzoyldiethoxyphosphine oxide, bis (2,6
-Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, benzoyl alkyl ether (for example, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, n-butyl benzoin ether), 1- (4 -Isopropylphenyl) -2
-Hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, p-tert-butyltrichloroacetophenone,
p-tert-butyldichloroacetophenone, benzyl, benzoyl, acetophenone, benzophenone, thioxanthones (2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone,
2,4-diisopropylthioxanthone,), dibenzosuberone, 4,4'-dichlorobenzophenone, 4,4 '
-Bis (dimethylamino) benzophenone, 4,4'-
Bis (diethylamino) benzophenone, 3,3 ′,
4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, benzalacetone, biacetyl, α, α-dichloro-4-phenoxyacetophenone, tetramethylthiuram disulfide, α, α′-azobisisobutyronitrile, Benzoyl peroxide, 3,3′-dimethyl-4-methoxybenzophenone, methylbenzoyl formate, 2,2-diethoxyacetophenone, acyloxime ester, chlorinated acetophenone, hydroxyacetophenone, acetophenone diethyl ketal, 4′-isopropyl-2 -Hydroxy-2-methylpropiophenone, methyl phenylglyoxylate, methyl o-benzoylbenzoate, methyl p-dimethylaminobenzoate, 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5 '- Tiger phenyl -
1,2′-biimidazole, 10-butyl-2-chloroacridone, camphorquinone, 3-ketocoumarin, anthraquinones (eg, anthraquinone, 2-ethylanthraquinone, α-chloroanthraquinone, 2-te
rt-butylanthraquinone, etc.), acenaphthene,
4,4'-dimethoxybenzyl, 4,4'-dichlorobenzyl and the like can be mentioned. These are either one or two
One or more species may be used, and the amount used is generally preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the unsaturated urethane compound.

If desired, a reactive diluent or an additive may be added to the ultraviolet curable composition of the present invention together with the unsaturated urethane compound and the ultraviolet curable composition.

The reactive diluent is generally added to reduce the viscosity of the composition, but is added to improve the coating performance such as the adhesion of the composition (cured coating) to the object to be coated. Sometimes Examples of the reactive diluent include a reactive diluent having one unsaturated bond, a reactive diluent having two unsaturated bonds, and a reactive diluent having three or more unsaturated bonds. These reactive diluents can be used alone or in combination of two or more kinds. The amount of the reactive diluent used is preferably 500 parts by weight or less, and more preferably 100 parts by weight or less, with respect to 100 parts by weight of the unsaturated urethane compound. If the amount used exceeds 500 parts by weight, the physical properties of the coating film such as recoatability of the cured coating film may deteriorate. The amount of the reactive diluent used is preferably 5 parts by weight or more with respect to 100 parts by weight of the unsaturated urethane compound in terms of dilution viscosity. In addition, if it does not affect the production of the unsaturated urethane compound (the above-mentioned urethane reaction), it is preliminarily blended in the reaction system together with the raw materials of the unsaturated urethane compound (isocyanate compound, hydroxyl compound). Good.

Examples of the monofunctional compound (having one unsaturated bond) include (meth) acrylic acid and (meth)
Alkyl acrylate, dialkylaminoalkyl (meth) acrylate, glycidyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, acryloylmorpholine, styrene, acrylonitrile, vinyl acetate, vinyltoluene, N- Examples thereof include vinylpyrrolidone.

The alkyl moiety in the above alkyl (meth) acrylate is a linear or branched alkyl group having preferably 1 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and a hydroxy group or a phenoxy group. 1 or more may be substituted with a glycidyl group, a carboxyl group or the like. Specific examples of the alkyl (meth) acrylate include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate,
Hexyl (meth) acrylate, (meth) acrylic acid 2-
Ethylhexyl, isooctyl (meth) acrylate, 2
-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate and the like can be mentioned.

The alkyl moiety in the above-mentioned dialkylaminoalkyl (meth) acrylate is a linear or branched alkyl group having preferably 1 to 20 carbon atoms, more preferably 2 to 8 carbon atoms. Alkyl is
Independently, it may be the same or different, and is a straight chain or branched chain alkyl having preferably 1 to 20, and more preferably 2 to 8 carbon atoms. Specific examples of the dialkylaminoalkyl (meth) acrylate include N, N′-dimethylaminoethyl (meth) acrylate and N, N′-diethylaminoethyl (meth) acrylate.

Examples of the bifunctional compound (having two unsaturated bonds) include alkanediol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, diallyl phthalate, diallyl isophthalate and diallyl adipate. To be

The alkane portion in the above alkanediol di (meth) acrylate preferably has 1 to 10 carbon atoms.
A straight-chain, branched-chain or cyclic hydrocarbon having 20 or more preferably 2 to 8 and optionally substituted with one or more of a hydroxy group and a phenoxy group. Specific examples of the alkanediol di (meth) acrylate include 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
Examples thereof include ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, and 1,4-butanediol di (meth) acrylate.

The alkylene in the above polyalkylene glycol di (meth) acrylate is a straight chain or branched chain alkylene having preferably 1 to 20, and more preferably 2 to 10 carbon atoms. Specific examples of the polyalkylene glycol di (meth) acrylate include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and caprolactam-modified di (meth) acrylate.

Examples of the trifunctional or higher functional compound include trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, N,
Examples thereof include acrylic acid ester of N, N ′, N′-tetrakis (β-hydroxyethyl) ethyldiamine.

In the present invention, the reactive diluent preferably has the same functional group as the functional group from which the unsaturated bond of the unsaturated urethane compound is derived.

Additives that may be used in the present invention include:
For example, sensitizers, colorants, defoamers, defoamers, wetting agents, leveling agents, antistatic agents, viscosity modifiers, storage stabilizers, antibacterial agents, anti-slip agents, coating film crack preventing agents, adhesion promoting Agent,
Examples thereof include a dispersant, a surfactant, an extender pigment, a release agent, a silane coupling agent, a stabilizer, and a flame retardant, and any commonly used one can be used.

In addition to these, the composition of the present invention may contain organic metal salts such as cobalt naphthenate and cobalt octenoate, paraffin waxes, etc. as an auxiliary agent for improving the surface dryness.

Further, the composition of the present invention contains an unsaturated polyester resin, a vinyl urethane resin, a vinyl ester urethane resin, a polyisocyanate, a polyepoxide, an acrylic resin, an alkyd resin for the purpose of adjusting the curing shrinkage ratio of the coating film. , Urea resins, melamine resins, polyvinyl acetate, vinyl acetate copolymers, polydiene elastomers, saturated polyesters, saturated polyethers and nitrocellulose, cellulose derivatives such as cellulose acetate butyrate, rosin derivatives, flaxseed Oil, tung oil,
Natural and synthetic polymers such as oils and fats such as soybean oil, castor oil and epoxidized oil may be added.

In addition to these natural and synthetic polymers, calcium carbonate, talc, mica, clay, silica powder, colloidal silica, polymer particles, asbestos powder, barium sulfate, aluminum hydroxide, zinc stearate, titanium white, zinc. Various fillers, pigments and dyes such as white, red iron oxide, azo pigments, glass fibers, carbonic acid fibers, silicon carbide fibers and aramid fibers can also be added.

From the viewpoint of curing reactivity, the composition of the present invention is preferably a composition containing no solvent (solvent) (solvent-free composition). However, when the coatability of the composition is taken into consideration, the composition has a liquid state (viscosity (25 ° C.) of 10 to 10000 mPa ·
s liquid form), and may be diluted with an organic solvent to form the liquid form. As such an organic solvent,
For example, methanol, ethanol, isopropyl alcohol, ethyl acetate, toluene and the like can be mentioned.

The UV-curable composition of the present invention can be applied to various plastic products (eg, mobile phone casings, CDs, MDs).
Recording materials such as, PC screen shield cover, plastic cards (magnetic cards, IC cards, cash cards, prepaid cards, telephone cards, etc.), optical plastic moldings (glass lenses, goggles, etc.), floor materials, etc. or wooden products ( For example, it is applied to the surface of a wooden floor, furniture, stairs, etc., and is cured by irradiation with ultraviolet rays. As a result, the cured coating film covers the surface of various products. When the solvent remains in the coating film during curing, it is necessary to dry the coating film to remove the solvent. The coating film can be dried usually by a method of drying the coating material (for example, natural drying, hot air drying, etc.).

The material of the plastic product is, for example, polystyrene, acrylic polymer, polycarbonate, polyvinyl chloride, polyethylene, nylon, polypropylene, modified polypropylene, polyethylene terephthalate, polyethylene naphthalate, ethylene vinyl acetate,
Examples thereof include fibrin-based resins such as polyvinyl alcohol, cellulose acetate, and cellulose butyrate.

"Floor material" in plastic products
For example, vinyl chloride floor tiles such as composition vinyl floor tiles, vinyl floor floor tiles such as homogeneous vinyl floor tiles, foam vinyl floor sheets such as cushion floors, woven laminated vinyl floor sheets, non-woven laminated vinyl floor sheets and other vinyl chloride sheets. In addition to vinyl flooring materials, linoleum flooring materials, rubber tiles, etc. may be mentioned. Further, the composition of the present invention can be applied to a floor coating material provided with a coating film other than the coating film made of the composition of the present invention (that is, the composition of the present invention is further applied repeatedly). . The material of the coating film provided on the surface of the coating floor material is not particularly limited as long as it is usually used, and epoxy resin type, urethane resin type, acrylic resin type, MMA resin type, polyester resin type, etc. Can be mentioned.

The UV-curable composition of the present invention is coated so that the thickness of the cured coating film formed by one-time coating and curing (coating film forming treatment) is 1 μm or more, preferably 5 μm or more. It is recommended that it be provided on the surface of the object. If the thickness of the cured coating film is less than 1 μm, curing failure due to oxygen may occur, which is not preferable. Further, the thickness of the cured coating film formed by one-time coating and curing (coating film forming treatment) is 150 μm.
It is preferably provided on the surface of the object to be coated so as to have a thickness of m or less, preferably 20 μm or less. The thickness of the cured coating is 15
When it is more than 0 μm, the base (the base is the surface of the object to be coated when the cured coating is the first layer anchor coat film, and the cured coating is the second or subsequent anchor coat film or top layer). In the case of a coat film, the adhesion with the surface of the anchor coat film) tends to decrease, which is not preferable.

The total thickness of the multiple coated cured coating film is preferably about 2 to 1000 μm, and more preferably 10 μm.
It is about 100 μm. If the total thickness of the multiple-coat cured coating film exceeds 1000 μm, there is a possibility that the adhesion to the base may be poor and the cost may increase, which is not preferable, and when it is less than 2 μm, the surface of the target coating object Properties (scratch resistance, acid resistance, alkali resistance, solvent resistance, etc.)
May not be sufficiently improved, which is not preferable.

Forming a resin film for a sealer on the surface of an object to be coated with the ultraviolet curable composition of the present invention suppresses the penetration of the composition into the object to be coated, It is preferable because the dry thickness of the coating film can be accurately controlled.
In particular, it is preferable to form a resin film for a sealer on a coating object to which the composition easily penetrates. The coating thickness of the resin film for a sealer can be freely set according to various functions required for the surface of the coating target, and prevents the composition of the present invention from penetrating inside the coating target and is required. The thickness is not particularly limited as long as the coating film performance is exhibited.

The sealer resin is not particularly limited as long as it is a resin usually used as a sealer paint, and examples thereof include urethane-based, acrylic-based, epoxy-based, vinyl acetate-based resins and the like, and organic solvent-based resins. , Aqueous system,
The form thereof may be any one such as an aqueous emulsion system and an aqueous dispersion system. The resin film for a sealer can be dried by an ordinary coating material drying method such as photocuring, natural drying, or hot air drying. Generally, a method in which the drying time is short and light deterioration is small is preferable. It is preferable to dry the resin film for a sealer before applying the composition of the present invention.

As the light source used for curing the composition of the present invention, a light source in the visible light region such as a halogen lamp or a xenon lamp, a light source in the ultraviolet region such as a high pressure mercury lamp or a metal halide lamp, or the sun can be used. it can.
For good curing, it is preferable to use a light source that emits light containing a large amount of short wavelength components.

The irradiation light quantity on the irradiation surface is preferably 10 to 10.
50,000 mJ / cm ² , more preferably 50 to
It is 2000 mJ / cm ² . The irradiation light quantity on the irradiation surface is 1
If it is less than 0 mJ / cm ² , it may be difficult to sufficiently cure it, and it may be difficult to develop the desired coating film physical properties. Also, the irradiation light quantity on the irradiation surface is 5000
When it exceeds 0 mJ / cm ² , a long irradiation time is required when using equipment with low irradiation capacity, and when it is attempted to irradiate the irradiation light amount in a short time, equipment with high irradiation capacity is required. The equipment cost is high, and the coating film may be deteriorated.

[0073]

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

The constituent components in Examples and Comparative Examples are shown below. AGMA is 2-hydroxy-3-allyloxypropyl methacrylate (molecular weight: 200, OHV (mgKOH / g): 280) manufactured by Shin Nakamura Chemical Co., Ltd., A
GAA is 2-hydroxy-3-made by Shin Nakamura Chemical Co., Ltd.
Allyloxypropyl acrylate (Molecular weight: 186,
OHV (mgKOH / g): 301), NK ester 7
01A is 2-hydroxy-3-made by Shin Nakamura Chemical Co., Ltd.
Methacryloxypropyl acrylate (Molecular weight: 21
4, OHV (mgKOH / g): 262), NK ester A-TMM-3L is tetramethylol methane triacrylate (50-55%) and tetramethylol methane tetraacrylate (40-45) manufactured by Shin Nakamura Chemical Co., Ltd.
%) Of the mixture (molecular weight of tetramethylolmethane triacrylate: 298, OHV of the mixture (mgKOH /
g): 110) and Delanate TPA-100 are tris (6-isocyanatohexyl) isocyanurate (molecular weight: 540, NCO equivalent: 23.3, manufactured by Asahi Kasei Corporation).
%,), IPPI is isophorone diisocyanate manufactured by Asahi Kasei (molecular weight: 222, NCO equivalent: 37.8).
%) And HDI are 1,6-hexanediisocyanate (NCO equivalent: 50%, molecular weight: 168) manufactured by Asahi Kasei.

Example 1 [Synthesis of Unsaturated Urethane Compound] (Synthesis Example 1) In a four-necked flask equipped with a thermometer, a condenser, a stirrer and an inert gas inlet, 3 mol of AGMA (600
g), 1 mol of Delanate TPA-100 (540
g), 1 g of hydroquinone as a polymerization inhibitor and 0.5 g of dibutyltin laurate were charged, the reaction was continued at 70 ° C. for 8 hours, and the reaction was stopped when the absorption of isocyanate by FT-IR disappeared, Cooled. Then, the reaction product was diluted with 124.5 g of toluene to obtain an unsaturated urethane compound (composition) solution.

[Preparation of UV-curable composition (coating composition)] 100 g of the unsaturated urethane compound solution produced above, 100 g of isopropyl alcohol, 50 g of ethyl cellosolve, Dolka Gure 651 (manufactured by Ciba Specialty Chemicals Co., Ltd.) Was blended to prepare a coating composition. The solid content concentration of the obtained coating composition is 90%,
The viscosity was 30,000 mPa · s / 25 ° C.

Examples 2 to 8 and Comparative Example 1 An unsaturated urethane compound solution was prepared according to the same procedure and conditions as in Synthesis Example 1 except that the formulation shown in Table 1 was changed (Synthesis Examples 2 to 9) and obtained. An ultraviolet curable composition (coating composition) was prepared in the same manner as in Example 1 using the obtained unsaturated urethane compound solution.

[0078]

[Table 1]

Examples 1 to 8 and Comparative Example 1 prepared above
The following tests were carried out on the ultraviolet curable composition (coating composition).

Curable UV-curable composition (coating composition) was coated on a polycarbonate plate with a wire bar # 10, dried at 80 ° C. for 5 minutes, and then irradiated with ultraviolet rays to be completely cured to a thickness of 5 to 6 μm. A cured coating film was formed. At this time, 100 to 300 mJ / m
Curable Yu those completely cured by ultraviolet irradiation amount of J / cm ² (◎), ultraviolet irradiation of greater than 300 mJ / cm ² (exceed ^{300mJ / cm 2, 800mJ / cm} 2 or less of the amount of UV irradiation) What was completely cured by (3) was evaluated as good curability (◯). Hardness An ultraviolet curable composition (coating composition) is applied to a polycarbonate plate with a wire bar # 10, dried at 80 ° C. for 5 minutes, and then cured at an ultraviolet irradiation dose of 300 mJ / cm ² to obtain a cured coating film ( The pencil hardness of an anchor coat film having a thickness of 5 to 6 μm) was measured. Further, an ultraviolet curable composition (coating composition) was applied onto the cured coating film (anchor coat film) in the same manner as described above, dried, and irradiated with ultraviolet rays (ultraviolet irradiation amount 300 mJ / cm ² ). Then, a cured coating film (top coat film) having a thickness of 5 to 6 μm was formed, and the pencil hardness of this cured coating film was measured. The hardness measurement was based on JIS K5400. A recoatable UV curable composition (coating composition) is applied to a polycarbonate plate with a wire bar # 10, dried at 80 ° C. for 5 minutes, and then irradiated with ultraviolet rays to complete curing without complete curing. A film (thickness 5 to 6 μm) is formed, and a mark (mark) is put on the surface of the cured coating film (anchor coat film) with an oil-based marker, and then an ultraviolet curable composition (paint) is applied to the surface of the cured coating film. The composition) was coated and dried in the same manner as described above, and was completely cured by irradiation with ultraviolet rays to form a cured coating film (top coat film) having a thickness of 5 to 6 μm. After that, a cellophane tape (Nichiban: registered trademark) was attached to the cured coating film (top coat film), and the cellophane tape was peeled off at an angle of 45 ° to the coating film, and then a mark (mark). When the mark remained, the recoatability was evaluated as good (◯), and when the mark (mark) was removed, the recoatability was not evaluated (x). That is, when the mark is removed, the cured coating film (top coat film) is peeled off. In the curing of the coating film, the ultraviolet irradiation amount was adjusted within the range of 100 to 1200 mJ / cm ² . Adhesion to the object to be coated A cellotape peeling test was carried out in accordance with JIS K5400. That is, 2 m of cellotape (Nichiban: registered trademark) was applied to the multiple coating cured coating film prepared above.
m width cross cut test (make a cut in the coating film using a cutter to make 25 squares of 2 mm square (that is, make 6 cuts at 2 mm intervals in the length and width), and above the square Then, a test was conducted in which a cellophane tape was applied to the cellophane tape and the cellophane tape was peeled off at an angle of 45 ° C. with the coating film, and the adhesion was judged by the presence or absence of the squares where the cured coating film peeled off. The case where there is no square was marked (◯), and the case where even one square where the cured coating was peeled off was rejected (x) Solvent resistance Top coat film of the multiple-coat cured coating prepared above Rubbing the surface of the coating with toluene (100
No.), the case where the coating film did not drop off was rated as pass (◯), and the case where the coating film dropped off was rated as fail (x). Acid resistance After dropping 0.1N sulfuric acid (1 mL) onto the top coat film of the multiple coating cured coating film prepared above, leave it at room temperature for 20 hours and reject the whitened coating film (x), whitening, etc. Those with no change in state were rated as pass (◯). Alkali resistance After dropping a 0.1N sodium hydroxide solution (1 mL) onto the top coat film of the multiple-coat cured coating film prepared above,
It was left at room temperature for 20 hours, and when the coating film was whitened, it was rejected (x), and when there was no state change such as whitening, it was passed (◯).

Table 2 shows the physical properties of the coating compositions of Examples 1 to 8 and Comparative Example 1, and Table 3 shows the test results.

[0082]

[Table 2]

[0083]

[Table 3]

From the test results shown in Table 3, the UV-curable composition of the present invention (UV-curable composition of the Examples) shows that the anchor coat film (that is, the cured coating film thereon) having excellent recoatability is obtained. It can be seen that a cured coating film can be achieved which can be overcoated with good adhesion. In particular, the ultraviolet curable compositions of Examples 4, 5, and 8 can realize an anchor coat film having excellent recoatability, and have high hardness (excellent scratch resistance),
Moreover, since an excellent solvent-resistant, alkali-resistant and acid-resistant topcoat film can be realized, a high-performance and highly durable multi-coating UV-curable coating film can be formed only by using it.

[0085]

As is apparent from the above description, according to the present invention, there is provided an ultraviolet-curable composition capable of forming a high adhesion with a top coat film when applied to an anchor coat film. Obtainable. In addition, the stacked coatings firmly adhere to each other, have high hardness (scratch resistance is good), and also have excellent solvent resistance, alkali resistance and acid resistance, and are highly functional and highly durable. It is possible to obtain an ultraviolet curable composition which can realize a coated ultraviolet curable coating film.

Claims (10)

[Claims] 1. An ultraviolet curable composition comprising an isocyanate compound and a hydroxyl compound as raw materials, and at least one unsaturated urethane compound obtained by using a compound having an unsaturated bond in at least one of the raw materials. And at least a part of the unsaturated bonds of the one or more unsaturated urethane compounds are unsaturated bonds derived from an allyl group, for anchor coat film of multi-coat UV curable coating film UV curable composition. 2. The ultraviolet curable composition according to claim 1, wherein an unsaturated bond derived from an allyl group accounts for 8% or more of the unsaturated bonds in one or more unsaturated urethane compounds. 3. The unsaturated bond contained in one or more unsaturated urethane compounds comprises an unsaturated bond derived from an allyl group and an unsaturated bond derived from a (meth) acryloyl group.
The ultraviolet curable composition according to 1 or 2. 4. An unsaturated bond derived from a (meth) acryloyl group is an unsaturated bond derived from a methacryloyl group, and
The product of the average number of unsaturated bonds per molecule of the compound having an unsaturated bond used in one or more unsaturated urethane compounds and the average number of isocyanato groups per molecule of the isocyanate compound is 6.0 or more. The ultraviolet curable composition according to claim 3, which is 5. The unsaturated bond derived from a (meth) acryloyl group is an unsaturated bond derived from an acryloyl group, and 1
When the product of the average number of unsaturated bonds per molecule of the compound having an unsaturated bond used in one or more unsaturated urethane compounds and the average number of isocyanato groups per molecule of the isocyanate compound is 4.0 or more. The ultraviolet-curable composition according to claim 3, which is present. 6. The ultraviolet curable composition according to claim 1, wherein the isocyanate compound is an isocyanate compound having 2 or more isocyanato groups. 7. The ultraviolet curable composition according to claim 1, wherein the hydroxyl compound has an unsaturated bond. 8. An ultraviolet curable composition comprising an isocyanate compound and a hydroxyl compound as raw materials, and at least one unsaturated urethane compound obtained by using a compound having an unsaturated bond in at least one of the raw materials. The unsaturated bond of the one or more unsaturated urethane compound is composed of an unsaturated bond derived from an allyl group and an unsaturated bond derived from a (meth) acryloyl group, and an unsaturated bond derived from the allyl group thereof. Is 8% or more, and the following condition 1 or condition 2 is satisfied, a UV-curable composition for a multi-coat UV-curable coating film. Condition 1: The average per molecule of the compound having an unsaturated bond derived from a (meth) acryloyl group is an unsaturated bond derived from a methacryloyl group and used in one or more unsaturated urethane compounds. The product of the number of unsaturated bonds and the average number of isocyanato groups per molecule of the isocyanate compound is 6.0 or more. Condition 2: The average per molecule of the compound having an unsaturated bond derived from a (meth) acryloyl group is an unsaturated bond derived from an acryloyl group and used in one or more unsaturated urethane compounds. The product of the number of unsaturated bonds and the average number of isocyanato groups per molecule of the isocyanate compound is 4.0 or more. 9. The ultraviolet curable composition according to claim 7, wherein the isocyanate compound comprises an isocyanate compound having 2 or more isocyanato groups. 10. The ultraviolet curable composition according to claim 8 or 9, wherein the hydroxyl compound has an unsaturated bond.