JPS63150304A - Ultraviolet-curable resin - Google Patents

Abstract

PURPOSE:To obtain the title resin which can give a cured product excellent in adhesion to polyolefins, etc., solvent resistance, weathering resistance, low- temperature flexibility, etc., by esterifying a maleic acid (anhydride) adduct of a specified copolymer with a specified compound having an ethylenically unsaturated double bond and a hydroxyl group. CONSTITUTION:An ultraviolet-curable resin prepared by esterifying a maleic acid or maleic anhydride adduct of at least one member selected from the group consisting of a styrene/butadiene/styrene triblock copolymer, a styrene/ butadiene diblock copolymer and hydrogenation products thereof with a compound of formula I [wherein R<1> is H or CH3, R2 is a group of any one of formulas II, III, IV and V (wherein n is 1-8) or a group of formula VI]. This resin before curing can be easily formulated into a paint or an ink and, when cured, it can give a cured product excellent in adhesion to various plastics such as polyolefin resins, solvent resistance, weathering resistance, low-temperature flexibility and plasticity, so that it is useful as a coating agent, a priming agent, a paint or the like for various plastics and metals, etc.

Description

[Detailed Description of the Invention] (,) Purpose of the Invention What is the invention? The present invention relates to a radiation curable resin that provides a hexagonally cured product that has excellent adhesion to lyolefin and the like, and has excellent solvent resistance, weather resistance, low temperature flexibility, and flexibility.

(Industrial Application Field) The ultraviolet curable resin of the present invention can be widely used in applications such as coating agents for various plastics and metals such as polyolefins, undercoating agents, paints, and vehicles for printing inks. .

(Prior Art) In recent years, tetraolefins such as polyethylene and polypropylene have come to be widely used in automobile parts, household electrical appliances, etc. because they are inexpensive and lightweight. However, when polyolefin molded products are coated or bonded with paint or other resins on their surfaces to increase their commercial value, their low polarity makes it difficult for paints or other coatings to adhere to them. was there.

Methods known to improve this drawback of polyolefin include treating the surface of the olefin molded product with chromic acid, treating it with flame, or treating it with a solvent, but all of these methods require complicated treatment methods. It takes time and effort,
There are drawbacks such as the use of corrosive chemicals, which is dangerous, and the need for strict process control to provide stable adhesion.

In addition, as a method for surface modification of polyolefin molded products, there is a method of molding polypropylene modified with an alicyclic cargenic acid having a cis-type double bond in the ring or its anhydride, or a method of molding polypropylene modified with an alicyclic cargenic acid having a cis-type double bond in the ring, or a method of molding the above-mentioned resin on the surface of a polyolefin molded product. Methods for chemically bonding cyclic carboxylic acids or their anhydrides have been proposed and devised. However, the former method requires the entire molding polypropylene to be modified in order to modify the surface of the molded product, which is economically disadvantageous, while the latter method requires a complicated treatment process and takes a long time. It is impractical because it requires a lot of time.

Furthermore, methods have been proposed in which the surface of polyolefin molded articles is coated with various treatment agents, paints, ink vehicles, etc. that have adhesion to polyolefins. For example, Japanese Patent Publication No. 44-958 discloses a treatment agent for polyolefins in which amorphous polypropylene modified with maleic acid or its anhydride is dissolved in a solvent.
The publication describes that an amorphous polyolefin is chemically prepared from alicyclic carganic acid having a cis-type non-conjugated double bond in the ring, α,β-unsaturated carganic acid, or anhydride of these carmenic acids. A primer for polyolefins has been proposed containing a modified polyolefin bonded to a polyolefin. Furthermore, chlorinated polypropylene reacted with an unsaturated compound and chlorinated maleic anhydride/lipropylene were proposed as primers for polypropylene or vehicles for paints.

Methods using these processing agents and primers have the advantage of being able to impart adhesion through simple processing and short processing times, so they can be processed on a series of lines that are continuous with the painting process. In the case of a treatment agent using polyolefin, the surface of the molded product becomes sticky after the treatment agent is applied, which tends to cause uneven thickness, and the smoothness of the coating film after applying the finishing paint is poor, and the adhesion performance provided is poor. It has the disadvantage that it decreases over time. In addition, modified polypropylene chlorinated esters, ketones, chlorinated hydrocarbons, etc. are easily dissolved in many solvents, and have the disadvantage of poor solvent resistance and poor weather resistance.

(Problems to be Solved by the Invention) The present invention aims to improve the drawbacks of conventional resins used in processing agents and primer staining agents to improve adhesion to polyolefins, especially before curing. ■The resin itself has excellent heat dissolving properties in solvents or reactive diluents and pigment dispersibility, making it highly suitable for making into paints or inks.
Moreover, after curing, we aim to provide an ultraviolet curable resin that has excellent adhesion to glass materials such as polyolefins, and can provide a cured product with excellent solvent resistance, weather resistance, low-temperature flexibility, and flexibility. It is something to do.

(b) Structure of the invention (means for solving the problem) As a result of repeated research in order to solve the above problem, the inventors have developed a styrene-butano double block copolymer. , maleic acid or maleic anhydride adduct K of hydrogen acetate of these copolymers, esterified product obtained by esterification reaction of a specific compound having an ethylenically unsaturated double bond and a hydroxyl group (high・The molecular compound) has excellent solubility and pigment dispersibility in various solvents or reactive diluents, and is highly suitable for forming into paints or inks.Moreover, it can be easily cured by UV irradiation, making it a polyolefin. The present invention was achieved based on the knowledge that a cured product can be obtained which has excellent adhesion to plastics such as, and also has excellent solvent resistance, weather resistance, low-temperature flexibility, and flexibility.

That is, the ultraviolet curable resin of the present invention includes a styrene-butadiene-styrene triblock copolymer, a styrene-butadiene-styrene triblock copolymer,
A maleic acid or maleic anhydride adduct of at least one copolymer selected from tutadiene diblock copolymers and hydrogenated products of these copolymers, and a compound of the general formula [wherein R1 is hydrogen or - CH, represents a group and R2 is +0
CH2CH2+ group (wherein n represents an integer of 1 to 8).

), 0M3 40CH2-CH+ group (wherein n represents an integer of 1 to 8).

10+cH2÷ group (wherein, n represents an integer of 1 to 8.

), n represents an integer of 1 to 8. ), or -NH-CH2
- indicates a group. ] It is an esterified product with the compound represented by.

Examples of the starting material styrene-butadiene-styrene triblock copolymer used to produce the ultraviolet curable resin (esterified product) of the present invention include, for example, the trademark "
Kraton 1101” and “Kraton 11
02" sold by Shell Chemical Company.

This styrene-butadiene-styrene triblock copolymer and styrene-butadiene dipro.

Methods for making these copolymers are well known to those skilled in the art, and typical procedures are described in U.S. Pat. No. 3,265,765:
(August 9, 1966).

This method generally involves styrene monomer and butadiene-1
, 3 monomers in the presence of a catalyst represented by the formula R(Li), where is a hydrocarbon residue selected from the group consisting of

In addition, as a hydrogenated product of styrene-butadiene-styrene triblock copolymer, for example, the trademark "Krat"
on G-1652', "Kraton G-
1657”.

”Kraton G-1650=and”Krato
It is also sold by Shell Chemical Company as n G-1651=. In addition, as a hydrogenated product of styrene-butadiene diblock copolymer, for example,
Kraton G-1726X' is a 7:3 (weight ratio) mixture of hydrogenated styrene-butadiene dipro-copolymer and hydrogenated styrene-prodiene-styrene tripro-copolymer. Commercially available from Chemical Company. The structure of such a block copolymer with hydrogenated double bonds in the molecule is disclosed in, for example, Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 6636-1973, Japanese Patent Publication No. 20504-1977, and Japanese Patent Publication No. 48-3555. etc. are stated in each specification.

In order to produce the ultraviolet curable resin of the present invention using such a block copolymer or a copolymer which is a hydrogenated product thereof, maleic acid or maleic anhydride is first added to these block copolymers or a hydrogenated product thereof. Addition reaction is performed.

The maleic acid or maleic anhydride addition reaction is carried out by dissolving the raw material copolymer such as a block copolymer or its water bulk additive in an appropriate organic solvent, and then adding maleic acid or maleic anhydride.
It may be carried out by a solution reaction method in which the graft reaction is carried out by adding a carcinoid/nocal generating catalyst such as peroxides or azonitrile all at once or in portions while heating and stirring, or by adding styrene/butadiene.・Maleic acid or maleic anhydride and the above-mentioned radical generating catalyst are added to a raw material copolymer such as a polycopolymer or its hydrogenated product into a styrene mold mouth, and the mixture is melt-kneaded in an extrusion mode to perform a graft reaction. This may be carried out by a melt intermixing method.

or 1 to 20% by weight, preferably 3 to 15% by weight, based on the maleic acid or maleic anhydride adduct of the raw material copolymer, such as a hydrogenated product thereof. If the amount of maleic acid or maleic anhydride added is too small, the compound of general formula (1) (hereinafter sometimes referred to as "unsaturated alcohol") cannot be esterified in a sufficient amount. First, the esterified product cannot exhibit sufficient ultraviolet curing performance. Moreover, if the amount added is too large, the cohesive force of the esterified product will decrease, and the flexibility of the cured resin coating will decrease.

The maleic anhydride adduct of the copolymer obtained by K as described above is used for producing the esterified product of the present invention, that is, the ultraviolet curable resin. What is necessary is to carry out an esterification reaction with the compound represented by the above-mentioned general formula (1) (ie, unsaturated alcohol). For example, a comonomeric maleic acid or maleic anhydride adduct is dissolved in a suitable solvent, the unsaturated alcohol mentioned above is added in portions or all at once, and the mixture is heated and stirred to effect an esterification reaction. At this time, it is preferable to add an appropriate amount of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, or phenothiazone to the reaction system in order to prevent the formation of a homopolymer of unsaturated alcohol. Further, in order to promote the esterification reaction, an acid or a basic compound may be used as a catalyst. For example, sulfuric acid, paratoluenesulfonic acid, zinc chloride, sodium acetate, pyridine, etc. are used.

This esterification reaction is carried out using I.
The unsaturated alcohol may be directly added to the reaction product obtained by grafting the raw material copolymer onto maleic acid or maleic anhydride by a solution reaction method to carry out the esterification reaction.

The esterification degree of this esterified product is determined by the maleic acid or maleic anhydride unit contained in the maleic acid or maleic anhydride adduct of the raw material copolymer such as a styrene/butadiene/styrene triblock monomer or its hydrogenated product. 25 to 100% of the carboxyl group based on When the degree of esterification is less than 25 degrees, curing by ultraviolet rays is insufficient and satisfactory solvent resistance, weather resistance, etc. cannot be obtained.

The unsaturated alcohol represented by formula (1) used for esterification is, for example, 2-hydroxyethyl acrylate, 2-hydroxymethacrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, N-methylol acrylamide, Examples include 2-hydroxyethyl acrylate-6-hexanolide addition polymer (degree of polymerization 1 to 8).

K is used to obtain the desired ultraviolet curable resin (esterified product) from the esterified reaction product after esterification, since the esterified product will precipitate if a poor solvent such as acetone is added to the esterified reaction product. , filter, wash and dry.

The ultraviolet curable resin (esterified product) thus obtained easily undergoes a crosslinking reaction and is cured when exposed to ultraviolet rays.

In order to use an uninvented ultraviolet curable resin (esterified product) as an ultraviolet curable resin, it usually contains a photoradical polymerization initiator. Furthermore, a radical polymerization accelerator may also be contained.

The content of the photoradical polymerization initiator is 0.05 to 10% by weight, preferably 0.1 to 7% by weight based on the esterified product.

Various kinds of photoradical polymerization initiators can be used. Examples include benzoin ethers such as isobutyl benzoin ether and isobutyl benzoin ether; penzophenones such as inzophenone and Michler's ketone; thioxanthone such as polythioxanthone and dodecylthioxanthone; ketals such as benzyl dimethyl ketal and acetophenone diethyl ketal.

Examples of the photoradical polymerization accelerator include amines such as triethanolamine and triethylamine.

Furthermore, ultraviolet m-curable resin compositions using the ultraviolet curable resin of the present invention include epoxy-based, urethane-based, acrylic-based, and aluminum Φ-based resins for the purpose of improving the heat resistance, smoothness, etc. of the coating film. A resin for a vehicle of a general paint can be contained as appropriate within a range that does not inhibit ultraviolet curability.

Examples of such resins include those described in "Synthetic Resin Paints" (Kobunshi Publishing Co., Ltd., published on December 1, 1960).

The ultraviolet curable resin composition using the ultraviolet curable resin of the present invention can be used in various ways for elegant purposes. For example, by dissolving it in various concentrations using various solvents or extremely reactive diluents, coating agents, undercoating agents, It can be used as an adhesive, an obstetric agent, etc., and can also be used as a vehicle for printing ink, etc. In addition, in addition to dissolving it in various organic solvents and reactive diluents, it can also be used with nonionic, anionic, and cationic surfactants (for example, nonylphenoloxyalkylene ether, alkylbenzene sulfonic acid salts, etc.). , higher alcohol oxyalkylene ethers, etc.) in the form of an aqueous emulsion.

Further, when used as a paint, ordinary paint additives such as pigments and dispersants may be added.

The blending ratio of these additives for paint is usually 3
It is less than 0 times f[chi. All conventional methods can be used for applying the paint to the substrate, such as brush coating, roll coating, sglazing, dipping, and the like. Further, K used as an ink vehicle can be converted into ink according to a conventional method and then printed by various conventional printing methods.

Painted films and printed surfaces using UV curable resin compositions using the UV curable resin of the present invention as coating agents, undercoat treatment agents, adhesives, paints, vehicles for printing inks, etc. After water evaporates and dries, it can be easily cured by UV irradiation.

A regular ultraviolet irradiation device can be used as is. In addition, if the paint does not contain a large amount of solvent, it is possible to cure the paint by irradiating it with ultraviolet rays after the usual drying process, or by omitting the drying process and irradiating it with ultraviolet rays after applying the paint. Furthermore, even when a reactive diluent is used without using a solvent or water, the coating can be cured by irradiating ultraviolet rays after coating.

(Examples, etc.) Next, examples, comparative examples, and test examples will be given to further describe in detail. In these examples, "parts" and "chi" mean parts and weight %, unless otherwise specified.

Example 1 In a stainless steel pressure-resistant reaction vessel equipped with a thermometer and a stirrer,
Xylene IL, hydrogenated styrene/butadiene/styrene triblock copolymer "Krayton G-1652' (
Shell Chemical Co., Ltd., trade name) 100# was charged, the system was replaced with nitrogen gas, the temperature was raised to 125'CK, and then a xylene solution of maleic anhydride and a xylene solution of dicumyl oxide (maleic anhydride) were charged using a pump. : 11/
10td, dicumyl peroxide 0.15M'/10t
/) from separate conduits over 6 hours, and finally maleic anhydride s, oy, zocumyl peroxide 0.9#
was supplied into the system. After the reaction was completed, the system was cooled to around room temperature, acetone was added to slow down the maleic anhydride grafted block copolymer, and the precipitate was washed repeatedly with acetone. The precipitate after washing is dried under reduced pressure at elevated temperature to a solid content of 100.
A modified resin in the form of a white powder was obtained. As a result of infrared absorption spectrum measurement and neutralization titration of this modified resin, the content of maleic anhydride groups was 4.6% by weight.

Next, 100.9 of the obtained maleic anhydride grafted block/copolymer, p-)luenesulfonic acid II and 300.9 of toluene were put into a reaction apparatus, heated to 60°C, and dissolved by stirring. Then, 8.015 Ii of hydroquinone monomethyl ether was added as a polymerization inhibitor and dissolved.

While this solution was maintained at 60° C., a solution prepared by dissolving 5.4 g of 2-hydroxyethyl acrylate in 100 J' of toluene was added over 2 hours, and after the addition was completed, the reaction was continued for an additional 8 hours.

After the reaction was completed, the amount of free 2-hydroxyethyl acrylate in the reaction solution was determined to be 01%. Therefore,
50% of the carboxyl groups based on maleic anhydride units contained in the maleic anhydride grafted block copolymer
has been esterified.

The obtained esterified solution of the maleic anhydride grafted pro- and polycopolymer was diluted with toluene to obtain a resin solid content of 2.
A 0% resin solution was prepared.

Example 2 Maleic anhydride grafted block copolymer (maleic anhydride content: 4.6%) 10 before esterifying 2-hydroxyethyl acrylate obtained in the middle of Example 1
0N,) 300 Jl of luene and p-) 11 luenesulfonic acid were charged to the anti-ERGFC.

The mixture was heated and stirred at 60DK to dissolve it. Next, hydroquinone monomethyl ether o, o a as a polymerization inhibitor
y was added and dissolved.

While maintaining this solution at 60°C, a solution of 9.7 Ii (2-hydroxyethyl acrylate) dissolved in 1001i of toluene was added over 2 hours, and after the addition was completed, the water was distilled off and the reaction was continued for 15 hours. I let it happen.

After the reaction was completed, free 2-human-oxyethyl acrylate in the reaction solution was quantified and found to be Ots. Therefore, 90 of the carboxyl groups based on the maleic anhydride units contained in the maleic anhydride grafted block copolymer
This means that Q has been esterified.

The obtained esterified solution of the maleic anhydride grafted block copolymer was diluted with toluene to obtain a resin and a solid oxide of 2
0% resin solution.

Example 3 In a stainless steel pressure-resistant reaction vessel equipped with a thermometer and a stirrer,
Xylene 11. Hydrogenated styrene/butadiene/styrene triblock copolymer “Krayton G-1652” 1
After charging 001, replacing the inside of the system with nitrogen gas, and raising the temperature to 125°C, ? A xylene solution of maleic anhydride and a xylene solution of dicumyl peroxide (maleic anhydride: III/10-, dicumyl peroxide 0.1
5II/10-) was fed through separate conduits over a period of 6 hours, resulting in a final maleic anhydride of 18.0! After the completion of the reaction, the system was cooled to around room temperature, acetone was added, the water-saving maleic acid grafted block copolymer was filtered, and further precipitated with acetone. Washed repeatedly. The precipitate after washing is dried under reduced pressure at an elevated temperature to reduce the solid content to 1. A modified resin in the form of white powder with a concentration of 0% was obtained. Infrared of this modified resin.

As a result of performing line absorption spectroscopy and neutralization titration, the content of maleic anhydride groups was 9.9 M.

Next, the obtained maleic anhydride 7 totsuro y/copolymer 1001 top p-) toluene sulfonic acid 111 and toluene 300Ii were put into a reactor, and 6.0t
Dissolve the mixture by heating and stirring, and then add 0.03 J of hydroquinone monomethyl ether as a polymerization inhibitor and dissolve.

This solution was maintained at 60° C., and a solution obtained by dissolving 2-hydroxyethyl acrylate (11.7) II in 100 g of toluene was added over 2 hours, and after the addition was completed, the reaction was continued for another 10 hours.

After the reaction was completed, the amount of free 2-hydroxylethyl acrylate in the reaction solution was determined to be 0%. Therefore, 50% of the xyl groups based on the maleic anhydride units contained in the maleic anhydride grafted block copolymer were esterified.

The obtained solution of the esterified maleic anhydride grafted block copolymer was diluted with toluene to give a resin solid content of 20
Example 4 Maleic anhydride grafted block copolymer (maleic anhydride content 9.9%) before esterifying 2-hydroxyethyl acrylate obtained in the middle of Example 3 (maleic anhydride content 9.9%) 10
0#,) 300.9 of luene and 19 of p-) luene sulfonic acid were charged into a reactor and heated to 60°C with stirring to dissolve them. Next, hydroquinone monomethyl ether 0,06,! is used as a polymerization inhibitor. ii was added and dissolved.

The solution was maintained at 60°C and 2-hydroxyethyl acrylate 21.1 I! A solution obtained by dissolving 100y of toluene was added over 2 hours, and after the addition was completed, the reaction was continued for 15 hours while water was distilled off.

After the reaction was completed, the amount of free 2-hydroxyethyl acrylate in the reaction solution was determined to be 0%. Therefore, 90% of the cargexyl groups based on maleic anhydride units contained in the maleic anhydride grafted block copolymer were esterified.

The obtained solution of the esterified maleic anhydride grafted block copolymer was diluted with toluene to give a resin solid content of 20
% resin solution.

Example 5 Maleic anhydride grafted pro-copolymer (maleic anhydride content 4.6%) 10 before esterifying 2-hydroxyethyl acrylate obtained in the middle of Example 1
0i) Luzy300# and p-) Luenesulfonic acid 1
g was charged into a reactor, heated to 60°C and stirred to dissolve. Next, 0.03.9% of hydroquinone monomethyl ether was added as a polymerization inhibitor and dissolved.

While maintaining this solution at 60°C, a solution of 2-hydroxyethyl acrylate combined, 1.9 dissolved in 1009 in toluene, was added over 2 hours, and after the addition was completed, an additional 14
Allowed time to react.

After the reaction was completed, free 2-hydroxyethyl acrylate in the reaction solution was quantified and found to be 0%. Therefore, based on the maleic anhydride units contained in the maleic anhydride grafted block copolymer, 50 units of the xyl groups were esterified.

The obtained solution of the esterified maleic anhydride grafted block copolymer was diluted with toluene to give a resin solid content of 20
% resin solution.

Example 6 Maleic anhydride grafted block copolymer (maleic anhydride content: 4.6%) 10 before esterifying 2-hydroxyethyl acrylate obtained in the middle of Example 1
0I! ,) 300 g of toluene and p-toluenesulfonic acid II were charged into a reactor and heated to 60° C. with stirring to dissolve them. Next, 0.0311 of hydroquinone monomethyl ether was added as a polymerization inhibitor and dissolved.

While maintaining this solution at 60° C., a solution prepared by dissolving 4.7 I of N-methylolacrylamide in 1009 toluene was added over 2 hours, and after the addition was completed, the reaction was continued for another 10 hours.

After the reaction was completed, free N-methylolacrylamide in the reaction solution was quantified and found to be 0%.

Therefore, 50% of the calxyl groups based on the maleic anhydride units contained in the maleic anhydride gly7pro-pro-copolymer were esterified.

The obtained solution of the esterified maleic anhydride grafted block copolymer was diluted with toluene.

A resin solution with a resin solid content of 20% was prepared.

Example 7 The maleic anhydride grafted block copolymer before esterifying the 2-hydroxyethyl acrylate obtained in the middle of Example 1 had a maleic anhydride content of 4.6 10
0.9, 300 y of toluene, and 11 y of p-)luenesulfonic acid were charged into a reactor and heated to 60° C. with stirring to dissolve them. Next, 0.1.9 g of hydroquinone monomethyl ether as a polymerization inhibitor was added and dissolved.

Plaxel FA4 (trade name, Daicel Chemical Co., Ltd., 2-hydroxyethyl acrylate-6-hexanolide addition polymer (degree of polymerization 4)) while maintaining this solution at 60°C.26.
8. A solution prepared by dissolving 10011 F in toluene was added over 2 hours, and after the addition was completed, the reaction was continued for an additional 18 hours. After the reaction was completed, free plaxel FA4 in the reaction solution was quantified and found to be 0%. Ta. Therefore, 50ts of carmexyl groups based on maleic anhydride units contained in the maleic anhydride graft block copolymer were esterified.

The obtained solution of the esterified maleic anhydride grafted block copolymer was diluted with toluene.

A resin solution with a resin solid content of 20 cm was prepared.

Example 8 In a stainless steel pressure-resistant reaction vessel equipped with a thermometer and a stirrer, a mixture of xylene 7)-t'is"/
v-) After charging yGX-1726'l 00 jF, purging the system with nitrogen gas and raising the temperature to 125°C, a xylene solution of maleic anhydride and dicumyl 9 were added using a pump.
-xylene solution of oxide (maleic anhydride: I g
/l 0m, dicumyl/mother oxide 0.15J'71
0 m) was fed through separate conduits over a period of 6 hours, and finally the maleic anhydride/acid 8. OI, Zikmirno J? -Oxide 1
．． 011 was supplied into the system. After the reaction was completed, the system was cooled to around room temperature, acetone was added, the maleic anhydride grafted block copolymer was filtered, and the precipitate was washed repeatedly with acetone. The washed precipitate was dried under reduced pressure at an elevated temperature to obtain a modified resin in the form of a white powder with a solid content of 100%.

As a result of infrared absorption spectrum measurement and neutralization titration of this modified resin, the content of maleic anhydride groups was found to be 5.
．． It was 1% by weight.

Next, 100 g of the obtained maleic anhydride grafted block copolymer and p-)luenesulfone@! 111 and 300 I of toluene were placed in a reactor, heated to 60°C, stirred and dissolved, and further added 0.015 l of hydroquinone monomethyl ether as a polymerization inhibitor. F was added and dissolved.

While maintaining this solution at 60°C, a solution of 2-hydroxyethyl acrylate 6, OIl dissolved in 1001 toluene was added over 2 hours, and after the addition was completed, the reaction was continued for another 8 hours. The amount of free 2-hydroxyethyl acrylate was determined to be 0. Therefore,
The cal based on the maleic anhydride units contained in the maleic anhydride grafted block copolymer is 50% of the xyl group.
has been esterified.

The obtained solution of the esterified maleic anhydride grafted block copolymer was diluted with toluene to give a resin solid content of 20
% resin solution.

Example 9 Maleic anhydride grafted block copolymer (maleic anhydride content 4.6%) obtained in the middle of Example 1 and before esterifying 92-hydroxyethyl acrylate (maleic anhydride content 4.6%) 10
0#, toluene 30011, and 1 g of p-)luenesulfonic acid were charged into a reactor and heated to 60° C. with stirring to dissolve them. Next, 0.015 JF of hydroquinone monomethyl ether was added as a polymerization inhibitor and dissolved.

While this solution was maintained at 60° C., a solution obtained by dissolving 2-hydroxyethyl acrylate (2.711) in 100.9 parts of toluene was added over 2 hours, and after the addition was completed, the reaction was continued for an additional 8 hours.

After the reaction was completed, the amount of free 2-hydroxyethyl acrylate in the reaction solution was determined to be 0%. Therefore, 25% of the xyl groups based on the maleic anhydride units contained in the maleic anhydride grafted block copolymer were esterified.

□The obtained esterified solution of the maleic anhydride grafted block copolymer was diluted with toluene to obtain a resin solution with a resin solid content of 20. □Example i.

Maleic anhydride grafted block copolymer (maleic anhydride content 9.9%) 10 before esterifying 2-hydroxyale acrylate obtained in the middle of Example 3
0I, ) Lezy301) # and p-)Luenesulfonic acid 11 were charged into a reactor and heated to 60° C. with stirring to dissolve them. Next, 0.06 I of hydroquinone monomethyl ether was added as a polymerization inhibitor and dissolved.

While this solution was maintained at 60° C., a solution obtained by dissolving 2-hydroxyethyl acrylate (5.8.9) in 1009 toluene was added over 2 hours, and after the addition was completed, the reaction was continued for another 8 hours.

After the reaction was completed, the amount of free 2- and droxyethyl acrylate in the reaction solution was determined to be 0%. Therefore, 25% of the carboxyl groups based on maleic anhydride units contained in the maleic anhydride grafted block copolymer were esterified.

The resulting solution of the esterified maleic anhydride grafted block copolymer was diluted with toluene to give a resin solid content of 20
A resin solution was obtained.

Comparative Example 1 "Krayton G-1652" (trade name, Shell Chemical Co., Ltd.), a hydrogenated product of styrene fist butadiene φ styrene triblock copolymer, was directly dissolved in toluene to prepare a solution with a resin solid content of 15%. Comparative Example 2 Maleic anhydride grafted block copolymer (maleic anhydride content: 4.6%) before esterifying 2-hydroxyethyl acrylate obtained in the middle of Example 1
was dissolved in toluene to obtain a solution with a resin solid content of 15%.

Comparative Example 3 The maleic anhydride grafted block copolymer (maleic anhydride content: 9.9%) obtained in the middle of Example 3 before esterification of 2-hydroxyethyl acrylate was dissolved in toluene to reduce the resin solid content. It was made into a solution of 15-.

Comparative Example 4 "Krayton GX-1726" (trade name of Shell Chemical Co.), which is a mixture of styrene Φ butadiene-styrene triplicate copolymer and styrene-butadiene diplolytic copolymer hydrogenated, was directly dissolved in toluene. , a solution having a resin solid content of 15% was prepared.

Comparative Example 5 Maleic anhydride grafted block copolymer (maleic anhydride content: 5.1%) before esterifying 2-hydroxyethyl acrylate obtained in the middle of Example 8
was dissolved in toluene to obtain a solution with a resin solid content of 15%.

Experimental Examples 1 to 15 Each resin solution obtained in Examples 1 to 10 was diluted with toluene to prepare each paint A, each having a resin solid content of lO-,
~A1o was obtained. Similarly, each resin solution obtained in Comparative Examples 1 to 5 was diluted with toluene to obtain each paint A'5 having a resin solid content of 10%.

Furthermore, each resin liquid 10 obtained in Examples 1 to 12
0 parts, 5 parts of titanium oxide, and 2 parts of phthalocyanine/2
．． Add 5 parts of each, dilute each with toluene so that the resin solids content is 10%, and add 2 parts with an attritor.
After kneading for 4 hours, each paint B1 to B1o was obtained. Similarly, 5 parts of titanium oxide and 2.5 parts of phthalocyanine blue were added to 100 parts of each resin solution obtained in Comparative Examples 1 to 5, and each was diluted so that the resin solid content was 10%. The mixture was kneaded for 24 hours using an attritor to obtain each paint B1 to B'i.

The storage stability and coating film property test results of each of the obtained paints are as shown in Table 1.

[)1 Notes to Table 1: The test methods and evaluation criteria for test results for each test listed in Table 1 are as follows.

(1) Storage stability of paints (Concern 1): The storage stability of paints is determined by placing each paint in a glass pin, sealing it, leaving it at room temperature for 3 months, then visually observing its appearance, and using the following evaluation criteria: It was evaluated according to the following.

○...No precipitation, no separation Δ...Some precipitation υ ×...A lot of precipitation (11) How to apply paint (1) 2): (Coating to glass) Each plastic 1~ mentioned below ■The surface of the molded test piece is 1
．． 1.1-) After degreasing with lychloroethane vapor for 91 minutes, each paint was spray-painted to obtain a dry film of 10 μm. Next, it was dried for 10 minutes at 50° C. using a hot air dryer.

Furthermore, in the case of the paint of Experimental Side Light~↓4 using the resin of each example, it was dried at 80°C for 30 minutes in a dryer using a 20 W/cm high pressure mercury lamp.

The test pieces of Glasstic 1 to ① used in this case were obtained by the method described below.

Plastic I: 25 parts of Kraton G-1652 (trade name, Shell Chemical Company), which is a commercially available hydrogenated styrene-butadiene-styrene triblock copolymer, and 25 parts of ethylene (<75%)/propylene copolymer rubber with a Mooney viscosity of 32. , and commercially available propylene/ethylene manufactured by Mitsubishi Yuka Co., Ltd. (7%
) Block copolymer (MFR45h/10min) 50 parts were blended, mixed for 2 minutes using a super mixer (manufactured by Shuen Seisakusho), and kneaded at 220°C using a PCM twin-screw kneader (manufactured by Ikegai Tekko Co., Ltd.). The composition is granulated into pellets, and the pellets are used in a screw in-line injection molding machine.
It was molded at 40°C into a test piece with a wall thickness of 2mm and a size of 100mm x 100+z.

f2 stick ■ Commercially available polypropylene manufactured by Mitsubishi Yuka Co., Ltd. was injection molded to form a test piece with a wall thickness of 100 m x 100*x.

Plastic■ Made using propylene/ethylene (7%) block copolymer manufactured by Mitsubishi Yuka Co., Ltd., with a wall thickness of 2 mys.
A test piece measuring 0 mm x 100 mm was formed.

Plastic■ Commercially available polyamide resin (trade name: PA manufactured by Ube Industries, Ltd.)
1013 RW-1) was molded into a 100 mm x 100 mm test piece with a wall thickness of 2 positive using an injection molding machine at 280°C.

Glasstic ■ Commercially available polybutylene tele-7 tallate resin (Toshi Co., Ltd. trade name PBT 5201-Xll) was molded into a 100 m x 100 mm test piece with a wall thickness of 2 mm using an injection molding machine at 250°C.

Plastic ■ A commercially available unsaturated polyester resin molded product (trade name: SMC-N12, manufactured by Takeda Pharmaceutical Company Limited) was cut into test pieces.

(Coating on steel plate) 0,8+sX 70 *mX 150 mm cold rolled m&t.

Zinc phosphate treatment was performed using the surface treatment agent Sonderytona 3004 (trade name of Nippon Parkerizing Co., Ltd.), and each paint was applied in the same manner as in the case of painting plastics, and dried and other treatments were performed in the same manner.

(111) Initial adhesion (Bone 3): On each painted film, 11 cuts were made in the vertical and horizontal directions at 1 inch intervals, reaching the material.
Apply cellophane tape to 00 squares, carefully peel it off, and check the number of squares that remained without peeling off.
Evaluation was made according to the following criteria.

O...100/100 Δ...(99-80)/Zo.

×...(79~50)/100 ××...(49~O)/100 (1■) Moisture resistance (Courage 4): Each coated test piece was kept at a temperature of 5o±1'C1 relative humidity 98
% or more, and after 240 hours, the appearance of the coating film was examined for blistering, and evaluated according to the following criteria.

O... Good appearance, no blistering Δ... Bulging less than 0.211 m in diameter ×... Bulging more than 0.2 f1 in diameter M Toluene resistance (tatami 5): Each painted test piece was immersed in toluene at 25° C. for 1 minute and 1 hour, respectively, and the resulting coating film was visually observed and evaluated according to the following criteria.

○... Good appearance, no abnormalities ∆ - Slight loss of gloss, cloudiness, etc. After cooling each test piece to -20°C, it was bent at xso°C using an inch mandrel, and the state of the coating film was visually examined and evaluated according to the following criteria.

O: No change Δ: Some small cracks occur ×: Many cracks occur As is clear from the test results in Table 1, the paint using the resin of the example of this invention The coating film, which is coated and cured by ultraviolet irradiation, has excellent initial adhesion to various plastics and steel plates, and also has excellent moisture resistance, toluene resistance, and low-temperature flexibility.

Note that the test results for moisture resistance and toluene resistance were the same for each plastic and steel plate coating.

(c) Effects of the Invention The ultraviolet curable resin of the present invention can be easily made into a paint or ink before curing with ultraviolet rays, and after curing, it has excellent adhesion to various plastics including polyolefin resins. It is possible to provide an a-oxide having excellent solvent resistance, weather resistance, low-temperature flexibility, and flexibility.

Claims (1)

[Scope of Claims] 1) At least one selected from styrene-butadiene-styrene triblock copolymers, styrene-butadiene diblock copolymers, and hydrogenated products of these copolymers.
There are maleic acid or maleic anhydride adducts of copolymers of species, and the general formula▲mathematical formula, chemical formula, table, etc.▼ [In the formula, R^1 represents hydrogen or -CH3 group, and R^2 represents -( OCH_2CH_2)-_n group (wherein, n is 1 to 8
indicates an integer. ) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ Groups (in the formula, n represents an integer from 1 to 8), -O-(CH_
2) -_n group (in the formula, n represents an integer of 1 to 8), -
O-CH_2CH_2-(O-C-CH_2CH_2C
H_2CH_2CH_2)-_n group (wherein, n is 1 to 8
indicates an integer. ), or -NH-CH_2- group. ] An ultraviolet curable resin that is an esterified product with a compound represented by: 2) The esterified product contains 25 to 1 carboxyl groups based on maleic acid or maleic anhydride units contained in the maleic acid or maleic anhydride adduct of the copolymer.
The ultraviolet curable resin according to claim 1, which is an esterified product in which 00% of the resin is esterified. 3) A patent in which the maleic acid or maleic anhydride adduct of a copolymer to be esterified is a maleic acid or maleic anhydride adduct of a copolymer containing 1 to 20% by weight of maleic acid or maleic anhydride units. The ultraviolet curable resin according to claim 1 or 2.