JP2601103B2 - Overcoat agent for untreated polyester resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an untreated polyester tree.
It relates to an overcoat agent for fat . More specifically cured by irradiation such as ultraviolet or electron beam, yet untreated polyester which comprises an active energy ray curable resin composition having excellent adhesion to untreated port <br/> Riesuteru resin
It relates to an overcoat agent for a resin .

[0002]

2. Description of the Related Art Conventionally, active energy ray-curable resins have been used in various fields such as overcoat agents for various plastics and papers, binders for printing inks, binders for overprint varnishes, binders for paints, and solder resists. ing.

For example, various active energy ray-curable resins such as unsaturated polyester, epoxy acrylate and urethane acrylate are known.
Protects the base material such as plastic, gloss of the surface to be coated,
It has improved friction resistance, blocking resistance, and the like.

However, conventional active energy ray-curable resins generally adhere to plastic substrates such as polyvinyl chloride resin, polycarbonate resin and ABS resin, but adhere to plastic substrates such as acrylic resin and polyester resin. However, there is a disadvantage that the adhesion is insufficient. For example, the coating of acrylic resin or polyester resin, when printing or the like, once or subjected to corona treatment or flame treatment, or after Ankako computing, further coating the base material, it is necessary to print such, very A complicated process was required, and it was extremely difficult to directly coat or print an acrylic resin or a polyester resin with an active energy ray-curable resin.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems. That is, the purpose of the present invention is not yet
Untreated polyester containing active energy ray-curable resin composition with excellent adhesion to treated polyester resin
An object of the present invention is to provide an overcoat agent for a steal resin .

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, a specific styrene-
It has been found that the above problems can be completely solved by using a specific composition containing a (meth) acrylic copolymer as a base polymer, and the present invention has been completed.

That is, the present invention relates to (A) amino (meth)
35 to 90% by weight of at least one selected from acrylate and amino (meth) acrylamide, 10 to 65 % of styrenes
% By weight, and a weight average molecular weight obtained by copolymerizing 0 to 55 % by weight of an α, β-unsaturated monomer copolymerizable therewith.
5 to 60% by weight of a copolymer (hereinafter referred to as copolymer (A)) having a content of 5,000 to 50,000 (B) pentaerythritol polyacrylate and / or dipentaerythritol polyacrylate in the reactive diluent at least. 80-80% by weight of reactive diluent 40-95% by weight, (C) additive 0-
10 wt%, and comprising (D) a photopolymerization initiator 0 consists to 20% by weight of active energy ray curable resin composition
It relates to an overcoat agent for untreated polyester resin .

[0008] The copolymer (A) in the present invention comprises at least one of the essential components amino (meth) acrylate and amino (meth) acrylamide (hereinafter referred to as monomer a) and styrenes (hereinafter referred to as monomer b). ), And the optional monomer a
And an α, β-unsaturated monomer (hereinafter, monomer c) copolymerizable with the monomer b.

As the monomer a, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl ( (Meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, etc. Further, these quaternized compounds can be exemplified, and these can be used alone or in combination of two or more. As the quaternizing agent, various known quaternizing agents such as alkyl bromide and epihalohydrin can be selected and used.

The amount of the monomer (a) is determined in consideration of the adhesiveness and curability of the resin composition to the polyester resin substrate, and is usually in the range of 35 to 90% by weight, preferably 40 to 50 % by weight. .

As the monomer b, for example, styrene, α
-Methylstyrene, vinyltoluene and the like.
The amount of the monomer b is determined in consideration of the adhesion of the obtained resin composition to the polyester resin substrate, and is usually 10 to 65% by weight, preferably 50 to 60% by weight in the copolymer.
It is said.

On the other hand, the monomer c is an optional component. For example, a linear or branched alkyl, cycloalkyl, alkenyl, cycloalkenyl or aralkyl group having 1 to 8 carbon atoms is substituted by an oxygen atom of a carboxyl group. Acrylates and methacrylates (hereinafter referred to as (meth) acrylates), specifically, methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic acid Propyl,
Butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, cyclohexyl (meth) acrylate, allyl (meth) acrylate, (meth)
Benzyl acrylate and the like. In addition, organic acid vinyls such as vinyl acetate and vinyl propionate, (meth) acrylonitrile, alkyl (meth) acrylamide, maleic diester, N-vinylpyrrolidone and the like can also be used.

The amount of the monomer c is usually from 0 to 55 % by weight, and if it exceeds 55 % by weight, the adhesion to the polyester resin becomes insufficient. Monomer c as an optional component
Is mainly used to adjust the glass transition point and viscosity of the copolymer (A) and to improve the solubility of the copolymer (A) with a reactive diluent. Is appropriately determined depending on various uses.

The copolymer (A) comprises the monomer a,
It can be easily produced by using a predetermined amount of each of the monomer b and, if necessary, the monomer c, and subjecting the monomer mixture to radical polymerization. The method of radical polymerization is not particularly limited, and a known method such as a solution polymerization, a suspension polymerization, or a bulk polymerization method can be appropriately selected, but the solution polymerization method is usually most suitable. In the polymerization, ordinary reaction conditions can be appropriately adopted. For example, when a solution polymerization method is adopted, the monomer may be charged dropwise, charged simultaneously, or dividedly charged.The polymerization temperature is generally about 60 to 120 ° C., and the reaction time is 2 to 2 hours.
About 8 hours. As the polymerization solvent and the radical polymerization initiator, various known ones may be appropriately selected and used. The copolymer (A) obtained as described above has a weight average molecular weight of 5
000 to 50,000, preferably 10,000 to 20,000. When the molecular weight is less than 5,000, the adhesion and curability of the obtained resin composition to the substrate become poor, and
If it exceeds 50,000, the compatibility between the copolymer (A) and the reactive diluent (B) is reduced, so neither is preferred.

The amount of the copolymer (A) to be used can be determined in consideration of the adhesion of the obtained resin composition to the polyester resin and the scratch resistance, and is usually 5 to 60% by weight, preferably 5 to 60% by weight in the resin composition. 15 to 30% by weight.

The reactive diluent (B) in the present invention is:
Acrylic oligomer and acrylic monomer are selected in consideration of adhesiveness and scratch resistance, and specifically, pentaerythritol polyacrylate and / or dipentaerythritol polyacrylate are preferable.
The acrylate is at least 80 in reactive diluent (B).
It is essential that it be contained in an amount of at least% by weight. In addition, pentaerythritol polyacrylate and dipentaerythritol polyacrylate include a complete esterified product and a partial esterified product of the polyhydric alcohol and acrylic acid, and a complete esterified product of the polyhydric alcohol and acrylic acid oligomer (Michael adduct). Esterified products and the partial esterified products are included. The reactive diluent that can be used in addition to the pentaerythritol polyacrylate and dipentaerythritol polyacrylate is not particularly limited. For example, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, bisphenol A
Various known compounds such as tetraethylene glycol diacrylate, N-vinylpyrrolidone, and hexamethylene glycol diacrylate are used, and the amount of these used is less than 20% by weight in the reactive diluent (B). The amount of the reactive diluent (B) to be used can be determined by focusing on the adhesion and scratch resistance of the obtained resin composition to the polyester resin substrate, and is usually 40 to 95% by weight, preferably in the resin composition. Is 70-85% by weight.

The additive (C) is an optional component in the resin composition of the present invention, and can be selectively used as needed. The amount of the additive (C) is about 10% by weight or less in the resin composition. is there. Specific examples of the additive (C) include a slip agent, a leveling agent, and an antifoaming agent.

In the present invention, a photopolymerization initiator (D) is usually used when curing with ultraviolet rays, and is unnecessary when curing with electron beams. As the photopolymerization initiator, various known ones can be used without any particular limitation, and the amount of the photopolymerization initiator used is 0 to 20 in the resin composition.
% By weight, preferably 0 to 10% by weight. Specific examples of the photopolymerization initiator (D) include Darocur 11 ( registered trademark ).
73 (Merck), registered trademark Irgacure 651, registered
Trade mark Irgacure 184, registered trade mark Irgacure 907
(Manufactured by Ciba-Geigy), benzophenone, o-benzoylbenzoic acid methyl ester, p-dimethylaminobenzoic acid ester, p-dimethylacetophenone, thioxanthone,
Examples include alkylthioxanthone and amines.

As described above, the resin composition of the present invention comprises a copolymer (A) and a reactive diluent (B) as essential components, and an additive (C) and a photopolymerization initiator (D) as optional components. ) Can be easily obtained by blending them in predetermined amounts. The proportion of those used is such that the copolymer (A)
5-60% by weight, preferably 10-30% by weight, reactive diluent (B) 40-95% by weight, preferably 70-90% by weight, additive (C) 0-10% by weight, photopolymerization Initiator (D) is 0-20
% By weight, preferably in the range of 0 to 10% by weight.

When the amount of the copolymer (A) is less than 5% by weight, the adhesion to a polyester resin substrate or the like is insufficient.
Both are not preferred because the scratch resistance of the cured film of the line-curable resin composition is significantly reduced.

In addition to the copolymer (A), the reactive diluent (B), the additive (C), and the photopolymerization initiator (D), an organic compound for preventing resin precipitation and adjusting the viscosity. Solvents can also be added. Any organic solvent may be used as long as it does not attack the base material and can sufficiently dissolve the resin composition. For example, toluene and isopropyl alcohol are suitable. The amount of the organic solvent used is arbitrary, and is appropriately determined according to various uses.

The thus obtained active energy of the present invention
Untreated polyester containing a line-curable resin composition
The viscosity at the time of application of the resin overcoating agent differs depending on the use in which the composition is used, and is appropriately determined in consideration of coating film performance, coating film leveling, and the like.

The coating method is not particularly limited, and known means such as a roll coater, a spray coater, a gravure coater, a flexo coater, an offset printing machine, and a screen printing machine are appropriately employed. be able to.

[0024]

The effect of the present invention for the untreated polyester resin
Bar coating agents have excellent adhesion to various substrates. In particular, it is excellent in adhesion to an untreated polyester resin, which was poor in adhesion and could not be directly coated.

[0025]

EXAMPLES The present invention will be described in more detail with reference to Production Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples. In each of the following examples
Are parts by weight unless otherwise indicated.

Synthesis Example 1 (Production of copolymer) 192.5 parts of styrene (hereinafter referred to as St) was placed in a reactor equipped with a stirrer, a cooling pipe, a dropping funnel and a nitrogen inlet pipe.
N, N-dimethylaminoethyl methacrylate (hereinafter referred to as D
After adding 157.5 parts of xylene, 350 parts of xylene and 10.5 parts of 2,2'-azobisisobutyronitrile (hereinafter referred to as AIBN), the system temperature was about 90 ° C. over about 1 hour under a nitrogen stream. And kept for 1 hour. Next, from a dropping funnel previously charged with a mixture consisting of 192.5 parts of St, 157.5 parts of DM, 350 parts of xylene and 10.5 parts of AIBN, the mixture was introduced into the system in about 1 hour under a nitrogen stream. The solution was added dropwise and kept at the same temperature for 4 hours to complete the polymerization.
After the completion of the reaction, the temperature was raised to 170 ° C., the pressure was reduced to about 30 mmHg, and xylene was distilled off to obtain a target copolymer. This is designated as resin A.

Synthetic Example 2 In Synthetic Example 1, the amount of monomer used during initial charging and post-charging was changed from 192.5 parts to 175 parts of St, respectively.
The reaction was carried out in the same manner as in Synthesis Example 1 except that DM was changed from 157.5 parts to 175 parts to obtain a target copolymer. This is called resin B.

Synthesis Example 3 In Synthesis Example 1, the amount of the monomer used during the initial preparation and the amount after the preparation were changed from 192.5 parts St to 210 parts, respectively.
The reaction was carried out in the same manner as in Synthesis Example 1 except that M was changed from 157.5 parts to 140 parts to obtain a target copolymer. This is called resin C.

Synthesis Example 4 A reaction was carried out in the same manner as in Synthesis Example 1 except that DM was changed to N, N-dimethylaminopropylacrylamide (hereinafter referred to as DMAPAA) to obtain a target copolymer. This is designated as resin D.

Example 1 (Preparation of Resin Composition) 20 parts of resin A, pentaerythritol tetraacrylate ( trademark beam set 71 manufactured by Arakawa Chemical Industries, Ltd.)
0) 80 parts (hereinafter referred to as Bs-710), 3 parts of a leveling agent (silicone-based acrylate), 5 parts of a photopolymerization initiator (manufactured by Ciba Geigy, registered trademark Irgacure 184), and 40 parts of toluene were weighed into a beaker. It was stirred and dissolved.

[0031] (Test Film preparation) corona treated PET film (Toray Co., Ltd., registered trademark Le <br/> mirror T-type) and untreated PET film (Toray Co., Ltd., registered trademark Lumirror S type) above The varnish was applied using a bar coater # 3, and passed twice using a high-pressure mercury lamp under the conditions of 120 W / cm × 1 light, irradiation distance of 20 cm, and belt speed of 30 m / min. Prepared.

(Evaluation of Performance) (1) Adhesion In accordance with JIS K 5400, a cut was made on the test film as a cross cut, and then a cellophane tape peeling test was performed to evaluate based on the following evaluation criteria. ：: The cured film does not peel off from the substrate at all. Δ: Part of the cured film was peeled off from the substrate. X: The cured film is completely peeled off from the substrate. (2) Scratch resistance The cured film was rubbed with steel wool and evaluated based on the following evaluation criteria. ：: No damage at all. Δ: Slightly damaged. ×: Damaged. Table 2 shows the evaluation results of the adhesion and the scratch resistance.

Examples 2 to 5 In the same manner as in Example 1, except that the type of the copolymer (A) or the type of the reactive diluent (B) was changed as shown in Table 1, I did it. Table 2 shows the evaluation results.

Comparative Examples 1 and 2 The procedure of Example 1 was repeated except that the type of the copolymer (A) or the type of the reactive diluent (B) was changed as shown in Table 1. I did it. Table 2 shows the evaluation results.

Examples 6 to 9 The procedure of Example 1 was repeated, except that the varnish composition was changed as shown in Table 3. Table 3 shows the evaluation results.

Comparative Examples 3 and 4 The procedure of Example 1 was repeated except that the varnish composition was changed as shown in Table 3. Table 3 shows the evaluation results.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

 ──────────────────────────────────────────────────続 き Continuation of the front page Examiner Yumiko Isshiki (56) References JP-A-3-215543 (JP, A) JP-A-59-47245 (JP, A)

Claims (2)

(57) [Claims] 1. (A) 35 to 90% by weight of at least one selected from amino (meth) acrylate and amino (meth) acrylamide, 10 to 65 % by weight of styrenes, and α, β-non-copolymerizable therewith. Saturated monomer 0 to 55 % by weight
(B) pentaerythritol polyacrylate and / or dipentaerythritol polyacrylate having a content of at least 80% in a reactive diluent. 40-95% by weight of a reactive diluent, which is 0% by weight;
10 wt%, and (D) consisting of photoinitiator 0-20% by weight, contain an active energy ray curable resin composition
Overcoat agent for untreated polyester resin . 2. The copolymer (A) has a weight average molecular weight of
2. The untreated polyester according to claim 1, wherein the amount is from 10,000 to 20,000.
Overcoat agent for resin .